US3716464A - Method for electrodepositing of alloy film of a given composition from a given solution - Google Patents

Method for electrodepositing of alloy film of a given composition from a given solution Download PDF

Info

Publication number
US3716464A
US3716464A US00889106A US3716464DA US3716464A US 3716464 A US3716464 A US 3716464A US 00889106 A US00889106 A US 00889106A US 3716464D A US3716464D A US 3716464DA US 3716464 A US3716464 A US 3716464A
Authority
US
United States
Prior art keywords
given
current
solution
approximately
concentration
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
US00889106A
Other languages
English (en)
Inventor
Z Kovac
J Olsen
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.)
International Business Machines Corp
Original Assignee
International Business Machines 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 International Business Machines Corp filed Critical International Business Machines Corp
Application granted granted Critical
Publication of US3716464A publication Critical patent/US3716464A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • 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
    • 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

  • ABSTRACT The effect of superimposing a sinusoidal alternating current on a direct current during electrodeposition of NiFe alloys is disclosed in terms of the following factors: (a) maintaining the pH at the electrode equal to that of the bulk electrolyte; (b) ionic diffusion processes; and (c) chemical processes in solution prior to electrochemical reduction.
  • the effect of frequency, amplitude and the rate of a-c current to d-c current on the composition of electrodepo'sited alloy are given for acid solutions of different pH and for alkaline solutions of metallic complexes with a variable concentration of complexing agent. It is shown that by proper choice of conditions, electrodeposited FeNi alloys can be prepared with a desired uniform composition throughout their thickness.
  • alternating current is superimposed on direct current to prevent the pH in the layer of solution adjacent to the electrode from increasing and thus influence the electrodeposition of iron group metals or alloys of any metals which readily form hydroxide. Formation of hydroxides is thus prevented and their inclusion into deposited film is precluded.
  • the a-c current beneficially affects the rate of deposition of a metal which is controlled by diffusion.
  • l and Fe plate out at the same rate for thickness of film approximately in the range of 300A. to 4,000A.
  • a severe problem in plating Ni-Fe magnetic films results when a plating current is initially applied to a Ni-Fe bath.
  • the initial deposit is very rich in iron content and thereafter decreases in iron content until an equilibrium condition is reached and the alloy having the desired proportion of nickel and iron is plated. Since it is only in the initial layers plated that this variance in the proportions of nickel and iron is produced, usually the principal variance is produced within the first 500A. of film deposited. Therefore, this problem has not been too severe when the plated film is very thick.
  • the final film is to have a thickness of about 1,000A. or less, and the films are to be used in computer memories, which demand constant magnetic characteristics across the entire film, this initial iron rich deposit becomes a severe problem.
  • Electrodeposition of Ni-Fe alloys is accompanied by considerable hydrogen evolution which gives rise to alkalization in the vicinity of an electrode with subsequent formation of metallic hydroxides. Consequently, there is preferential deposition of Fe with the characteristics: (a) gradient in composition across film thickness up to approximately 1,000A.; (b) nonuniformity in composition in the plane of the film; and (c) inclusions in the films.
  • the ratio of the metals in the deposit is not the same as the ratio of metal ions in the solution.
  • Ni-Fe films for memory application with thickness in the range of approximately 1,000A. to 1,200A. must satisfy stringent requirements in uniformity of both composition and physical properties.
  • copending patent application Ser. No. 601,951 by J. M. Brownlow et al. filed Dec. 15, 1966, now abandoned, and commonly assigned discloses use of specially shaped current pulses for satisfying these stringent requirements.
  • the noted copending application by J. M. Brownlow et al. discloses that a shaped continuous current or a series of shaped current pulses are applied to effect the plating.
  • the magnitude of the plating current, or of each of the plating current pulses is initially significantly higher than that required to plate the desired alloy under equilibriumconditions in the bath.
  • the current, or each current pulse is thereafter decreased with time, preferably in inverse proportion to the square root of time, to provide films with uniform proportions of Ni and Fe throughout the film thickness.
  • Alternating current is known to have a significant influence on many electrode processes and it has been used in such electrochemical investigations as: (a) the study of electrical double layers as reported in the articles by Wien, Ann. Phys. Lpz., Vol. 58, page 815 (1896); D. C. Graham, J.Amer.Chem.S0c., Vol. 63, page 1207 (1941) and Vol. 68, page 301 (1946); and M. A. Proskurin et al., Trans. Faraday 500., Vol. 31, page 1 10 (1935); (b) the kinetics of the formation and dissolution of oxide films as reported in the article by B. V. Ershler, Trans. 2nd Meeting on Metal Corrosion, Acad.
  • this invention provides a method of electrodepositing an alloy layer therefrom. There are in the solution a first concentration of a given metal and a second concentration of a given alloying agent and the layer is obtained by utilizing an applied alternating current superimposed on an applied direct current.
  • the steps of the method of this invention for electrodeposition of NiFe alloys comprise:
  • b controlling the peak value excursions of the applied alternating current in relationship to the value of the applied direct current such that oxidation of the adsorbed hydrogen is the main anodic reaction of the electroplating solution; and v c. fixing the frequency of the applied alternating current in accordance with a plot of percentage of a component of the metallic alloy deposited from the electroplating solution versus frequency of the applied alternating current.
  • the difference between the pH of solution at the surface of the cathode and pH in the bulk of the solution can be maintained approximately the same to limit hydroxide formation for iron group metals, and also in all cases where metal ions are used which readily form hydroxides, e.g., Zn, In, Cd.
  • composition of an alloy electrodeposited from the same solution can be varied in the approximate range of 6 to percent Fe by varying only the frequency.
  • composition of an electrodeposited alloy film can be maintained constant over a thickness range of approximately 400A to 4,000A.
  • the ratio of the concentration of the metal to the concentration of the alloying constituent or agent in an electrodeposited alloy film can be made to reflect exactly the ratio of the concentrations of the respective ions in the solution.
  • inventive method as summarized above, is disclosed in this application as being applied principally to the fabrication of binary alloy films which include only nickel and iron, the inventive method can be employed to prepare ternary Ni-Fe alloys. Further, the Ni-Fe alloys, to which this method is principally directed, are only one example of a rather broad class of alloys which present similar problems when it is desired to plate a film which is uniform in composition throughout its thickness.
  • FIG. 1A presents a schematic diagram illustrating an electrical arrangement for electrodeposition of an alloy film with combined d-c and a-c currents.
  • FIG. 18 illustrates the net current curve for the electrical arrangement of FIG. 1A.
  • FIG. 1C illustrates the net voltage curve for the electrical arrangement of FIG. 1A.
  • FIG. 2 illustrates the Fe content and the rate of alloy deposition as a function of log f in low Ni concentration solutions of pH 3.0 and pH 4.6 for (Fe/Ni) 20/80, with I 2 mA/cm and I 1.13.7 mA/cm
  • FIG. 4 illustrates the Fe content and the rate of alloy deposition in high Ni concentration solution of pH 3.8 with I, of 2 mA/cm and 5 mA/cm and I 13.75 mA/cm.
  • FIG. 5 illustrates the log of the direct current density versus potential in high citrate solution of pH 9.25.
  • FIG. 6 illustrates the Fe content and the rate of alloy deposition as a function of log f with I of 2 and 4 mA/cm 1 peak 15 maA/cm and (Fe/Ni) 20/80.
  • PC peak FIG. 7 illustrates the Fe content and the rate of alloy deposition in low citrate solution of pH 9.25
  • FIG. 8 illustrates the Fe content as a function of direct current density for f 0, 30 and 400 Hz with [peak 13.75 mA/cm, (Fe/Ni) 5/95, and pH 3.8.
  • FIG. 9 illustrates the Fe content as a function of direct current density for f 0, 30 and 400 Hz in high citrate solution of pH 9.25, and (Fe/Ni) 20/80 and I 16.7 mA/cm.
  • FIG. 11 illustrates the Fe content and the rate of alloy deposition as a function of log f in high citrate solution, with I, 2 mA/cm, l mA/cm for T 25C and 40C.
  • FIG. 12 illustrates the rate of alloy Ni-Fe deposition as a function of ar in low nickel solution, (Fe/Ni) /80 and pH 3,00, 1, 2 (mA/cm, peak 13.75 A/ +2b.
  • FIG. 13 illustrates the rate of Fe deposition as a function of ar in high Ni solution, (fe/Ni),,,, 5/95 at pH 3, 38 and 4.6, I, 2 mA/cm, peak 13.75 mA/cm
  • FIG. 14 illustrates the rate of Fe deposition as a function of ar at I of 2 and 4 mA/cm in low and high citrate solution.
  • FIG. 15 illustrates the rate of Ni deposition as a function of ar at 2 and 4 mA/cm in low and high citrate solutions.
  • FIG. 16 illustrates the Fe content as a function of film thickness in acid and alkaline solutions.
  • FIG. 1A APPARATUS FOR THE INVENTION Apparatus for electrodepositing an alloy film for the practice of this invention is presented schematically in FIG. 1A and the net current and voltage curves therefor are shown in FIGS. 13 and 1C, respectively.
  • the electrolytic cell 10 consists of two compartments l2'and 14.
  • the working compartment 12 includes a vessel 16 electrolyte 18, horizontal working electrode 20 masked on one surface with insulating material 22, and a platinum mesh auxiliary electrode 24.
  • the working electrode 20 and auxiliary electrode 24 are connected to the external electrical circuit 23 by means of conductors 21 and 25, respectively.
  • the working compartment 12 is connected to the reference compartment 14 by means of a Luggin capillary 26.
  • the reference compartment 14 includes an electrolyte 30 contained in a vessel 28.
  • the reference electrode 32 is saturated Calomel Electrode suspended in electrolyte 30.
  • Reference electrode 32 is connected to the external electrical circuit 23 by conductor 33.
  • the electrical circuit 23 includes a d-c power supply 36 having positive and negative terminals 38 and 40.
  • a signal generator 42 is provided to produce an a-c current which is superimposed on the d-c current.
  • a by pass capacitor 43 connected between terminals 38 and 14 provides a path for the a-c current.
  • the negative terminal 40 of the d-c power supply 36 is connected to the working electrode 20 through conductor 41, variable resistor 44, conductor 49 ampere meter 66, and conductor 21.
  • the current through the circuit as a function of time is monitored by dual-beam oscilloscope 50 via terminals 54 and 55 which is connected across the variable resistor 44 at connections 46 and 48.
  • the potential on the working electrode 20 with respect to the saturated Calomel Electrode 32 is measured by volt-meter 62 which is monitored as a function of time by oscilloscope 50 at connections 56 and 57.
  • Oscilloscope 50 presents trace 51 as function of time on tube face 52 of either the current measured by ampere-meter 66 or the voltage measured by volt-meter 62 as selected.
  • Case 2 In Case 2 the current is controlled by ionic diffusion in the electrolyte.
  • C for t 0 and l-lere, C is the concentration at the electrode surface and c is the bulk concentration.
  • Equation 1 for constant d-c current is:
  • i is the current density, tis time, n is the number of electrons involved in the electrode reaction and F is Faraday s constant.
  • Equation l For sinusoidal a-c current the solution of Equation l is:
  • I is the amplitude of the current density
  • w 21rf where f is the a-c current frequency
  • Equation 4 becomes I 1r t AC nFvDw sin (0: (n)
  • Equation 6 is applicable to only 925 constituent of the alloyarid the other constituent will be deposited as if the a-c current were not present, since a-c current does not effect charge transfer reactions.
  • Electrodeposition is carried out from a solution of complex ions, a reduction to the metallic state can take place either directly from the complex ion or this electrochemical step can be preceded by a chemical step or several steps in series.
  • Equation (7) can be written as v v kc (8) where v, is the reaction exchange rate, k k c is the reaction rate constant, and p is the reaction order.
  • Equation 9 applies to both direct and alternating currents.
  • the concentration wave will be able to follow the slowly varying current, and that the penetration depth would be of the same length as d-c reaction layer thickness.
  • the formation and decomposition of metal complexes will be increasingly less important, since they cannot follow fast changes of current.
  • the penetration depth of the concentration wave will become smaller. For both these reasons, it is to be expected that at high frequencies the d-c current behavior will dominate.
  • FIG. 1A PRACTICE OF THE INVENTION Measurements were performed with two compartment cells as shown in FIG. 1A.
  • the cathode was Cu-sheet or evaporated Ag on glass (2 X 2 cm), placed horizontally in one compartment 12 of the cell.
  • the back of the electrode was masked by mask 22 so that electrodeposition was carried out on one side only.
  • a Pt-mesh auxiliary electrode 24 was placed approximately 2 cm above the working electrode 20.
  • the reference containing electrode 9 compartment 14 saturated Calomel electrode was connected with the main compartment 12 through a Luggin capillary 26 carefully bent to avoid any shielding effect.
  • FIG. 1A Current time and potential time curves, FIGS. 1B and 1C, respectively, were simultaneously recorded on a dual-beam oscilloscope 50. It is important that the A. potential is recorded, since this provides a way of determining the conditions under which the oxidation of hydrogen takes place by an electrochemical mechanism which minimizes dissolution of alloy and avoids its oxidation.
  • the acid solutions had the following com positions: Low Ni": 0.024 M NiSO 0.006 M FeSO.,, 0.035 M NaKC H O pH 3 or 4.6.
  • the molar ratio of (Fe/Ni) in solution was 20/80.
  • High Ni had composition as above for Low Ni, but with 0.114 M NiSO and pH 3, 3.8 or 4.6.
  • the (Fe/Ni) ratio in solution was 5/95.
  • the alkaline solutions were ammoniacalcitrate solutions, the compositions of which were: High citrate": 0.125 M NiCO 0.032 M Fe dust, 0.301 M C H O 0.332 M (NH.,) M C H O and NH OH for pH 9.25.
  • the low citrate solution had the same pH and concentration of Ni and Fe but it contained 0.127 M C H O and 0.137 M (NH H C I-l O-,.
  • the molar ratio of (Fe/Ni) in solution was 20/80.
  • the solutions were made of reagent grade chemicals and deionized water.
  • the citrate solutions were prepared according to British Pat. No. 925,144.
  • FIG. 5 shows a log current vs. voltage plot for the high citrate solution. It can be seen that for high values of total current, 1 reaches a limiting value, which is taken as the limiting reaction current according to Vetters criteria as set forth hereinbefore in the Theory of the Invention section.
  • FIGS. 6 and 7 the deposition rates and percent Fe are given as a function of log frequency for two values of direct current density.
  • rates of Fe deposition are given as a function of ar for two values of d-c current and two concentrations of complexes of citrate ions.
  • I qnA cm a quite surprising effect is found, namely, Fe deposits with a higher rate from the solution containing more of its-complexing agent.
  • I is increased to 4 mA cm, Fe deposits with the same rate from both citrate solutions in low frequency region.
  • the situation becomes normal, i.e., with more complexing agent less Fe ions are available for deposition. This abnormality can be explained if tee values of the rate constant are compared for low and high citrate solution.
  • the reaction exchange rate, v can be calculated from Equation 11 if the limiting reaction current, i is determined experimentally.
  • i 1.54 mA cm', giving v, 2.06 l0"
  • k is calculated to be 4.63 10 and 1.19 10 sec for high and low citrate, respectively.
  • the rate depends not only on ar but also on the ratio of k to w. This ratio varies from 37 to 0.74 in the high citrate solution, but only from 9.5 to 0.l9 in the low citrate, when f is varied from 20 to l,000 Hz.
  • the rate constant is equal to m at 740 Hz and 190 Hz for high and low citrate, respectively. Since k is an order of magnitude larger than (u at low frequencies in the high citrate solution, Fe deposits with a higher rate than from low citrate solution where k and w are of the same order of magnitude. At 1,000 Hz the ratio of k/m in both solutions are of same magnitude, i.e., 0.74 and 0.19, and there is very little difference in Fe rates as shown on the left side of FIG. 15.
  • NiCO 16.2 g/l Fe dust 1.78 g/l Citric acid 26.6 g/l NIL-citrate 3 L0 g/l pH 9.25 at approximately C I, 2 ma/cm I, 15 ma/cm Rate IOOA/min.
  • NiSO 6H O 6.3 g/l NaK-tartrate 10.0 g/l pH 3.0 at approximately 25C Rate 22A/min.
  • Method of electrodepositing a Fe-Ni alloy film with a given composition from an electroplating solution having a given pH, a first concentration of a given metal Fe and a second concentration of a given alloying agent Ni comprising the steps of:
  • said electroplating solution having an electrodeposition characteristic of percentage of said alloying agent deposited cathodically from said solution versus frequency of said applied alternating current exhibiting a given slope in a first portion over a given low range of frequencies
  • NaK-tartrate 10.0 g/l
US00889106A 1969-12-30 1969-12-30 Method for electrodepositing of alloy film of a given composition from a given solution Expired - Lifetime US3716464A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US88910669A 1969-12-30 1969-12-30

Publications (1)

Publication Number Publication Date
US3716464A true US3716464A (en) 1973-02-13

Family

ID=25394514

Family Applications (1)

Application Number Title Priority Date Filing Date
US00889106A Expired - Lifetime US3716464A (en) 1969-12-30 1969-12-30 Method for electrodepositing of alloy film of a given composition from a given solution

Country Status (4)

Country Link
US (1) US3716464A (de)
JP (1) JPS4946692B1 (de)
DE (1) DE2061225A1 (de)
GB (1) GB1333254A (de)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994694A (en) * 1975-03-03 1976-11-30 Oxy Metal Industries Corporation Composite nickel-iron electroplated article
US4170739A (en) * 1977-12-23 1979-10-09 Frusztajer Boruch B Apparatus and method for supplying direct current with superimposed alternating current
US5100559A (en) * 1989-08-21 1992-03-31 Battelle Memorial Institute Treatment methods for breaking certain oil and water emulsions
WO1998040539A1 (en) * 1997-03-13 1998-09-17 Quantum Corporation Electroplating apparatus and process for reducing oxidation of oxidizable plating anions and cations
DE19983254C2 (de) * 1999-05-06 2002-09-12 Union Steel Mfg Co Ltd Vorrichtung und Verfahren zur Herstellung einer dünnen Folie aus einer Ni-Fe-Legierung
US20040188260A1 (en) * 2003-03-31 2004-09-30 Matthias Bonkabeta Method of plating a semiconductor structure
US20040200731A1 (en) * 2003-04-11 2004-10-14 Sullivan John Timothy Apparatus and method for generating and using multi-direction DC and AC electrical currents
WO2010005993A2 (en) * 2008-07-07 2010-01-14 Modumetal Llc Low stress property modulated materials and methods of their preparation
US20100147800A1 (en) * 2008-12-16 2010-06-17 City University Of Hong Kong Method of making foraminous microstructures
US20100270164A1 (en) * 2007-12-21 2010-10-28 Kentaro Kubota Manufacturing method for surface-treated metallic substrate and surface-treated metallic substrate obtained by said manufacturing method, and metallic substrate treatment method and metallic substrate treated by said method
CN105586614A (zh) * 2016-03-18 2016-05-18 厦门大学 一种三价铁体系碱性溶液电沉积因瓦合金的电镀溶液及电镀方法
US10253419B2 (en) 2009-06-08 2019-04-09 Modumetal, Inc. Electrodeposited, nanolaminate coatings and claddings for corrosion protection
US10513791B2 (en) 2013-03-15 2019-12-24 Modumental, Inc. Nanolaminate coatings
US10662542B2 (en) 2010-07-22 2020-05-26 Modumetal, Inc. Material and process for electrochemical deposition of nanolaminated brass alloys
US10781524B2 (en) 2014-09-18 2020-09-22 Modumetal, Inc. Methods of preparing articles by electrodeposition and additive manufacturing processes
US10808322B2 (en) 2013-03-15 2020-10-20 Modumetal, Inc. Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes
US10844504B2 (en) 2013-03-15 2020-11-24 Modumetal, Inc. Nickel-chromium nanolaminate coating having high hardness
US10961635B2 (en) 2005-08-12 2021-03-30 Modumetal, Inc. Compositionally modulated composite materials and methods for making the same
US11180864B2 (en) 2013-03-15 2021-11-23 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US11286575B2 (en) 2017-04-21 2022-03-29 Modumetal, Inc. Tubular articles with electrodeposited coatings, and systems and methods for producing the same
US11293272B2 (en) 2017-03-24 2022-04-05 Modumetal, Inc. Lift plungers with electrodeposited coatings, and systems and methods for producing the same
US11365488B2 (en) 2016-09-08 2022-06-21 Modumetal, Inc. Processes for providing laminated coatings on workpieces, and articles made therefrom
US11519093B2 (en) 2018-04-27 2022-12-06 Modumetal, Inc. Apparatuses, systems, and methods for producing a plurality of articles with nanolaminated coatings using rotation
US11692281B2 (en) 2014-09-18 2023-07-04 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US11866841B1 (en) * 2018-03-15 2024-01-09 Seagate Technology Llc Electrodeposited materials and related methods

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH629542A5 (de) * 1976-09-01 1982-04-30 Inoue Japax Res Verfahren und vorrichtung zur galvanischen materialablagerung.
US4468293A (en) * 1982-03-05 1984-08-28 Olin Corporation Electrochemical treatment of copper for improving its bond strength
US4515671A (en) * 1983-01-24 1985-05-07 Olin Corporation Electrochemical treatment of copper for improving its bond strength

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2443599A (en) * 1942-05-04 1948-06-22 Poor & Co Electroplating method employing pulsating current of adjustable wave form
US2515192A (en) * 1944-09-27 1950-07-18 Poor & Co Method of electroplating
US2619454A (en) * 1945-08-30 1952-11-25 Brush Dev Co Method of manufacturing a magnetic recording medium by electrodeposition
US2706170A (en) * 1951-11-15 1955-04-12 Sperry Corp Electroforming low stress nickel
US2824830A (en) * 1955-08-03 1958-02-25 Hausner Johann Karl Electroplating
US3152974A (en) * 1962-07-18 1964-10-13 Hughes Aircraft Co Electroplating magnetic cobalt alloys
US3239437A (en) * 1960-07-28 1966-03-08 Atomic Energy Authority Uk Methods of depositing magnetic alloy films

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2443599A (en) * 1942-05-04 1948-06-22 Poor & Co Electroplating method employing pulsating current of adjustable wave form
US2515192A (en) * 1944-09-27 1950-07-18 Poor & Co Method of electroplating
US2619454A (en) * 1945-08-30 1952-11-25 Brush Dev Co Method of manufacturing a magnetic recording medium by electrodeposition
US2706170A (en) * 1951-11-15 1955-04-12 Sperry Corp Electroforming low stress nickel
US2824830A (en) * 1955-08-03 1958-02-25 Hausner Johann Karl Electroplating
US3239437A (en) * 1960-07-28 1966-03-08 Atomic Energy Authority Uk Methods of depositing magnetic alloy films
US3152974A (en) * 1962-07-18 1964-10-13 Hughes Aircraft Co Electroplating magnetic cobalt alloys

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
The Electrochemical Soc., Extended Abstracts of Battery Div., Vol. 13, Abstract No. 487, (1968). *

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994694A (en) * 1975-03-03 1976-11-30 Oxy Metal Industries Corporation Composite nickel-iron electroplated article
US4170739A (en) * 1977-12-23 1979-10-09 Frusztajer Boruch B Apparatus and method for supplying direct current with superimposed alternating current
US5100559A (en) * 1989-08-21 1992-03-31 Battelle Memorial Institute Treatment methods for breaking certain oil and water emulsions
WO1998040539A1 (en) * 1997-03-13 1998-09-17 Quantum Corporation Electroplating apparatus and process for reducing oxidation of oxidizable plating anions and cations
US5883762A (en) * 1997-03-13 1999-03-16 Calhoun; Robert B. Electroplating apparatus and process for reducing oxidation of oxidizable plating anions and cations
DE19983254C2 (de) * 1999-05-06 2002-09-12 Union Steel Mfg Co Ltd Vorrichtung und Verfahren zur Herstellung einer dünnen Folie aus einer Ni-Fe-Legierung
US20040188260A1 (en) * 2003-03-31 2004-09-30 Matthias Bonkabeta Method of plating a semiconductor structure
US20040200731A1 (en) * 2003-04-11 2004-10-14 Sullivan John Timothy Apparatus and method for generating and using multi-direction DC and AC electrical currents
US7041203B2 (en) * 2003-04-11 2006-05-09 John Timothy Sullivan Apparatus and method for generating and using multi-direction DC and AC electrical currents
US10961635B2 (en) 2005-08-12 2021-03-30 Modumetal, Inc. Compositionally modulated composite materials and methods for making the same
US8702954B2 (en) * 2007-12-21 2014-04-22 Kansai Paint Co., Ltd. Manufacturing method for surface-treated metallic substrate and surface-treated metallic substrate obtained by said manufacturing method, and metallic substrate treatment method and metallic substrate treated by said method
US20100270164A1 (en) * 2007-12-21 2010-10-28 Kentaro Kubota Manufacturing method for surface-treated metallic substrate and surface-treated metallic substrate obtained by said manufacturing method, and metallic substrate treatment method and metallic substrate treated by said method
WO2010005993A3 (en) * 2008-07-07 2010-07-29 Modumetal Llc Low stress property modulated materials and methods of their preparation
EP2310557A2 (de) * 2008-07-07 2011-04-20 Modumetal, LLC Materialien mt modulierten eigenschaften und herstellungsverfahren dafür
US20110180413A1 (en) * 2008-07-07 2011-07-28 Modumental LLC Property modulated materials and methods of making the same
US9938629B2 (en) 2008-07-07 2018-04-10 Modumetal, Inc. Property modulated materials and methods of making the same
WO2010005993A2 (en) * 2008-07-07 2010-01-14 Modumetal Llc Low stress property modulated materials and methods of their preparation
US9234294B2 (en) 2008-07-07 2016-01-12 Modumetal, Inc. Property modulated materials and methods of making the same
US10689773B2 (en) 2008-07-07 2020-06-23 Modumetal, Inc. Property modulated materials and methods of making the same
US9758891B2 (en) 2008-07-07 2017-09-12 Modumetal, Inc. Low stress property modulated materials and methods of their preparation
US20100147800A1 (en) * 2008-12-16 2010-06-17 City University Of Hong Kong Method of making foraminous microstructures
US9011706B2 (en) * 2008-12-16 2015-04-21 City University Of Hong Kong Method of making foraminous microstructures
US11242613B2 (en) 2009-06-08 2022-02-08 Modumetal, Inc. Electrodeposited, nanolaminate coatings and claddings for corrosion protection
US10544510B2 (en) 2009-06-08 2020-01-28 Modumetal, Inc. Electrodeposited, nanolaminate coatings and claddings for corrosion protection
US10253419B2 (en) 2009-06-08 2019-04-09 Modumetal, Inc. Electrodeposited, nanolaminate coatings and claddings for corrosion protection
US10662542B2 (en) 2010-07-22 2020-05-26 Modumetal, Inc. Material and process for electrochemical deposition of nanolaminated brass alloys
US10513791B2 (en) 2013-03-15 2019-12-24 Modumental, Inc. Nanolaminate coatings
US11851781B2 (en) 2013-03-15 2023-12-26 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US10808322B2 (en) 2013-03-15 2020-10-20 Modumetal, Inc. Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes
US10844504B2 (en) 2013-03-15 2020-11-24 Modumetal, Inc. Nickel-chromium nanolaminate coating having high hardness
US11118280B2 (en) 2013-03-15 2021-09-14 Modumetal, Inc. Nanolaminate coatings
US11168408B2 (en) 2013-03-15 2021-11-09 Modumetal, Inc. Nickel-chromium nanolaminate coating having high hardness
US11180864B2 (en) 2013-03-15 2021-11-23 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US10781524B2 (en) 2014-09-18 2020-09-22 Modumetal, Inc. Methods of preparing articles by electrodeposition and additive manufacturing processes
US11560629B2 (en) 2014-09-18 2023-01-24 Modumetal, Inc. Methods of preparing articles by electrodeposition and additive manufacturing processes
US11692281B2 (en) 2014-09-18 2023-07-04 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
CN105586614A (zh) * 2016-03-18 2016-05-18 厦门大学 一种三价铁体系碱性溶液电沉积因瓦合金的电镀溶液及电镀方法
US11365488B2 (en) 2016-09-08 2022-06-21 Modumetal, Inc. Processes for providing laminated coatings on workpieces, and articles made therefrom
US11293272B2 (en) 2017-03-24 2022-04-05 Modumetal, Inc. Lift plungers with electrodeposited coatings, and systems and methods for producing the same
US11286575B2 (en) 2017-04-21 2022-03-29 Modumetal, Inc. Tubular articles with electrodeposited coatings, and systems and methods for producing the same
US11866841B1 (en) * 2018-03-15 2024-01-09 Seagate Technology Llc Electrodeposited materials and related methods
US11519093B2 (en) 2018-04-27 2022-12-06 Modumetal, Inc. Apparatuses, systems, and methods for producing a plurality of articles with nanolaminated coatings using rotation

Also Published As

Publication number Publication date
DE2061225A1 (de) 1971-09-09
GB1333254A (en) 1973-10-10
JPS4946692B1 (de) 1974-12-11

Similar Documents

Publication Publication Date Title
US3716464A (en) Method for electrodepositing of alloy film of a given composition from a given solution
Golodnitsky et al. Study of Nickel‐Cobalt Alloy Electrodeposition from a Sulfamate Electrolyte with Different Anion Additives
Gangasingh et al. Anomalous Electrodeposition of Nickel‐Iron
US4105531A (en) Plated metallic cathode
US4652348A (en) Method for the production of alloys possessing high elastic modulus and improved magnetic properties by electrodeposition
Sasaki et al. Electrodeposition of Binary Iron‐Group Alloys
Grande et al. Electrodeposition of Thin Films of Nickel‐Iron: I. Experimental
US4673469A (en) Method of plating plastics
Ernst et al. Cathode potentials during the electrodeposition of molybdenum alloys from aqueous solutions
US3844909A (en) Magnetic film plated wire and substrates therefor
Ballesteros et al. Electrodeposition of Cu-Zn intermetallic compounds for its application as electrocatalyst in the hydrogen evolution reaction
Golodnitsky et al. Cathode process in nickel-cobalt alloy deposition from sulfamate electrolytes--application to electroforming
Kovac The Effect of Superimposed AC on DC in Electrodeposition of Ni‐Fe Alloys
Li et al. Influence of ultrasonic in low thermal expansion Fe-Ni electrodeposition process for micro-electroforming
US3749650A (en) Method of electrodepositing gold alloys
US3920526A (en) Process for the electrodeposition of ductile palladium and electroplating bath useful therefor
Makrides Kinetics of the Fe+++/Fe++ Reaction on Fe‐Cr Alloys
US4564426A (en) Process for the deposition of palladium-nickel alloy
Swathirajan et al. Characterization of New Corrosion Resistant Nickel‐Zinc‐Phosphorus Alloys Obtained by Electrodeposition
Omi et al. Phase Structure and Composition of Fe‐W Alloy Electrodeposits
US3445351A (en) Process for plating metals
US3239437A (en) Methods of depositing magnetic alloy films
Wang et al. Effect of additives on anomalous deposition in zinc-cobalt alloy electrogalvanizing
Popov et al. The effect of deposition process exchange current density on the thin metal film formation on inert substrate
US3272727A (en) Process for electroplating magnetic alloy onto a platinized chromium substrate