US1951893A - Electrodeposition of metal alloys - Google Patents

Electrodeposition of metal alloys Download PDF

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Publication number
US1951893A
US1951893A US609071A US60907132A US1951893A US 1951893 A US1951893 A US 1951893A US 609071 A US609071 A US 609071A US 60907132 A US60907132 A US 60907132A US 1951893 A US1951893 A US 1951893A
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anodes
voltage
metals
anode
alloy
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US609071A
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Jr Julius Winkler
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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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C25D5/617—Crystalline layers
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • Myinvention refers to the art of electroplating and more particularly to the electrolytic deposition of metal alloys on cathodical surfaces.
  • Still another object of my invention is to facilitate the maintaining of an electrolyte for the electrodeposition of metal alloys, at a composition suitable for obtaining deposits of the desired composition.
  • the deposit obtained in electroplating with a solution of more than one metal does not contain the metals in the same proportion as the solution, since at low cathodical current densities the deposition of the more positive metals such as gold, silver or copper predominates, while at high current densities which cause an increased drop of potential at the surface of the cathode, the deposition of the more electronegative metals such as nickel, iron, zinc and even chromium becomes more and more intense.
  • the composition of the electrolytic bath is by no means without influence on the ratio.
  • Another difficulty encountered in the electrodeposition of alloys is due to the fact that it is extremely difficult to maintain an electrolyticbath at the desired composition by the electrolytic dissolution of metallic anodes irrespective of whether alloyed anodes or a plurality of nonalloyed anodes are used.
  • invention I overcome part or all of these difliculties by applying to the electrodes i. e., the cathode on which the alloy is to be deposited, and the anode or anodes,
  • I may select the voltage in the period of higher voltageat such values that highly negative metals may be readily deposited, and I may thus incorporate'in the alloyed de- 78 posit materially greater proportions of electronegative metals than was heretofore possible.
  • my invention enables me to use different anodes in different periods of the voltage applied so as to more precisely control 80 the dssolution of the metals desired in the electrodeposit.
  • I may use for instance a small copper anode inserted during the period of lower voltage, and a bigger gold 86 anode inserted in the period of higher voltage, and I may thus control the dissolution of the two metals at such a rate as is desred for maintaining a constant and satisfactory composition of the bath.
  • I prefer making the single pulsations substantially constant in voltage at such values as can be readily ascertained by separate tests regarding the rate of dissolut'on at such voltage.
  • anodes I may also use alloyed anodes containing the metals to be deposited,.in the desired ratio, the even dissolution of such anodes being highly facilitated by the periodically varyfng voltage.
  • the anodical current density and the anodical drop of potential are also higher, which results in an increased dissolution of the more electronegative constituent of the alloy, t 8 other constituent being more intensely dissolve during the other period.
  • I may adjust the voltage prevailing in the various periods so as to comply with the requirements for a satisfactory cathodical deposition of a corresponding number of metals. Similarly I may use an increased number of anodesconsisting of the various metals to obtain a dissolution at the ratio required in the bath.
  • the electrolyte which I use in the practice of my invention does not differ in princple from those commonly in use in the electrod'eposition of metal alloys. It contains dissolved compounds of all of the metals to be deposited in a ratio which will depend on various cfrcumstances. It is an advantage of my invention that any desired composition of the bath may be readily maintained throughout very long periods of operation.
  • I may, however, also start from a solution of suitable auxiliary compounds such as alkali salts, alkali cyanides, or the like, and I may introduce the required salts by keeping the bath in operation for a suificient time, preferably with a comparatively high voltage.
  • suitable auxiliary compounds such as alkali salts, alkali cyanides, or the like.
  • I may use a single alloyed anode, or a plurality of such alloyed anodes containing the metals to be electrodeposited, and I may so connect these anodes with the positive pole of the source of electricity that they are permanently inserted in the cycle. In such a case the varying anodical conditions required for the dissolution may be adjusted by controlling the value of the subsequent voltages.
  • I may, however, also use two or more anodes consisting of the single metals, respectively, or of alloys of part of the metals, and I may so connect them that either all or only part of them is inserted during the period of higher voltage, while the rest is inserted during the period of lower voltage, or vice versa.
  • I may also combine these two ways of providing and inserting the anodes.
  • I may provide two or more anodes, each of which contains either one metal only, or an alloy of twoor more metals, the only condition being that all the metals to be deposited are present in the anodes.
  • I may connect the anodes in such way thatone part is inserted during one period of voltage, and another part durin another period of voltage.
  • the surfaces and the composition of the various anodes as well as the voltages applied to them should be controlled with respect to each other so that the desired ratio of dissolution is obtained.
  • the positive pole of the source b of electric current which may be a galvanic battery or a dynamo, as usual in electroplating, is connected with a brush a sliding on a rotary distributor c, the surface of which is provided with three segmental metal strips rl, e, j. While these strips are insulated from each other by insulating strips x, y, 2, they are connected with three slip or collector rings i, h, g, respectively. These rings are connected by sliding contacts 101, wz, wz'with three adjustable resistances m, n, k, respectively.
  • the other poles of these resistances may be connected with three separate anodes s, t, 1', respectively, of an electrolytic cell 1), and for such purpose switches 31, n, n are provided in the connecting lines.
  • the electrolytic cell 1), to which these anodes appertain, is further provided with a cathode bar a", which carries the cathode pi. e. one or more of the articles to be plated-and is connected to the negative pole of the electrical source.
  • Another electrolytic cell u which may be used instead of the cell 1;, contains a single anode 0 which is connected to the poles of the three resistances m, n, k by switches 02, 03, 01, respectively, all of which should be operated w :2 using this cell.
  • the cathode p inserted in this cell is also connected with the negative pole of the electrical source b.
  • the distributor c When the distributor c is rotated the three resistances m and the anodes connected therewith will be inserted in the cycle alternatingly, but as these resistances may be adjusted to differentvalues, the voltage applied to the electrolytic cell it or to the electrolytic cell 1; will vary accordingly.
  • the three difierent voltages will be applied to the same anode which is accordingly dissolved at difierent current densities and drops of potential, i. e. under varying conditions of dissolution.
  • the three anodes s, t, r, provided in the cell 11 are, however, connected each with the poles of one resistance, and it will be understood that during the insertion of one of these anodes the other two will not be inserted.
  • Example 1 The electrolytic cell u shown in the drawing is filled with an electrolyte consisting of a solution of 20 parts by weight sodium pyrophosphate, 20
  • the anode 0 consists of an alloy of 500 parts gold, 425 parts copper and '15 parts nickel, the distance between the anode and the cathode being about 8 cms, while the ratio of the surfaces of the anode and of the cathode should be about 2:1.
  • the method of electrolytically depositing a dm The duration of the three alternating pulsations may be equal, and I have obtained highly satisfactory results with 150 single pulsations per minute.
  • the temperature of the bath should be kept at about 20 C.
  • the anode After one hour the anode is found to be plated with 0.72 grs. of an alloy having a pale red colour and consisting of 695 parts gold, 282parts copper and 23 parts nickel. It has a particularly fine grain, aconsiderable hardness and takes a high polish.
  • composition of the anodes or the voltages in each of the three alternating periods or by a combined variation of both I may vary the composition of the alloy deposited on the cathode within particularly wide ranges, and I may impart to it a nickel contents as high as 5 a per cent or as low as 0.2 per cent of the whole, and the colour will then vary accordingly be-- tween whitish, pale yellowish, yellowish, pale reddish and reddish shades.
  • the method of electrolytically depositing a metal alloy on a cathodical surface comprising applying to the electrodes 8. direct voltage of periodically varying intensity.
  • metal alloy on a cathodical surface comprising applying to the electrodes not less than three alternating pulsations of direct current voltage of different intensity.
  • the method of electrolytically depositing a metalalloy on a cathodical surface comprising applying a direct voltage of periodically varying intensity to a cathode and an anode, the anode containing all the metals to be deposited.
  • the method of electrolytically depositing a gold, copper and nickel alloy on a cathodical surface comprising applying a direct voltage of periodically varying intensity to a cathode and an anode, the anode consisting of an alloy of gold, copper and nickel.
  • the method of electrolytically depositing a metal alloy on" a cathodical surface comprising alternatingly applying a direct voltage of lower intensity to the cathode and one anode, and a direct voltage of higher intensity to the same cathode and to another anode.
  • the method of electrolytically depositing a metal alloy on a cathodical surface comprising alternatingly applying a direct voltage of lower intensity to the cathode and one anode, and a direct voltage of higher intensity to the same cathode and to another anode, one of these anodes consisting of a single metal.
  • these anodes consisting at least partly of alloys least one anode, the frequency of alternation being about 50 complete cycles per minute.

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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)
  • Contacts (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US609071A 1931-05-13 1932-05-04 Electrodeposition of metal alloys Expired - Lifetime US1951893A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEW85951D DE576585C (de) 1931-05-13 1931-05-13 Verfahren zur Herstellung legierter galvanischer Niederschlaege
GB13849/32A GB396191A (en) 1931-05-13 1932-05-13 Electrodeposition of metal alloys

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US1951893A true US1951893A (en) 1934-03-20

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US (1) US1951893A (fr)
DE (1) DE576585C (fr)
FR (1) FR737031A (fr)
GB (1) GB396191A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2696466A (en) * 1949-10-14 1954-12-07 Jr John F Beaver Method of electroplating
US3833481A (en) * 1972-12-18 1974-09-03 Buckbel Mears Co Electroforming nickel copper alloys
US4167459A (en) * 1979-01-08 1979-09-11 The United States Of America As Represented By The Secretary Of The Interior Electroplating with Ni-Cu alloy

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE748266C (de) * 1941-02-11 1944-10-31 Dr Max Hischmann Verfahren zur Erzeugung galvanischer Niederschlaege von Goldlegierungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2696466A (en) * 1949-10-14 1954-12-07 Jr John F Beaver Method of electroplating
US3833481A (en) * 1972-12-18 1974-09-03 Buckbel Mears Co Electroforming nickel copper alloys
US4167459A (en) * 1979-01-08 1979-09-11 The United States Of America As Represented By The Secretary Of The Interior Electroplating with Ni-Cu alloy

Also Published As

Publication number Publication date
GB396191A (en) 1933-08-03
FR737031A (fr) 1932-12-05
DE576585C (de) 1933-05-13

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