EP1826294A1 - Verfahren zum Galvanisieren von Metallfolien und Metallmatrix-Verbundenfolien und Mikrokomponenten - Google Patents

Verfahren zum Galvanisieren von Metallfolien und Metallmatrix-Verbundenfolien und Mikrokomponenten Download PDF

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Publication number
EP1826294A1
EP1826294A1 EP07002944A EP07002944A EP1826294A1 EP 1826294 A1 EP1826294 A1 EP 1826294A1 EP 07002944 A EP07002944 A EP 07002944A EP 07002944 A EP07002944 A EP 07002944A EP 1826294 A1 EP1826294 A1 EP 1826294A1
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Prior art keywords
process according
anode
cathode
range
electrolyte
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Application number
EP07002944A
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English (en)
French (fr)
Inventor
Gino Palumbo
Ian Brooks
Jonathan Mccrea
Glenn D. Hibbard
Francisco Gonzales
Klaus Tomantschger
Uwe Erb
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Integran Technologies Inc
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Integran Technologies Inc
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Publication of EP1826294A1 publication Critical patent/EP1826294A1/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
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • 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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • 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
    • C25D5/04—Electroplating with moving electrodes
    • C25D5/06—Brush or pad plating
    • 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
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • 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
    • C25D5/20—Electroplating using ultrasonics, vibrations
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/67—Electroplating to repair workpiece
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/04—Tubes; Rings; Hollow bodies

Definitions

  • the invention relates to a process for forming coatings of pure metals, metal alloys or metal matrix composites on a work piece which is electrically conductive or contains an electrically conductive surface layer or forming free-standing deposits of nanocrystalline metals, metal alloys or metal matrix composites by employing pulse electrodeposition.
  • the process employs a drum plating process for the continuous production of nanocrystalline foils of pure metals, metal alloys or metal matrix composites or a selective plating (brush plating) process, the processes involving pulse electrodeposition and a non-stationary anode or cathode. Novel nanocrystalline metal matrix composites are disclosed as well.
  • the invention also relates to a pulse plating process for the fabrication or coating of micro-components.
  • the invention also relates to micro-components with grain sizes below 1,000nm.
  • the novel process can be applied to establish wear resistant coatings and foils of pure metals or alloys of metals selected from the group of Ag, Au, Cu, Co, Cr, Ni, Fe, Pb, Pd, Pt, Rh, Ru, Sn, V, W and Zn and alloying elements selected from C, P, S and Si and metal matrix composites of pure metals or alloys with particulate additives such as metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; nitrides of Al, B and Si; C (graphite or diamond); carbides of B, Cr, Bi, Si, W; and organic materials such as PTFE and polymer spheres.
  • the selective plating process is particularly suited for in-situ or field applications such as the repair or the refurbishment of dies and moulds, turbine plates, steam generator tubes, core reactor head penetrations of nuclear power plants and the like.
  • the continuous plating process is particularly suited for producing nanocrystalline foils e.g. for magnetic applications.
  • the process can be applied to high strength, equiaxed micro-components for use in electronic, biomedical, telecommunication, automotive, space and consumer applications.
  • Nanocrystalline materials also referred to as ultra-fine grained materials, nano-phase materials or nanometer-sized materials exhibiting average grains sizes smaller or equal to 100nm, are known to be synthesized by a number of methods including sputtering, laser ablation, inert gas condensation, high energy ball milling, sol-gel deposition and electrodeposition. Electrodeposition offers the capability to prepare a large number of fully dense metal and metal alloy compositions at high production rates and low capital investment requirements in a single synthesis step.
  • the prior art primarily describes the use of pulse electrodeposition for producing nanocrystalline materials.
  • Mori in US 5,496,463 (1996 ) describes a process and apparatus for composite electroplating a metallic material containing SiC, BN, Si 3 N 4 , WC, TiC, TiO 2 , Al 2 O 3 , ZnB 3 , diamond, CrC, MoS 2 , coloring materials, polytetrafluoroethylene (PTFE) and microcapsules.
  • the solid particles are introduced in fine form into the electrolyte.
  • Adler in US 4,240,894 (1980 ) describes a drum plater for electrodeposited Cu foil production.
  • Cu is plated onto a rotating metal drum that is partially submersed and rotated in a Cu plating solution.
  • the Cu foil is stripped from the drum surface emerging from the electrolyte, which is clad with electroformed Cu.
  • the rotation speed of the drum and the current density are used to adjust the desired thickness of the Cu foil.
  • the Cu foil stripped from the drum surface is subsequently washed and dried and wound into a suitable coil.
  • Icxi in US 2,961,395 (1960 ) discloses a process for electroplating an article without the necessity to immerse the surface being treated into a plating tank.
  • the hand-manipulated applicator serves as anode and applies chemical solutions to the metal surface of the work piece to be plated.
  • the work piece to be plated serves as cathode.
  • the hand applicator anode with the wick containing the electrolyte and the work piece cathode are connected to a DC power source to generate a metal coating on the work piece by passing a DC current.
  • Micromechanical systems are machines constructed of small moving and stationary parts having overall dimensions ranging from 1 to 1,000 ⁇ m e.g. for use in electronic, biomedical, telecommunication, automotive, space and consumer technologies.
  • Such components are made e.g. by photo-electroforming, which is an additive process in which powders are deposited in layers to build the desired structure e.g. by laser enhanced electroless plating.
  • photo-electroforming is an additive process in which powders are deposited in layers to build the desired structure e.g. by laser enhanced electroless plating.
  • Lithography, electroforming and molding (LIGA) and other photolithography related processes are used to overcome aspect ratio (parts height to width) related problems.
  • Other techniques employed include silicon micromachining, through mask plating and microcontact printing.
  • the present invention is directed to a process for cathodically electrodepositing a selected metallic material as defined in independent claim 1 and to a micro component as defined in independent claim 33.
  • the present invention provides a pulse plating process, consisting of a single cathodic on time or multiple cathodic on times of different current densities and single or multiple off times per cycle.
  • Periodic pulse reversal, a bipolar waveform alternating between cathodic pulses and anodic pulses, can optionally be used as well.
  • the anodic pulses can be inserted into the waveform before, after or in between the on pulse and/or before, after or in the off time.
  • the anodic pulse current density is generally equal to or greater than the cathodic current density.
  • the anodic charge (Q anodic ) of the "reverse pulse" per cycle is always smaller than the cathodic charge (Q cathodic ).
  • Cathodic pulse on times range from 0.1 to 50 msec (1-50), off times from 0 to 500msec (1-100) and anodic pulse times range from 0 to 50 msec, preferably from 1 to 10msec.
  • the duty cycle expressed as the cathodic on times divided by the sum of the cathodic on times, the off times and the anodic times, ranges from 5 to 100 %, preferably from 10 to 95 %, and more preferably from 20 to 80 %.
  • the frequency of the cathodic pulses ranges from 1 Hz to 1 kHz and more preferably from 10Hz to 350Hz.
  • Nanocrystalline coatings or free-standing deposits of metallic materials were obtained by varying process parameters such as current density, duty cycle, work piece temperature, plating solution temperature, solution circulation rates over a wide range of conditions.
  • process parameters such as current density, duty cycle, work piece temperature, plating solution temperature, solution circulation rates over a wide range of conditions.
  • suitable operating parameter ranges for practicing the invention are described below:
  • the present invention preferably provides a process for plating nanocrystalline metals, metal matrix composites and microcomponents at deposition rates of at least 0,05 mm/h, preferably at least 0.075 mm/h, and more preferably at least 0,1 mm/h.
  • the electrolyte preferably may be agitated by means of pumps, stirrers or ultrasonic agitation at rates of 0 to 750 ml/min/A (ml solution per minute per applied Ampere average current), preferably at rates of 0 to 500 ml/min/A.
  • a grain refining agent or a stress relieving agent selected from the group of saccharin, coumarin, sodium lauryl sulfate and thiourea can be added to the electrolyte.
  • This invention provides a process for plating nanocrystalline metal matrix composites on a permanent or temporary substrate optionally containing at least 5% by volume particulates, preferably 10% by volume particulates, more preferably 20% by volume particulates, even more preferably 30% by volume particulates and most preferably 40% by volume particulates for applications such as hard facings, projectile blunting armor, valve refurbishment, valve and machine tool coatings, energy absorbing armor panels, sound damping systems, connectors on pipe joints e.g. used in oil drilling applications, refurbishment of roller bearing axles in the railroad industry, computer chips, repair of electric motors and generator parts, repair of scores in print rolls using tank, barrel, rack, selective (e.g. brush plating) and continuous (e.g.
  • the particulates can be selected from the group of metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; nitrides of Al, B and Si; C (graphite or diamond); carbides of B, Bi, Cr, Si, W; MoS 2 ; and organic materials such as PTFE and polymer spheres.
  • the particulate average particle size is typically below 10 ⁇ m, preferably below 1,000nm (1 ⁇ m), preferably 500nm, and more preferably below 100nm.
  • the process of this invention optionally provides a process for continuous (drum or belt) plating nanocrystalline foils optionally containing solid particles in suspension selected from metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; nitrides of Al, B and Si; C (graphite or diamond); carbides of B, Bi, Si, W; MoS 2 , and organic materials such as PTFE and polymer spheres to impart desired properties including hardness, wear resistance, lubrication, magnetic properties and the like.
  • the drum or belt provides a temporary substrate from which the plated foil can be easily and continuously removed.
  • Brush or tampon plating is a suitable alternative to tank plating, particularly when only a portion of the work piece is to be plated, without the need to mask areas not to be plated.
  • the brush plating apparatus typically employs a soluble or dimensionally stable anode wrapped in an absorbent separator felt to form the anode brush. The brush is rubbed against the surface to be plated in a manual or mechanized mode and electrolyte solution containing ions of the metal or metal alloys to be plated is injected into the separator felt.
  • this solution also contains solid particles in suspension selected from metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; nitrides of Al, B and Si; C (graphite or diamond); carbides of Bi, Si, W; MoS 2 ; and organic materials such as PTFE and polymer spheres to impart desired properties including hardness, wear resistance, lubrication and the like.
  • solid particles in suspension selected from metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; nitrides of Al, B and Si; C (graphite or diamond); carbides of Bi, Si, W; MoS 2 ; and organic materials such as PTFE and polymer spheres to impart desired properties including hardness, wear resistance, lubrication and the like.
  • belt or brush plating the relative motion between anode and cathode ranges from 0 to 600meters per minute, preferably from 0.003 to 10meters per minute.
  • micro components for micro systems including micro-mechanical systems (MEMS) and micro-optical-systems with grain sizes equal to or smaller than 1,000nm can be produced.
  • the maximum dimension of the microcomponent part is equal to or below 1mm and the ratio between the maximum outside dimension of the microcomponent part and the average grain size is equal to or greater than 10, preferably greater than 100.
  • micro components of the present invention preferably may have an equiaxed microstructure throughout the plated component, which is relatively independent of component thickness and structure.
  • micro components according to this invention have significantly improved property-dependent reliability and improved and tailor-made desired properties of MEMS structures for overall performance enhanced microsystems by preferably equiaxed electrodeposits, eliminating the fine grain to columnar grain transition in the microcomponent, and simultaneously reducing the grain size of the deposits below 1,000nm.
  • FIG 1 schematically shows of a plating tank or vessel (1) filled with an electrolyte (2) containing the ions of the metallic material to be plated.
  • the cathode in the form of a rotating drum (3) electrically connected to a power source (4).
  • the drum is rotated by an electric motor (not shown) with a belt drive and the rotation speed is variable.
  • the anode (5) can be a plate or conforming anode, as shown, which is electrically connected to the power source (4).
  • Conformal anodes as shown in Figure 1, that follow the contour of the submerged section of the drum (3), vertical anodes positioned at the walls of the tank (1) and horizontal anode positioned on the bottom of the tank (1).
  • the foil (16) is pulled from the drum surface emerging from the electrolyte (2), which is clad with the electroformed metallic material.
  • FIG. 2 schematically shows a work piece (6) to be plated, which is connected to the negative outlet of the power source (4).
  • the anode (5) consists of a handle (7) with a conductive anode brush (8).
  • the anode contains channels (9) for supplying the electrolyte solution (2) from a temperature controlled tank (not shown) to the anode wick (absorbent separator) (10).
  • the electrolyte dripping from the absorbent separator (10) is optionally collected in a tray (11) and recirculated to the tank.
  • the absorbent separator (10) containing the electrolyte (2) also electrically insulates the anode brush (8) from the work piece (6) and adjusts the spacing between anode (5) and cathode (6).
  • the anode brush handle (4) can be moved over the work piece (6) manually during the plating operation, alternatively, the motion can be motorized as shown in figure 3.
  • Figure 3 schematically shows a wheel (12) driven by an adjustable speed motor (not shown).
  • a traversing arm (13) can be rotatably attached (rotation axis A) to the rotating wheel (12) at various positions x at a slot (14) with a bushing and a set screw (not shown) to generate a desired stroke.
  • the stroke length can be adjusted by the position x (radius) at which the rotation axis A of traversing arm is mounted at the slot (14).
  • the traversing arm (13) is shown to be in an no-stroke, neutral position with rotation axis A in the center of the wheel (12).
  • the traversing arm (13) has a second pivot axis B defined by a bearing (not shown), that is slidably mounted in a track (15).
  • Nanocrystalline coatings for wear resistant applications to date have focused on increasing wear resistance by increasing hardness and decreasing the friction coefficient though grain size reduction below 100nm. It has now been found that incorporating a sufficient volume fraction of hard particles can further enhance the wear resistance of nanocrystalline materials.
  • the material properties can also be altered by e.g. the incorporation of lubricants (such as MoS 2 and PTFE).
  • lubricants such as MoS 2 and PTFE.
  • the particulates can be selected from the group of metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; nitrides of Al, B and Si; C (graphite or diamond); carbides of B, Bi, Si, W; MoS 2 ; and organic materials such as PTFE and polymer spheres.
  • Nanocrystalline Co based nanocomposites were deposited onto a rotating Ti drum as described in example 3 immersed in a modified Watts bath for cobalt.
  • the nanocrystalline foil 15cm wide was electroformed onto the drum cathodically, using a soluble cobalt anode contained in a Ti wire basket and a Dynatronix (Dynanet PDPR 20-30-100) pulse power supply. The following conditions were used:
  • the Co/P-SiC foil had a grain size of 12 nm, a hardness of 690 VHN, contained 1.5% P and 22volume% SiC.
  • Nanocrystalline nickel-iron alloy foils were deposited on a rotating Ti drum partially immersed in a modified Watts bath for nickel.
  • the nanocrystalline foil, 15cm wide was electroformed onto the drum cathodically, using a soluble anode made of a titanium wire basket filled with Ni rounds and a Dynatronix (Dynanet PDPR 50-250-750) pulse power supply. The following conditions were used:
  • Selective or brush plating is a portable method of selectively plating localized areas of a work piece without submersing the article into a plating tank. There are significant differences between selective plating and tank and barrel plating applications. In the case of selective plating it is difficult to accurately determine the cathode area and therefore the cathodic current density and/or peak current density is variable and usually unknown. The anodic current density and/or peak current density can be determined, provided that the same anode area is utilized during the plating operation, e.g. in the case of flat anodes. In the case of shaped anodes the anode area can not be accurately determined e.g.
  • the "effective" anode area also changes during the plating operation.
  • Selective plating is performed by moving the anode, which is covered with the absorbent separator wick and containing the electrolyte, back and forth over the work piece, which is typically performed by an operator until the desired overall area is coated to the required thickness.
  • the plating tools used comprise the anode (DSA or soluble), covered with an absorbent, electrically non-conductive material and an insulated handle.
  • anodes are typically made of graphite or Pt-clad titanium and may contain means for regulating the temperature by means of a heat exchanger system.
  • the electrolyte used can be heated or cooled and passed through the anode to maintain the desired temperature range.
  • the absorbent separator material contains and distributes the electrolyte solution between the anode and the work piece (cathode), prevents shorts between anode and cathode and brushes against the surface of the area being plated.
  • a Sifco brush plating unit (model 3030 - 30A max) was set up.
  • the graphite anode tip was inserted into a cotton pouch separator and either attached to a mechanized traversing arm in order to generate the "brushing motion" or moved by an operator by hand back and forth over the work piece, or as otherwise indicated.
  • the anode assembly was soaked in the plating solution and the coating was deposited by brushing the plating tool against the cathodically charged work area that was composed of different substrates.
  • a peristaltic pump was used to feed the electrolyte at predetermined rates into the brush plating tool.
  • the electrolyte was allowed to drip off the work piece into a tray that also served as a "plating solution reservoir" from which it was recirculated into the electrolyte tank.
  • the anode had flow-through holes/channels in the bottom surface to ensure good electrolyte distribution and electrolyte/work piece contact.
  • the anode was fixed to a traversing arm and the cyclic motion was adjusted to allow uniform strokes of the anode against the substrate surface.
  • the rotation speed was adjusted to increase or decrease the relative anode/cathode movement speed as well as the anode/substrate contact time at any one particular location.
  • Brush plating was normally carried out at a rate of approximately 35-175 oscillations per minute, with a rate of 50-85 oscillations per minute being optimal. Electrical contacts were made on the brush handle (anode) and directly on the work piece (cathode). Coatings were deposited onto a number of substrates, including copper, 1018 low carbon steel, 4130 high carbon steel, 304 stainless steel, a 2.5in OD steel pipe and a weldclad I625 pipe. The cathode size was 8cm 2 , except for the 2.5in OD steel pipe where a strip 3cm wide around the outside diameter was exposed and the weldclad 1625 pipe on which a defect repair procedure was performed.
  • a Dynatronix programmable pulse plating power supply (Dynanet PDPR 20-30-100) was employed.
  • Nanocrystalline Co was deposited using the same set up described under the following conditions:
  • Microcomponents having overall dimensions below 1,000 ⁇ m (1mm), are gaining increasing importance for use in electronic, biomedical, telecommunication, automotive, space and consumer applications.
  • Metallic macro-system components with an overall maximum dimension of 1cm to over 1m containing conventional grain sized materials (1-1,000 ⁇ m) exhibit a ratio between maximum dimension and grain size ranges from 10 to 10 6 . This number reflects the number of grains across the maximum part dimension.
  • the maximum component size is reduced to below 1mm using conventional grain-sized material, the component can be potentially made of only a few grains or a single grain and the ratio between the maximum micro-component dimension and the grain size ranges approaches 1. In other words, a single or only a few grains stretch across the entire part, which is undesirable.
  • the ratio between maximum part dimension and grain size ranges must be increased to over 10 through the utilization of a small grained material, as this material class typically exhibits grain size values 10 to 10,000 times smaller than conventional materials.
  • micro-spring fingers require high yield strength and ductility.
  • a 25 ⁇ m thick layer of nanocrystalline Ni was plated on 500 ⁇ m long gold-coated CrMo fingers using the following conditions:
  • the nano-fingers exhibited a significantly higher contact force when compared to "conventional grain-sized" fingers.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Manufacture Of Switches (AREA)
EP07002944A 2002-06-25 2002-06-25 Verfahren zum Galvanisieren von Metallfolien und Metallmatrix-Verbundenfolien und Mikrokomponenten Withdrawn EP1826294A1 (de)

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EP02754753A EP1516076B1 (de) 2002-06-25 2002-06-25 Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten
PCT/EP2002/007023 WO2004001100A1 (en) 2002-06-25 2002-06-25 Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents

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EP02754753A Expired - Lifetime EP1516076B1 (de) 2002-06-25 2002-06-25 Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten

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Cited By (12)

* Cited by examiner, † Cited by third party
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WO2013083987A1 (en) * 2011-12-09 2013-06-13 Mahle International Gmbh Method of manufacture a sliding bearing
EP2617877A1 (de) * 2012-01-23 2013-07-24 Seagate Technology LLC Verfahren zur galvanischen Abscheidung von CoFe-Legierungen
WO2014205330A1 (en) * 2013-06-20 2014-12-24 Baker Hughes Incorporated Method to produce metal matrix nanocomposite with graphene
WO2016044171A1 (en) * 2014-09-18 2016-03-24 Baker Hughes Incorporated Methods of coating substrates with composite coatings of diamond nanoparticles and metal
US9873827B2 (en) 2014-10-21 2018-01-23 Baker Hughes Incorporated Methods of recovering hydrocarbons using suspensions for enhanced hydrocarbon recovery
US9938629B2 (en) 2008-07-07 2018-04-10 Modumetal, Inc. Property modulated materials and methods of making the same
CN108368625A (zh) * 2015-12-11 2018-08-03 日立金属株式会社 电极装置和使用该装置的金属箔的制造方法
US10155899B2 (en) 2015-06-19 2018-12-18 Baker Hughes Incorporated Methods of forming suspensions and methods for recovery of hydrocarbon material from subterranean formations
US10167392B2 (en) 2014-10-31 2019-01-01 Baker Hughes Incorporated Compositions of coated diamond nanoparticles, methods of forming coated diamond nanoparticles, and methods of forming coatings
CN109989081A (zh) * 2019-04-17 2019-07-09 浙江宏途电气科技有限公司 便于操作的电刷镀工件修复装置
US10662542B2 (en) 2010-07-22 2020-05-26 Modumetal, Inc. Material and process for electrochemical deposition of nanolaminated brass alloys
US10961635B2 (en) 2005-08-12 2021-03-30 Modumetal, Inc. Compositionally modulated composite materials and methods for making the same

Families Citing this family (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004090361A2 (en) * 2003-04-03 2004-10-21 The Timken Company Corrosion tolerant rolling element bearing
WO2004092450A1 (en) 2003-04-11 2004-10-28 Lynntech, Inc. Compositions and coatings including quasicrystals
US8152810B2 (en) 2004-11-23 2012-04-10 Jackson Roger P Spinal fixation tool set and method
US7387578B2 (en) 2004-12-17 2008-06-17 Integran Technologies Inc. Strong, lightweight article containing a fine-grained metallic layer
US7320832B2 (en) 2004-12-17 2008-01-22 Integran Technologies Inc. Fine-grained metallic coatings having the coefficient of thermal expansion matched to the one of the substrate
US7354354B2 (en) 2004-12-17 2008-04-08 Integran Technologies Inc. Article comprising a fine-grained metallic material and a polymeric material
US7425255B2 (en) 2005-06-07 2008-09-16 Massachusetts Institute Of Technology Method for producing alloy deposits and controlling the nanostructure thereof using negative current pulsing electro-deposition
US8202627B2 (en) * 2006-01-24 2012-06-19 Usc, Llc Electrocomposite coatings for hard chrome replacement
US20070170068A1 (en) * 2006-01-24 2007-07-26 Usc, Llc Electrocomposite coatings for hard chrome replacement
US7897265B2 (en) 2006-01-26 2011-03-01 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
JP4724581B2 (ja) * 2006-03-28 2011-07-13 新日本製鐵株式会社 磁気特性に優れた表面処理金属材およびその製造方法
US7521128B2 (en) * 2006-05-18 2009-04-21 Xtalic Corporation Methods for the implementation of nanocrystalline and amorphous metals and alloys as coatings
US20070275262A1 (en) * 2006-05-23 2007-11-29 Dechao Lin Reducing formation of tin whiskers on a tin plating layer
US9005420B2 (en) * 2007-12-20 2015-04-14 Integran Technologies Inc. Variable property electrodepositing of metallic structures
US7955721B2 (en) * 2008-01-16 2011-06-07 Hamilton Sundstrand Corporation Article having cobalt-phosphorous coating and method for heat treating
JP4564545B2 (ja) * 2008-03-25 2010-10-20 株式会社東芝 コーティング方法
US8309233B2 (en) * 2009-06-02 2012-11-13 Integran Technologies, Inc. Electrodeposited metallic-materials comprising cobalt on ferrous-alloy substrates
US8247050B2 (en) 2009-06-02 2012-08-21 Integran Technologies, Inc. Metal-coated polymer article of high durability and vacuum and/or pressure integrity
EP3009532A1 (de) 2009-06-08 2016-04-20 Modumetal, Inc. Elektroplattierte nanolaminierte beschichtungen und verkleidungen für korrosionsschutz
DE102009043594B4 (de) 2009-09-25 2013-05-16 Siemens Aktiengesellschaft Verfahren zum elektrochemischen Beschichten und Einbau von Partikeln in die Schicht
DE102009060937A1 (de) 2009-12-22 2011-06-30 Siemens Aktiengesellschaft, 80333 Verfahren zum elektrochemischen Beschichten
US9694562B2 (en) 2010-03-12 2017-07-04 Xtalic Corporation Coated articles and methods
KR20130006658A (ko) * 2010-03-12 2013-01-17 엑스탤릭 코포레이션 코팅된 물품 및 방법
KR101304846B1 (ko) * 2011-06-10 2013-09-05 주식회사 포스코 우수한 방열성을 갖는 플렉서블 디스플레이용 기판 및 그 제조방법
KR101322024B1 (ko) 2011-06-13 2013-10-28 주식회사 포스코 우수한 가요성 및 내구성을 갖는 태양전지용 Ｆｅ-Ｎｉ합금 기판 및 그 제조방법
US9274395B2 (en) 2011-11-15 2016-03-01 Ashwin-Ushas Corporation, Inc. Complimentary polymer electrochromic device
KR101491752B1 (ko) * 2012-05-04 2015-02-11 강원대학교산학협력단 연료 전지용 바이폴라 플레이트 및 그 제조방법과 이를 포함하는 연료 전지
DE102012211941B4 (de) * 2012-07-09 2021-04-22 Hilti Aktiengesellschaft Werkzeugmaschine und Herstellungsverfahren
KR101370966B1 (ko) * 2012-10-17 2014-03-07 단국대학교 천안캠퍼스 산학협력단 선택적 전자기파 흡수 및 차폐 기능을 동시에 가지는 복합 금속박판 제조장치 및 제조방법
JP6296491B2 (ja) * 2013-03-14 2018-03-20 セイコーインスツル株式会社 金属構造体、金属構造体の製造方法、ばね部品、時計用発停レバーおよび時計
EP2971261A4 (de) 2013-03-15 2017-05-31 Modumetal, Inc. Elektroplattierte zusammensetzungen und nanolaminierte legierungen für durch ein additivherstellungsverfahren hergestellte artikel
BR112015022078B1 (pt) 2013-03-15 2022-05-17 Modumetal, Inc Aparelho e método para eletrodepositar um revestimento nanolaminado
US9207515B2 (en) 2013-03-15 2015-12-08 Ashwin-Ushas Corporation, Inc. Variable-emittance electrochromic devices and methods of preparing the same
CN105189828B (zh) 2013-03-15 2018-05-15 莫杜美拓有限公司 具有高硬度的镍铬纳米层压涂层
CN105283587B (zh) 2013-03-15 2019-05-10 莫杜美拓有限公司 纳米叠层涂层
US10102930B2 (en) 2013-11-13 2018-10-16 Framatome Inc. Nuclear fuel rod cladding including a metal nanomaterial layer
CN106794673B (zh) * 2014-09-18 2021-01-22 莫杜美拓有限公司 通过电沉积和添加制造工艺制备制品的方法
CA2961508C (en) 2014-09-18 2024-04-09 Modumetal, Inc. A method and apparatus for continuously applying nanolaminate metal coatings
US9632059B2 (en) 2015-09-03 2017-04-25 Ashwin-Ushas Corporation, Inc. Potentiostat/galvanostat with digital interface
US9482880B1 (en) 2015-09-15 2016-11-01 Ashwin-Ushas Corporation, Inc. Electrochromic eyewear
US9945045B2 (en) 2015-12-02 2018-04-17 Ashwin-Ushas Corporation, Inc. Electrochemical deposition apparatus and methods of using the same
WO2018049062A1 (en) 2016-09-08 2018-03-15 Modumetal, Inc. Processes for providing laminated coatings on workpieces, and articles made therefrom
CA3057836A1 (en) 2017-03-24 2018-09-27 Modumetal, Inc. Lift plungers with electrodeposited coatings, and systems and methods for producing the same
WO2018195516A1 (en) 2017-04-21 2018-10-25 Modumetal, Inc. Tubular articles with electrodeposited coatings, and systems and methods for producing the same
KR101977469B1 (ko) * 2017-07-03 2019-05-13 주식회사 포스코 금속 포일 연마 장치 및 금속 포일의 표면특성 개선 방법
KR102439621B1 (ko) * 2017-09-01 2022-09-01 에스케이넥실리스 주식회사 전해동박, 그 제조방법 및 이를 포함하는 고용량 Li 이차전지용 음극
EP3784823A1 (de) 2018-04-27 2021-03-03 Modumetal, Inc. Vorrichtungen, systeme und verfahren zur herstellung einer vielzahl von gegenständen mit nanolaminierten beschichtungen mittels rotation
DE102018120028A1 (de) * 2018-08-17 2020-02-20 Bolta-Werke Gmbh Verfahren zur Herstellung einer Metallfolie, Metallfolie, Bauteil, Elektrolytlösung und Vorrichtung
CN110724983B (zh) * 2019-10-12 2022-02-08 天津大学 一种利用脉冲电沉积法制备纳米铜包覆碳化钨核壳结构粉体的方法
CN112676561B (zh) * 2020-11-19 2023-05-12 四川有色金源粉冶材料有限公司 一种新型合金粉末及其制备方法、耐磨涂层及其制备工艺

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352266A (en) * 1992-11-30 1994-10-04 Queen'university At Kingston Nanocrystalline metals and process of producing the same
US5433797A (en) * 1992-11-30 1995-07-18 Queen's University Nanocrystalline metals

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL68330C (de) * 1950-11-03
JPS57171691A (en) * 1981-04-13 1982-10-22 Tadashi Hoashi Automatic brush plating method
US6030851A (en) * 1995-06-07 2000-02-29 Grandmont; Paul E. Method for overpressure protected pressure sensor
US6080504A (en) * 1998-11-02 2000-06-27 Faraday Technology, Inc. Electrodeposition of catalytic metals using pulsed electric fields

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352266A (en) * 1992-11-30 1994-10-04 Queen'university At Kingston Nanocrystalline metals and process of producing the same
US5433797A (en) * 1992-11-30 1995-07-18 Queen's University Nanocrystalline metals

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10961635B2 (en) 2005-08-12 2021-03-30 Modumetal, Inc. Compositionally modulated composite materials and methods for making the same
US10689773B2 (en) 2008-07-07 2020-06-23 Modumetal, Inc. 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
US10662542B2 (en) 2010-07-22 2020-05-26 Modumetal, Inc. Material and process for electrochemical deposition of nanolaminated brass alloys
WO2013083987A1 (en) * 2011-12-09 2013-06-13 Mahle International Gmbh Method of manufacture a sliding bearing
CN104105821A (zh) * 2011-12-09 2014-10-15 马勒国际有限公司 制造滑动轴承的方法
EP2617877A1 (de) * 2012-01-23 2013-07-24 Seagate Technology LLC Verfahren zur galvanischen Abscheidung von CoFe-Legierungen
WO2014205330A1 (en) * 2013-06-20 2014-12-24 Baker Hughes Incorporated Method to produce metal matrix nanocomposite with graphene
US10006141B2 (en) 2013-06-20 2018-06-26 Baker Hughes, A Ge Company, Llc Method to produce metal matrix nanocomposite
WO2016044171A1 (en) * 2014-09-18 2016-03-24 Baker Hughes Incorporated Methods of coating substrates with composite coatings of diamond nanoparticles and metal
US10669635B2 (en) 2014-09-18 2020-06-02 Baker Hughes, A Ge Company, Llc Methods of coating substrates with composite coatings of diamond nanoparticles and metal
US9873827B2 (en) 2014-10-21 2018-01-23 Baker Hughes Incorporated Methods of recovering hydrocarbons using suspensions for enhanced hydrocarbon recovery
US10167392B2 (en) 2014-10-31 2019-01-01 Baker Hughes Incorporated Compositions of coated diamond nanoparticles, methods of forming coated diamond nanoparticles, and methods of forming coatings
US10155899B2 (en) 2015-06-19 2018-12-18 Baker Hughes Incorporated Methods of forming suspensions and methods for recovery of hydrocarbon material from subterranean formations
CN108368625A (zh) * 2015-12-11 2018-08-03 日立金属株式会社 电极装置和使用该装置的金属箔的制造方法
US10633753B2 (en) 2015-12-11 2020-04-28 Hitachi Metals, Ltd. Electrode device and metal foil manufacturing method using same
EP3388557A4 (de) * 2015-12-11 2019-05-22 Hitachi Metals, Ltd. Elektrodenvorrichtung und verfahren zur herstellung einer metallfolie damit
CN109989081A (zh) * 2019-04-17 2019-07-09 浙江宏途电气科技有限公司 便于操作的电刷镀工件修复装置

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AU2002321112A1 (en) 2004-01-06
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