US2797194A - Method of electrolytically recovering precious metals from other metal bases - Google Patents

Method of electrolytically recovering precious metals from other metal bases Download PDF

Info

Publication number
US2797194A
US2797194A US445848A US44584854A US2797194A US 2797194 A US2797194 A US 2797194A US 445848 A US445848 A US 445848A US 44584854 A US44584854 A US 44584854A US 2797194 A US2797194 A US 2797194A
Authority
US
United States
Prior art keywords
metal
bath
nickel
article
bichromate
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
US445848A
Inventor
Robert C Anderson
Russel E Harr
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.)
AT&T Corp
Original Assignee
Western Electric Co 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
Application filed by Western Electric Co Inc filed Critical Western Electric Co Inc
Priority to US445848A priority Critical patent/US2797194A/en
Application granted granted Critical
Publication of US2797194A publication Critical patent/US2797194A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00Electrolytic stripping of metallic layers or coatings

Definitions

  • This invention relates to methods of and electrolytic baths for recovering precious metals from other metal bases, and more particularly to methods of and electrolytic baths for selectively eroding metals bonding precious metals to other metal bases.
  • An object of the invention is to provide methods of removing precious metals from metal bases.
  • Another object of the invention is to provide methods of and electrolytic baths for selectively eroding bonding metals securing precious metals to baser metals to recover the precious metals.
  • a further object of the invention is to provide methods baths for eroding nickel previously bonding palladium contact metal and brass contact springs to recover the brass springs and the palladium contacts.
  • an article comprising a precious metal cap secured to a metal base by a bonding metal, such as, for example, nickel, is made an anode in a bath in an aqueous solution of ammonium chloride and ammonium bichromate or sodium bichromate, and the nickel is eroded away electrolytically without affecting the cap which drops into the bath and may be recovered.
  • a bonding metal such as, for example, nickel
  • FIG. 1 is a fragmentary view of an article to be selectively eroded by methods forming specific embodiments of the invention
  • Fig. 2 is a top plan view of an apparatus for effecting a method forming one embodiment of the invention.
  • the barrel 12 is made anodic with respect to cathodes 14 composed of copper, nickel, graphite or other suitable material, and suitable means (not shown) are provided for applying this potential.
  • Articles 16, which have brass bases or bodies 17, palladium contacts 18 and bonding metal 19 composed of nickel brazed or welded to the caps 18 and the bodies 17, are placed in the barrel 12 and the barrel is immersed into the electrolyte, after which a potential is applied to the barrel and the cathodes, and the bonding metal is dissolved completely without affecting the body members 17 or the caps 18.
  • the temperature need not be regulated.
  • the caps 13 drop off the bodies 17 and drop through holes in the barrel into the bottom of the container, they may be recovered whenever desired, the electrolyte being non-corrosive to the caps.
  • the electrolyte comprises an aqueous solution containing as the essential ingredients thereof ammonium chloride and ammonium bichromate or sodium bichromate, about ten percent ammonium chloride and about five percent ammonium bichromate or sodium bichromate being optimum proportions.
  • the pH of the bath should be maintained within a range of from about five to seven and one-half and the pH of the bath is preferably kept at 6.8. Ammonium hydroxide additions are made to the bath from time to time to keep the pH of the bath within this range and as close as possible to the optimum value.
  • the nickel goes into the solution as nickel chloride and the nickel is attacked before any of the palladium of the precious metal contacts 18.
  • the chromate ions in the solution inhibit dissolving of the brass and form dark brown complex chromate layers over the brass to prevent erosion thereof by the solution.
  • the chromate combines with the copper and nickel to form .precipitations which protect the brass against erosion of the recovery processes. Voltage of fifteen volts and an amperage of 600 amperes are maintained fora period of three hours and are effective to provide one hundred percent recovery of forty-four pounds of electrical contacts, nickel bonds and palladium caps in this time. In such electrical contacts, the caps or contacts 18 constitute the predominant portion of the weight.
  • the articles are loosely contained in the barrel which rotates to thoroughly tumble the articles in the barrel and flush off all dissolved nickel.
  • the method and bath described hereinabove are very etfective for removing any previous metal, such as gold, platinum and other platinum metals and silver, which are secured to the bodies of a non-precious metal by a third non-precious metal and maintain the precious metal parts intact without erosion.
  • the bath is highly effective and efficient, While inexpensive and economical both in the cost of the materials of the bath and in the use thereof.
  • the method of recovering a precious metal part from an article in which the part is secured to a cupric metal base by a nickel metal bond which comp-rises making the article an anode in an electrolytic bath having a pH in the range of from about 5 to about 7.5 and composed of an aqueous solution of ammonium chloride and a salt of the group consisting of ammonium bichromate and sodium bichromate to dissolve the metal bond.
  • the method of recovering a precious metal cap from an article in which the cap is secured to a cupric metal base by a nickel bond which comprises making the article an anode in an electrolytic bath of an aqueous solution of ammonium chloride and ammonium bichromate and having a pH in the range of from about 5 to about 7.5 to dissolve the metal bond.
  • the method of recovering a precious metal cap from an article in which the cap is secured to a cupric metal base by a nickel bond which comprises making the article an anode in an electrolytic bath of an aqueous solution of ammonium chloride and sodium bichromate and having a pH in the range of from about 5 to about 7.5 to dissolve the bond' 4.
  • the method of selectively eroding polymetal parts which comprises immersing an article including a precious metal member, a base metal member including copper as the major ingredient thereof and a nickel bonding member in an aqueous bath having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent of a salt of the group consisting of ammonium bichromate and sodium bichromate, making the article anodic in the bath, and adding ammonium hydroxide from time to time in such quantities to the bath as to maintain the pH of the bath within a range of from about to about 7.5.
  • the method of selectively eroding polymetal parts which comprises immersing an article including a precious metal member, a base metal member having copper as the major ingredient thereof and a nickel bonding member in an aqueous bath having a pH within the range of from about 5 to about 7.5 and having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent of a passivating salt of the group consisting of ammonium bichromate and sodium bichromate, and making the article anodic in the bath.
  • the method of selectively eroding polymetal parts which comprises immersing an article including a precious metal member, a copper-bearing base metal member and a nickel bonding member in an aqueous bath having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent ammo- 4 nium bichromate, making the article lanodic in the bath, and adding ammonium hydroxide from time to time in such quantities to the bath as to maintain the pH of the bath within a range of from about 5 to about 7.5.
  • the method of selectively eroding polymetal parts which comprises immersing an article including a precious metal member, a copper-bearing base metal member and a nickel bonding member in an aqueous bath having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent sodium bichromate, making the article anodic in the bath, and adding ammonium hydroxide from time to time ⁇ in such quantities to the bath as to maintain the pH of the bath within a range of from about 5 to about 7.5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Description

ETAL 2,797,194 RING PRECIOUS METALS BASES 954 June 1957 R. c. ANDERSON METHOD OF ELECTROLYTICALLY RECOVE FROM OT R METAL Filed July 26, 1
INVENTORS. R. C. ANDERSON R. E. HAR/P ,6 AM.
of and electrolytic United Sttes Patent METHOD OF ELECTROLYTIC-ALLY RECOVERING PRECIOUS METALS FROM OTHER METAL BASES Robert C. Anderson, Scotch Plains, N. J., and Russel E. Harr, Downers Grove, Ill.. assignors to Western Electric Company, Incorporated, New York, N. Y., a corporation of New York Application July 26, 1954, Serial No. 445,848 7 Claims. (Cl. 204-146) This invention relates to methods of and electrolytic baths for recovering precious metals from other metal bases, and more particularly to methods of and electrolytic baths for selectively eroding metals bonding precious metals to other metal bases.
When scrapping articles of manufacture, such as, for example, spring contact springs having precious metal contacts secured by a bonding metal, such as nickel or the like brazed to brass or bronze springs, it has been impossible in the past to recover the precious metal contacts, no process having been known which would economically recover one or more of these components without damage to the others.
An object of the invention is to provide methods of removing precious metals from metal bases.
Another object of the invention is to provide methods of and electrolytic baths for selectively eroding bonding metals securing precious metals to baser metals to recover the precious metals.
A further object of the invention is to provide methods baths for eroding nickel previously bonding palladium contact metal and brass contact springs to recover the brass springs and the palladium contacts.
In a method illustrating certain features of the invention, an article comprising a precious metal cap secured to a metal base by a bonding metal, such as, for example, nickel, is made an anode in a bath in an aqueous solution of ammonium chloride and ammonium bichromate or sodium bichromate, and the nickel is eroded away electrolytically without affecting the cap which drops into the bath and may be recovered.
A complete understanding of the invention may be obtained from the following detailed description of methods and baths forming specific embodiments thereof when read in conjunction with the appended drawing, in which- Fig. 1 is a fragmentary view of an article to be selectively eroded by methods forming specific embodiments of the invention, and
Fig. 2 is a top plan view of an apparatus for effecting a method forming one embodiment of the invention.
Referring now in detail to the drawing, there is shown therein a tank 10 containing an electrolyte 11 into which is immersed a tumbling barrel 12 of a well known type. The barrel 12 is made anodic with respect to cathodes 14 composed of copper, nickel, graphite or other suitable material, and suitable means (not shown) are provided for applying this potential. Articles 16, which have brass bases or bodies 17, palladium contacts 18 and bonding metal 19 composed of nickel brazed or welded to the caps 18 and the bodies 17, are placed in the barrel 12 and the barrel is immersed into the electrolyte, after which a potential is applied to the barrel and the cathodes, and the bonding metal is dissolved completely without affecting the body members 17 or the caps 18. The temperature need not be regulated. When the caps 13 drop off the bodies 17 and drop through holes in the barrel into the bottom of the container, they may be recovered whenever desired, the electrolyte being non-corrosive to the caps. v
The electrolyte comprises an aqueous solution containing as the essential ingredients thereof ammonium chloride and ammonium bichromate or sodium bichromate, about ten percent ammonium chloride and about five percent ammonium bichromate or sodium bichromate being optimum proportions. The pH of the bath should be maintained within a range of from about five to seven and one-half and the pH of the bath is preferably kept at 6.8. Ammonium hydroxide additions are made to the bath from time to time to keep the pH of the bath within this range and as close as possible to the optimum value. During the process, the nickel goes into the solution as nickel chloride and the nickel is attacked before any of the palladium of the precious metal contacts 18. The chromate ions in the solution inhibit dissolving of the brass and form dark brown complex chromate layers over the brass to prevent erosion thereof by the solution. The chromate combines with the copper and nickel to form .precipitations which protect the brass against erosion of the recovery processes. Voltage of fifteen volts and an amperage of 600 amperes are maintained fora period of three hours and are effective to provide one hundred percent recovery of forty-four pounds of electrical contacts, nickel bonds and palladium caps in this time. In such electrical contacts, the caps or contacts 18 constitute the predominant portion of the weight. The articles are loosely contained in the barrel which rotates to thoroughly tumble the articles in the barrel and flush off all dissolved nickel.
The method and bath described hereinabove are very etfective for removing any previous metal, such as gold, platinum and other platinum metals and silver, which are secured to the bodies of a non-precious metal by a third non-precious metal and maintain the precious metal parts intact without erosion. The bath is highly effective and efficient, While inexpensive and economical both in the cost of the materials of the bath and in the use thereof.
It is to be understood that the above-described arrangements are simply illustrative of the application of the principles of the invention. Numerous other arrangements may be readily devised by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof.
What is claimed is:
l. The method of recovering a precious metal part from an article in which the part is secured to a cupric metal base by a nickel metal bond, which comp-rises making the article an anode in an electrolytic bath having a pH in the range of from about 5 to about 7.5 and composed of an aqueous solution of ammonium chloride and a salt of the group consisting of ammonium bichromate and sodium bichromate to dissolve the metal bond.
2. The method of recovering a precious metal cap from an article in which the cap is secured to a cupric metal base by a nickel bond, which comprises making the article an anode in an electrolytic bath of an aqueous solution of ammonium chloride and ammonium bichromate and having a pH in the range of from about 5 to about 7.5 to dissolve the metal bond.
3. The method of recovering a precious metal cap from an article in which the cap is secured to a cupric metal base by a nickel bond, which comprises making the article an anode in an electrolytic bath of an aqueous solution of ammonium chloride and sodium bichromate and having a pH in the range of from about 5 to about 7.5 to dissolve the bond' 4. The method of selectively eroding polymetal parts, which comprises immersing an article including a precious metal member, a base metal member including copper as the major ingredient thereof and a nickel bonding member in an aqueous bath having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent of a salt of the group consisting of ammonium bichromate and sodium bichromate, making the article anodic in the bath, and adding ammonium hydroxide from time to time in such quantities to the bath as to maintain the pH of the bath within a range of from about to about 7.5.
5. The method of selectively eroding polymetal parts, which comprises immersing an article including a precious metal member, a base metal member having copper as the major ingredient thereof and a nickel bonding member in an aqueous bath having a pH within the range of from about 5 to about 7.5 and having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent of a passivating salt of the group consisting of ammonium bichromate and sodium bichromate, and making the article anodic in the bath.
6. The method of selectively eroding polymetal parts, which comprises immersing an article including a precious metal member, a copper-bearing base metal member and a nickel bonding member in an aqueous bath having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent ammo- 4 nium bichromate, making the article lanodic in the bath, and adding ammonium hydroxide from time to time in such quantities to the bath as to maintain the pH of the bath within a range of from about 5 to about 7.5.
7. The method of selectively eroding polymetal parts, which comprises immersing an article including a precious metal member, a copper-bearing base metal member and a nickel bonding member in an aqueous bath having therein as the essential ingredients thereof about ten percent ammonium chloride and about five percent sodium bichromate, making the article anodic in the bath, and adding ammonium hydroxide from time to time \in such quantities to the bath as to maintain the pH of the bath within a range of from about 5 to about 7.5.
References Cited in the file of this patent UNITED STATES PATENTS 64,189 Bird Apr. 30, 1867 311,853 Roberts Feb. 3, 1885 918,623 Whitcomb Apr. 20, 1909 1,405,320 Pedersen Jan. 31, 1922 1,696,873 Wood Dec. 25, 1928 OTHER REFERENCES Transactions of the Electrochem. Soc, vol. (1946), page 505 cited.

Claims (1)

1. THE METHOD OF RECOVERING A PRECIOUS METAL PART FROM AN ARTICLE IN WHICH THE PART IS SECURED TO A CUPRIC METAL BASE BY A NICKEL METAL BOND,WHICH COMPRISES MAKING THE ARTICLE AN ANODE IN AN ELECTROLYTIC BATH HAVING A PH IN THE RANGE OF FROM ABOUT 5 TO ABOUT 7.5 AND COMPOSED OF AN AQUEOUS SOLUTION OF AMMONIUM CHLORIDE AND A SALT OF THE GROUP CONSISTING OF AMMONIUM BICHROMATE AND SODIUM BICHROMATE TO DISSOLVE THE METAL BOND.
US445848A 1954-07-26 1954-07-26 Method of electrolytically recovering precious metals from other metal bases Expired - Lifetime US2797194A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US445848A US2797194A (en) 1954-07-26 1954-07-26 Method of electrolytically recovering precious metals from other metal bases

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US445848A US2797194A (en) 1954-07-26 1954-07-26 Method of electrolytically recovering precious metals from other metal bases

Publications (1)

Publication Number Publication Date
US2797194A true US2797194A (en) 1957-06-25

Family

ID=23770433

Family Applications (1)

Application Number Title Priority Date Filing Date
US445848A Expired - Lifetime US2797194A (en) 1954-07-26 1954-07-26 Method of electrolytically recovering precious metals from other metal bases

Country Status (1)

Country Link
US (1) US2797194A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201282A (en) * 1958-07-19 1965-08-17 Varta Ag Catalyst electrode
US3619390A (en) * 1969-02-21 1971-11-09 Horst Dillenberg Aqueous electrolytic stripping bath to remove metal coatings from bases of steel
US4123340A (en) * 1976-11-22 1978-10-31 Gotzelmann Kg Industrieabwasser-Anlagen Method and apparatus for treating metal containing waste water
US4159235A (en) * 1976-11-22 1979-06-26 Gotzelmann Kg Method and apparatus for treating metal containing waste water
US4261804A (en) * 1979-11-13 1981-04-14 United Technologies Corporation Selective removal of nickel-based alloys from ferrous-based metals
US4324626A (en) * 1979-11-13 1982-04-13 United Technologies Corporation Selective removal of nickel-based braze alloy from nickel-based metals

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US64189A (en) * 1867-04-30 Improved for cleansing the human body fbom offensive odors
US311853A (en) * 1885-02-03 Isaiah l
US918623A (en) * 1908-09-29 1909-04-20 William H Wilson Electrolyte for primary batteries.
US1405320A (en) * 1920-10-13 1922-01-31 Arthur Z Pedersen Noncorroding antifreeze mixture
US1696873A (en) * 1925-08-05 1928-12-25 American Magnesium Corp Magnesium primary cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US64189A (en) * 1867-04-30 Improved for cleansing the human body fbom offensive odors
US311853A (en) * 1885-02-03 Isaiah l
US918623A (en) * 1908-09-29 1909-04-20 William H Wilson Electrolyte for primary batteries.
US1405320A (en) * 1920-10-13 1922-01-31 Arthur Z Pedersen Noncorroding antifreeze mixture
US1696873A (en) * 1925-08-05 1928-12-25 American Magnesium Corp Magnesium primary cell

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201282A (en) * 1958-07-19 1965-08-17 Varta Ag Catalyst electrode
US3619390A (en) * 1969-02-21 1971-11-09 Horst Dillenberg Aqueous electrolytic stripping bath to remove metal coatings from bases of steel
US4123340A (en) * 1976-11-22 1978-10-31 Gotzelmann Kg Industrieabwasser-Anlagen Method and apparatus for treating metal containing waste water
US4159235A (en) * 1976-11-22 1979-06-26 Gotzelmann Kg Method and apparatus for treating metal containing waste water
US4261804A (en) * 1979-11-13 1981-04-14 United Technologies Corporation Selective removal of nickel-based alloys from ferrous-based metals
US4324626A (en) * 1979-11-13 1982-04-13 United Technologies Corporation Selective removal of nickel-based braze alloy from nickel-based metals

Similar Documents

Publication Publication Date Title
US4033837A (en) Plated metallic cathode
US2646396A (en) Method of making electroformed articles
US2797194A (en) Method of electrolytically recovering precious metals from other metal bases
CA1041944A (en) Non-contaminating anode suitable for electrowinning applications
US3497425A (en) Electrodes and methods of making same
GB1175613A (en) Electrochemical Process for the Surface Treatment of Titanium or Alloys thereof or Niobium or Tantalum
US2185858A (en) Method of removing gold, silver, palladium, or the like
US2200782A (en) Detinning
US3793172A (en) Processes and baths for electro-stripping plated metal deposits from articles
DE2536985A1 (en) ELECTRICAL CONTACT AND METHOD OF MANUFACTURING IT
US3684577A (en) Removal of conductive coating from dimensionally stable electrodes
US3400056A (en) Electrolytic process for preparing electrochemically active cadmium
US4548791A (en) Thallium-containing composition for stripping palladium
US3914161A (en) Electroplating solutions for depositing silver alloys and a method of forming silver alloys by electroplating
JPS597359B2 (en) Metsuki method
NL8004057A (en) PROCESS FOR MANUFACTURING CATHODES WITH LOW HYDROGEN SPAN.
GB1134620A (en) Method of producing a platinum group metal or alloy electrode
US3841983A (en) Surface preparation process for recoating of used coated metallic electrodes
US4012298A (en) Process for the electrolytic recovery of gallium and/or alkali metals
US2442195A (en) Cleaning and electroplating process
US1397008A (en) Method of preparing finely-divided metals
US1417896A (en) Electrodeposition of metals upon iron and alloys of iron
US3556962A (en) Method for reclaiming copper scrap containing titanium and/or iron
US2796394A (en) Separating and recovering nonferrous alloys from ferrous materials coated therewith
JPS63270421A (en) Method for recovering platinum group metals from platinum group metallic oxide electrode