EP3109348A1 - Elektrolyt und verfahren zum elektrolytischen polieren eines metallischen substrats - Google Patents
Elektrolyt und verfahren zum elektrolytischen polieren eines metallischen substrats Download PDFInfo
- Publication number
- EP3109348A1 EP3109348A1 EP15173718.6A EP15173718A EP3109348A1 EP 3109348 A1 EP3109348 A1 EP 3109348A1 EP 15173718 A EP15173718 A EP 15173718A EP 3109348 A1 EP3109348 A1 EP 3109348A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- range
- amount
- acid
- electrolyte
- metallic substrate
- 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
- 239000003792 electrolyte Substances 0.000 title claims abstract description 160
- 239000000758 substrate Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000005498 polishing Methods 0.000 title claims abstract description 36
- 239000008139 complexing agent Substances 0.000 claims abstract description 78
- 239000002253 acid Substances 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- -1 fluoride compound Chemical class 0.000 claims abstract description 31
- 230000003746 surface roughness Effects 0.000 claims description 28
- 239000000654 additive Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 12
- 238000007517 polishing process Methods 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 241001582429 Tetracis Species 0.000 claims description 6
- WDLRUFUQRNWCPK-UHFFFAOYSA-N Tetraxetan Chemical compound OC(=O)CN1CCN(CC(O)=O)CCN(CC(O)=O)CCN(CC(O)=O)CC1 WDLRUFUQRNWCPK-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229940048195 n-(hydroxyethyl)ethylenediaminetriacetic acid Drugs 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 3
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000001226 triphosphate Substances 0.000 claims description 3
- 235000011178 triphosphate Nutrition 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims 4
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 8
- QPCDCPDFJACHGM-UHFFFAOYSA-K pentetate(3-) Chemical compound OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QPCDCPDFJACHGM-UHFFFAOYSA-K 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910003407 AlSi10Mg Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000816 inconels 718 Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
Definitions
- the shaping and surface finishing of metallic substrates has often proven a challenge.
- the shaping and surface finishing of metallic substrates obtained from generative processes such as additive layer manufacturing often exhibit rough surfaces.
- the commonly known shaping and surface finishing methods such as abrasive flow machining are often not applicable to complex surfaces.
- electrochemical methods are known, such as electrolytic polishing.
- the electrolytic polishing effect relies on a dissolution reaction occurring on a metallic substrate forming part of an electrolytic cell when a current is applied, wherein the metallic substrate is dissolved into the electrolyte in form of ions.
- the finding of the present invention is an electrolyte (EL) for the application in an electrolytic polishing process for metallic substrates, resulting in an excellent reduction of surface roughness.
- EL electrolyte
- the invention is directed at an electrolyte (EL) for the electrolytic polishing of a metallic substrate comprising
- the electrolyte (EL) comprises
- the electrolyte (EL) consists of
- the electrolyte (EL) comprises
- the at least one acid compound (A) is selected from the group consisting of inorganic or organic acids such as sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid propionic acid, or mixtures thereof, preferably is selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, or mixtures thereof, more preferably is sulfuric acid.
- the at least one fluoride compound (F) is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, trifluoracetic acid, or mixtures thereof, preferably is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, or mixtures thereof, more preferably is ammonium fluoride.
- the at least one complexing agent is selected from the group consisting of metylglycindiacetic acid (MGDA), ethylenediaminetetraacetate (EDTA), diethylenetriaminepentakismethylenephosphonic acid (DTPMP) aminopolycarboxilic acids (APC) diethylenetriaminepentaacetate (DTPA), nitrilotriacetate (NTA), triphosphate, 1,4,7,10 tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA), phosphonate, diethylenetriaminepentakismethylenephosphonic acid (DTPMP), gluconic acid, ⁇ -alaninediactetic acid (ADA), N-bis[2-(1,2 dicarboxy-ethoxy)ethyl]glycine (BCA5), N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspatic acid (BCA6), tetracis(2-hydroxypropyl, ethylene
- the present invention is directed at a process for the electrolytic polishing of a metallic substrate comprising the steps of
- the current is applied at a voltage of not more than 100 V, preferably of not more than 80 V, more preferably of not more 50 V, even more preferably of not more than 20 V, like in the range of 1 to 100 V, preferably in the range of 1 to 80 V, more preferably in the range of 1 to 50 V, even more preferably in the range of 1 to 20 V, yet even more preferably in the range of 5 to 20 V.
- the electrolyte has a temperature in the range of 10 to 95 °C, preferably a temperature in the range of 40 to 95 °C, more preferably a temperature in the range of 60 to 95 °C, even more preferably a temperature in the range of 70 to 90 °C, yet even more preferably a temperature in the range of 75 to 85 °C.
- the current is applied at a current density in the range of 0.05 to 10 A/cm 2 , preferably at a current density in the range of 0.05 to 5 A/cm 2 , more preferably at a current density in the range of 0.1 to 2.5 A/cm 2 , even more preferably at a current density in the range of 0.1 to 2.0 A/cm 2 , yet even more preferably at a current density in the range of 0.1 to 1.5 A/cm 2 .
- the current is applied for a time in the range of 1 to 240 min, preferably for a time in the range of 1 to 120 min, more preferably for a time in the range of 1 to 60 min, even preferably for a time in the range of 1 to 30 min, yet even more preferably for a time in the range of 2 to 20 min.
- the process comprises at least one additional process step of treating the metallic substrate with a cleaning composition.
- the present invention is directed at the use of at least one complexing agent (CA) in an electrolyte to increase the efficiency of surface roughness reduction in an electrolytic polishing process of a metallic substrate.
- CA complexing agent
- the present invention is directed at the use of at least one complexing agent (CA) in an electrolyte to increase the lifetime of the electrolyte when applied in an electrolytic polishing process of a metallic substrate.
- CA complexing agent
- the invention is directed at an electrolyte (EL).
- EL electrolyte
- electrolyte electrolyte
- electrolyte as used according to the present invention is directed at a fluid that can be applied in an electrolytic cell as conducting medium in which the flow of current is accompanied by the movement of matter in the form of ions.
- the electrolyte (EL) for the electrolytic polishing of a metallic substrate comprises at least one acid compound (A), at least one fluoride compound (F), and at least one complexing agent (CA).
- the electrolyte (EL) does not comprise any other acid compounds, fluoride compounds and complexing agents beside the at least one acid compound (A), the at least one fluoride compound (F), and the at least one complexing agent (CA).
- the electrolyte (EL) is acidic. It is appreciated that the electrolyte has a pH of not more than 6.5, preferably a pH of not more than 6.0, more preferably a pH of not more than 5.5, like a pH in the range of 0.5 to 6.5, preferably a pH in the range of 1.0 to 6.0, more preferably a pH in the range of 2.0 to 5.5, even more preferably a pH in the range of 3.0 to 5.0.
- acid compound as used according to the present invention is directed at an organic or inorganic compound that can accept a pair of electrons to form a covalent bond.
- the at least one acid compound (A) is an essential constituent of the electrolyte (EL).
- the at least one acid compound (A) increases the conductivity of the electrolyte and may benefit an electrolytic polishing process as a catalyst depending on the metallic substrate to be treated.
- the at least one acid compound (A) is comprised in the electrolyte (EL) in an amount of not more than 20 wt.-%, preferably in an amount of not more than 15 wt.-%, more preferably in an amount of not more than 10 wt.-%, even more preferably in an amount of not more than 5 wt.-%, like an amount in the range of in the range of 0.05 to 20 wt.-%, preferably an amount in the range of 0.5 to 15 wt.-%, more preferably an amount in the range of 1 to 10 wt.-%, even more preferably an amount in the range of 1 to 5 wt.-%, based on the weight of the electrolyte (EL).
- the at least one acid compound (A) is selected from the group consisting of inorganic or organic acids such as sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid propionic acid, or mixtures thereof, preferably is selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, or mixtures thereof, more preferably is sulfuric acid.
- the at least one acid compound (A) is aqueous sulfuric acid, wherein sulfuric acid is comprised in an amount in the range of 100 to 20 wt.-%, preferably in an amount in the range of 98 to 50 wt.-%, more preferably in an amount in the range of 98 to 80 wt.-%, even more preferably in an amount in the range of 98 to 90 wt.-%, based on the weight of the at least one acid compound (A).
- fluoride compound as used according to the present invention is directed at a compound that can serve as a source of fluoride ions.
- fluoride ions may be required to support the dissolution process, for example by forming stable complexes with dissolved metal ions.
- the at least one fluoride compound (F) is comprised in the electrolyte (EL) in an amount of not more than 40 wt.-%, preferably in an amount of not more than 30 wt.-%, more preferably in an amount of not more than 15 wt.-%, even more preferably in an amount of not more than 10 wt.-%, like an amount of in the range of 1 to 40 wt.-%, preferably an amount in the range of 1 to 30 wt.-%, more preferably in an amount the range of 2 to 15 wt.-%, even more preferably an amount in the range of 4 to 10 wt.-%, based on the weight of the electrolyte (EL).
- the at least one fluoride compound (F) is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, trifluoracetic acid, or mixtures thereof, preferably is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, , or mixtures thereof, more preferably is ammonium fluoride.
- ammonium fluoride additionally benefits the process of electrolytic polishing of metallic substrates by providing a cationic wetting agent (NH 4 + ) which modifies the polarization of the electrodes.
- complexing agent as used according to the present invention is directed at compounds that form coordinate bonds with a metal atom or ion.
- Chelating agents are complexing agents that form a particular type of complex, that involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a multivalent single central atom.
- these ligands are organic compounds, and are called chelants, chelators, chelating agents, or sequestering agents.
- complexing agent includes both non-chelating complexing agents and chelating complexing agents, the latter being preferred.
- the at least one complexing agent (CA) is an essential constituent of the electrolyte (EL).
- the at least one complexing agent (CA) benefits the long-term stability of the electrolyte (EL) and increases the efficiency of surface roughness reduction achieved by electrolytic polishing of a metallic substrate.
- the at least one complexing agent (CA) is comprised in the electrolyte (EL) in an amount of not more than 30 wt.-%, preferably in an amount of not more than 20 wt.-%, more preferably in an amount of not more than 10 wt.-%, even more preferably in an amount of not more than 5 wt.-%, like an amount in the range of 0.5 to 30 wt.-%, preferably an amount in the range of 0.5 to 20 wt.-%, more preferably an amount in the range of 0.5 to 10 wt.-%, even more preferably an amount in the range of 0.5 to 5 wt.-%, yet even more preferably an amount in the range of 1 to 3 wt.-%, based on the weight of the electrolyte (EL)
- the at least one complexing agent is selected from the group consisting of metylglycindiacetic acid (MGDA), ethylenediaminetetraacetate (EDTA), diethylenetriaminepentakismethylenephosphonic acid (DTPMP) aminopolycarboxilic acids (APC) diethylenetriaminepentaacetate (DTPA), nitrilotriacetate (NTA), triphosphate, 1,4,7,10 tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA), phosphonate, diethylenetriaminepentakismethylene-phosphonic acid (DTPMP), gluconic acid, ⁇ -alaninediactetic acid (ADA), N-bis[2-(1,2 dicarboxy-ethoxy)ethyl]glycine (BCA5), N-bis[2-(1,2-dicarboxyethoxy)ethyl]-aspatic acid (BCA6), tetracis(MGDA), ethylened
- the electrolyte (EL) may comprise at least one medium (M).
- the term "medium” as used according to the present invention is directed at any organic or inorganic compound suitable for providing a medium wherein the electrolytic polishing of metallic substrates can be conducted.
- the at least one medium (M) benefits the process of electrolytic polishing of metallic substrates, for example by increasing the conductivity of the electrolytic cell, by stabilizing the complexes formed by the at least one complexing agent (CA) and/or by providing a sufficient solubility with respect to the compounds comprised in the electrolyte (EL).
- the at least one medium (M) is comprised in the electrolyte (EL) in an amount of at least 10 wt.-%, preferably in an amount of at least 30 wt.-%, more preferably in an amount of at least 50 wt.-%, even more preferably in an amount of at least 70 wt.-%, like an amount in the range of 10 to 98.5 wt.-%, preferably an amount in the range of 30 to 95 wt.-%, more preferably an amount in the range of 50 to 90 wt.-%, even more preferably an amount in the range of 70 to 85 wt.-%, based on the weight of the electrolyte (EL).
- the at least one medium (M) is selected from the group consisting of water, alcohols, ethers, esters, carboxylic acids, and mixtures thereof, like C 1 to C 8 aliphatic alcohols, C 1 to C 8 aliphatic ethers, C 1 to C 8 aliphatic esters, C1 to C8 aliphatic carboxylic acids, and mixtures thereof, preferably from the group consisting of water, alcohols, ethers, and mixtures thereof, like C 1 to C 8 aliphatic alcohols, C 1 to C 8 aliphatic ethers, and mixtures thereof.
- the at least one medium (M) is water.
- water is directed at deionized water.
- the at least one medium (M) is an electrolyte which is compounded with the at least one acid compound (A), the at least one fluoride compound (F), the at least one complexing agent (CA) and optionally additives (AD) to form the electrolyte (EL).
- the at least one medium (M) is water which is compounded with the at least one acid compound (A), the at least one fluoride compound (F), the at least one complexing agent (CA) and optionally additives (AD) to form the electrolyte (EL).
- the electrolyte (EL) is an aqueous electrolyte comprising the at least one acid compound (A), the at least one fluoride compound (F) and the at least one complexing agent (CA).
- the electrolyte (EL) may comprise additional additives (AD) that are applied in the electrolytic polishing of metallic substrates to benefit the process.
- AD additional additives
- Typical additives are known to a person skilled in the art of electrolytic polishing of metallic substrates and are applied according to needs.
- Typical additives for the electrolytic polishing of metallic substrates are for example surfactants, polyvalent alcohols, silicates, thickeners, and the like.
- the additives (AD) are present in the electrolyte (EL) in an amount of not more than 25 wt.-%, preferably in an amount of not more than 15 wt.-%, more preferably in an amount of not more than 10 wt.-%, even more preferably in an amount of not more than 5 wt.-%, yet even more preferably in an amount of not more than 2 wt.-%, like an amount in the range of 0.01 to 25 wt.-%, preferably an amount in the range of 0.01 to 10 wt.-%, more preferably an amount in the range of 0.01 to 5 wt.-%, even more preferably an amount in the range of 0.01 to 2 wt.-%, based on the weight of the electrolyte (EL).
- the invention is further directed at a process for the electrolytic polishing of a metallic substrate.
- a process for the electrolytic polishing of a metallic substrate comprising the steps of
- electrolytic cell as used according to the present invention is directed at an electrochemical cell that undergoes a redox reaction when electrical energy is applied.
- the electrolytic cell can be used to decompose a metallic substrate, in a process called electrolysis.
- the electrolyte (EL) is provided in an electrolytic cell which also contains a suitable cathode.
- the electrolytic cell comprises a container receiving the electrolyte wherein the container is made the cathode of the electrolytic cell.
- at least one separate electrode is present in the electrolytic cell which is made the cathode of the electrolytic cell.
- the electrolytic cell comprises a container receiving the electrolyte and at least one separate electrode, wherein both container and the at least one separate electrode are made the cathode of the electrolytic cell.
- the cathode material is not critical and suitable materials include copper, nickel, mild steel, stainless steel, graphite, carbon and the like.
- the surface of the cathode and the surface of the anode have a surface ratio of at least 10:1, preferably a surface ratio of at least 12:1, even more preferably a surface ratio of at least 15:1, like a surface ratio in the range of 10:1 to 100:1, preferably a surface ratio in the range of 12:1 to 100:1, more preferably a surface ratio in the range of 12:1 to 50:1, even more preferably a surface ratio in the range of 12:1 to 20:1.
- the current from a power source is applied between the at least one electrode and the metallic substrate, i.e. between the cathode and the anode of the electrolytic cell before the metallic substrate is immersed in the electrolyte (EL).
- process step (iii) is conducted before process step (iv).
- the current from a power source is applied between the at least one electrode and the metallic substrate, i.e. between the cathode and the anode of the electrolytic cell after the metallic substrate has been immersed in the electrolyte (EL).
- process step (iii) is conducted after process step (iv).
- the composition of the electrolyte (EL) is critical. It is to be understood that the information provided above and below with respect to the electrolyte (EL) mutually applies to the inventive process for the electrolytic polishing of a metallic substrate in presence of the electrolyte (EL).
- the electrolyte (EL) for the electrolytic polishing of a metallic substrate comprises at least one acid compound (A), at least one fluoride compound (F), and at least one complexing agent (CA).
- the electrolyte (EL) for the electrolytic polishing of a metallic substrate consists of at least one acid compound (A), at least one fluoride compound (F), at least one complexing agent (CA), at least one medium (M), and optionally additives (AD).
- the information provided above and below with respect to the at least one acid compound (A), the at least one fluoride compound (F), the at least one complexing agent (CA), the at least one medium (M) and optionally additives (AD) mutually applies to the inventive process for the electrolytic polishing of a metallic substrate in presence of at least one acid compound (A), at least one fluoride compound (F), at least one complexing agent (CA), at least one medium (M) and/or optionally additives (AD).
- the process for the electrolytic polishing of a metallic substrate can inter alia be applied to metallic substrates with complex surfaces.
- the metallic substrate may be in any form such as, for example, bars, plates, flat sheets, sheets of expanded metal, cuboids, or complex structures.
- the term "metallic substrate” as used herein is meant to encompass substrates comprising at least one conductive metal or metal alloy.
- the metallic substrate consists of at least one conductive metal or metal alloy.
- the metallic substrate comprises, preferably consists of, metals selected from the group consisting of aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, silver, hafnium, tungsten, platinum, gold, steel and combinations thereof, such as alloys, preferably selected from the group consisting of aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, steel and combinations thereof, such as alloys, more preferably selected from the group consisting of aluminium, titanium and vanadium, and combinations thereof, such as alloys.
- the metal substrate is selected from the group consisting of Ti-6Al-4V, AlSi 10 Mg, Al
- the current is applied at a voltage of not more than 100 V, preferably of not more than 80 V, more preferably of not more 50 V, even more preferably of not more than 20 V, like in the range of 1 to 100 V, preferably in the range of 1 to 80 V, more preferably in the range of 1 to 50 V, even more preferably in the range of 1 to 20 V, yet even more preferably in the range of 5 to 20 V.
- the current is applied at a voltage of at least 20 V, preferably of at least 50 V, more preferably of at least 100 V, even more preferably of at least 200 V, yet even more preferably of at least 250 V, like in the range of 20 to 800 V, preferably a voltage in the range of 50 to 600 V, more preferably a voltage in the range of 100 to 500 V, even more preferably a voltage in the range of 200 to 400 V, yet even more preferably a voltage in the range of 250 to 350 V.
- the current is applied at a current density in the range of 0.05 to 10 A/cm 2 , preferably at a current density in the range of 0.05 to 5 A/ cm 2 , more preferably at a current density in the range of 0.1 to 2.5 A/cm 2 , even more preferably at a current density in the range of 0.1 to 2.0 A/cm 2 , yet even more preferably at a current density in the range of 0.1 to 1.5 A/cm 2 .
- the temperature of the electrolyte is at least 10 °C, preferably is at least 40 °C, more preferably is at least 60 °C, even more preferably is at least 70 °C, yet even more preferably is at least 75 °C, like a temperature in the range of 10 to 95 °C, preferably a temperature in the range of 40 to 95 °C, more preferably a temperature in the range of 60 to 95 °C, even more preferably a temperature in the range of 70 to 90 °C, yet even more preferably a temperature in the range of 75 to 85 °C.
- the treatment time is generally within the range of 1 to 240 min.
- the treatment of some metallic substrates may require a shorter or longer treatment for the desired reduction in surface roughness, depending on factors such as initial surface roughness and desired surface roughness, surface area, surface geometry and the like.
- the current is applied for a time in the range of 1 to 240 min, preferably for a time in the range of 1 to 120 min, more preferably for a time in the range of 1 to 60 min, even preferably for a time in the range of 1 to 30 min, yet even more preferably for a time in the range of 2 to 20 min.
- the electrolyte is continuously agitated during the process for the electrolytic polishing of a metallic substrate.
- the agitation may be achieved by immersing a pressurized gas. Suitable gases for immersion are for example, nitrogen, hydrogen helium, argon, and combinations thereof.
- a pressurized gas may have a pressure in the range of 0.01 to 1000 kg/cm 2 , preferably a pressure in the range of 1 to 1000 kg/cm 2 .
- the process for the electrolytic polishing of a metallic substrate comprises a post-treatment step of treating the metallic substrate with a cleaning composition, preferably a post-treatment step of treating the metallic substrate with water, preferably deionized water.
- the process for the electrolytic polishing of a metallic substrate provides metallic substrate with reduced surface roughness.
- the average surface roughness (R a ) of a metallic substrate treated according to the process for the electrolytic polishing of a metallic substrate described is reduced by at least 0.1 ⁇ m, preferably is reduced by at least 0.5 ⁇ m, even more preferably is reduced by at least 1.0 ⁇ m, like in the range of 0.1 to 100 ⁇ m, preferably in the range of 0.5 to 10 ⁇ m, even more preferably in the range of 1.0 to 5.0 ⁇ m.
- a metallic substrate is obtained with an average surface roughness (R a ) of not more than 10 ⁇ m, preferably of not more than 5 ⁇ m, more preferably of not more than 1 ⁇ m, even more preferably of not more than 0.5 ⁇ m, yet even more preferably of not more than 0.1 ⁇ m, like an average surface roughness (R a ) in the range of 10 to 0.01 ⁇ m, preferably an average surface roughness (R a ) in the range of 5 to 0.01 ⁇ m, more preferably an average surface roughness (R a ) in the range of 1 to 0.01 ⁇ m, even more preferably an average surface roughness (R a ) in the range of 0.5 to 0.01 ⁇ m, yet even more preferably an average surface roughness (R a ) in the range of 0.1 to 0.01 ⁇ m.
- R a average surface roughness
- the electrolyte (EL) can be applied for electrolytic polishing of metallic substrates comprising metals or metal alloys. It is a finding of the present invention that the efficiency of surface roughness reduction in an electrolytic polishing process of a metallic substrate can be improved when providing at least one complexing agent (CA). In addition hereto it is a finding of the present invention that the lifetime of an electrolyte can be increased when providing at least one complexing agent (CA).
- CA complexing agent
- the invention is further directed at the use of at least one complexing agent (CA) in an electrolyte to increase the efficiency of surface roughness reduction in an electrolytic polishing process of a metallic substrate.
- CA complexing agent
- the invention is further directed at the use of at least one complexing agent (CA) in an electrolyte to increase the lifetime of the electrolyte when applied in an electrolytic polishing process of a metallic substrate.
- CA complexing agent
- the at least one complexing agent (CA) is described in more detail above and below, in particular in the section "The Complexing Agent (CA)”.
- the average surface roughness (R a ) is determined according to DIN EN 4287:1998-10 using the tactile incision technique according to DIN EN ISO 3274 (Hommel Tester T1000 Wave of Jenoptik, tipradius 5 ⁇ m, taper angle 90°)
- the pH is determined according to DIN 19261:2005-6.
- a current of 20 V is applied from a direct current power source between the cathode and the metallic substrate.
- the metallic substrate is immersed in an electrolyte consisting of 6 wt.-% NH 4 F, 4 wt.-% H 2 SO 4 and 1 wt.-% MGDA.
- the electrolyte has a pH of 3.5.
- the metallic substrate is treated for 10 min.
- a current of 20 V is applied from a direct current power source between the cathode and the metallic substrate.
- the metallic substrate is immersed in an electrolyte consisting of 6 wt.-% NH 4 F and 1 wt.-% H 2 SO 4 .
- the electrolyte has a pH of 3.5.
- the metallic substrate is treated for 10 min.
- the building of oxide layers can be partially be observed on the surface.
- a current of 20 V is applied from a direct current power source between the cathode and the metallic substrate.
- the metallic substrate is immersed in an electrolyte consisting of 6 wt.-% NH 4 F, 4 wt.-% H 2 SO 4 and 1 wt.-% MGDA.
- the electrolyte has a pH of 3.5.
- the metallic substrate is treated for 10 min.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- ing And Chemical Polishing (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15173718.6A EP3109348B1 (de) | 2015-06-24 | 2015-06-24 | Elektrolyt und verfahren zum elektrolytischen polieren eines metallischen substrats |
US15/189,170 US20160376724A1 (en) | 2015-06-24 | 2016-06-22 | Electrolyte and process for the electrolytic polishing of a metallic substrate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15173718.6A EP3109348B1 (de) | 2015-06-24 | 2015-06-24 | Elektrolyt und verfahren zum elektrolytischen polieren eines metallischen substrats |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3109348A1 true EP3109348A1 (de) | 2016-12-28 |
EP3109348B1 EP3109348B1 (de) | 2020-06-03 |
Family
ID=53491314
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15173718.6A Active EP3109348B1 (de) | 2015-06-24 | 2015-06-24 | Elektrolyt und verfahren zum elektrolytischen polieren eines metallischen substrats |
Country Status (2)
Country | Link |
---|---|
US (1) | US20160376724A1 (de) |
EP (1) | EP3109348B1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102016125244A1 (de) * | 2016-12-21 | 2018-06-21 | Airbus Defence and Space GmbH | Verfahren für das Elektropolieren von einem metallischen Substrat |
EP3744445A2 (de) | 2019-05-28 | 2020-12-02 | Airbus Operations GmbH | Verfahren zur herstellung eines komplexen bauteils und trennwerkzeug |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3269848B1 (de) * | 2016-07-13 | 2019-09-11 | Airbus Defence and Space GmbH | Verfahren zur oberflächenbehandlung von metallen und legierungen |
JP7177425B2 (ja) * | 2017-12-28 | 2022-11-24 | 株式会社日本科学エンジニアリング | ステンレス鋼用電解研磨液 |
CN113862769A (zh) * | 2021-11-08 | 2021-12-31 | 中国工程物理研究院机械制造工艺研究所 | 一种用于AlSi10Mg合金表面的电解抛光方法及工件 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4740280A (en) * | 1986-06-20 | 1988-04-26 | Poligrat Gmbh | Electrolyte for electrochemically polishing metal surfaces |
JPS63195300A (ja) * | 1987-02-09 | 1988-08-12 | Mitsubishi Metal Corp | ジルコニウムおよびジルコニウム合金の電解研摩用電解液 |
CN1249367A (zh) * | 1998-09-25 | 2000-04-05 | 李伟明 | 一种无腐蚀脉冲电化学抛光溶液及工艺 |
US20070029209A1 (en) * | 2003-05-09 | 2007-02-08 | Poligrat-Holding Gmbh | Electrolyte for electrochemically polishing metallic surfaces |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005042810A2 (en) * | 2003-10-31 | 2005-05-12 | E.I Du Pont De Nemours And Company | Membrane -mediated electropolishing |
JP4883503B2 (ja) * | 2005-06-21 | 2012-02-22 | 独立行政法人情報通信研究機構 | 多重光路の固体スラブレーザロッドまたは非線形光学結晶を用いたレーザ装置 |
US9127194B2 (en) * | 2006-08-04 | 2015-09-08 | Halliburton Energy Services, Inc. | Treatment fluids containing a boron trifluoride complex and methods for use thereof |
US20090107851A1 (en) * | 2007-10-10 | 2009-04-30 | Akira Kodera | Electrolytic polishing method of substrate |
-
2015
- 2015-06-24 EP EP15173718.6A patent/EP3109348B1/de active Active
-
2016
- 2016-06-22 US US15/189,170 patent/US20160376724A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4740280A (en) * | 1986-06-20 | 1988-04-26 | Poligrat Gmbh | Electrolyte for electrochemically polishing metal surfaces |
JPS63195300A (ja) * | 1987-02-09 | 1988-08-12 | Mitsubishi Metal Corp | ジルコニウムおよびジルコニウム合金の電解研摩用電解液 |
CN1249367A (zh) * | 1998-09-25 | 2000-04-05 | 李伟明 | 一种无腐蚀脉冲电化学抛光溶液及工艺 |
US20070029209A1 (en) * | 2003-05-09 | 2007-02-08 | Poligrat-Holding Gmbh | Electrolyte for electrochemically polishing metallic surfaces |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102016125244A1 (de) * | 2016-12-21 | 2018-06-21 | Airbus Defence and Space GmbH | Verfahren für das Elektropolieren von einem metallischen Substrat |
EP3339483A1 (de) * | 2016-12-21 | 2018-06-27 | Airbus Defence and Space GmbH | Verfahren zum elektrolytischen polieren eines metallischen substrats |
US11162185B2 (en) | 2016-12-21 | 2021-11-02 | Airbus Defence and Space GmbH | Process for the electrolytic polishing of a metallic substrate |
EP3744445A2 (de) | 2019-05-28 | 2020-12-02 | Airbus Operations GmbH | Verfahren zur herstellung eines komplexen bauteils und trennwerkzeug |
DE102019207857A1 (de) * | 2019-05-28 | 2020-12-03 | Airbus Operations Gmbh | Verfahren zur Herstellung eines komplexen Bauteils und Trennwerkzeug |
US11471944B2 (en) | 2019-05-28 | 2022-10-18 | Airbus Operations Gmbh | Method for the manufacture of a complex component and separating tool |
Also Published As
Publication number | Publication date |
---|---|
US20160376724A1 (en) | 2016-12-29 |
EP3109348B1 (de) | 2020-06-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11136689B2 (en) | Method for the surface finishing of metals and alloys | |
US20160376724A1 (en) | Electrolyte and process for the electrolytic polishing of a metallic substrate | |
CN108221041B (zh) | 用于金属基材的电解抛光的方法 | |
Bentiss et al. | Effect of iodide ions on corrosion inhibition of mild steel by 3, 5-bis (4-methylthiophenyl)-4H-1, 2, 4-triazole in sulfuric acid solution | |
KR101497349B1 (ko) | 알루미늄 또는 알루미늄 합금용 에칭제 | |
Taylor et al. | Electrochemical surface finishing | |
CN102428213A (zh) | 金属的表面处理方法 | |
US20080099345A1 (en) | Electropolishing process for niobium and tantalum | |
JP2019119909A (ja) | ステンレス鋼用電解研磨液 | |
JP5799037B2 (ja) | プラズマ電解酸化による皮膜形成方法 | |
JP5365153B2 (ja) | 耐食性に優れた表面処理鋼材 | |
EP2321449B1 (de) | Verfahren zur entfernung von lötspuren bei aluminiumartikeln | |
JP5893066B2 (ja) | ステンレス鋼用中性電解液及び電解方法 | |
KR100618165B1 (ko) | 무전해니켈을 박리하기 위한 전해방법 및 혼합물들 | |
JP2007321219A (ja) | 電解リン酸塩化成処理を用いた潤滑処理方法 | |
JP2004156129A (ja) | 金属の酸化皮膜又は錆除去水、該酸化被膜又は錆除去水を使用した金属の酸化被膜又は錆除去方法 | |
Sanina et al. | Inhibition of pitting formation on copper by microadditives of halide ions in alkaline glycinate media | |
WO2023218390A1 (en) | Chemical solution suitable for polishing niobium and alloys thereof by plasma electropolishing | |
JP2004156129A5 (de) | ||
JP2007302976A (ja) | 高耐食性Niメッキ鋼板の製造方法 | |
Parshutin et al. | Promotion of steel corrosion resistance by chemical-thermal treatment in electrolytes | |
EP4060080A1 (de) | Verfahren zum polieren von teilen aus aluminium | |
JPH07316899A (ja) | 電解加工用電解液組成物 | |
JP2019119908A (ja) | ステンレス鋼用電解研磨液 | |
Parshutin et al. | Corrosion inhibition of steels by calcii borogluconas in electrolytes for electrochemical dimensional processing |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170515 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20170904 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C25F 3/16 20060101AFI20191105BHEP Ipc: C22C 14/00 20060101ALI20191105BHEP Ipc: C22C 28/00 20060101ALI20191105BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20191213 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1277117 Country of ref document: AT Kind code of ref document: T Effective date: 20200615 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015053647 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200904 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200903 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200903 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1277117 Country of ref document: AT Kind code of ref document: T Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201006 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201003 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015053647 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200624 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200624 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200630 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200630 |
|
26N | No opposition filed |
Effective date: 20210304 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200630 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200603 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240621 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240619 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240628 Year of fee payment: 10 |