EP1911862B1 - Elektropolierverfahren für Niob und Tantal - Google Patents

Elektropolierverfahren für Niob und Tantal Download PDF

Info

Publication number: EP1911862B1
Authority: EP; European Patent Office
Prior art keywords: electrolyte; niobium; tantalum; electropolishing; concentration
Prior art date: 2006-10-09
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.): Not-in-force

Application number

EP07018328.0A

Other languages

German (de)

English (en)

French (fr)

Other versions

EP1911862A3 (de

EP1911862A2 (de

Inventor

Siegfried Piesslinger-Schweiger

Olaf BÖHME

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Poligrat GmbH

Original Assignee

Poligrat GmbH

Priority date (The priority date 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 date listed.)

2006-10-09

Filing date

2007-09-18

Publication date

2017-03-01

2007-09-18 Application filed by Poligrat GmbH filed Critical Poligrat GmbH

2008-04-16 Publication of EP1911862A2 publication Critical patent/EP1911862A2/de

2010-08-25 Publication of EP1911862A3 publication Critical patent/EP1911862A3/de

2017-03-01 Application granted granted Critical

2017-03-01 Publication of EP1911862B1 publication Critical patent/EP1911862B1/de

Status Not-in-force legal-status Critical Current

2027-09-18 Anticipated expiration legal-status Critical

Links

238000000034 method Methods 0.000 title claims description 37
GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims description 25
239000010955 niobium Substances 0.000 title claims description 24
229910052758 niobium Inorganic materials 0.000 title claims description 23
229910052715 tantalum Inorganic materials 0.000 title claims description 16
GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims description 16
239000003792 electrolyte Substances 0.000 claims description 46
AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 26
229910052751 metal Inorganic materials 0.000 claims description 24
239000002184 metal Substances 0.000 claims description 24
150000002739 metals Chemical class 0.000 claims description 14
229940098779 methanesulfonic acid Drugs 0.000 claims description 13
MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 10
229910001092 metal group alloy Inorganic materials 0.000 claims description 10
229910001257 Nb alloy Inorganic materials 0.000 claims description 7
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
229910001362 Ta alloys Inorganic materials 0.000 claims description 7
239000002253 acid Substances 0.000 claims description 5
150000007513 acids Chemical class 0.000 claims description 4
KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 7
238000005498 polishing Methods 0.000 description 5
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 4
239000000203 mixture Substances 0.000 description 4
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
239000000463 material Substances 0.000 description 3
239000000126 substance Substances 0.000 description 3
231100000331 toxic Toxicity 0.000 description 3
230000002588 toxic effect Effects 0.000 description 3
NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
239000000470 constituent Substances 0.000 description 2
239000007789 gas Substances 0.000 description 2
239000001257 hydrogen Substances 0.000 description 2
229910052739 hydrogen Inorganic materials 0.000 description 2
229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
229910052500 inorganic mineral Inorganic materials 0.000 description 2
239000011707 mineral Substances 0.000 description 2
238000007517 polishing process Methods 0.000 description 2
GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
239000000654 additive Substances 0.000 description 1
229910045601 alloy Inorganic materials 0.000 description 1
239000000956 alloy Substances 0.000 description 1
229910052782 aluminium Inorganic materials 0.000 description 1
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
229910000147 aluminium phosphate Inorganic materials 0.000 description 1
229910002056 binary alloy Inorganic materials 0.000 description 1
150000001875 compounds Chemical class 0.000 description 1
238000010276 construction Methods 0.000 description 1
230000000694 effects Effects 0.000 description 1
230000007613 environmental effect Effects 0.000 description 1
-1 fluoride ions Chemical class 0.000 description 1
238000011010 flushing procedure Methods 0.000 description 1
238000009499 grossing Methods 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
229910000765 intermetallic Inorganic materials 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
238000005259 measurement Methods 0.000 description 1
229910017604 nitric acid Inorganic materials 0.000 description 1
238000010943 off-gassing Methods 0.000 description 1
230000001681 protective effect Effects 0.000 description 1
230000009257 reactivity Effects 0.000 description 1
239000007790 solid phase Substances 0.000 description 1
229910001220 stainless steel Inorganic materials 0.000 description 1
150000003481 tantalum Chemical class 0.000 description 1
239000010936 titanium Substances 0.000 description 1
229910052719 titanium Inorganic materials 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
- C25F3/22—Polishing of heavy metals
- C25F3/26—Polishing of heavy metals of refractory metals

Definitions

the present invention relates to a process for the electrochemical polishing of surfaces of metals and metal alloys, in particular of such metals and metal alloys, which are selected from the group consisting of niobium, niobium alloys, tantalum and tantalum alloys.
the present invention includes an electrolyte for electropolishing surfaces of these metals and metal alloys. This electrolyte contains methanesulfonic acid and ammonium bifluoride, NH 4 HF 2 .
the process of electrochemical polishing or electropolishing serves to produce metal surfaces of high purity, to smooth and deburr metal surfaces. Smoothing in the micro-region causes the surfaces thus treated to be high-gloss. In addition, by the electropolishing stresses in the outer material layers can be removed.
the prior art discloses a variety of different electropolishing methods that can be used to process various metals and metal alloys. In general, these methods are based on the use of electrolytes containing a concentrated mineral acid or a mixture of concentrated mineral acids, to which additives are often added in order to further improve the effect of the electrolytes, and thus to obtain smoother and more lustrous metal surfaces.
Niobium often called niobium
niobium and tantalum are used both as pure metals and as constituents of alloys with one another and / or with other metals in the production of workpieces, for example of gas turbines or in engine construction.
a method using an electrolyte consisting of a mixture of concentrated sulfuric acid and hydrofluoric acid in the ratio of about 90:10 is used for the electropolishing of niobium.
this electrolyte releases large quantities of gaseous hydrogen fluoride, which is toxic and corrosive. In order to minimize the risk to humans and the environment, this procedure can therefore only be carried out under the strictest and most complex safety measures.
Another disadvantage of this method is that this electrolyte also chemically attacks the niobium surface, especially when the current flow is interrupted. Significant amounts of hydrogen are released, some of which also diffuse into the metal surface and then have to be removed again at great expense by heating under vacuum.
the machined workpieces In order to keep the chemical attack of the electrolyte on the electropolished surface as low as possible, therefore, the machined workpieces usually have to be cooled very rapidly after switching off the current. be taken out of the bath within a few seconds and be completely rinsed. This rapid flushing often requires special equipment and is therefore also associated with high costs. Therefore, the method quickly reaches its limits, especially when working with larger components, and has limited application.
the patent application WO 01/71068 A1 discloses electrolytic polishing processes wherein, among others, tantalum and niobium are electropolished with an electrolyte of methanesulfonic acid and methanol. While this tantalum electropolishing process appears to have good results, there is no indication of the quality of the electropolishing process in niobium surface processing.
the Japanese patent application JP 60092500 A2 uses a mixture of sulfuric acid and fluorosulfonic acid (fluorosulfuric acid). Although no toxic hydrofluoric acid gases are released, the use of fluorosulphonic acid is extremely complex and expensive because of the high reactivity to a contact between fluorosulfonic acid and air to avoid largely, as this toxic vapors may also arise.
FIG. 1 Fig. 10 shows the decrease in roughness values Ra and Rz in electropolishing a niobium sheet according to the method of the present invention (see Example 1).
the present invention is a process for electropolishing surfaces of metals and metal alloys, which is particularly suitable for the processing of surfaces of niobium, niobium alloys, tantalum and tantalum alloys.
Niobium and tantalum alloys are understood as meaning both solid phase mixtures and compounds of niobium and tantalum with one another and of one or both metals with other elements which have a metallic character or else form intermetallic compounds.
the application of this procedure is largely safe for humans and the environment.
an electrolyte containing no sulfuric acid, over 80% by weight of methanesulfonic acid, and ammonium bifluoride (ammonium hydrogen difluoride, NH 4 + HF 2 - ) is used. This electrolyte is also an object of the present invention.
the concentration of methanesulfonic acid used in the electrolyte is at least 90%.
the concentration of ammonium hydrogendifluoride in the electrolyte is between 5 and 100 g / l, preferably between 20 and 70 g / l. If the metal surface is a niobium or niobium alloy surface is particularly preferred that the concentration of ammonium hydrogen difluoride in the electrolyte is about 40 g / l. If the metal surface consists predominantly or exclusively of tantalum or a tantalum alloy, the best results can be obtained with a concentration of ammonium hydrogen difluoride of about 60 g / l in the electrolyte.
the electrolyte contains no further acids in addition to the methanesulfonic acid.
the electrolyte contains no appreciable constituents of phosphoric acid, nitric acid and free hydrofluoric acid.
an electrolyte according to the present invention may form about a binary system consisting only of methanesulfonic acid and ammonium bifluoride.
electropolishing method allows the rinsing of the machined workpieces not to take place within a few seconds, but can take place in a period of time which is usual for other metals in conventional electropolishing processes. This makes it possible for the first time also a trouble-free electrochemical polishing of surfaces of larger components or components with difficult to flush surfaces.
the process according to the invention is carried out at a temperature between 10 ° C and 50 ° C.
the electrolyte can safely remain on the electropolished surfaces for a long time Components remain and are subsequently rinsed with water without the surfaces being attacked during one of the steps.
a significant advantage of using the method described here is that no special measures for the protection of man and the environment are required.
the handling of an electrolyte containing methanesulfonic acid and ammonium bifluoride can be carried out without further safety precautions, which go beyond the usual protective measures for the handling of strong concentrated acids.
the fluoride ions from the ammonium hydrogen difluoride are chemically bound by the metal removed in the course of the electropolishing process.
Example 1 Electropolishing of niobium
the sheet was rinsed in demineralized water and dried in air.
the sheet was rinsed in demineralized water and dried in air.

Landscapes

Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
ing And Chemical Polishing (AREA)
Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
Electroplating Methods And Accessories (AREA)

EP07018328.0A 2006-10-09 2007-09-18 Elektropolierverfahren für Niob und Tantal Not-in-force EP1911862B1 (de)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
DE102006047713A DE102006047713B3 (de)	2006-10-09	2006-10-09	Elektropolierverfahren für Niob und Tantal und Elektrolyt

Publications (3)

Publication Number	Publication Date
EP1911862A2 EP1911862A2 (de)	2008-04-16
EP1911862A3 EP1911862A3 (de)	2010-08-25
EP1911862B1 true EP1911862B1 (de)	2017-03-01

Family

ID=38786963

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP07018328.0A Not-in-force EP1911862B1 (de)	2006-10-09	2007-09-18	Elektropolierverfahren für Niob und Tantal

Country Status (5)

Country	Link
US (1)	US20080099345A1 (ja)
EP (1)	EP1911862B1 (ja)
JP (1)	JP2008095192A (ja)
CA (1)	CA2605859A1 (ja)
DE (1)	DE102006047713B3 (ja)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US20100213078A1 (en) *	2009-02-25	2010-08-26	Ryszard Rokicki	Electrolyte composition for electropolishing niobium and tantalum and method for using same
CA2781613C (en) *	2009-11-23	2017-11-14	Metcon, Llc	Electrolyte solution and electropolishing methods
KR20170138575A (ko) *	2010-11-22	2017-12-15	메트콘, 엘엘씨	전해질 용액 및 전기화학적 표면 개질 방법
US8580103B2 (en)	2010-11-22	2013-11-12	Metcon, Llc	Electrolyte solution and electrochemical surface modification methods
ES2604830B1 (es)	2016-04-28	2017-12-18	Drylyte, S.L.	Proceso para alisado y pulido de metales por transporte iónico mediante cuerpos sólidos libres, y cuerpos sólidos para llevar a cabo dicho proceso.
WO2018102845A1 (de) *	2016-12-09	2018-06-14	Hirtenberger Engineered Surfaces Gmbh	Elektropolierverfahren und elektrolyt hierzu
AT520365B1 (de) *	2017-08-29	2019-10-15	Hirtenberger Eng Surfaces Gmbh	Elektrolyt zum elektropolieren von metalloberflächen
ES2734499B2 (es)	2018-11-12	2020-06-03	Drylyte Sl	Uso de ácidos sulfónicos en electrolitos secos para pulir superficies metálicas a través del transporte de iones

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* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4663005A (en) *	1985-11-15	1987-05-05	Edson Gwynne I	Electropolishing process
US5632966A (en) *	1996-03-07	1997-05-27	Alliedsignal Inc.	Process for hydrogen fluoride separation
US6352636B1 (en) *	1999-10-18	2002-03-05	General Electric Company	Electrochemical system and process for stripping metallic coatings
US6407047B1 (en) *	2000-02-16	2002-06-18	Atotech Deutschland Gmbh	Composition for desmutting aluminum
NL1014727C2 (nl) *	2000-03-23	2001-09-25	Univ Eindhoven Tech	Werkwijze voor het elektrolytisch polijsten van een metaal in aanwezigheid van een elektrolytsamenstelling, alsmede een vormdeel verkregen volgens een dergelijke werkwijze.
DE10259934B3 (de) *	2002-12-20	2004-10-14	H.C. Starck Gmbh	Verfahren zur Herstellung von Formteilen aus Niob oder Tantal durch elektrochemisches Ätzen und so erhältliche Formteile
DE10320909A1 (de) *	2003-05-09	2004-11-18	Poligrat Holding Gmbh	Elektrolyt zum elektrochemischen Polieren von Metalloberflächen

2006
- 2006-10-09 DE DE102006047713A patent/DE102006047713B3/de not_active Expired - Fee Related
2007
- 2007-09-18 EP EP07018328.0A patent/EP1911862B1/de not_active Not-in-force
- 2007-10-03 JP JP2007259899A patent/JP2008095192A/ja active Pending
- 2007-10-05 CA CA002605859A patent/CA2605859A1/en not_active Abandoned
- 2007-10-09 US US11/869,383 patent/US20080099345A1/en not_active Abandoned

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number	Publication date
DE102006047713B3 (de)	2008-03-27
JP2008095192A (ja)	2008-04-24
US20080099345A1 (en)	2008-05-01
CA2605859A1 (en)	2008-04-09
EP1911862A3 (de)	2010-08-25
EP1911862A2 (de)	2008-04-16

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