US1975239A - Method of chromium plating - Google Patents

Method of chromium plating Download PDF

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Publication number
US1975239A
US1975239A US678258A US67825833A US1975239A US 1975239 A US1975239 A US 1975239A US 678258 A US678258 A US 678258A US 67825833 A US67825833 A US 67825833A US 1975239 A US1975239 A US 1975239A
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US
United States
Prior art keywords
chromium
black
bath
acid
chromium plating
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
US678258A
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English (en)
Inventor
Ungelenk Alfred
Fischer Johannes
Endrass Heinz
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.)
Siemens and Halske AG
Siemens Corp
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Siemens 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
Application filed by Siemens Corp filed Critical Siemens Corp
Application granted granted Critical
Publication of US1975239A publication Critical patent/US1975239A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI

Definitions

  • the invention relates to methods of chromium plating.
  • nickel may be plated with nickel oxide, which has a much greater tendency of emitting rays.
  • nickel oxide re use of nickel oxide, however, is not suitable in many cases because its melting as well as its decomposition takes place at relatively low temperatures. Besides the nickel oxide has a remarkable inconstancy to the bombardment by ions or by electrons.
  • Chromium for instance, can be electrolytically deposited in such a form by diminishing the anodic current density and thereby varying the distribution of the current lines within the bath.
  • Grey coloured chromium layers can be obtained by increasing the cathodic current density very much with respect to the values usual in practical chromium plating, that means about 50 amperes per square meter of cathode surface. But the grey colour of the chromium coatings only happens when passing the current through the bath for a short time and disappears afterwards when depositing long enough so as to make/an homogeneous layer.
  • a layer of quite black colour and of excellent qualities for the said purpose is deposited by the use of a cathodic current density from ten to twenty times higher than the usual one, that is lying between about 10,000
  • Chromic acid containing baths may be employed if desired.
  • this black deposit is not exactly known even now. It is supposed that it consists of chromium oxide or of metallic chromium in a very fine distribution or perhaps of both these components.
  • the qualities of this electrolytically produced coating are a very great constancy and capacity of resistance to temperatures up to 2000 C. It is of importance that in the said layer no vapours or gases are present or can be developed during the normal use of a so treated article. Such gases could give disturbing effects and eventually destroy other parts of the apparatus.
  • the metal the surface of which is to be darkened can be treated as a cathode in a chromium bath, for instance, consisting of a solution of chromic acid (H2CrO4) 0 and very small percentage of sulphuric acid (S04), using a current density of about 15,000 amperes per square meter.
  • a chromium bath for instance, consisting of a solution of chromic acid (H2CrO4) 0 and very small percentage of sulphuric acid (S04), using a current density of about 15,000 amperes per square meter.
  • H2CrO4 chromic acid
  • S04 very small percentage of sulphuric acid
  • the article at first in a normal chromic acid bath until a white or bright chromium coating appears.
  • a second layer of black colour is separated out of a chromium bath free of sulphuric acid (S04) by the use of a current density of 10,000 up to 20,000 amperes per square meter.
  • S04 sulphuric acid
  • the first layer on the article to be treated may also consist of electrolytically deposited nickel upon which the dark coloured chromium containing layer is formed.
  • several intermediate layers can be used, for instance, a first nickel layer and a second white chromium layer which serves as a base for the dark deposit.
  • Bright chromium deposits of black colour are obtained out of normal chromic acid baths suitable for chromium plating by removing the sulphuric acid (S04) therefrom as completely as possible. This can be executed in any well known manner, for instance, by the chemical precipitation with barium compounds which are added to the chromium plating bath.
  • sulphuric acid grey-black deposits can be produced by electrolysis, such deposits being very proper to serve as a source for the emission of rays or of electrons. It was found that carbonic acids such as acetic acid, formic acid, propionic acid and oxalic acid can be used as additions to standard chromium plating baths from which sulphuric acid is removed.
  • the new method is applicable for blackening metallic articles in order to change their power of emission as for instance at thermic apparatus, screens, electrodes or other metallic parts of vacuum tubes, especially anodes of discharging tubes of high effect. no
  • Tungsten electrodes of electronic tubes are plated with white chromium layers in the usual manner. After rinsing the so prepared tungsten electrodes for a short time, they are treated in a solution containing 35 per cent of chromic acid and 0,05 per cent of sulphuric acid (S04) by means of an electric current. The current density amounts to about 10,000 amperes per square meter and the voltage 10 volts. The temperature of the bath is maintained at below 20 C., if necessary by cooling. After about ten minutes the tungsten article connected as cathode carries a black chromium coating.
  • the sulphuric acid (S04) is at first separated in any well known manner. Thereafter from 0,5 to 0,8 cubic centimeters of concentrated acetic acid per liter are added to the bath. The electrolysis was performed with a cathodic current density of 10,000 to 20,000 amperes per square meter, a voltage of about 9 volts and a temperature of bath below 28 C. The anode was made of lead and the cathode was formed by a tungsten article. The result was a pale-black cathodic layer of chromium showing excellent qualities of heat or electron emission.

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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)
  • Electroplating And Plating Baths Therefor (AREA)
US678258A 1929-10-16 1933-06-29 Method of chromium plating Expired - Lifetime US1975239A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1975239X 1929-10-16

Publications (1)

Publication Number Publication Date
US1975239A true US1975239A (en) 1934-10-02

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ID=7849873

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US678258A Expired - Lifetime US1975239A (en) 1929-10-16 1933-06-29 Method of chromium plating

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US (1) US1975239A (is")
FR (1) FR754360A (is")

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2482308A (en) * 1947-02-21 1949-09-20 Du Pont Catalyst preparation
US2542994A (en) * 1945-07-09 1951-02-27 Armco Steel Corp Electrolytic surface treatment of steel
US2623847A (en) * 1947-09-10 1952-12-30 Lloyd O Gilbert Black chromium plating
US2739108A (en) * 1952-06-14 1956-03-20 Westinghouse Electric Corp Electroplating chromium-nickel alloy coatings
US2739109A (en) * 1952-06-14 1956-03-20 Westinghouse Electric Corp Black chromium-nickel-vanadium electrodeposits
US2772227A (en) * 1953-06-29 1956-11-27 Westinghouse Electric Corp Protection of molybdenum and tungsten at high temperatures
US2801214A (en) * 1956-03-23 1957-07-30 Melvin R Zell Chromium plating bath
US2824829A (en) * 1953-02-27 1958-02-25 Westinghouse Electric Corp Electrodepositing black chromiumvanadium coatings and members therewith
US2826538A (en) * 1955-05-03 1958-03-11 Columbia Broadcasting Syst Inc Metal blackening process
US2917817A (en) * 1955-03-25 1959-12-22 Res Council Of Israel Receiver for solar energy collectors
US2985567A (en) * 1959-03-16 1961-05-23 Allied Chem Electrodeposition of black chromium coatings
US3069333A (en) * 1961-07-25 1962-12-18 Du Pont Chromium plating
US3419481A (en) * 1966-04-08 1968-12-31 Diamond Shamrock Corp Electrolyte and process for electroplating black chromium and article thereby produced
US3454474A (en) * 1966-11-23 1969-07-08 Corillium Corp Chromium plating process
US3620935A (en) * 1967-01-18 1971-11-16 Kewanee Oil Co Process of black chromium plating
US4857436A (en) * 1987-12-28 1989-08-15 Nouel Jean Marie Offset plates with two chromium layers
US4996131A (en) * 1987-12-28 1991-02-26 Nouel Jean Marie Offset plate with thin chromium layer and method of making
CN110252135A (zh) * 2019-07-01 2019-09-20 天津商业大学 一种甲醛净化处理装置

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542994A (en) * 1945-07-09 1951-02-27 Armco Steel Corp Electrolytic surface treatment of steel
US2482308A (en) * 1947-02-21 1949-09-20 Du Pont Catalyst preparation
US2623847A (en) * 1947-09-10 1952-12-30 Lloyd O Gilbert Black chromium plating
US2739108A (en) * 1952-06-14 1956-03-20 Westinghouse Electric Corp Electroplating chromium-nickel alloy coatings
US2739109A (en) * 1952-06-14 1956-03-20 Westinghouse Electric Corp Black chromium-nickel-vanadium electrodeposits
US2824829A (en) * 1953-02-27 1958-02-25 Westinghouse Electric Corp Electrodepositing black chromiumvanadium coatings and members therewith
US2772227A (en) * 1953-06-29 1956-11-27 Westinghouse Electric Corp Protection of molybdenum and tungsten at high temperatures
US2917817A (en) * 1955-03-25 1959-12-22 Res Council Of Israel Receiver for solar energy collectors
US2826538A (en) * 1955-05-03 1958-03-11 Columbia Broadcasting Syst Inc Metal blackening process
US2801214A (en) * 1956-03-23 1957-07-30 Melvin R Zell Chromium plating bath
US2985567A (en) * 1959-03-16 1961-05-23 Allied Chem Electrodeposition of black chromium coatings
US3069333A (en) * 1961-07-25 1962-12-18 Du Pont Chromium plating
US3419481A (en) * 1966-04-08 1968-12-31 Diamond Shamrock Corp Electrolyte and process for electroplating black chromium and article thereby produced
US3454474A (en) * 1966-11-23 1969-07-08 Corillium Corp Chromium plating process
US3620935A (en) * 1967-01-18 1971-11-16 Kewanee Oil Co Process of black chromium plating
US4857436A (en) * 1987-12-28 1989-08-15 Nouel Jean Marie Offset plates with two chromium layers
US4996131A (en) * 1987-12-28 1991-02-26 Nouel Jean Marie Offset plate with thin chromium layer and method of making
CN110252135A (zh) * 2019-07-01 2019-09-20 天津商业大学 一种甲醛净化处理装置

Also Published As

Publication number Publication date
FR754360A (is") 1933-11-03

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