US2470775A - Electroplating nickel and cobalt with periodic reverse current - Google Patents

Electroplating nickel and cobalt with periodic reverse current Download PDF

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Publication number
US2470775A
US2470775A US759796A US75979647A US2470775A US 2470775 A US2470775 A US 2470775A US 759796 A US759796 A US 759796A US 75979647 A US75979647 A US 75979647A US 2470775 A US2470775 A US 2470775A
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nickel
current
cobalt
cathodic
period
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US759796A
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English (en)
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George W Jernstedt
Ceresa Myron
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CBS Corp
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Westinghouse Electric Corp
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Priority to NL72938D priority Critical patent/NL72938C/xx
Application filed by Westinghouse Electric Corp filed Critical Westinghouse Electric Corp
Priority to US759796A priority patent/US2470775A/en
Priority to GB13708/48A priority patent/GB642101A/en
Priority to FR968931D priority patent/FR968931A/fr
Priority to CH274247D priority patent/CH274247A/de
Application granted granted Critical
Publication of US2470775A publication Critical patent/US2470775A/en
Priority to DEW1917A priority patent/DE809002C/de
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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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the 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

  • This invention relates to the electro-deposition of nickel, cobalt and alloys with each other by means of a periodically reversed current.
  • the electrodepositing of nickel presents great dimculties where heavy deposits of the order of 0.005" or greater are required.
  • the nickel tends to become rough and dull even with the greatest of care and considerable buffing and polishing must be subsequently applied to the electroplated members to secure commercially acceptable surface appearance in the nickel plate.
  • Members having sharp corners, for example square plates and the like, have required considerable care in locating them in the plating bath with respect to anodes and the use of quite low current density current is required in order to prevent excessive build up at the corners.
  • a further object of this invention is to produce bright ductile electrodeposits of nickel, cobalt and alloys with each other directly from an electrolyte thereof by employing periodic reverse current.
  • a still further object of this inventio is to provide a process of the electrodepositing nickel, cobalt or alloys with each other from an electrolyte thereof which comprises applying to the member being plated a periodic reverse current of such a cycle that the cathodic portion of the cycle is two seconds or less in duration and the anodic current portion of the cycle is of a duration of from to /25 of the cathodic current portion.
  • Figure 1 is a view in elevation partly in section of an electroplating tank operating in accordance with the invention.
  • Fig. 2 is a diagrammatic representation of the periodic reverse current cycle of this invention.
  • nickel, cobalt and alloys with each other may be electroplated on members from an electrolyte containing nickel, cobalt or both with a remarkable increase in brightness, speed of plating and smoothness of electrodeposits by applying to the member being plated a periodically reversed current consisting of a series of successive cycles, of which each cycle first renders the member being plated cathodic for a period of time of not more than two seconds to electrodeposit a microscopic increment of metal on the member and then renders the member anodic for a period of time of from to /25 of the cathodic period to deplate a portion of the previously deposited metal increment, the
  • the object of the present invention isto pro- A vide for expediting the electrodeposition of nickel, cobalt and alloys with each other from an elecanodic period being of such duration and the current density being of such an extent that there is applied to the member coulombs of anodic electrical current corresponding to from 4% to 60% of the coulombs of currents applied during the preceding cathodic period.
  • the most unexpected and improved results have been obtained by employing a periodic reverse current cycle of this nature in electroplating nickel. Where 50 amperes per square foot was previously regarded as maximum current density for plating nearly all types of base members with nickel or cobalt or their alloys by means of continuous direct current,
  • Nickel plated work produced by periodic reversed current plating has been exceptionally smooth and free from nodules, burrs, pores, fogging, burning, and pitting as well as other plating defects. Other advantages of the periodic reverse current cycle applied to nickel plating will be set forth hereinafter.
  • Nickel-containing electrolytes suitable for electroplating nickel may be any acidic nickel salt solutions employed in the art for plating. It has been found that the single or double nickel sulfate and nickel chloride salts alone or in any combination may be employed for electroplating with periodic reverse current. Other platable nickel salts may be employed.
  • the nickel plating baths are acidic, having a pH of from 0.5 to 6. In many cases buiIers, such as boric acid, and other addition agents, may be present; in some case marked beneficial results are obtained when they are present.
  • Suitable addition agents are organicsulfonates, such as naphthalene-1,5-disulfonic acid, ammonium sulfate, formaldehyde, nickel formate, sodium sulfate, sodium lauryl sulfate, and ammonium chloride. Gum arabic and gum tragacanth and the like may be present. If required, additions of hydrochloric or sulfuric acid may be made to the electrolytes.
  • the electrolyte may contain cobalt sulfate, cobalt chloride or mixtures thereof. Similar addition agents to those used with nickel electrolytes may be added to these solutions to advantage.
  • the pH of the aqueous electrolytes may be from 0.5 to 6.
  • nickel-cobalt alloys mixtures of nickel salts and cobalt salts are dissolved in the aqueous electrolyte.
  • the baths have a pH range of from 0.5 to 6.
  • cobalt-nickel anodes are used.
  • Particularly useful alloys are those containing irom 80% to 97% nickel by weight and 20% to 3% cobalt by weight. However alloys containing greater amounts of cobalt may be readily plated.
  • a nickel or cobalt or alloy electroplating cell I consisting of a tank l2 which may be provided if required, with an insulating and corrosion resistant liner H of synthetic rubber, glass or the like. Disposed within the tank [2 is an aqueous electrolyte [6. A nickel, cobalt or nickel-cobalt alloy anode I8 is disposed in the electrolyte I6. The anode 18 may contain small amounts of common impurities, or be prepared in any desired or conventional way. The anode I8 is supported by a conductor bar 20. A member 22 to be plated with metal is supported by a hanger 24 depending from a conductor bar 26.
  • the member 22 to beplated with nickel may be a metal body or may be prepared from any suitable electrically conducting material capable of being electroplated.
  • it may be of graphite or it may be a wax or plastic body having a surface coated with silver, 9. graphitic, metallic or other electrically conducting material to enable electroplating to be carried out on the surface thereof.
  • a suitable source 28 of periodically reversed current is supplied to the conductor bar 20 and 26 by leads 30 from a suitable source 28 of periodically reversed current.
  • the particular mechanism for supplying the periodically reversed current forms no part of the present invention, but suitable means to accomplish periodic current reversal will be obvious to those skilled in the art.
  • directcurrent from a source such as a rectifier, generator or a battery may be periodically reversed by a doublethrow reversing switch operated by hand or by a suitable mechanism.
  • Drum contacts operated by a motor or other timed driving means may be constructed and arranged so that direct current flowing in one direction is applied for a period to the conductor bars 20 and 2B and then reversed, in accordance with the present iiivention.
  • an electrical generator may be constructed so that its field is reversed at intervals, thereby producing the periodically reversed current or else the windings of an alternating current generator may be so arranged that a periodically reversed current of the type described is generated.
  • the anodic portion of the cycle should be from to /25 of the cathodic portion of the cycle and the current densities adjusted so that the anodic portion of the cycle applies from 4% to 60% of the'coulombs of current applied during the cathodic portion cycle.
  • the periodic reverse current cycle of this invention is illustrated in Fig. 2 of the drawing.
  • Current is initiall applied to the member 22 rising from 0 to a current value A and rendering the member cathodic for a time interval X of one second or less to the point B where the current is reversed and the member is rendered anodic at a current density value C.
  • a microscopic increment of nickel for example, is plated on the member.
  • the nickel increment is partly deplated to remove inferior and unsound nickel during the time interval Y which is from to /25 of the time interval X.
  • D the current is reversed and the current density passes through a zero value at E and the member is again rendered cathodic at a current density F.
  • the cycle is repeated until a predetermined thickness of nickel is electrodeposited on the member.
  • While the current from A to B is shown as a steady or constant value, it need not be as uniform or steady as shown. may be rippled or uneven between A and B, and between C and D, or have any selected or unavoidable fluctuations. Also the current may take an appreciable time to rise from to A; likewise from B to C the reversal of the current may take an appreciable length of time so that the lines 0A and 3-0 slope or even dwell at the 0 axis. Thus, in one case, where the anode interval at the 0 axis was /500 of a second, oscillographsshowed actual current flowing in the member for about 0.001 second.
  • the critical factor is that nickel or cobalt .be plated over the interval X and nickel or cobalt be deplated during the interval Y.
  • the current densities at A and C may be substantially the same, it is not necessary that the value 0 be the same as the value A. Good results have been secured where the current density at C has been 2 and 3 times that of the current density at A. The practical limits on the current densities at A and C is that they be not so great that the metal is burned or otherwise harmed.
  • the critical requirement is that the coulombs of current applied during the cathodic portion of the cycle be sufiicient to deposit an increment of metal while the anodic portion of the cycle applies from 4%- to 60% of the coulombs of current applied during the cathodic portion of the cycle to deplate a substantial proportion of the previously plated increment.
  • inferior metal is believed to be preferentially removed from the previously plated increment; for example, nodules, .burrs, and rough projections appear to be removed or deplated substantially more than other portions. A smoothening effect is thus produced.
  • the net result of a complete cycle is that an increment of sound, bright nickel or cobalt or nickel-cobalt alloy is produced.
  • an electrodeposit composed of a series of high quality nickel or cobalt increments.
  • the increments are all united into a homogeneous, sound plate.
  • the nickel or cobalt plate so produced is of a relatively uniform thickness and conforms closely to the shape of the base member.
  • a further advantage of periodic reverse current plating as disclosed herein is that a relatively rough base member may be plated to produce an electrodeposit smoother than itself. While the periodic reverse current cycle of Fig. 2 appears to be relatively inefficient due to the fact that plated metal is anodically removed, thereby requiring a proportionate increase in wattage of current and in the overall time to Thus the current odic reverse current plating to be much more emcient than as calculated. Thus the experience has been that the nickel removed during the anodic portion.
  • the nickel so electrodeposited appears to be superior in protective value and corrosion resistance as compared to nickel deposited by any known continuous direct current commercial process.
  • the nickel deposits produced by periodic reversed current are usually suitable for the electrodeposition of chromium directly thereupon without any intervening bufling or polishing. It will be appreciated, however, that in many cases the speed of nickel electroplating may be greatly increased with some moderate sacrifice in brilliancy .of the nickel electrodeposit.
  • the time X during which the member being plated with nickel or cobalt or nickel-cobalt alloy is cathodic may be reduced to a small fraction of a second with considerable benefits.
  • the time X is reduced to from /5 of a second to A00 of a second, optimum plating is secured from many electrolytes.
  • certain nickel electrolyte compositions that do not produce satisfactory nickel plating with continuous direct current under any plating conditions have produced particularly bright and smooth nickel electroplates when the periodic reverse current cycle is such that the cathodic time X is /25 of a second and ess.
  • peri- 7 odic reverse current is so much more adaptable and is not as responsive to changes in member shape, it may be employed at the high current densities even for shapes that are difficult to plate by direct current.
  • Example I An aqueous electrolyte was prepared with the following:
  • Nickel sulfate NISO4.6H2O 200 Nickel chloride (NiCl26H2O) 175 Boric acid 40
  • the composition had a pH of 1.5.
  • the temperature of the electrolyte was about 115 F. Rectangular brass plates approximately square foot in total surface area were plated in this electrolyte using a periodic reverse current having a cathodic time of second and anodic time of & second. Smooth, bright deposits of nickel were produced up to current densities of 150 amperes/square foot, the anodic and cathodic current densities being equal.
  • the rate of nickel deposition was more than twice that using continuous direct current of 50 amperes/square foot, the maximum usable with the bath.
  • Example II A bath composition was prepared from:
  • Example III A bath was prepared from:
  • the alloy composition using the bath of Example III, was plated by employing a periodic reverse current cycle having a cathodic portion in which the time duration was V second and the anodic portion was /25 second.
  • the plat- Example IV A bath was prepared by dissolving in water nickel choloride (hexahydrate)--40 ounces per gallonand boric acid4 ounces per gallon.
  • pH of the bath was 2.
  • the temperature of the bath was maintained at F. while plating nickel therefrom using a periodic reverse current cycle having a cathodic time of second and an anodic time of /25 second.
  • This bath when employed with continuous direct current produces a dull semi-hard nickel plate.
  • Current densities commercially employed with this bath are from 20 to 100 amperes per square foot with continuous direct current.
  • Employing periodic reverse current bright smooth plates were deposited upon rectangular brass plates 3 /2 by 2" in size at current densities up to 300 amperes per square foot for both cathodic and anodic portions of the cycle.
  • the nickel was smooth and relatively bright throughout this range of current densities. Nickel plate of this character could not be produced under any known conditions using continuous direct current with this bath composition.
  • Example V An all sulfate nickel electrolyte was prepared hydrate)40 ounces per ga1lon-and boric acid 4 ounces per gallon. Using continuous direct current the nickel plate produced under any known condition was rough and commercially unacceptable. Periodic reverse current employed with this composition produced electrodeposits that were very bright and smooth at current densities of amperes per square foot and higher. A periodic reverse current cycle having a cathodic period of second and an anodic period of /25 second produced an extremely bright electrodeposit at current densities of 150 amperes per square foot for both portions of the cycle. With decreased cathodic and anodic time periods higher current densities of up to 250 amperes per square foot produced good bright nickel plate.
  • Example VII A nickel electrolyte was prepared by dissolving in water the following:
  • Example VIII An aqueous electrolyte was prepared to contain Ounces per gallon- Cobalt chloride (hexahydrate) 58 Boric acid 6 The cobalt was plated from the electrolyte with the following periodic reverse current cycles:
  • the voltage varied from 1 to 3 volts. Obviously the voltage may be arranged to produce the particular current density desired.
  • the periodic reverse current cyclesgiven are only examples indicative of the practice of the invention.
  • the cycles may be reduced in time to as little as of a second cathodic period and /500 second anodic period with benefit,
  • the anodic current does not deplate metaleflfectively and such short time reverse current cycles do not function to give the advantages of the invention.
  • the electrolytes may be agitated or stirred with advantage while plating with periodic reverse current. Alsoflltering, preferably continuously, is recommended to secure the smoothest plated work.
  • the preparation of the base members to be plated with periodic reverse current may include brushing, degreasing, grinding, sandblasting, anodic cleaning and the like. It should be such as to produce chemically clean surfaces as is conventional.
  • Nickel or cobalt may be readily plated with nickel or cobalt by the periodic reverse current of this invention.
  • Brass, copper, iron, steel, zinc, tin, cadmium, gold, silver, nickel and the ike, either solid or plated or coated in any desired manner on a base may be nickel plated with periodic reverse current applied thereto.
  • an initial electrodeposit of nickel or other metal by continuous direct current may be overplated with nickel or cobalt applied by means of periodic reverse current.
  • Nickel, cobalt and nickel-cobalt alloys electrodeposited as disclosed herein may be subsequently plated with other metals.
  • the high quality electrodeposits produced by this invention will provide improved corrosion resistance, a better base for the later applied metal and other advantages.
  • the steps comprising applying to the member, while in contact with the electrolyte, a periodically reversed electrical current consisting of successive cycles, of which each cycle renders the member cathodic for a period of time of less than two seonds to electrodeposit an increment of metal on the member and then renders the member anodic for a period of time of from /2 to /25 of the cathodic time period to deplate the metal, the anodic period being not less than /500 of a second, the current density during the anodic period being substantially equal to the current density applied during the cathodic period.
  • the steps comprising applying to the member, while in contact with the electrolyte, a periodically reversed electrical current consisting of successive cycles, of which each cycle renders the member cathodic for a period of time of less than two seconds to electrodeposit an increment of the metal on the member and then renders the member anodic for time period to deplate part of the metal increment, the anodic period being not less than /500 of a second, the current density during the anodic period being suilicient to apply from 4% to 60% of the coulombs of current applied during the preceding cathodic period.
  • the steps comprising contacting the member with the electrolyte and applying to the member an electrical current, the electrical current being periodically reversed to render the member cathodic for a period of time of no longer than one-half second to electrodeposit an increment of metal thereon, and then to render the current anodic between successive cathodic periods for a period of time equal to about one-fifth the cathodic time period to deplate metal, the anodic period being not less than /500 of a second, the current density on the member being substantially the same during the anodic and cathodic periods.
  • the steps comprising contacting the member with the electrolyte and passing an electrical current through the member and electrolyte, the electrical current being periodically re versed whereby to render the member cathodic for a time period of not over one-half second to electrodeposit an increment of nickel on the base member and to render the base member anodic betweensuccessive cathodic periods for a period of time of from to of the preceding cathodic period, the anodic period being more than /500 of a second, the current density being sufficient during the anodic period to deplate a substantial portion of the previously plated increment.
  • steps comprising contacting the member with the electrolyte and passing an electrical current through the member and electrolyte, the electrical current being periodically reversed whereby to render the member cathodic for a time period of not over one-half second to electrodeposit an increment of the metal on the base member and to render the base member anodic between successive cathodic periods for a period of time of from to /25 of Number period.
  • the preceding cathodic period the anodic period being not less than /500 of a second
  • the current density being sufllcient during the anodic period to apply from 4% to of the coulombs of current applied during the preceding cathodic 6.
  • the steps comprising applying to the member an aqueous electroplating electrolyte comprising a nickel salt solute selected from at least one of the group consisting of nickel sulfate and nickel chloride, the pH of the electrolyte being from 0.5 to 6, passing a periodically reversed electrical current through the member and the electrolyte, the current being alternately anodic and cathodic, the cathodic current periods being from 1 second to has second during which time interval an increment of nickel is electrodeposited on the member and the anodic current period being from to /25 the cathodic time interval, the anodic period being not less than /500 of a second, the current density of each anodic period being sufficient to apply from 4% to 60% of the coulombs of current applied during the cathodic period.
  • aqueous electroplating electrolyte comprising a nickel salt solute selected from at least one of the group consisting of nickel sulfate and nickel chloride, the pH of the electrolyte being from 0.5 to 6,
  • the step comprising passing a periodically reversed electrical current through the member while in contact with the electrolyte, the periodically reversed electrical current composed of a succession of cycles composed of portions first rendering the member cathodic for a period of time from 2 seconds to 0.01 second to plate nickel on the member and then rendering the member anodic for a period of time of from 1 second to /500 second to deplate nickel, the current density being proportional to provide during the anodic portion from 4% to 60% of the coulombs of current applied during the cathodic portion of the cycle.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
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US759796A 1947-07-09 1947-07-09 Electroplating nickel and cobalt with periodic reverse current Expired - Lifetime US2470775A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL72938D NL72938C (ja) 1947-07-09
US759796A US2470775A (en) 1947-07-09 1947-07-09 Electroplating nickel and cobalt with periodic reverse current
GB13708/48A GB642101A (en) 1947-07-09 1948-05-20 Improvements in or relating to electroplating
FR968931D FR968931A (fr) 1947-07-09 1948-07-08 Revêtement électrolytique de nickel et de cobalt par renverse périodique de courant
CH274247D CH274247A (de) 1947-07-09 1948-07-09 Verfahren zur elektrolytischen Abscheidung eines metallischen Überzuges.
DEW1917A DE809002C (de) 1947-07-09 1950-05-04 Verfahren zur Erzeugung eines Niederschlages aus Nickel, Kobalt oder einer Nickel-Kobalt-Legierung auf einem Grundkoerper durch Elektrolyse

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US759796A US2470775A (en) 1947-07-09 1947-07-09 Electroplating nickel and cobalt with periodic reverse current

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US (1) US2470775A (ja)
CH (1) CH274247A (ja)
DE (1) DE809002C (ja)
FR (1) FR968931A (ja)
GB (1) GB642101A (ja)
NL (1) NL72938C (ja)

Cited By (33)

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US2541721A (en) * 1948-04-22 1951-02-13 Int Nickel Co Process for replenishing nickel plating electrolyte
US2579636A (en) * 1948-08-27 1951-12-25 Weisberg Louis Electrodeposition of nickel
US2635075A (en) * 1948-02-28 1953-04-14 Knapp Monarch Co Plating process
US2678909A (en) * 1949-11-05 1954-05-18 Westinghouse Electric Corp Process of electrodeposition of metals by periodic reverse current
US2726201A (en) * 1950-08-02 1955-12-06 Int Nickel Co Anodic pickling and nickel plating of tank interior using single electrolyte
US2798036A (en) * 1954-07-12 1957-07-02 Joseph J Utz Electroplating of beryllium
US2989446A (en) * 1956-10-29 1961-06-20 Rockwell Standard Co Electroplating
US3093557A (en) * 1961-08-25 1963-06-11 Westinghouse Electric Corp Methods and electrolytes for depositing nickel and cobalt
US3349016A (en) * 1965-01-12 1967-10-24 Int Nickel Co Process for employing an auxiliary anode made of high purity nickel
WO1992005952A1 (en) * 1990-10-09 1992-04-16 Diamond Technologies Company Nickel-cobalt-boron alloy, implement, plating solution and method for making
US5489488A (en) * 1992-12-02 1996-02-06 Matsushita Electric Industrial Co., Ltd. Soft magnetic film with compositional modulation and method of manufacturing the film
WO1997000980A1 (en) * 1995-06-21 1997-01-09 Peter Torben Tang An electroplating method of forming platings of nickel, cobalt, nickel alloys or cobalt alloys
US6183546B1 (en) 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron
DE10061186C1 (de) * 2000-12-07 2002-01-17 Astrium Gmbh Verfahren und Anordnung zur galvanischen Abscheidung von Nickel, Kobalt, Nickellegierungen oder Kobaltlegierungen mit periodischen Strompulsen und Verwendung des Verfahrens
US6724067B2 (en) 2001-04-13 2004-04-20 Anadigics, Inc. Low stress thermal and electrical interconnects for heterojunction bipolar transistors
US20120118745A1 (en) * 2008-07-07 2012-05-17 Zhi Liang Bao Low stress property modulated materials and methods of their preparation
WO2012148250A1 (es) * 2011-04-28 2012-11-01 Mam Tecnología Anticorrosivas, S.A.P.I. De C.V. Proceso mejorado para la deposición epitaxial de una aleación ternaria sobre un sustrato metálico, y producto de dicho proceso
US20130321983A1 (en) * 2011-01-06 2013-12-05 Sungkyunkwan University Foundation For Corporate Collaboration Nano-porous electrode for super capacitor and manufacturing method thereof
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
US11118280B2 (en) 2013-03-15 2021-09-14 Modumetal, Inc. Nanolaminate coatings
US11180864B2 (en) 2013-03-15 2021-11-23 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US11242613B2 (en) 2009-06-08 2022-02-08 Modumetal, Inc. Electrodeposited, nanolaminate coatings and claddings for corrosion protection
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
US12076965B2 (en) 2016-11-02 2024-09-03 Modumetal, Inc. Topology optimized high interface packing structures
US12077876B2 (en) 2016-09-14 2024-09-03 Modumetal, Inc. System for reliable, high throughput, complex electric field generation, and method for producing coatings therefrom

Citations (4)

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US1260661A (en) * 1917-09-04 1918-03-26 British America Nickel Corp Ltd Method of recovering metals from alloys.
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US2635075A (en) * 1948-02-28 1953-04-14 Knapp Monarch Co Plating process
US2541721A (en) * 1948-04-22 1951-02-13 Int Nickel Co Process for replenishing nickel plating electrolyte
US2579636A (en) * 1948-08-27 1951-12-25 Weisberg Louis Electrodeposition of nickel
US2678909A (en) * 1949-11-05 1954-05-18 Westinghouse Electric Corp Process of electrodeposition of metals by periodic reverse current
US2726201A (en) * 1950-08-02 1955-12-06 Int Nickel Co Anodic pickling and nickel plating of tank interior using single electrolyte
US2798036A (en) * 1954-07-12 1957-07-02 Joseph J Utz Electroplating of beryllium
US2989446A (en) * 1956-10-29 1961-06-20 Rockwell Standard Co Electroplating
US3093557A (en) * 1961-08-25 1963-06-11 Westinghouse Electric Corp Methods and electrolytes for depositing nickel and cobalt
US3349016A (en) * 1965-01-12 1967-10-24 Int Nickel Co Process for employing an auxiliary anode made of high purity nickel
US5213907A (en) * 1990-10-09 1993-05-25 Diamond Technologies Company Nickel-cobalt-boron-alloy deposited on a substrate
WO1992005952A1 (en) * 1990-10-09 1992-04-16 Diamond Technologies Company Nickel-cobalt-boron alloy, implement, plating solution and method for making
US5314608A (en) * 1990-10-09 1994-05-24 Diamond Technologies Company Nickel-cobalt-boron alloy, implement, plating solution and method for making same
US5489488A (en) * 1992-12-02 1996-02-06 Matsushita Electric Industrial Co., Ltd. Soft magnetic film with compositional modulation and method of manufacturing the film
WO1997000980A1 (en) * 1995-06-21 1997-01-09 Peter Torben Tang An electroplating method of forming platings of nickel, cobalt, nickel alloys or cobalt alloys
US6036833A (en) * 1995-06-21 2000-03-14 Tang; Peter Torben Electroplating method of forming platings of nickel
US6183546B1 (en) 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron
DE10061186C1 (de) * 2000-12-07 2002-01-17 Astrium Gmbh Verfahren und Anordnung zur galvanischen Abscheidung von Nickel, Kobalt, Nickellegierungen oder Kobaltlegierungen mit periodischen Strompulsen und Verwendung des Verfahrens
EP1213372A2 (de) 2000-12-07 2002-06-12 Astrium GmbH Verfahren und Anordnung zur galvanischen Abscheidung von Nickel, Kobalt, Nickellegierungen oder Kobaltlegierungen mit periodischen Strompulsen und Verwendung des Verfahrens
EP1213372A3 (de) * 2000-12-07 2004-02-04 Astrium GmbH Verfahren und Anordnung zur galvanischen Abscheidung von Nickel, Kobalt, Nickellegierungen oder Kobaltlegierungen mit periodischen Strompulsen und Verwendung des Verfahrens
US6790332B2 (en) 2000-12-07 2004-09-14 Astrium Gmbh Method for the galvanic deposition of nickel, cobalt, nickel alloys or cobalt alloys with periodic current pulses
US6724067B2 (en) 2001-04-13 2004-04-20 Anadigics, Inc. Low stress thermal and electrical interconnects for heterojunction bipolar transistors
US10961635B2 (en) 2005-08-12 2021-03-30 Modumetal, Inc. Compositionally modulated composite materials and methods for making the same
US9234294B2 (en) 2008-07-07 2016-01-12 Modumetal, Inc. Property modulated materials and methods of making the same
US20120118745A1 (en) * 2008-07-07 2012-05-17 Zhi Liang Bao Low stress property modulated materials and methods of their preparation
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FR968931A (fr) 1950-12-08
GB642101A (en) 1950-08-30
NL72938C (ja)
DE809002C (de) 1951-07-23
CH274247A (de) 1951-03-31

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