EP1516076B1 - Procede de placage electrochimique de feuilles metalliques et de composites a matrice metallique, de revetements et de microcomposants - Google Patents
Procede de placage electrochimique de feuilles metalliques et de composites a matrice metallique, de revetements et de microcomposants Download PDFInfo
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- 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
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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
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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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/20—Electroplating using ultrasonics, vibrations
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/67—Electroplating to repair workpiece
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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
- 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.
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- Chemical & Material Sciences (AREA)
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- 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)
- Procédé d'électrodéposition par voie cathodique d'un matériau métallique choisi sur un substrat permanent ou temporaire sous une forme nanocristalline avec une dimension de grain moyenne inférieure à 100 nm en utilisant une électrodéposition à impulsions à un débit de dépôt d'au moins 0,05 mm/h, comprenant :la fourniture d'un électrolyte aqueux renfermant des ions dudit matériau métallique, le maintien dudit électrolyte à une température comprise dans la gamme entre 0 et 85°C, la fourniture d'une anode et d'une cathode en contact avec ledit électrolyte, le passage d'impulsions de courant cathodique de courant continu simples ou multiples entre ladite anode et ladite cathode à une fréquence d'impulsions de courant cathodique dans la gamme d'environ 0 à 1000 Hz, à des intervalles pulsés au cours desquels ledit courant passe pendant une période de temps tact dans la gamme d'environ 0,1 à 50 ms et ne passe pas pendant une période de temps tdésact dans la gamme d'environ 0 à 500 ms et le passage d'impulsions de courant anodique de courant continu simples ou multiples entre ladite cathode et ladite anode à des intervalles pendant lesquels ledit courant passe pendant une période de temps tanodique dans la gamme de 0 à 50 ms, un cycle de service dans la gamme de 5 à 100 % et une charge cathodique (Qcathodique) par intervalle qui est toujours supérieure à une charge anodique (Qanodique).
- Procédé selon la revendication 1, caractérisé en ce que les impulsions de courant cathodique de courant continu simples ou multiples entre ladite anode et ladite cathode ont une densité de courant de pic dans la gamme d'environ 0,01 à 20 A/cm2.
- Procédé selon la revendication 2, caractérisé en ce que la densité de courant de pic des impulsions de courant cathodique se situe dans la gamme d'environ 0,1 à 20 A/cm2, de préférence dans la gamme d'environ 1 à 10 A/cm2.
- Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ledit matériau métallique choisi est (a) un métal pur choisi parmi le groupe comprenant Ag, Au, Cu, Co, Cr, Ni, Fe, Pb, Pd, Rt, Rh, Ru, Sn, V, W, Zn ou (b) un alliage renfermant au moins un des éléments du groupe (a) et des éléments d'alliage choisis dans le groupe comprenant C, P, S et Si.
- Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la période de temps tact se situe dans la gamme d'environ 1 à environ 50 ms, la période de temps tdésact se situe dans la gamme d'environ 1 à 100 ms et la période de temps tanodique se situe dans la gamme d'environ 1 à 10 ms.
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le cycle de service se situe, de préférence, dans la gamme de 10 à 95 % et mieux encore se situe dans la gamme de 20 à 80 %.
- Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la fréquence d'impulsions de courant cathodique se situe de 10 Hz à 350 Hz.
- Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la vitesse de dépôt est, de préférence, d'au moins 0,075 mm/h et mieux encore d'au moins 0,1 mm/h.
- Procédé selon l'une quelconque des revendications 1 à 8, caractérisé par l'agitation de l'électrolyte à une vitesse d'agitation dans la gamme de 0 à 750 ml/(min x A), de préférence dans une gamme de 0 à 500 ml/(min x A).
- Procédé selon l'une quelconque des revendications 1 à 8, caractérisé par l'agitation de l'électrolyte à une vitesse d'agitation dans la gamme de 0,0001 à 10 1/(min x cm2) (litre par min par cm2 de surface d'anode ou de cathode).
- Procédé selon la revendication 9 ou 10, caractérisé par l'agitation de l'électrolyte au moyen de pompes, d'agitateurs ou une agitation par ultrasons.
- Procédé selon l'une quelconque des revendications 1 à 11, caractérisé par un mouvement relatif entre l'anode et la cathode.
- Procédé selon la revendication 12, caractérisé en ce que la vitesse du mouvement relatif entre l'anode et la cathode se situe de 0 à 600 m/min, de préférence de 0,003 à 10 m/min.
- Procédé selon la revendication 12, caractérisé en ce que le mouvement relatif est obtenu par rotation de l'anode et de la cathode relativement l'une à l'autre.
- Procédé selon la revendication 14, caractérisé par une vitesse de rotation de l'anode et de la cathode relativement l'une à l'autre dans la gamme de 0,03 à 0,15 tour par minute et, de préférence, de 0,003 à 0,05 tour par minute.
- Procédé selon la revendication 12 ou la revendication 13, caractérisé en ce que le mouvement relatif est obtenu par un mouvement mécanisé générant une course de l'anode et de la cathode relativement l'une à l'autre.
- Procédé selon la revendication 12 ou 16, caractérisé en ce que l'anode est enveloppée dans un séparateur absorbant.
- Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que ledit électrolyte renferme un agent de libération de contrainte ou un agent de raffinage de grain choisi dans le groupe de la saccharine, de la coumarine, du lauryl sulfate de sodium et de la thiourée.
- Procédé selon l'une quelconque des revendications 1 à 18, caractérisé en ce que ledit électrolyte renferme des additifs particulaires en suspension choisis parmi les poudres de métal pur, les poudres d'alliage de métal et les poudres d'oxydes métalliques de Al, Co, Cu, In, Mg, Ni, Si, Sn, V et Zn, les nitrures de Al, B et Si, le carbone C (graphite ou diamant), les carbures de B, Bi, Si, W ou des matériaux organiques comme PTFE et des sphères de polymères, de sorte que le matériau métallique électrodéposé renferme au moins 5 % desdits additifs particulaires.
- Procédé selon la revendication 19, caractérisé en ce que le matériau métallique électrodéposé renferme au moins 10 % desdits additifs particulaires.
- Procédé selon la revendication 19, caractérisé en ce que le matériau métallique électrodéposé renferme au moins 20 % desdits additifs particulaires.
- Procédé selon la revendication 19, caractérisé en ce que le matériau métallique électrodéposé renferme au moins 30 % desdits additifs particulaires.
- Procédé selon la revendication 19, caractérisé en ce que ledit matériau métallique électrodéposé renferme au moins 40 % desdits additifs particulaires.
- Procédé selon l'une quelconque des revendications 19 à 23, caractérisé en ce que la dimension de particule moyenne des additifs particulaires est inférieure à 10 µm, de préférence inférieure à 1000 nm, plus particulièrement inférieure à 500 nm et mieux encore inférieure à 100 nm.
- Microcomposant produit par un procédé d'électrodéposition à impulsions selon l'une quelconque des revendications 1 à 23, ayant une dimension maximum de 1 mm, une dimension de grain moyenne inférieure à 100 nm, le rapport entre la dimension maximum et la dimension de grain moyenne étant supérieur à 10.
- Microcomposant selon la revendication 25, caractérisé en ce que le rapport entre la dimension maximum du microcomposant et la dimension de grain moyenne est supérieur à 100.
- Microcomposant selon la revendication 25 ou 26, caractérisé en ce qu'il présente une microstructure équiaxiale.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP07002944A EP1826294A1 (fr) | 2002-06-25 | 2002-06-25 | Processus de dépôt électrique métallique, et microcomposants et feuilles composites de matrice métallique |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/EP2002/007023 WO2004001100A1 (fr) | 2002-06-25 | 2002-06-25 | Procede de placage electrochimique de feuilles metalliques et de composites a matrice metallique, de revetements et de microcomposants |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP07002944A Division EP1826294A1 (fr) | 2002-06-25 | 2002-06-25 | Processus de dépôt électrique métallique, et microcomposants et feuilles composites de matrice métallique |
Publications (2)
Publication Number | Publication Date |
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EP1516076A1 EP1516076A1 (fr) | 2005-03-23 |
EP1516076B1 true EP1516076B1 (fr) | 2008-02-27 |
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EP02754753A Expired - Lifetime EP1516076B1 (fr) | 2002-06-25 | 2002-06-25 | Procede de placage electrochimique de feuilles metalliques et de composites a matrice metallique, de revetements et de microcomposants |
EP07002944A Withdrawn EP1826294A1 (fr) | 2002-06-25 | 2002-06-25 | Processus de dépôt électrique métallique, et microcomposants et feuilles composites de matrice métallique |
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EP07002944A Withdrawn EP1826294A1 (fr) | 2002-06-25 | 2002-06-25 | Processus de dépôt électrique métallique, et microcomposants et feuilles composites de matrice métallique |
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EP (2) | EP1516076B1 (fr) |
JP (1) | JP2005530926A (fr) |
KR (1) | KR100890819B1 (fr) |
AT (1) | ATE387522T1 (fr) |
AU (1) | AU2002321112B2 (fr) |
BR (1) | BR0215787B1 (fr) |
CA (1) | CA2490464C (fr) |
DE (1) | DE60225352T2 (fr) |
DK (1) | DK1516076T3 (fr) |
ES (1) | ES2301666T3 (fr) |
HK (1) | HK1075278A1 (fr) |
IL (1) | IL165904A0 (fr) |
MX (1) | MXPA04011940A (fr) |
PT (1) | PT1516076E (fr) |
WO (1) | WO2004001100A1 (fr) |
ZA (1) | ZA200410368B (fr) |
Cited By (1)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004090361A2 (fr) * | 2003-04-03 | 2004-10-21 | The Timken Company | Palier a element roulant tolerant a la corrosion |
EP1616047A1 (fr) | 2003-04-11 | 2006-01-18 | Lynntech, Inc. | Compositions et revetements comprenant des quasicristaux |
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 (fr) | 2005-08-12 | 2007-02-22 | Isotron Corporation | Materiaux composites a composition modulee et leurs procedes de fabrication |
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 (fr) | 2008-07-07 | 2011-04-20 | Modumetal, LLC | Matières modulées à propriété de faible contrainte et leurs procédés de fabrication |
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 (fr) | 2009-06-08 | 2018-09-11 | Modumetal Llc | Revetements nanostratifies electrodeposes et gaines pour la protection contre la corrosion |
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 (fr) | 2013-03-15 | 2016-12-14 | Modumetal Inc | Revêtement nanostratifié de chrome et de nickel ayant une dureté élevée |
US9207515B2 (en) | 2013-03-15 | 2015-12-08 | Ashwin-Ushas Corporation, Inc. | Variable-emittance electrochromic devices and methods of preparing the same |
EP2971264A4 (fr) | 2013-03-15 | 2017-05-31 | Modumetal, Inc. | Revêtements nanostratifiés |
CA2905575C (fr) | 2013-03-15 | 2022-07-12 | Modumetal, Inc. | Procede et appareil d'application en continu de revetements metalliques nanostratifies |
WO2016044720A1 (fr) | 2014-09-18 | 2016-03-24 | Modumetal, Inc. | Procédé et appareil d'application en continu de revêtements métalliques nanostratifiés |
EP2971261A4 (fr) | 2013-03-15 | 2017-05-31 | Modumetal, Inc. | Compositions électrodéposées et alliages nanostratifiés pour des articles préparés par des procédés de fabrication additive |
US10006141B2 (en) * | 2013-06-20 | 2018-06-26 | Baker Hughes, A Ge Company, Llc | Method to produce metal matrix nanocomposite |
CA2961507C (fr) | 2014-09-18 | 2024-04-09 | Modumetal, Inc. | Procedes de preparation d'articles par procedes de depot electrochimique et de fabrication rapide |
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 (fr) | 2017-03-24 | 2018-09-27 | Modumetal, Inc. | Plongeurs de levage dotes de revetements deposes par electrodeposition, et systemes et procedes de production de ceux-ci |
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL68330C (fr) * | 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 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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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 (fr) | 2003-12-31 |
WO2004001100A1 (fr) | 2003-12-31 |
CA2490464C (fr) | 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 (fr) | 2005-03-23 |
DK1516076T3 (da) | 2008-06-23 |
MXPA04011940A (es) | 2005-03-31 |
DE60225352T2 (de) | 2008-06-12 |
EP1826294A1 (fr) | 2007-08-29 |
AU2002321112A1 (en) | 2004-01-06 |
ATE387522T1 (de) | 2008-03-15 |
KR20050024394A (ko) | 2005-03-10 |
BR0215787A (pt) | 2005-03-01 |
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