US2145745A - Electroplating method and product - Google Patents

Electroplating method and product Download PDF

Info

Publication number
US2145745A
US2145745A US744566A US74456634A US2145745A US 2145745 A US2145745 A US 2145745A US 744566 A US744566 A US 744566A US 74456634 A US74456634 A US 74456634A US 2145745 A US2145745 A US 2145745A
Authority
US
United States
Prior art keywords
tungsten
acid
bath
metal
solution
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
Application number
US744566A
Other languages
English (en)
Inventor
Armstrong Harry Howard
Menefee Arthur Burley
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.)
TUNGSTEN ELECTRODEPOSIT Corp
Original Assignee
TUNGSTEN ELECTRODEPOSIT CORP
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.)
Filing date
Publication date
Priority to BE414790D priority Critical patent/BE414790A/xx
Priority to BE416235D priority patent/BE416235A/xx
Application filed by TUNGSTEN ELECTRODEPOSIT CORP filed Critical TUNGSTEN ELECTRODEPOSIT CORP
Priority to US744566A priority patent/US2145745A/en
Priority to US14372A priority patent/US2145241A/en
Priority to GB12972/35A priority patent/GB460886A/en
Priority to GB2722/36A priority patent/GB460931A/en
Priority to GB12973/35A priority patent/GB460840A/en
Priority to FR789883D priority patent/FR789883A/fr
Priority to DEA76135D priority patent/DE654270C/de
Priority to US28187A priority patent/US2160322A/en
Priority to FR809371D priority patent/FR809371A/fr
Priority to GB17574/36A priority patent/GB477519A/en
Priority to DEA79761D priority patent/DE683879C/de
Application granted granted Critical
Publication of US2145745A publication Critical patent/US2145745A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

Definitions

  • yOurinvention relates to a process ⁇ for electroplating tungsten alloys i'rom 'aqueous solutions, and alloys of metals other than tungstenv from f the same type of electrolyte. 5
  • the object of our invention is theproduction of 'tungsten alloy plates, of dense, closely adherent quality which are highly resistant to the corrosive action of acids and saltsand withstand high temperature.
  • tungsten -or tungsten any disclosed methods have been .far from being resistant to strong acids, have been produced-from decidedly alkaline electrolytes (pH 9 l to 13), high current densities have been required (75 to 400 amperes per square foot of submerged cathode area) with excessive evolution of hydrogen at the cathode, and in most cases less than 1% currentefilciency.
  • I v Our invention specifically relates to alpractical and economical method of producing tungsten alloy plate, of variable tungsten content, which may'be applied by means of standard equipment and common reagents,- and which maybe 5 controlled and operated as contiruinusly and readily as are the conventional nickel, chrome,
  • FIG. 1 is a diagrammatic view ofl a cell which may be utilized in practicing the'invention.
  • I is the cell box :.5 within which are placed an anode oranodes or cathode or cathodes 2 and 3, respectively.- Wires 4 and'5 lead from the anode andcathode respectively,.to asource ofv current supply ,'6.
  • the cell box is adapted to hold 4an (m electrolyte '
  • alloy plates which have been produced by known v As descriptive of our process, approximately 4% by weight of NAHP; 'or KHF; or the equivalent amountV o1' HF is dissolved in 100 parts of waterand approximately 5% by weight of NaCl and 1% by weight offconcentrated HCl is added to the solution. .This solution is then heated to between 40 and 75 C.
  • a metal in the form oi' an acid soluble salt such as NiCh,2NiC03-3Nl (OH) 24H20 or Ni (OH) s,
  • the pH of the solution is usually below 4.
  • 'I'he pH is then adjust- 4.5 and 6.8 bythe Aadditionof o y Na(OH) K2(OH)
  • the temperature of the solution is kept between 35 and 85 C. or even higher.
  • the cathode to be plated is then placed in the solution, and electrolyzed at approximately 14 amperes per square foot of submerged cathode area. Small vadditions of the acid soluble salts of the metal or metals to be alloyed with the tungsten are'required from time to time as the solution becomes vdepleted of these salts. Where a tungsten-nickel carbide anode is used,
  • Na(OH) and'HCl are used as reagents for the control of the pH of the electrolyte.
  • tungsten or tungsten carbide alloy anodes oreven, inert conductive anodes, such as platinum or carbon.
  • our invention is not intended to be limited to the production of tungsten alloy deposits, 'as the following single metals (Ni, Co, Sb, Zn, Cd, Aq, Hg, and Sn) have been plated through substantially the same acid fluoride bath as -above described, by either straight anode corrosions or adding acid soluble salts of the metals. Also, a chrome-nickel alloy has been produced under approximately the same conditions, and
  • CoF2-5HF- 6H20, etc. or those metals which form two luorides, such as SbFa and SbF5, CuFa-2H2O and CuzFa, CrFaand CrFz, etc., will, under substantially the same conditions as y'described above,
  • tungsten carbide orv tungsten carbide alloy anodes have not been employed or suggested by past disclosures or used by operators. Nor do We find any suggestion or disclosures of the use of tungsten dioxide (W02) dissolved in any acid electrolyte. Nor do we find any mention or suggestion of any direct attempt to produce tungsten alloys, where the soluble metal salt, the metal of which to be alloyed with l tungsten, is added to the electrolyte for the direct purpose of producing tungsten alloy plates of variable tungsten content, suitable for various specific purposes.
  • W02 tungsten dioxide
  • Mariguac states that when normal or metatung'states are dissolved in hydroiluoric acid, compounds of the metal iiuorides with tungsten dioxyfluorides are formed. These salts are usually soluble in water.
  • Mariguacs result that when noriiuoric acid, compounds of the metal iluoride-s with tungsten dioxyfluori'des .are formed, it should be possible to produce from these compounds an lelectrolyte from which ytungsten alloys could be plated.
  • Our experience has been i'rom the attempted use of W03, various tungstates, metatungstates and paratungstates in various acid fluoride-bathathathat the solutions are in all cases diilicult to control. In most cases, the solutions when heated and electrolyzed, turn blue due vto the formation probably of some WaOs coml pound and also precipitate out large' amounts of radical hydrated W03.
  • the process of electroplating with tungsten l' alloys which comprises electrolyzing tungsten suiiicient lengtli of time to build up the ion conu carbide anodes in an aqueous acid iiuoride bath, to produce available tungsten ions in said bath; adding an acid soluble 'salt of a metal of group 8, series 4 of the periodic table to be alloyed with the tungsten to said bath, adjusting the pH of said bath to between 4.5 to 6.8; maintaining the solution at a temperature between 35 C. to 80 C., with a current density of about 14 amp eres per square foot of submerged cathode area. 4.
  • the process of electroplating with tungsten alloys which comprises electrolyzing tungsten alloy carbide ano'des -in an aqueous acid iuoride bath, to produce available tungsten ions in said bath; adding an acid soluble salt of a metal of group 8, series 4 of the periodic table to be alloyed with the tungsten to said bath, adjusting the pH of ⁇ said bath to; between 4.5 to 6.8; maintaining the solution at a temperature between 35 C. to 80 C., with a current density of about 14 amperes per square foot of submerged cathode.
  • a process for producing tungsten nickel alloy plates consisting of electrolyzing tungsten containing alloy anodes in an acid fluoride bath a cntration of the metals in the alloy anodes, for
  • a process of electroplating tungsten nickel alloys which' comprises electrolyzing an acid bath containinga iluorlde and available tungsten and nickel ions.
  • That method of preparing an electroplating bath which comprises anodically corroding ⁇ a tungsten containing electrode in contact with an aqueousv acid solution containing a uoride, adding a compound containing available nickel, adjusting the pH of the solution to between 4 and a suitable metallic cathode.
  • An electroplating bath for electrodepositing tungsten alloys comprising an aqueous solution formed by dissolving tungsten dioxide /in an aqueous solution of an alkali biiluoride and adding thereto a solution containing a soluble salt of a metal of group 8, series 4 of the periodic table.
  • a method of producing tungsten alloys of variable tungsten content which comprises dissolving a tungsten containing compound in a hot aqueous solution of an alkali acid uoride, adding thereto a salt of a metal o'f group 8,series 4 of the periodic table, and electrolyzing the solution while it is maintained definitely acid to codeposit tungsten and said second metal from the solution.
  • codeposition of tungsten with other metals comprising an aqueous acid solution containing a fluoride together with available tungsten ions and ions of a metal of group 8, series 4 of the periodic table, and an organic acid.
  • a process for arresting and preventing corrosion of metals which consists in rst electro- 6.8 and plating out a tungsten nickel -alloy upon plating said metal with a metal close to it in the l electromotive series, ⁇ then immersing the preliminarily plated metal as a cathode in an aqueous uoride bath having an acid reaction, which bath contains ions of tungsten and ions of a metal of group 8, series 4 oi' the periodic table.
  • An electrolyte bath for producing alloys by codeposition of tungsten with other metals comprising an aqueous acid solution containing availableiiuoride ions together with available tungsten ions and ions of a 'metal of group 8, series 4 of the periodictable.
  • a method of producing tungsten alloys of "variable tungsten content by electrodeposition from an aqueous solution comprising, establishving an aqueous solution of deilnite acidity containing iiuoride ions, ions of tungsten and ions of a metal of group 8, series 4 of the periodic table, and controlling the amount of tungsten in the alloy deposit by varying the metal ion concenf tration in the bath of the metal to be alloyedA with the tungsten.
  • a method of producing electrodeposited plates c! tungsten which comprises electrolyzing a tungsten-containing anode in an aqueous, strongly acid bath which contains uoride ionsand ions of a metal of group 8, series 4 of the periodic table, and then plating out tungsten from the bath at a lower acid concentration.
  • a method of preparing an aqueous electrolyte forthe electrodepositing of tungsten which 'comprises electroiyzing a tungsten containing anode in an aqueous solution of an acid iiuoride at a pH oi substantially 4, adding to the bath a salt of a metal ot group 8, series 4 of the periodic table, then adjusting the :acidconcentration to approximately a pH oi' 4.5 to 6.8.
  • a method of preparing an velectrolyte from which tungsten may be' eiectrodeposited which comprises, electrolytically corroding a tungstencontaining anode in contact with aqueous hydrochloric acid, adding to the bath a fluoride and a soluble salt oi a metal of group 8. series 4 oi the periodic table.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Electroplating Methods And Accessories (AREA)
US744566A 1934-09-18 1934-09-18 Electroplating method and product Expired - Lifetime US2145745A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
BE414790D BE414790A (enrdf_load_stackoverflow) 1934-09-18
BE416235D BE416235A (enrdf_load_stackoverflow) 1934-09-18
US744566A US2145745A (en) 1934-09-18 1934-09-18 Electroplating method and product
US14372A US2145241A (en) 1934-09-18 1935-04-02 Electroplating method and product
GB2722/36A GB460931A (en) 1934-09-18 1935-05-01 Improvements in the electrodeposition of tungsten alloys
GB12973/35A GB460840A (en) 1934-09-18 1935-05-01 Improvements in the electrodeposition of tungsten and tungsten alloys
GB12972/35A GB460886A (en) 1934-09-18 1935-05-01 Electrodeposition of tungsten and tungsten alloys
FR789883D FR789883A (fr) 1934-09-18 1935-05-10 Perfectionnements aux procédés galvanoplastiques et produits en résultant
DEA76135D DE654270C (de) 1934-09-18 1935-05-29 Verfahren zur elektrolytischen Herstellung von UEberzuegen aus Wolframlegierungen
US28187A US2160322A (en) 1934-09-18 1935-06-24 Electrodeposition of tungsten alloys
FR809371D FR809371A (fr) 1934-09-18 1936-06-23 Dépôt électrolytique d'alliages de tungstène
GB17574/36A GB477519A (en) 1934-09-18 1936-06-24 Electrodeposition of tantalum and tantalum alloys
DEA79761D DE683879C (de) 1934-09-18 1936-06-25 Verfahren zur elektrolytischen Herstellung von UEberzuegen aus Wolfram und Tantal enthaltenden Legierungen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US744566A US2145745A (en) 1934-09-18 1934-09-18 Electroplating method and product

Publications (1)

Publication Number Publication Date
US2145745A true US2145745A (en) 1939-01-31

Family

ID=32713886

Family Applications (1)

Application Number Title Priority Date Filing Date
US744566A Expired - Lifetime US2145745A (en) 1934-09-18 1934-09-18 Electroplating method and product

Country Status (4)

Country Link
US (1) US2145745A (enrdf_load_stackoverflow)
BE (1) BE414790A (enrdf_load_stackoverflow)
FR (1) FR789883A (enrdf_load_stackoverflow)
GB (2) GB460931A (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2456370A (en) * 1945-02-19 1948-12-14 Int Nickel Co Process for producing electrodeposited nickel strip containing boron
US2486464A (en) * 1947-01-08 1949-11-01 Canadian Copper Refiners Ltd Method of producing sodium selenate
US2702232A (en) * 1951-01-30 1955-02-15 Du Pont Metal tungstites
US2760928A (en) * 1952-05-01 1956-08-28 Ceresa Myron Apparatus for electroplating studies
US3007861A (en) * 1959-04-06 1961-11-07 Incar Inc Pilot electroplating cell
US3412004A (en) * 1965-09-10 1968-11-19 Enthone Test plating equipment and method
US4049024A (en) * 1976-06-04 1977-09-20 Gte Laboratories Incorporated Mandrel and method of manufacturing same
US10385462B2 (en) 2015-07-09 2019-08-20 Saudi Arabian Oil Company Electrode material for electrolytic hydrogen generation
US11187044B2 (en) 2019-12-10 2021-11-30 Saudi Arabian Oil Company Production cavern
US11460330B2 (en) 2020-07-06 2022-10-04 Saudi Arabian Oil Company Reducing noise in a vortex flow meter

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2435191A (en) * 1943-11-06 1948-02-03 Nat Standard Co Rubber coated steel object
US2653128A (en) * 1946-11-08 1953-09-22 Brenner Abner Method of and bath for electrodepositing tungsten alloys
US5389226A (en) * 1992-12-17 1995-02-14 Amorphous Technologies International, Inc. Electrodeposition of nickel-tungsten amorphous and microcrystalline coatings

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2456370A (en) * 1945-02-19 1948-12-14 Int Nickel Co Process for producing electrodeposited nickel strip containing boron
US2486464A (en) * 1947-01-08 1949-11-01 Canadian Copper Refiners Ltd Method of producing sodium selenate
US2702232A (en) * 1951-01-30 1955-02-15 Du Pont Metal tungstites
US2760928A (en) * 1952-05-01 1956-08-28 Ceresa Myron Apparatus for electroplating studies
US3007861A (en) * 1959-04-06 1961-11-07 Incar Inc Pilot electroplating cell
US3412004A (en) * 1965-09-10 1968-11-19 Enthone Test plating equipment and method
US4049024A (en) * 1976-06-04 1977-09-20 Gte Laboratories Incorporated Mandrel and method of manufacturing same
US10385462B2 (en) 2015-07-09 2019-08-20 Saudi Arabian Oil Company Electrode material for electrolytic hydrogen generation
US11384439B2 (en) 2015-07-09 2022-07-12 Saudi Arabian Oil Company Electrode material for electrolytic hydrogen generation
US11187044B2 (en) 2019-12-10 2021-11-30 Saudi Arabian Oil Company Production cavern
US11460330B2 (en) 2020-07-06 2022-10-04 Saudi Arabian Oil Company Reducing noise in a vortex flow meter

Also Published As

Publication number Publication date
GB460840A (en) 1937-02-01
GB460931A (en) 1937-02-01
FR789883A (fr) 1935-11-07
BE414790A (enrdf_load_stackoverflow)

Similar Documents

Publication Publication Date Title
US2145745A (en) Electroplating method and product
US3576724A (en) Electrodeposition of rutenium
US2250556A (en) Electrodeposition of copper and bath therefor
US2693444A (en) Electrodeposition of chromium and alloys thereof
US2990343A (en) Chromium alloy plating
Ksycki et al. The electrodeposition of molybdenum from aqueous solutions
EP0035667A1 (en) Trivalent chromium electroplating solution and bath
US3855089A (en) Process for the electrolytic refining of heavy metals
US1970950A (en) Electrodeposition of platinum metals
US1993623A (en) Electrodeposition of platinum metals
US2453757A (en) Process for producing modified electronickel
US2436244A (en) Metalworking and strippingplating process
NO830044L (no) Elektrobelegningsprosess med trivalent krom.
US2398614A (en) Electrodeposition of manganese
US2414438A (en) Electrodeposition of selenium
US3772167A (en) Electrodeposition of metals
US2577365A (en) Rhodium plating
US1466126A (en) Electrolytic refining or depositing of tin
US2489523A (en) Electrodeposition of tin or lead-tin alloys
US2233103A (en) Production of nickel powder
US2546547A (en) Electrodeposition of manganese
US2160322A (en) Electrodeposition of tungsten alloys
US3347757A (en) Electrolytes for the electrodeposition of platinum
US3123544A (en) Electrodeposition of ruthenium
Linford Indium Plating