US2616840A - Rhenium plating - Google Patents

Rhenium plating Download PDF

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Publication number
US2616840A
US2616840A US59674A US5967448A US2616840A US 2616840 A US2616840 A US 2616840A US 59674 A US59674 A US 59674A US 5967448 A US5967448 A US 5967448A US 2616840 A US2616840 A US 2616840A
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US
United States
Prior art keywords
rhenium
crystalline
layer
plating
base
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
US59674A
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English (en)
Inventor
Levi Roberto
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.)
Philips Laboratories Inc
Original Assignee
Philips Laboratories Inc
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 NL72568D priority Critical patent/NL72568C/xx
Application filed by Philips Laboratories Inc filed Critical Philips Laboratories Inc
Priority to US59674A priority patent/US2616840A/en
Priority to GB28727/49A priority patent/GB661153A/en
Priority to FR999519D priority patent/FR999519A/fr
Priority to DEN141A priority patent/DE805213C/de
Priority to CH281449D priority patent/CH281449A/de
Application granted granted Critical
Publication of US2616840A publication Critical patent/US2616840A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/619—Amorphous layers

Definitions

  • My invention relatesto. a method for plating rhenium upon a base metal giving a durable, impervious rhenium. layer. e v
  • Rhenium is an element occurringin minutely small amounts throughout the surface of the a desirable plating material.
  • Fig. 3a shows an X-ray diffraction photograph attack by hydrochloric acid, a volatilization less indicating the crystallographic structure of than tungsten in vacuo,-and an electron emisrhenium and the characteristic lines'thereof, sivity approximately equivalent to tungsten; it is Fig. 3b shows an X-ray diffraction photograph V of the crystallographic structure of the element My invention is particularly advantageous to tungsten.
  • Fig. 3c shows an X-ray difiraction photograph expensive metals, giving. such other metals 9. immediately after plating of rhenium upon a hard, massive coating of rhenium.
  • Fig. 3d shows an X-ray diffraction photograph refractory metals, for example tungsten and of plated rhenium on the base of a tungsten metal molydenum, as base metals, 1 shall describe the after treatment in accordancewith the method invention in this connection.
  • the inof the invention. vention is not limited to the use of tungsten and Referring to Fig.
  • the cathode and anode, 2 d respectively, are T t ng objection is be found in the fact connected as electrodes in an electric circuit, in that even a t b platmg 9 'P made by accordance with the ordinary techniques of platj ordinaltfly thlck .electro' 40 ing, including a source of direct current potenqeposit-pn of rhemilm Wm mtmducfe lzltemal tial 4, and a current indicating device 3, strgsseslm gg glyer i gi i de- The plating operation is continued at a given poslt extreme y bn e an Wea empera ures current density depending upon the solution or It is an object of my invention to provide an both uIl'fill P ed layer 1: dfigtis i tefid p'ggser improved method.
  • Another important object of a current denslty of 10 to 14 atnp/dmr 1s i my invention is to provide rhenium plated articles factory- The Plated cathode-1.5 h removed from the electroplating solution.
  • a further object of my invention is to provide articles of pure rhenium such :as seamless hollow cylinders, rail and ribbon.
  • a phosphate bath maybe used, for example, potassium perrhenate, KReOi, 3 grams; phosphoric acid, sp. gr.
  • Fig. 2 shows a further step in the process according to the invention.
  • the cathode 2, now plated, is introduced into a reducing atmosphere 6, within a suitable enclosure 1.
  • a reducing atmosphere may be composed by way of example, of hydrogen. While the cathode 2 is within the reducing atmosphere the temperature of the cathode is raised to a high temperature for a short period of time. a temperature of 1000 C.
  • the melting point of the metal to be plated must be considered.
  • the foregoing may be easily accomplished when cathodes having a uniform cross section, by introducing a source of electric energy 8, at each end of the plated cathode introducing a sufiicient current flow in the oathode to cause it to reach the desired temperature.
  • induction or furnace heating has been found desirable.
  • the cathode After the cathode has been fired in accordance with the foregoing, it is returned to the electroplating process for further electrodeposition as shown in Fig. 1.
  • the entire process of electrodeposition and heat treatment, as outlined, is repeated until a layer of rhenium having the desired thickness has been obtained.
  • the plating of rhenium in relatively thin layers as described and the subsequent firing apparently serves to alter the crystallographic structure of the plated rhenium upon the base metal. Simultaneously the objectionable internal stresses that I found when a large deposit of rhenium is plated and fired are eliminated. These stresses will cause a failure of the plated material.
  • the effect of the plating process may be studied by X-ray diffraction analysis.
  • Massive rhenium when subject to X-ray diffraction analysis. displays a spectra of lines as illustrated in Fig. 3a.
  • the plating With the plating of rhenium upon a given base metal, the plating displays a structure which is apparently non crystalline as indicated by the lack of lines, Fig. 3c. It is this structure that is obtained when rhenium is plated without the process as described in my invention.
  • This plating is subject to the attack of moist air and the subsequent oxidation of the plated rhenium to perrhenic acid.
  • Fig. 3b it mat be seen that even the non crystalline electrodeposition of Fig. 30 upon the base metal tungsten shows none of the characteristic lines of tungsten perceptible through the plated layer.
  • the plated rhenium layer appears, by X-ray difiraction as shown in Fig. 3d.
  • the non crystalline structure. of the electrodep-osition has disappeared and is replaced by the chara I have found teristic crystalline structure first seen in the X- ray diifraction photograph of massive rhenium, per se, Fig. 3a.
  • still no characteristic lines of tungsten may be found visible through the plated layer of rhenium after treatment; indicative of the fact that a massive coating of rhenium has been deposited on the base metal, and that the coating has not split to reveal the underlying tungsten base.
  • Such articles as seamless hollow cylinders, foil and ribbon may be made by plating a suitably shaped base metal according to the invention.
  • a base metal for this purpose should have a melting point above 1000 C. and should be soluble in reagents that do not affect rhenium.
  • a reagent may be hydrochloric acid, HCl. Subsequent immersion of the plated article i-n hydrochloric acid will errode the base metal, leaving the desired article of pure rhenium.
  • a method of forming on a base of refractory metal a covering of substantial thickness of pure stable rhenium in crystalline form having an X-ray diffraction pattern containing all of the characteristic lines of crystalline rhenium which comprises the steps of electro-depositing on the base a thin layer of amorphous rhenium, transforming the amorphous rhenium layer into a layer of crystalline rhenium y heating the same in a reducing atmosphere at a temperature at which the rhenium crystallizes without melting, and successively repeating the steps until a coating of crystalline rhenium of substantial thickness is obtained.
  • a method of forming on a base of tungsten a stable covering of substantial thickness of pure stable rhenium in crystalline form having an X-ray diffraction pattern containing all of the characteristic lines of crystalline rhenium which comprises the steps of elcctro-depositing on the tungsten base a thin layer of amorphous rhenium, transforming the amorphous rhenium layer into a layer of crystalline rhenium by heating the same in a reducing atmosphere at a temperature at which the rhenium crystallizes without melting, and successively repeating the steps until a coating of crystalline rhenium of substantial thickness is obtained.
  • a method of forming on a base of tungsten a stable covering of substantial thickness of pure stable rhenium in crystalline form having an X-ray diffraction pattern containing all of the characteristic lines of crystalline rhenium which comprises the steps of electro-depositing on the tungsten base a thin layer of amorphous rhenium. transforming the amorphous rhenium into a layer of crystalline rhenium layer by heating the same in a reducing atmosphere at a temperature of about 1000 C. and successively repeating the steps until a coating of crystalline rhenium of substantial thickness is obtained.
  • a method of forming on a base of refractory metal a covering of substantial thickness of pure stable rhenium in crystalline form having an X-ray diffraction pattern containing all of the characteristic lines of rhenium which comprises the steps of electrodepositing on the base a thin layer of amorphous rhenium, transforming the amorphous rhenium into a layer of crystalline rhenium by heating the same in a. reducing at mosphere at a temperature of about 1000 C and successively repeating the steps until a coating of crystalline rhenium of substantial thickness is 20 obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
US59674A 1948-11-12 1948-11-12 Rhenium plating Expired - Lifetime US2616840A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL72568D NL72568C (en(2012)) 1948-11-12
US59674A US2616840A (en) 1948-11-12 1948-11-12 Rhenium plating
GB28727/49A GB661153A (en) 1948-11-12 1949-11-09 Improvements in and relating to the electrolytic deposition of rhenium
FR999519D FR999519A (fr) 1948-11-12 1949-11-10 Procédé d'application de couches de rhénium sur un fond métallique et objets recouverts d'une telle couche
DEN141A DE805213C (de) 1948-11-12 1949-11-10 Verfahren zur elektrolytischen Auftragung von Rheniumschichten auf einem metallenen Untergrund
CH281449D CH281449A (de) 1948-11-12 1949-11-10 Verfahren zur elektrolytischen Auftragung von Rhenium auf einen metallenen Untergrund und nach diesem Verfahren erhaltener Rheniumüberzug.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US59674A US2616840A (en) 1948-11-12 1948-11-12 Rhenium plating

Publications (1)

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US2616840A true US2616840A (en) 1952-11-04

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US59674A Expired - Lifetime US2616840A (en) 1948-11-12 1948-11-12 Rhenium plating

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US (1) US2616840A (en(2012))
CH (1) CH281449A (en(2012))
DE (1) DE805213C (en(2012))
FR (1) FR999519A (en(2012))
GB (1) GB661153A (en(2012))
NL (1) NL72568C (en(2012))

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2778786A (en) * 1953-11-17 1957-01-22 Pearlman Harry Coating a carbonaceous surface with rhenium
US2914639A (en) * 1957-08-20 1959-11-24 Royden R Freeland Coaxial switch
US3007855A (en) * 1958-12-29 1961-11-07 Bell Telephone Labor Inc Rhodium plating
US3285839A (en) * 1963-12-16 1966-11-15 American Chem & Refining Co Method and bath for electroplating rhenium
US3382100A (en) * 1965-09-14 1968-05-07 Melpar Inc Rhenium thin film resistors
US12398481B1 (en) 2023-09-20 2025-08-26 Triad National Security, Llc High-quality rhenium and rhenium alloy coatings through electrodeposition

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1565724A (en) * 1920-07-29 1925-12-15 Gen Electric Filament and method of manufacture thereof
US1838273A (en) * 1927-12-24 1931-12-29 Westinghouse Electric & Mfg Co Method of producing chromium plated tools
US2138573A (en) * 1934-09-01 1938-11-29 Ver Chemische Fabriken Zu Leop Electroplating
US2149656A (en) * 1935-11-06 1939-03-07 Tungsten Electrodeposit Corp Thermionic tube
US2195499A (en) * 1937-05-25 1940-04-02 Joseph K Schofield Process of metal coating
US2512141A (en) * 1945-06-14 1950-06-20 Westinghouse Electric Corp Coating articles with molybdenum

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1565724A (en) * 1920-07-29 1925-12-15 Gen Electric Filament and method of manufacture thereof
US1838273A (en) * 1927-12-24 1931-12-29 Westinghouse Electric & Mfg Co Method of producing chromium plated tools
US2138573A (en) * 1934-09-01 1938-11-29 Ver Chemische Fabriken Zu Leop Electroplating
US2149656A (en) * 1935-11-06 1939-03-07 Tungsten Electrodeposit Corp Thermionic tube
US2195499A (en) * 1937-05-25 1940-04-02 Joseph K Schofield Process of metal coating
US2512141A (en) * 1945-06-14 1950-06-20 Westinghouse Electric Corp Coating articles with molybdenum

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2778786A (en) * 1953-11-17 1957-01-22 Pearlman Harry Coating a carbonaceous surface with rhenium
US2914639A (en) * 1957-08-20 1959-11-24 Royden R Freeland Coaxial switch
US3007855A (en) * 1958-12-29 1961-11-07 Bell Telephone Labor Inc Rhodium plating
US3285839A (en) * 1963-12-16 1966-11-15 American Chem & Refining Co Method and bath for electroplating rhenium
US3382100A (en) * 1965-09-14 1968-05-07 Melpar Inc Rhenium thin film resistors
US12398481B1 (en) 2023-09-20 2025-08-26 Triad National Security, Llc High-quality rhenium and rhenium alloy coatings through electrodeposition

Also Published As

Publication number Publication date
GB661153A (en) 1951-11-14
DE805213C (de) 1951-05-10
FR999519A (fr) 1952-02-01
CH281449A (de) 1952-03-15
NL72568C (en(2012))

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