US2451341A - Electroplating - Google Patents

Electroplating Download PDF

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Publication number
US2451341A
US2451341A US610107A US61010745A US2451341A US 2451341 A US2451341 A US 2451341A US 610107 A US610107 A US 610107A US 61010745 A US61010745 A US 61010745A US 2451341 A US2451341 A US 2451341A
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US
United States
Prior art keywords
metal
current
base member
plating
plated
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
US610107A
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English (en)
Inventor
George W Jernstedt
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.)
Westinghouse Electric Corp
Original Assignee
Westinghouse Electric 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 NL69965D priority Critical patent/NL69965C/xx
Application filed by Westinghouse Electric Corp filed Critical Westinghouse Electric Corp
Priority to US610107A priority patent/US2451341A/en
Priority to GB9008/47A priority patent/GB630165A/en
Priority to CH272268D priority patent/CH272268A/de
Priority to FR950361D priority patent/FR950361A/fr
Application granted granted Critical
Publication of US2451341A publication Critical patent/US2451341A/en
Priority to DEW1589A priority patent/DE947657C/de
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
    • C25D5/18—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
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/09—Wave forms

Definitions

  • a square sheet is much harder to electroplate successfully than a cylinder while a member having projections, recesses and cavities requires specialized conditions to secure a good plating job.
  • the present invention is ⁇ directed to the application of a predetermined alternating or reversed current cycle to the base .member being plated. the current being so applied that at predetermined intervals a given vthickness of metal is electrodeposited on-the base member and then reversed sol that the given thickness of the electrodeposlt .is partially-.depleted whereby unsound andvinieriormetalis removed.
  • the object of this invention is to provide for electrodepositing on a base member a sound and homogeneous electroplat-e.
  • a further object of the invention is to electrodeposit on a base member a metal plate by a periodic alternating current process to build up a predetermined electrodeposit from which all .un-sound and inferior metal has been removed as 3 rent applied to -a member during the process of plating metal thereon in order to remove unsound or inferior metal, thereby to improve the quality of the plated metal and to impart greater speed and eiiiciency to the plating operation.
  • Figure 1 is a view in elevation in section through an electroplating system:
  • Fig. 2 is a graph plotting time against current employed in .the plating cycle
  • Fig. 3 is a fragmentary greatly enlarged crosssection through a. base member and the electroplate deposited thereon by conventional methods;
  • Fig. 4 is a greatly enlarged fragmentary crosssection of 'a base member and an electrodeposit produced thereon according to the present invention:
  • FIG. 5 is a perspective view of an electromagnet
  • Fig. 6 is a perspective through a rectangular frame.
  • electroplating may be accomplished not only at greater speeds than are ordinarily possible, but more important still, the quality of the electrodeposits produced may be so controlled that they are superior to any attained heretofore in the plating art.
  • anodic phase portion of the current cycle should be of suilicient current density and applied for a suflicient length of time to deplate unsound and inferior metal plated during the preceding cathodic phase portion of the cycle.
  • the anodic or deplating portion of the cycle should apply at least 10% of the coulombs of current applied to the base member during the c'athodic portion of the cycle.
  • the anodic current phase applies to the base member from to 40% of the coulombs of current applied during the cathodic phase portion of the cycle.
  • the cathodic portion of the current-plating cycle may be of a current density many times greater than the current dens-ity that may be applied to a base member using conventional direct current. Since lthe plating portion of the cycle only operates from about 2 to 40 seconds. polarization is negligible and it does not build up to as Ihigh a degree as would occur if the same current density were employed using direct current. When the current is reversed and the base member 'is rendered anodic, it frequently is desirable to impart a current density somewhat larger than the plating or cathodic current phase of the cycle. In many cases, excellent results were attained where the anodic current density has been 50% to 100% greater than the oathodic current density.
  • uniformity, color, and corrosion-resistance of the metal electrodeposited by the process of 'this invention are deiin-itely superior to the same metals deposited from the same electrolyte using direct current.
  • Other advantages of the invention will be disclosed hereinafter as the process is described in detail.
  • an electroplating tank i0 provided lwith a chemically resistant liner I2 in which is located the electrolyte I4 of a suitable composition to electroplate the desired metal.
  • the conducting bars i6 and I0 are each provided with current from the source 2l of alternating or periodically reversed current meeting the requirements herein set forth.
  • the source of alternating current 20 may be an alternatingcurrent generator designed to generate current accordinging to the desired cycle set forth. In other cases, the source of alternating current 20 may Y be a direct-current source, such as a battery,
  • conductor bar i6 carries a hanger 22 on which there is supported the base member 24 to be electroplated.
  • the hanger 26 supported by the conductor bar I8 carries a suitable anode electrode 28.
  • Fig. 2 of the drawing there is illustrated the alternating-current cycle applied to the member 24 by the current source 20.
  • the base member 2l becomes cathodic and metal is plated thereon.
  • the current density at A will be higher than that ordinarily employed, everything else being equal. using only direct current. However, it should be understood that it is not necessary to employ greater currents than arenormally employed using only direct current. Excellent plating will be secured on the base member even though the current density at A is a value which is less than that normally used.V
  • the present invention allows a wider latitude ,of current densities than previously possible.
  • the current density at A should not be of such a high value that the electroplated metal is burned or excessive gassing or other undesirable effects occur in the short time that the member is cathodic.
  • the time from A to B may be from about 2 to 40 seconds. The time which is selected will depend on the electrolyte in which the process is being carried out, the shape of the member being plated, and other conditions.
  • the anodic current density at C is ⁇ greater than the cathodic current density. In most cases, it will be found that a higher anodic current density is required. tov secure the desired results of the invention. However, l in many cases, it has been found that the-anodic current density may be the same as the cathodic current density.
  • the significant criterion ofthe anodic or reverse current at C A is that it beso correlated to the electrolyte that the plated member b e deplated to the extent-of removing a substantial amount of plated metal. applied for a period of time of from about onehalf to ten seconds based on the corresponding plating or. cathodic current.
  • the product of time and the anodic current should have a value in coulombs equal to at least and prefer'- ably 20% to 40%, of the coulombs applied during the cathodic portion of the cycle.
  • 'I'he cur-w rent from C to D need not be uniform as shown, but may be rippled or pulsating or may vary in y
  • the current is again reversed and the base member is made cathodic and the cycle repeated. In all cases, the cycle will benen-symmetrical.
  • the cycle O-A-B-QC-D-E is repeated until suitable thickness of metal has been plated on the base member. moved from the electrolyte il between the portions C and D of the cycle when the member is anodic since the polish of the plated metal is at an optimum at this point.
  • the metal is plated from the electrolyte I4 at a high rate of speed between the points A and B for from about 2 to 40, seconds.
  • the metal first
  • the anodic current is The base member is preferably re- ⁇ v trodeposit of metal tends to greatly accelerate its growth atr the burr I2 in accordance with well known phenomenon.
  • a nodule 3l. accordingly, is produced over the burr 32. particularly' if the plating is of any appreciable thickness. At the scratch il.
  • the electrodeposlted metal form an exaggerated valley Il which comprises relatively sharp ridges thicker than the main portion of the electrodeposited metal and a lesser thickness of metalis deposited in the valley of the scratch than the main portion -of the electrodeposited metal.v At the pore n. the electrodeposited v metal forms a slightly thicker lip surrounding the'pore with substantially no metal deposited over the relatively non-conducting inclusion. It.
  • the metal concentration adjacent the base member is abnormally high, and thereby plating starts and is maintained for part of the period at approximately 100% eillciency in many electrolytes.
  • the metal concentration within and near the scratch 34 is high enough to plate rapidly on .both sides of the scratch, and the scratch is filled up from its bottom at a greater rate than the main body of metal is being built up.
  • the projections such as M do not build up a much greater thickness of metal than does the main body of the plate. There fore, no nodular or treeing eiiects are secured.
  • the anodic portion of the cycle again reduces the projections in preference to the scratches or other microscopic depressions and thereby a progressively more uniform surface is secured. It will be apparent that the anodic portion in combination with the cathodic portion of the current cycle imparts new and unexpected characteristics to the plated metal.
  • the anodic portion of the cycle does not represent wasted energy since plating during the subsequent cathodic portion of the cycle is expedited and is more eflicient due to the replenishment of the metal in the closely adjacent electrolyte.
  • Electrodeposits of zinc, tin, cadmium, and gold have been produced superior in manyrespects to those obtained by any conventional plating method.
  • the electrolytes used were those employed in conventional plating practice. No substantial changes in composition are necessary in order to secure the benefits oi' the present invention.
  • the alternating-current cycle of this invention has been found to give good results not only with Conventional plating electrolytes but with electrolytes modified to provide for a better cooperation between the current and the metal being plated. The only exception was encountered in plating chromium; when the reverse or deplating current was applied-the base metal deplated instead of the chromium plate.
  • Example I An electrolyte was prepared containing:
  • the complex -shaped -base member 50 shown in Fig. of the drawing was electroplated in a bath as shown in Figure 1.
  • the member 50 is a cobalt ferrous alloy electromagnet having approximately Il; square foot of surface area.
  • the requirements called for electroplating a thickness of approximately 0.018 to 0.020 inch of copper having a total weight between 28 and 33 grams. It will be readily recognized that plating the member 50 would be quite dfllcult if a reasonably smooth.
  • the temperature of the electrolyte was varied from 140 F. to 210 F.
  • the pH was maintained at 12 and higher.A
  • the electrode 28 was a copper anode.
  • the member 60 was plated in the copper electrolyte according to the following alternating-current cycle:
  • Example 1V An electrolyte for plating brass was prepared as follows:
  • samples of steel were .plated in the cadmium electrolyte under the following square foot flashed with copper were plated in ⁇ conditions:
  • the brass electrolyte using the following dimin- -The eifective current density was amperes per square foot.
  • An unexpected result was that the electrodeposit was a very bright brass. As far as known, it has been desirable to secure a bright brass directly by plating, but this has not hitherto been commercially possible by any known plating process.
  • the tests of the brass plate indicated that it was smoother and more homogeneous than ordinary brass plate as well as being more tenaciously adherent and much more rcorrosion-resistant. The brass was denser than brass secured by direct current plating.
  • Example V A zinc-plating electrolyte was prepared withv the following constituents:
  • Example VIII An aqueous solution for plating-gold was prepared with essential ingredients as follows:
  • FIG. 6 of the drawing showing a rectangular open ended casing member 52.
  • the member 52 is a common form of casing for enclosing apparatus and instruments. Hitherto in plating members corresponding to or similar to the member 52, it was necessary to employ an anode inside the frame of member 52 as well as anodes about the exterior of the frame. Even then uneven electroplated deposits often occurred.
  • By using the alternating-current cycle of this invention it has been found possible to electroplate both the inner and outer surfaces of the frame member 52 quite uniformly without using any-internally located anodes or resorting to other time-consuming expedients.
  • the plating of copper on a steel casing corresponding to member 52 resulted in asmooth bright coating over both the interior and exterior surfaces of the member using only
  • the better distribution of plated metal secured bythe alternating-current cycle cf this invention as exemplified by the plating of the members of Figs. 5 and 6 constitutes an important feature of the invention.
  • the plating current densities; practicable even .with the complex surface mem- ⁇ bers are far higher than would be possible using direct-current plating.'
  • the eltrodeposits produced by the invention are superior in both mechanical and chemical properties to plating produced by conventional processes and, therefore, are advantageous for numerous applications requiring the best attainable properties of electroplated metal.
  • Automobile hardware which is subject to abrasion and exposure to moisture and deleterious gases may be advantageously plated with a more durable and corrosion-resistant plating by the process of the present invention.
  • Household appliances subject to heating, food acids, Iand other corrosive influences will be found to be capable of lasting longer and with better results if produced as herein disclosed.'
  • mechan- ⁇ ical buifing or polishing may be entirely eliminated since the plated member will be as bright as can be secured by any mechanical polishing operation.
  • Engraving dies, electrotypes, plastic ⁇ molds and similar members of complex' shape may be prepared by electroplating metal base members, graphitic or carbon bodies, wax or resin master patterns dusted with a conducting surface coating of metal powder or graphite in accordance With the present invention to produce a much more durable and wear-resisting plating than can be secured by any known process of plating.
  • the plated metal will be found to be much harder and more corrosion-resistant to conditions encountered in service than ordinary plated metal. The pattern will be followed faithfully without excessive plating on corners and projections. Accordingly, longer wearing dies and printing vplates will be attained.
  • the alternating current plating of the present invention may be carried out in anyV type of systeni or apparatus commonly employed for plating. Rubber-covered steel tanks will generally be found to give good results, though wood, glass, or other materials may be employed. The work may be hung on a stationary holder or on a moving conveyor. The size of the apparatus has not introduced any dilculties. Plating with the alternating-current cycle has been carried out as effectively in small glass beakers as well as in large tanks having a capacity of several hundred gallons of electrolyte.
  • alloys as Well as single metals may be electrodeposited bythe present alternating current process. Several successive deposits of metal in any desirable proportions may be plated on a single member.
  • the electrolyte may be agitated or distributed in accordance with well known practices in plating. It has been found desirable to maintain a clean electrolyte, for example, by filtering or the like, since the electrodeposits have such a highly polished surface that any solid impurities 13 from the electrolyte deposited on the plated work are much more apparent than in ordinary electroplating.
  • the temperature of the electrolyte may be varied to suit the plating requirements. The current cycle works aswell at temperatures of boiling water as at temperatures below room temperature.
  • the process oi' electropiatlng metal from the group consisting of copper, brass, silver, zinc, tin, cadmium and gold on a base member from an electroplating electrolyte in which the deposited metal is readily soluble on the passage ot electric current when thev base member is the anode, comprising the steps of connecting the base member to be plated into an electroplating circuit including the electrolyte, causing electric current to now in the plating circuit while the base member is in contact with the electrolyte,
  • the electric current flowing in-the plating cir/cyste@ being periodically reversed so as alternatelyA electroplate metal on and then deplate metal from the base member, the current for plating metal on the base member being caused to flow for a period of time of not over 40 seconds until a layer oi!
  • the deplating current being of a magnitude and applied for a sufilcient period of time to deliver at least of the coulombs delivered during the preceding platin-g,period so that a substantial amount of the plated metal is removed, and repeating the cycle of plating and deplating to cooperate in building up on the base member an electrodeposit in small increments to produce a smooth, sound, homogeneous plate.
  • electroplating sound metal from the group consisting of copper, brass, silver, zinc, tin, cadmium and gold from an electroplating electrolyte having the metal dissolved vtherein upon a base member immersed therein at an increased rate as compared to continuous direct current plating from the same electroplating electrolyte, the plated metal deposited on the base member being one that is readily soluble in the electrolyte upon the passage of a current making the member anodic, comprising the steps of applying to the base member successive cycles of current veach cycle composed of a cathodic portion and an anodic portion to deliver to the base member for a period of time of from about 2 to 40 seconds a cathodic plating current at a density substantially higher than can be effectively applied as continuous direct current to plate the same metal thereon, and then to deliver to the base member an anodic current of a suiilcient current density and for a suillcient period 'of -time to deliver to the base'member at least 10
  • the steps comprising passing a plating electric current through the base member while it is in contact with the electrolyte, the plating current being applied for a period of time not less than 2 seconds and not more than 40 seconds to electroplate an increment of the metal, then applying a deplating electric current to the base member to deplate a substantial portion of the preceding increment, the deplating current being of a magnitude and applied for a sufcient period ot time to deliver at least of the coulombs delivered during the preceding plating period to eiect removal of a part of the previously plated increment, and continuing the alternate plating and deplating until a desired thickness of metal has been applied to the base member.
  • the steps com-'- prising applying a plating electric current to the base member for not less than 2 seconds and not more than 40 seconds to electroplate an increment of the metal, then applying a deplating electric current for a period of from 1/2 to 10 seconds to the base member to deplate a substantial portion of the preceding increment, the deplating current being of a magnitude and applied for a suillcient period of time todeliver at Y least 10% of the coulombs delivered during the Cil an aqueous electroplating electrolyte having the metal to be plated dissolved therein and in which the base member is immersed, the steps comprising applying a plating electric current to the base member for not less than 2 seconds and not more than 40 seconds to
  • a. base member from an aqueous electroplating electrolyte having the metal to be plated -dissolved therein and in which the base member is immersed the steps comprising applying a plating electric current to the base member for not less than about 3 seconds and not more than about 30 seconds to electroplate an-increment of the metal, then applying a deplating electric current for a period of from about Vg second to about 3 seconds to the base member to deplate a substantial portion of the preceding increment, the deplating current being of a magnitude and applied for a suiiicient period of time to deliver at least 10% of the coulomb. delivered during the vpreceding plating period to effect removal of a part of the previously plated increment, and continuing alternate plating and deplating until a desired thickness of metal is applied to the base member.

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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 Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US610107A 1945-08-10 1945-08-10 Electroplating Expired - Lifetime US2451341A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL69965D NL69965C (en(2012)) 1945-08-10
US610107A US2451341A (en) 1945-08-10 1945-08-10 Electroplating
GB9008/47A GB630165A (en) 1945-08-10 1947-04-02 Improvements in or relating to electroplating
CH272268D CH272268A (de) 1945-08-10 1947-06-13 Verfahren zur galvanischen Abscheidung von Metall.
FR950361D FR950361A (fr) 1945-08-10 1947-07-16 Revêtement électrolytique
DEW1589A DE947657C (de) 1945-08-10 1950-04-05 Verfahren zur Erzeugung glatter, glaenzender Niederschlaege von Metallen auf einen Grundkoerper durch Elektrolyse

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US610107A US2451341A (en) 1945-08-10 1945-08-10 Electroplating

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US2451341A true US2451341A (en) 1948-10-12

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US610107A Expired - Lifetime US2451341A (en) 1945-08-10 1945-08-10 Electroplating

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CH (1) CH272268A (en(2012))
DE (1) DE947657C (en(2012))
FR (1) FR950361A (en(2012))
GB (1) GB630165A (en(2012))
NL (1) NL69965C (en(2012))

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Publication number Publication date
NL69965C (en(2012))
GB630165A (en) 1949-10-06
FR950361A (fr) 1949-09-26
CH272268A (de) 1950-12-15
DE947657C (de) 1956-08-23

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