US3314867A - Method of etching tantalum and niobium for electroplating - Google Patents
Method of etching tantalum and niobium for electroplating Download PDFInfo
- Publication number
- US3314867A US3314867A US320967A US32096763A US3314867A US 3314867 A US3314867 A US 3314867A US 320967 A US320967 A US 320967A US 32096763 A US32096763 A US 32096763A US 3314867 A US3314867 A US 3314867A
- Authority
- US
- United States
- Prior art keywords
- metal
- niobium
- tantalum
- ranging
- methyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims description 19
- 229910052715 tantalum Inorganic materials 0.000 title claims description 18
- 229910052758 niobium Inorganic materials 0.000 title claims description 16
- 239000010955 niobium Substances 0.000 title claims description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 12
- 238000005530 etching Methods 0.000 title description 7
- 238000009713 electroplating Methods 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 4
- 230000001464 adherent effect Effects 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000010953 base metal Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- -1 niobium metals Chemical class 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
-
- 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
- C25F3/02—Etching
- C25F3/08—Etching of refractory metals
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H6/00—Targets for producing nuclear reactions
Definitions
- the invention relates to a method of etching tantalum and nibium metal and, in particular, it relates to a method for forming an adherent electrodeposit of a metal such as nickel or copper on a tantalum or niobium base metal.
- the present invention is based on the discovery that tantalum and niobium metals can be successfully etched electrolytically in a bath composed of a solution of absolute methyl alcohol and a small but approximately equal amount of concentrated hydrofluoric (48 weight percent hydrogen fluoride in aqueous solution) and hydrochloric (38 weight percent hydrogen chloride in aqueous solution) acids.
- This etching solution it is possible to obtain a uniform pattern of small, deep pits in both niobium and tantalum with near vertical and in some cases undercut sides in the pits.
- the desired metal is then electrodeposited on the etched surface with the deposit entering these pits which provide a multitude of tiny anchors to secure the said deposited metal with a high degree of adhesion or bonding to the niobium or tantalum base metal.
- This method has been useful in obtaining a strongly adherent copper nickel metallic film on a tantalum tube heating element and on a tantalum cyclotron target assembly.
- this etching process is presently being used to plate a metallic film of nickel on the niobium metal base so as to prevent the formation of niobium oxide.
- the tantalum or niobium metal surface is scrubbed vigorously with any suitable fine abrasive paste such as pumice or powdered magnesium oxide. This surface is then dried and made anodic at 0.125 amp per square inch for 40 minutes in an absolute methyl alcohol solution containing 2.5 volume percent concentrated hydrofluoric acid and 2.5 volume percent concentrated hydrochloric acid at a temperature of 35 C. This treatment produces a uniform pattern of small, deep pits on the surface of the tantalum and/ or niobium metal surface. The etched surface is then electroplated with the desired metal, and the deposit which enters these pits forms anchors which provide a high degree of mechanical bonding of the film to the said base metal.
- any suitable fine abrasive paste such as pumice or powdered magnesium oxide.
- the tantalum metal surface is cleaned using any suitable abraisive.
- the cleaned metal is placed in an absolute methyl alcohol bath containing 5 volume percent concentrated hydrofluoric acid and 5 volume percent concen- It is understood that in all of the above examples that either niobium or tantalum can be substituted as the base metal.
- Critical parameters in this etching process are the following: time, temperature, current density, and the concentration of acid in the methyl alcohol solution.
- the time period necessary to obtain a satisfactory etched surface can vary between 10 and minutes dependent on the temperature, current density, and acid concentration. The higher the temperature, current density, and acid concentration, the shorter the time will be.
- the temperature of etching solution must be maintained at not less than 15 C. and not more than C.
- Current density of the tantalum or niobium base metal must be regulated between 0.05 and 0.5 amp per square inch. At higher temperatures or higher current density the tantalum or niobium surface is too severely etched leaving an uneven, partially polished surface not productive of adhesion. At lower current densities or temperatures (below the aforementioned limits) uniformity of attack metal to produce an. etched survolume percent in order to obtain a uniform etch of the tantalum or niobium surface.
- the use of either hydrofluoric or hydrochloric acids alone in the methyl alcohol bath tend to produce an uneven attack.
Description
United States Patent mission No Drawing. Filed Nov. 1, 1963, Ser. No. 320,967
4 Claims. (Cl. 204-32) The invention described herein was made in the course of, or under, a contract with the United States Atomic Energy Commission.
The invention relates to a method of etching tantalum and nibium metal and, in particular, it relates to a method for forming an adherent electrodeposit of a metal such as nickel or copper on a tantalum or niobium base metal.
The present invention is based on the discovery that tantalum and niobium metals can be successfully etched electrolytically in a bath composed of a solution of absolute methyl alcohol and a small but approximately equal amount of concentrated hydrofluoric (48 weight percent hydrogen fluoride in aqueous solution) and hydrochloric (38 weight percent hydrogen chloride in aqueous solution) acids. Using this etching solution it is possible to obtain a uniform pattern of small, deep pits in both niobium and tantalum with near vertical and in some cases undercut sides in the pits. The desired metal is then electrodeposited on the etched surface with the deposit entering these pits which provide a multitude of tiny anchors to secure the said deposited metal with a high degree of adhesion or bonding to the niobium or tantalum base metal.
This method has been useful in obtaining a strongly adherent copper nickel metallic film on a tantalum tube heating element and on a tantalum cyclotron target assembly. In the development of the plasma thermocouple, this etching process is presently being used to plate a metallic film of nickel on the niobium metal base so as to prevent the formation of niobium oxide.
It is therefore an object of this invention to provide a method of etching tantalum and niobium base metal surface so that any desired metal can be electrodeposited on said surface to form an adherent metallic film.
Further objects of this invention will become apparent from the following description of the preferred embodiment of this invention.
The tantalum or niobium metal surface is scrubbed vigorously with any suitable fine abrasive paste such as pumice or powdered magnesium oxide. This surface is then dried and made anodic at 0.125 amp per square inch for 40 minutes in an absolute methyl alcohol solution containing 2.5 volume percent concentrated hydrofluoric acid and 2.5 volume percent concentrated hydrochloric acid at a temperature of 35 C. This treatment produces a uniform pattern of small, deep pits on the surface of the tantalum and/ or niobium metal surface. The etched surface is then electroplated with the desired metal, and the deposit which enters these pits forms anchors which provide a high degree of mechanical bonding of the film to the said base metal.
The following are listed vention:
as specific examples of the in- Example I The tantalum metal surface is cleaned using any suitable abraisive. The cleaned metal is placed in an absolute methyl alcohol bath containing 5 volume percent concentrated hydrofluoric acid and 5 volume percent concen- It is understood that in all of the above examples that either niobium or tantalum can be substituted as the base metal.
Critical parameters in this etching process are the following: time, temperature, current density, and the concentration of acid in the methyl alcohol solution. The time period necessary to obtain a satisfactory etched surface can vary between 10 and minutes dependent on the temperature, current density, and acid concentration. The higher the temperature, current density, and acid concentration, the shorter the time will be.
The temperature of etching solution must be maintained at not less than 15 C. and not more than C. Current density of the tantalum or niobium base metal must be regulated between 0.05 and 0.5 amp per square inch. At higher temperatures or higher current density the tantalum or niobium surface is too severely etched leaving an uneven, partially polished surface not productive of adhesion. At lower current densities or temperatures (below the aforementioned limits) uniformity of attack metal to produce an. etched survolume percent in order to obtain a uniform etch of the tantalum or niobium surface. The use of either hydrofluoric or hydrochloric acids alone in the methyl alcohol bath tend to produce an uneven attack.
While the present invention What is claimed is: 1. A method for lie film on a metal centration of each of said acids ranging between 1.0l0.0 volume percent, the temperature of said bath ranging between 15-65 C., and the current density of the said metal ranging between 0.05-0.50 amp per square inch and electrodepositing any desired metal as a film on the etched surface of the said metal.
2. The method of claim 1 in Which said metal is tantalum and the methyl alcohol solution contains 2.5 volume percent concentrated hydrofluoric acid and 2.5 volume percent concentrated hydrochloric acid, the current density is 0.125 amp per square inch, making said metal anodic for a period of about 40 minutes and maintaining said bath at a temperature of about 35 C.
3. The method of claim 1 in which the surface of the tantalum and niobium metal is cleaned with an abrasive selected from the class consisting of pumice and powdered magnesium oxide prior to placing said metal in the methyl alcohol bath.
4. The method of claim 1 in Which said metal is niobium and the methyl alcohol solution contains 2.5 volume 1 percent hydrofluoric acid and 2.5 volume percent hydrochloric acid, the current density is 0.125 amp per square inch, the temperature is 35 C., and said metal is made anodic for a period of about 40 minutes.
References Cited by the Examiner UNITED STATES PATENTS FOREIGN PATENTS 8/1959 Canada. 7/1960 U.S.S.R.
JOHN H. MACK, Primary Examiner, G. KAPLAN, Assistant Examiner.
Claims (1)
1. A METHOD FOR ELECTRODEPOSITING AN ADHERENT METALLIC FILM ON A METAL SELECTED FROM THE CLASS CONSISTING OF TANTALUM AND NIOBIUM COMPRISING THE SEPS OF MAKING THE SAID METAL ANODIC IN A METHYL ALCOHOL BATH CONSISTING ESSENTIALLY OF APPROXIMATELY EQUAL AMOUNTS OF CONCENTRATED HYDROFLUORIC AND CONCENTRATED HYDROCHLORIC ACIDS, THE CONCENTRATION OF EACH OF SAID ACIDS RANGING BETWEEN 1.0-10.0 VOLUME PERCENT, THE TEMPERATURE OF SAID BATH RANGING BETWEEN 15-65*C., AND THE CURRENT DENSITY OF THE SAID METAL RANGING BETWEEN 0.05-0.50 AMP PER SQUARE INCH AND ELECTRODEPOSITING ANY DESIRED METAL AS A FILM ON THE ETCHED SURFACE OF THE SAID METAL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US320967A US3314867A (en) | 1963-11-01 | 1963-11-01 | Method of etching tantalum and niobium for electroplating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US320967A US3314867A (en) | 1963-11-01 | 1963-11-01 | Method of etching tantalum and niobium for electroplating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3314867A true US3314867A (en) | 1967-04-18 |
Family
ID=23248608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US320967A Expired - Lifetime US3314867A (en) | 1963-11-01 | 1963-11-01 | Method of etching tantalum and niobium for electroplating |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3314867A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663387A (en) * | 1970-03-05 | 1972-05-16 | Plessey Handel Investment Ag | Manufacture of electrode foil for electrolytic capacitors |
| US3784452A (en) * | 1971-02-12 | 1974-01-08 | Siemens Ag | Method of treating the surface of superconducting niobium cavity resonators |
| US4632734A (en) * | 1984-03-21 | 1986-12-30 | Deutsche Lufthansa Ag | Process for electrochemically or chemically coating niobium |
| US4655884A (en) * | 1985-08-19 | 1987-04-07 | General Electric Company | Nickel plating of refractory metals |
| EP1441049A1 (en) * | 2002-12-20 | 2004-07-28 | H.C. Starck GmbH | Process for the production of niobium or tantalum parts by electrochemical etching |
| US20040232211A1 (en) * | 2003-05-19 | 2004-11-25 | Kayser Gregory F. | Diffusion bonded composite material and method therefor |
| CN108456917A (en) * | 2018-04-19 | 2018-08-28 | 湖南工业大学 | A kind of preparation method of porous tantalum piece |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2481306A (en) * | 1944-03-15 | 1949-09-06 | Pennsylvania Salt Mfg Co | Electrochemical polishing of tantalum |
| US2728719A (en) * | 1951-11-30 | 1955-12-27 | Eastman Kodak Co | Method of reconditioning ferrotyping surfaces |
| US2863811A (en) * | 1955-05-09 | 1958-12-09 | Gen Electric | Method of etching capacitor electrodes |
| CA582140A (en) * | 1959-08-25 | Olin Mathieson Chemical Corporation | Zirconium | |
| SU138123A1 (en) * | 1960-07-28 | 1960-11-30 | Т.М. Андреева | The method of preparing the surface of niobium and its alloys and applying a nickel coating |
| US3079536A (en) * | 1959-09-21 | 1963-02-26 | Bell Telephone Labor Inc | Film-forming metal capacitors |
| US3190822A (en) * | 1961-01-09 | 1965-06-22 | Burnham John | Process for electrolytically etching valve metal surfaces |
-
1963
- 1963-11-01 US US320967A patent/US3314867A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA582140A (en) * | 1959-08-25 | Olin Mathieson Chemical Corporation | Zirconium | |
| US2481306A (en) * | 1944-03-15 | 1949-09-06 | Pennsylvania Salt Mfg Co | Electrochemical polishing of tantalum |
| US2728719A (en) * | 1951-11-30 | 1955-12-27 | Eastman Kodak Co | Method of reconditioning ferrotyping surfaces |
| US2863811A (en) * | 1955-05-09 | 1958-12-09 | Gen Electric | Method of etching capacitor electrodes |
| US3079536A (en) * | 1959-09-21 | 1963-02-26 | Bell Telephone Labor Inc | Film-forming metal capacitors |
| SU138123A1 (en) * | 1960-07-28 | 1960-11-30 | Т.М. Андреева | The method of preparing the surface of niobium and its alloys and applying a nickel coating |
| US3190822A (en) * | 1961-01-09 | 1965-06-22 | Burnham John | Process for electrolytically etching valve metal surfaces |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663387A (en) * | 1970-03-05 | 1972-05-16 | Plessey Handel Investment Ag | Manufacture of electrode foil for electrolytic capacitors |
| US3784452A (en) * | 1971-02-12 | 1974-01-08 | Siemens Ag | Method of treating the surface of superconducting niobium cavity resonators |
| US4632734A (en) * | 1984-03-21 | 1986-12-30 | Deutsche Lufthansa Ag | Process for electrochemically or chemically coating niobium |
| US4655884A (en) * | 1985-08-19 | 1987-04-07 | General Electric Company | Nickel plating of refractory metals |
| EP1441049A1 (en) * | 2002-12-20 | 2004-07-28 | H.C. Starck GmbH | Process for the production of niobium or tantalum parts by electrochemical etching |
| US20040178081A1 (en) * | 2002-12-20 | 2004-09-16 | Marianne Gottschling | Process for the production of shaped articles of niobium or tantalum by electrochemical etching |
| US7090763B2 (en) | 2002-12-20 | 2006-08-15 | H. C. Starck Gmbh | Process for the production of shaped articles of niobium or tantalum by electrochemical etching |
| US20040232211A1 (en) * | 2003-05-19 | 2004-11-25 | Kayser Gregory F. | Diffusion bonded composite material and method therefor |
| US8225481B2 (en) * | 2003-05-19 | 2012-07-24 | Pratt & Whitney Rocketdyne, Inc. | Diffusion bonded composite material and method therefor |
| CN108456917A (en) * | 2018-04-19 | 2018-08-28 | 湖南工业大学 | A kind of preparation method of porous tantalum piece |
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