[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP1516076B1 - Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten - Google Patents

Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten Download PDF

Info

Publication number
EP1516076B1
EP1516076B1 EP02754753A EP02754753A EP1516076B1 EP 1516076 B1 EP1516076 B1 EP 1516076B1 EP 02754753 A EP02754753 A EP 02754753A EP 02754753 A EP02754753 A EP 02754753A EP 1516076 B1 EP1516076 B1 EP 1516076B1
Authority
EP
European Patent Office
Prior art keywords
anode
cathode
range
electrolyte
cathodic
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
EP02754753A
Other languages
English (en)
French (fr)
Other versions
EP1516076A1 (de
Inventor
Gino Palumbo
Iain Brooks
Jonathan Mccrea
Glenn D. Hibbard
Francisco Gonzalez
Klaus Tomantschger
Uwe Erb
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.)
Integran Technologies Inc
Original Assignee
Integran Technologies Inc
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 Integran Technologies Inc filed Critical Integran Technologies Inc
Priority to EP07002944A priority Critical patent/EP1826294A1/de
Publication of EP1516076A1 publication Critical patent/EP1516076A1/de
Application granted granted Critical
Publication of EP1516076B1 publication Critical patent/EP1516076B1/de
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
    • 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 nano-crystalline 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 nano-crystalline 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 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 1Hz to 1kHz and more preferably from 10Hz to 350Hz.
  • Nano-crystalline 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.
  • 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.
  • the present invention it is also possible to produce nanocrystalline coatings by electroplating without the need to submerse the article to be coated into a plating bath.
  • 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).
  • FIG 2 schematically shows a workpiece (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 workpiece (6) and adjusts the spacing between anode (5) and cathode (6).
  • the anode brush handle (7) can be moved over the workpiece (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 lenght 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).
  • anode (5) having the same features as shown in Fig. 2 is attached to the traversing arm (13) and moves over the workpiece (6) in a motion depending on the position x.
  • the anode (5) and the workpiece (6) are connected to positive and negative outlets of a power source (not shown), respectively.
  • the cinematic relation is very similar to that of a steam engine.
  • This invention relies on producing nanocrystalline coatings, foils and microsystem components by pulse electrodeposition.
  • solid particles are suspended in the electrolyte and are included in the deposit.
  • 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 NiP-B 4 C nanocomposites were deposited onto Ti and mild steel cathodes immersed in a modified Watts bath for nickel using a soluble anode made of a nickel plate and a Dynatronix (Dynanet PDPR 20-30-100) pulse power supply. The following conditions were used:
  • the hardness values of metal matrix composites possessing a nanocrystalline matrix structure are typically twice as high as conventional coarse-grained metal matrix composites.
  • the hardness and wear properties of a nanocrystalline NiP-B 4 C composite containing 5.9weight% P and 45volume% B 4 C are compared with those of pure coarse-grained Ni, pure nanocrystalline Ni and electrodeposited Ni-P of an equivalent chemical composition in the adjacent table. Material hardening is controlled by Hall-Petch grain size strengthening, while abrasive wear resistance is concurrently optimized by the incorporation of B 4 C particulate.
  • NiP-B 4 C nanocomposite properties Sample Grain Size Vickers Hardness [VHN] Taber Wear Index [TWI] Pure Ni 90 ⁇ m 124 37.0 Pure Ni 13 nm 618 20.9 Ni-5.9P Amorphous 611 26.2 Ni-5.9P-45B 4 C 12 nm 609 1.5
  • Nanocrystalline Co based nanocomposites were deposited onto Ti and mild steel cathodes immersed in a modified Watts bath for cobalt using a soluble anode made of a cobalt plate and a Dynatronix (Dynanet PDPR 20-30-100) pulse power supply. The following conditions were used:
  • Nanocrystalline metal foils were deposited on a rotating Ti drum partially immersed in a plating electrolyte.
  • the nanocrystalline foil was electroformed onto the drum cathodically, using a soluble anode made of a titanium container filled with anode metal and using a pulse power supply.
  • a stream of the additional cation at a predetermined concentration was continuously added to the electrolyte solution to establish a steady state concentration of alloying cations in solution.
  • a stream of the composite addition was added to the plating bath at a predetermined rate to establish a steady state content of the additive.
  • Three different anode dispositions can be used: Conformal anodes that follow the contour of the submerged section of the drum, vertical anodes positioned at the walls of the vessel and horizontal anode positioned on the bottom of the vessel.
  • Foils were produced at average cathodic current densities ranging from 0.01 to 5A/cm 2 and preferably from 0.05 to 0.5A/cm 2 .
  • the rotation speed was used to adjust the foil thickness and this speed ranged from 0.003 to 0.15rpm (or 20 to 1000cm/hour) and preferably from 0.003 to 0.05rpm (or 20 to 330cm/hour)
  • Example 3 metal matrix composite drum plating
  • Nanocrystalline Co based nanocomposites were deposited onto a rotating Ti drum as described in example 2 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.
  • Selective plating techniques are particularly suited for repairing or refurbishing articles because brush plating set-ups are portable, easy to operate and do not require the disassembly of the system containing the work piece to be plated.
  • Brush plating also allows plating of parts too large for immersion into plating tanks. Brush plating is used to provide coatings for improved corrosion resistance, improved wear, improved appearance (decorative plating) and can be used to salvage worn or mismachined parts.
  • Brush plating systems and plating solutions are commercially available e.g. from Sifco Selective Plating, Cleveland. Ohio, which also provides mechanized and/or automated tooling for use in high volume production work.
  • 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.
  • This mechanical rubbing or brushing motion imparted to the work piece during the plating process influences the quality and the surface finish of the coating and enables fast plating rates.
  • Selective plating electrolytes are formulated to produce acceptable coatings in a wide temperature range ranging from as low as -20°C to 85°C. As the work piece is frequently large in comparison to the area being coated selective plating is often applied to the work piece at ambient temperatures, ranging from as low as -20°C to as high as 45°C.
  • the temperature of the anode, cathode and electrolyte can vary substantially. Salting out of electrolyte constituents can occur at low temperatures and the electrolyte may have to be periodically or continuously reheated to dissolve all precipitated chemicals.
  • 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 2.5 in (6.35 cm) OD steel pipe and a weldclad I625 pipe. The cathode size was 8cm 2 , except for the 2.5 in (6.35 cm) 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 pure nickel was deposited onto an 8cm 2 area cathode with a 35cm 2 anode using the set-up described.
  • the work piece has a substantially larger area than the anode.
  • a work piece (cathode) was selected to be substantially smaller than the anode to ensure that the oversized anode, although being constantly kept in motion, always covered the entire work piece to enable the determination of the cathodic current density.
  • NiCO 3 was periodically added to the plating bath to maintain the desired Ni 2+ concentration. The following conditions were used:
  • Nanocrystalline Co was deposited using the same set up described under the following conditions:
  • Nanocrystalline Ni/20%Fe was deposited using the set up described before.
  • a 1.5in wide band was plated on the OD of a 2.5 in (6,35 nm) pipe by rotating the pipe along its longitudinal axis while maintaining a fixed anode under the following conditions:
  • a defect (groove) in a weldclad pipe section was filled in with nanocrystalline Ni using the same set up as in Example 1.
  • the groove was about 4.5cm long, 0.5cm wide and had an average depth of approximately 0.175mm, although the rough finish of the defect made it impossible to determine its exact surface area.
  • the area surrounding the defect was masked off and nano Ni was plated onto the defective area until its original thickness was reestablished.
  • 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.
  • electrodeposition initially starts with a fine grain size at the substrate material. With increasing deposit thickness in the growth direction; however, the transition to columnar grains is normally observed. The thickness of the columnar grains typically ranges from a few to a few tens of micrometers while their lengths can reach hundreds of micrometers. The consequence of such structures is the development of anisotropic properties with increasing deposit thickness and the reaching of a critical thickness in which only a few grains cover the entire cross section of the components with widths below 5 or 10 ⁇ m. A further decrease in component thickness results in a bamboo structure resulting in a significant loss in strength. Therefore the microstructure of electrodeposited micro-components currently in use is entirely incommensurate with property requirements across both the width and thickness of the component on the basis of grain shape and average grain size.
  • Metal micro-spring fingers are used to contact IC chips with high pad count and density and to carry power and signals to and from the chips.
  • the springs provide high pitch compliant electrical contacts for a variety of interconnection structures, including chip scale semiconductor packages, high-density interposer connectors, and probe contactors.
  • the massively parallel interface structures and assemblies enable high speed testing of separated integrated circuit devices affixed to a compliant carrier, and allow test electronics to be located in close proximity to the integrated circuit devices under test.
  • 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.

Landscapes

  • 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)
  • Manufacture Of Switches (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (27)

  1. Verfahren zum kathodischen Elektroabscheiden eines ausgewählten metallischen Materials auf einem dauerhaften oder zeitweisen Substrat in nanokristalliner Form mit einer Durchschnittskorngröße von weniger als 100 nm, unter Verwendung von Puls-Elektroabscheiden, mit einer Abscheidungsgeschwindigkeit von wenigstens 0,05 mm/h, aufweisend:
    Vorsehen eines wässrigen Elektrolyts, welcher Ionen des metallischen Materials enthält, Halten des Elektrolyten bei einer Temperatur im Bereich zwischen 0 bis 85° C, Vorsehen einer Anode und einer Kathode in Kontakt mit dem Elektrolyt, Durchleiten von einzelnen oder mehreren Gleichstromkathodenstromimpulsen zwischen der Anode und Kathode mit einer Kathodenstrompulsfrequenz in einem Bereich zwischen 0 und 1000 Hz zu gepulsten Intervallen, während denen der Strom für eine tan-Zeitperiode im Bereich von ungefähr 0,1 bis 50 ms fließt und für eine taus-Zeitperiode im Bereich von 0 bis 500 ms nicht fließt, und Durchleiten von einzelnen oder mehreren Gleichstromanodenstrompulsen zwischen der Kathode und Anode zu Intervallen, während denen der Strom für eine tanodisch-Zeitperiode im Bereich von 0 bis 50 ms fließt, wobei ein Arbeitszyklus im Bereich von 5 bis 100% ist und eine kathodische Ladung (Qkathodisch) pro Intervall immer größer als eine anodische Ladung (Qanodisch) ist.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die einzelnen oder mehreren Gleichstrom-Kathodenstromimpulse zwischen der Anode und der Kathode eine Spitzenstromdichte im Bereich von etwa 0,01 bis 20 A/cm2 aufweisen.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Spitzenstromdichte der Kathodenstrompulse im Bereich von etwa 0,1 bis 20 A/cm2, bevorzugt im Bereich von 1 bis 10 A/cm2 liegt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das ausgewählte metallische Material (a) ein reines Metall ist, ausgewählt aus der Gruppe bestehend aus Ag, Au, Cu, Co, Cr, Ni, Fe, Pb, Pd, Rt, Rh, Ru, Sn, V, W, Zn oder (b) eine Legierung, bestehend aus zumindest einem der Elemente der Gruppe (a) und legierenden Elementen, ausgewählt aus der Gruppe bestehend aus C, P, S und Si.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die tan-Zeitperiode im Bereich von 1 bis etwa 50 ms liegt, die taus-Zeitperiode im Bereich von etwa 1 bis 100 ms und die tanodisch-Zeitperiode im Bereich von etwa 1 bis 10 ms liegt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Arbeitszyklus bevorzugt im Bereich von 10 bis 95% liegt, und bevorzugter im Bereich von 20 bis 80% liegt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Kathodenstrom-Pulsfrequenz von 10 Hz bis 350 Hz reicht.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Abscheidungsgeschwindigkeit bevorzugt zumindest 0,075 mm/h und bevorzugter zumindest 0,1 mm/h ist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, gekennzeichnet durch Umrühren des Elektrolyten bei einer Umrührgeschwindigkeit im Bereich von 0 bis 750 ml/min/A, bevorzugt im Bereich von 1 bis 500 ml/min/A.
  10. Verfahren nach einem der Ansprüche 1 bis 8, gekennzeichnet durch Umrühren des Elektrolyten bei einer Umrührbeschwindigkeit im Bereich von 0,0001 bis 10 l/min/cm2 (Liter pro Minute per cm2 Anoden- oder Kathodenfläche).
  11. Verfahren nach Anspruch 9 oder 10, gekennzeichnet durch Umrühren des Elektrolyten mittels Pumpen, Rührwerken oder Ultraschallanregung.
  12. Verfahren nach einem der Ansprüche 1 bis 11, gekennzeichnet durch eine relative Bewegung zwischen der Anode und Kathode.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die Geschwindigkeit der relativen Bewegung zwischen Anode und Kathode von 0 bis zu 600 m/min reicht, bevorzugt von 0,003 bis 10 m/min.
  14. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die relative Bewegung durch Drehung der Anode und der Kathode relativ zueinander erreicht wird.
  15. Verfahren nach Anspruch 14, gekennzeichnet durch eine Rotationsgeschwindigkeit der Rotation der Anode und der Kathode relativ zueinander, welche von 0,003 bis 0,15 Upm und bevorzugt von 0,003 bis 0,05 Upm reicht.
  16. Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, dass die relative Bewegung durch einen eine mechanisierte Bewegung erzeugenden Hub der Anode und der Kathode relativ zueinander erreicht wird.
  17. Verfahren nach Anspruch 12 oder 16, dadurch gekennzeichnet, dass die Anode in ein absorbierendes Abstandstück gewickelt ist.
  18. Verfahren nach irgendeinem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass der Elektrolyt ein spannungssenkendes Mittel oder ein Komverfeinerungsmittel enthält, ausgewählt aus der Gruppe von Saccharin, Coumarin, Natriumlaurylsulfat und Thio-Harnstoff.
  19. Verfahren nach irgendeinem der Ansprüche 1 bis 18, dadurch gekennzeichnet, dass der Elektrolyt aus Partikeln bestehende Zusätze in der Lösung enthält, ausgewählt aus reinen Metallpulvern, Metalllegierungspulvem oder Metalloxidpulvern von Al, Co, Cu, In, Mg, Ni, Si, Sn, V und Zn, Nitriden von Al, B und Si, Kohlenstoff C (Graphit oder Diamant), Carbide von B, Bi, Si, W oder organische Materialien wie PTFE und Polymerkugeln, wobei das elektro-abgeschiedene metallische Material zumindest 5% der aus Partikeln bestehenden Zusätze enthält.
  20. Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass das elektro-abgeschiedene metallische Material zumindest 10% der aus Partikeln bestehenden Zusätze enthält.
  21. Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass das elektro-abgeschiedene metallische Material zumindest 20% der aus Partikeln bestehenden Zusätze enthält.
  22. Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass das elektro-abgeschiedene metallische Material zumindest 30% der aus Partikeln bestehenden Zusätze enthält.
  23. Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass das elektro-abgeschiedene metallische Material zumindest 40% der aus Partikeln bestehenden Zusätze enthält.
  24. Verfahren nach irgendeinem der Ansprüche 19 bis 23, dadurch gekennzeichnet, dass die durchschnittliche Partikelgröße der aus Partikeln bestehenden Zusätze unter 10 µm liegt, bevorzugt unter 1000 nm, bevorzugter unter 500 nm, und am bevorzugtesten unter 100 nm.
  25. Mikrokomponente, hergestellt durch ein Pulselektroabscheidungsverfahren wie in einem der Ansprüche 1 bis 23 beansprucht, welche eine maximale Abmessung von 1 mm aufweist, eine Durchschnittskorngröße kleiner 100 nm, wobei das Verhältnis zwischen der maximalen Abmessung und der Durchschnittskorngröße größer als 10 ist.
  26. Mikrokomponente nach Anspruch 25, dadurch gekennzeichnet, dass das Verhältnis zwischen der maximalen Abmessung der Mikrokomponente und der Durchschnittskorngröße größer als 100 ist.
  27. Mikrokomponente nach Anspruch 25 oder 26, gekennzeichnet dadurch, dass sie eine gleichachsige Mikrostruktur aufweist.
EP02754753A 2002-06-25 2002-06-25 Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten Expired - Lifetime EP1516076B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07002944A EP1826294A1 (de) 2002-06-25 2002-06-25 Verfahren zum Galvanisieren von Metallfolien und Metallmatrix-Verbundenfolien und Mikrokomponenten

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2002/007023 WO2004001100A1 (en) 2002-06-25 2002-06-25 Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP07002944A Division EP1826294A1 (de) 2002-06-25 2002-06-25 Verfahren zum Galvanisieren von Metallfolien und Metallmatrix-Verbundenfolien und Mikrokomponenten

Publications (2)

Publication Number Publication Date
EP1516076A1 EP1516076A1 (de) 2005-03-23
EP1516076B1 true EP1516076B1 (de) 2008-02-27

Family

ID=29762587

Family Applications (2)

Application Number Title Priority Date Filing Date
EP02754753A Expired - Lifetime EP1516076B1 (de) 2002-06-25 2002-06-25 Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten
EP07002944A Withdrawn EP1826294A1 (de) 2002-06-25 2002-06-25 Verfahren zum Galvanisieren von Metallfolien und Metallmatrix-Verbundenfolien und Mikrokomponenten

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP07002944A Withdrawn EP1826294A1 (de) 2002-06-25 2002-06-25 Verfahren zum Galvanisieren von Metallfolien und Metallmatrix-Verbundenfolien und Mikrokomponenten

Country Status (16)

Country Link
EP (2) EP1516076B1 (de)
JP (1) JP2005530926A (de)
KR (1) KR100890819B1 (de)
AT (1) ATE387522T1 (de)
AU (1) AU2002321112B2 (de)
BR (1) BR0215787B1 (de)
CA (1) CA2490464C (de)
DE (1) DE60225352T2 (de)
DK (1) DK1516076T3 (de)
ES (1) ES2301666T3 (de)
HK (1) HK1075278A1 (de)
IL (1) IL165904A0 (de)
MX (1) MXPA04011940A (de)
PT (1) PT1516076E (de)
WO (1) WO2004001100A1 (de)
ZA (1) ZA200410368B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10102930B2 (en) 2013-11-13 2018-10-16 Framatome Inc. Nuclear fuel rod cladding including a metal nanomaterial layer

Families Citing this family (64)

* 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
EP1616047A1 (de) 2003-04-11 2006-01-18 Lynntech, Inc. Quasikristalle enthaltende zusammensetzungen und beschichtungen
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
US7354354B2 (en) 2004-12-17 2008-04-08 Integran Technologies Inc. Article comprising a fine-grained metallic material and a polymeric material
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
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
WO2007021980A2 (en) 2005-08-12 2007-02-22 Isotron Corporation Compositionally modulated composite materials and methods for making the same
US20070170068A1 (en) * 2006-01-24 2007-07-26 Usc, Llc Electrocomposite coatings for hard chrome replacement
US8202627B2 (en) * 2006-01-24 2012-06-19 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
EP2310556A2 (de) 2008-07-07 2011-04-20 Modumetal, LLC Modulierte materialien mit niedrigen spannungseigenschaften und herstellungsverfahren dafür
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
CA2764887C (en) 2009-06-08 2018-09-11 Modumetal Llc Electrodeposited, nanolaminate coatings and claddings for corrosion protection
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
JP5872492B2 (ja) * 2010-03-12 2016-03-01 エクスタリック コーポレイションＸｔａｌｉｃ Ｃｏｒｐｏｒａｔｉｏｎ 被覆物および方法
CN105386103B (zh) 2010-07-22 2018-07-31 莫杜美拓有限公司 纳米层压黄铜合金的材料及其电化学沉积方法
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
GB2497520A (en) * 2011-12-09 2013-06-19 Mahle Int Gmbh Method of electroplating a bearing surface
US20130186765A1 (en) * 2012-01-23 2013-07-25 Seagate Technology Llc Electrodeposition methods
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
EP2971265A4 (de) 2013-03-15 2016-12-14 Modumetal Inc Nickel-chrom-nanolaminatbeschichtung mit hoher härte
US9207515B2 (en) 2013-03-15 2015-12-08 Ashwin-Ushas Corporation, Inc. Variable-emittance electrochromic devices and methods of preparing the same
EP2971264A4 (de) 2013-03-15 2017-05-31 Modumetal, Inc. Nanolaminierte beschichtungen
CA2905575C (en) 2013-03-15 2022-07-12 Modumetal, Inc. A method and apparatus for continuously applying nanolaminate metal coatings
WO2016044720A1 (en) 2014-09-18 2016-03-24 Modumetal, Inc. A method and apparatus for continuously applying nanolaminate metal coatings
EP2971261A4 (de) 2013-03-15 2017-05-31 Modumetal, Inc. Elektroplattierte zusammensetzungen und nanolaminierte legierungen für durch ein additivherstellungsverfahren hergestellte artikel
US10006141B2 (en) * 2013-06-20 2018-06-26 Baker Hughes, A Ge Company, Llc Method to produce metal matrix nanocomposite
CA2961507C (en) 2014-09-18 2024-04-09 Modumetal, Inc. Methods of preparing articles by electrodeposition and additive manufacturing processes
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
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
JP6521074B2 (ja) * 2015-12-11 2019-05-29 日立金属株式会社 電極装置およびそれを用いた金属箔の製造方法
US11365488B2 (en) 2016-09-08 2022-06-21 Modumetal, Inc. Processes for providing laminated coatings on workpieces, and articles made therefrom
JP7051823B2 (ja) 2016-09-14 2022-04-11 モジュメタル インコーポレイテッド 高信頼性、高スループットの複素電界生成のためのシステム、およびそれにより皮膜を生成するための方法
US12076965B2 (en) 2016-11-02 2024-09-03 Modumetal, Inc. Topology optimized high interface packing structures
CA3057836A1 (en) 2017-03-24 2018-09-27 Modumetal, Inc. Lift plungers with electrodeposited coatings, and systems and methods for producing the same
CN110770372B (zh) 2017-04-21 2022-10-11 莫杜美拓有限公司 具有电沉积涂层的管状制品及其生产系统和方法
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
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
DE102018120028A1 (de) * 2018-08-17 2020-02-20 Bolta-Werke Gmbh Verfahren zur Herstellung einer Metallfolie, Metallfolie, Bauteil, Elektrolytlösung und Vorrichtung
CN109989081B (zh) * 2019-04-17 2021-05-25 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
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
JP7552548B2 (ja) 2021-10-14 2024-09-18 トヨタ自動車株式会社 金属皮膜の成膜装置および金属皮膜の成膜方法

Family Cites Families (6)

* 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
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
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10102930B2 (en) 2013-11-13 2018-10-16 Framatome Inc. Nuclear fuel rod cladding including a metal nanomaterial layer

Also Published As

Publication number Publication date
DE60225352D1 (de) 2008-04-10
CA2490464A1 (en) 2003-12-31
WO2004001100A1 (en) 2003-12-31
CA2490464C (en) 2008-09-02
ES2301666T3 (es) 2008-07-01
BR0215787B1 (pt) 2013-12-03
HK1075278A1 (en) 2005-12-09
JP2005530926A (ja) 2005-10-13
IL165904A0 (en) 2006-01-15
AU2002321112B2 (en) 2008-07-03
ZA200410368B (en) 2006-07-26
PT1516076E (pt) 2008-03-11
KR100890819B1 (ko) 2009-04-06
EP1516076A1 (de) 2005-03-23
DK1516076T3 (da) 2008-06-23
MXPA04011940A (es) 2005-03-31
DE60225352T2 (de) 2008-06-12
EP1826294A1 (de) 2007-08-29
AU2002321112A1 (en) 2004-01-06
ATE387522T1 (de) 2008-03-15
KR20050024394A (ko) 2005-03-10
BR0215787A (pt) 2005-03-01

Similar Documents

Publication Publication Date Title
EP1516076B1 (de) Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten
US20050205425A1 (en) Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents
US8062496B2 (en) Electroplating method and apparatus
US20040011432A1 (en) Metal alloy electrodeposited microstructures
CN103726083A (zh) 纳晶和非晶金属及合金作为涂层的实施方法
Biswal et al. Recent advances in energy field assisted hybrid electrodeposition and electroforming processes
DE10228323B4 (de) Verfahren zum kathodischen elektrolytischen Abscheiden und Mikrokomponenten, hergestellt durch ein solches Verfahren
Ayalew et al. A critical review of additive material manufacturing through electrochemical deposition techniques
Deshmukh et al. A systematic review on high speed selective jet electrodeposition manufacturing
US20060154084A1 (en) Production of metal glass in bulk form
Ming et al. Wear resistance of copper EDM tool electrode electroformed from copper sulfate baths and pyrophosphate baths
CN211135823U (zh) 一种原位共液电化学复合加工装置
Li et al. Advances in magnetic field-assisted ECM—from magnetoelectric effects to technology applications
DE10262102B4 (de) Verfahren zum kathodischen elektrolytischen Abscheiden
US20240309534A1 (en) Electroforming method and system
Rathod et al. Electrochemical Micromachining (EMM): Fundamentals and Applications
US20240026559A1 (en) Articles comprising heterogeneous and thermally stable grain-refined alloys
k Swain Preparation of coated microtools for electrochemical machining applications
Yu et al. Jinkai Xu, Wanfei Ren, Zhongxu Lian
Pandey et al. An optimal toolpath planning for realizing 3D micro metallic features via selective jet electrodeposition (SJED) process
김한 Micro-pattern Metallization using Jet-circulating Electrodeposition
Fallah Fabrication and optimization of 3D metallic parts using electroplating of additively manufactured parts
CN115505972A (zh) 一种基于熔融沉积制备掩膜的电化学沉积一体化装置
Lakra Synthesis and characterization of Pulsed-Electrodeposited Cr and Cr-ZrO2 Coating
Mulukutla Pulse electrodeposition of cobalt-tungsten and its composite coatings for hard chrome replacements

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041027

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HIBBARD, GLENN, D.

Inventor name: TOMANTSCHGER, KLAUS

Inventor name: BROOKS, IAIN

Inventor name: ERB, UWE

Inventor name: PALUMBO, GINO

Inventor name: GONZALEZ, FRANCISCO

Inventor name: MCCREA, JONATHAN

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1075278

Country of ref document: HK

17Q First examination report despatched

Effective date: 20060907

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20080228

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: HEPP, WENGER & RYFFEL AG

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60225352

Country of ref document: DE

Date of ref document: 20080410

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20080400940

Country of ref document: GR

REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1075278

Country of ref document: HK

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2301666

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

26N No opposition filed

Effective date: 20081128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080227

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20120524

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20130527

Year of fee payment: 12

Ref country code: IE

Payment date: 20130528

Year of fee payment: 12

Ref country code: CH

Payment date: 20130527

Year of fee payment: 12

Ref country code: LU

Payment date: 20130530

Year of fee payment: 12

Ref country code: DK

Payment date: 20130523

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20130607

Year of fee payment: 12

Ref country code: FI

Payment date: 20130523

Year of fee payment: 12

Ref country code: PT

Payment date: 20130619

Year of fee payment: 12

Ref country code: GR

Payment date: 20130523

Year of fee payment: 12

Ref country code: BE

Payment date: 20130523

Year of fee payment: 12

Ref country code: NL

Payment date: 20130524

Year of fee payment: 12

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20141226

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20140630

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20150101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140625

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141226

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140625

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140626

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 387522

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140625

REG Reference to a national code

Ref country code: GR

Ref legal event code: ML

Ref document number: 20080400940

Country of ref document: GR

Effective date: 20150105

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140630

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140625

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140630

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20150521

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60225352

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170103

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140625

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20190522

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20190522

Year of fee payment: 18

Ref country code: ES

Payment date: 20190701

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20200519

Year of fee payment: 19

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200625

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210625