KR100890819B1 - Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents - Google Patents

Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents Download PDF

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KR100890819B1
KR100890819B1 KR1020047021188A KR20047021188A KR100890819B1 KR 100890819 B1 KR100890819 B1 KR 100890819B1 KR 1020047021188 A KR1020047021188 A KR 1020047021188A KR 20047021188 A KR20047021188 A KR 20047021188A KR 100890819 B1 KR100890819 B1 KR 100890819B1
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KR20050024394A (en
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곤잘레스프란시스코
맥크리어조나단
브룩스이안
엘브우베
토만취거클라우스
팔룸보지노
히바드글렌디.
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인테그란 테크놀로지즈 인코포레이티드
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02Combined electrolytic and electrophoretic processes with charged materials
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02Electroplating of selected surface areas
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04Electroplating with moving electrodes
    • C25D5/06Brush or pad plating
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08Electroplating with moving electrolyte, characterised by electrolyte flow, e.g. jet electroplating
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18Electroplating using modulated, pulsed or reversing current
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/20Electroplating using ultrasonics, vibrations
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/04Tubes; Rings; Hollow bodies

Abstract

The present invention relates to a method of forming a coating or free deposit of a nanocrystalline metal, metal alloy or metal based composite material. The method uses drum plating or partial plating with pulse electrodeposition and non-fixed anodes or cathodes. Also disclosed are new nano-crystalline metal-based composite materials and microcomponents. Also disclosed are methods of forming microcomponents having a particle size of less than 1,000 nm.
Pulse Electrodeposition, Drum Plating, Partial Plating, Coating, Deposits, Micro Components

Description

PROCESS FOR ELECTROPLATING METALLIC AND METALL MATRIX COMPOSITE FOILS, COATINGS AND MICROCOMPONENTS} Methods for Electroplating Foils and Coatings of Metal and Metal Base Composites

The present invention forms a coating of a pure metal, metal alloy or metal matrix composite on a workpiece having an electrically conductive surface layer or which is itself electrically conductive, or by using pulse electrodeposition. A method of forming free-standing deposits of nanocrystalline metals, metal alloys or metal-based composite materials. The method utilizes a drum plating process or a selective plating (brush plating) process for the continuous production of nanocrystalline foils of pure metals, metal alloys or metal based composites. These processes involve pulse electrodeposition and a non-stationary anode or cathode. Also disclosed are new nanocrystalline metal-based composite materials. The invention also relates to a pulse plating method for the production or coating of microcomponents. The invention also relates to microcomponents having a particle size of less than 1,000 nm.

The new method of the present invention is an alloy selected from Ag, Au, Cu, Co, Cr, Ni, Fe, Pb, Pd, Pt, Rh, Ru, Sn, V, W and Zn, and C, P, S and Si Alloys or pure metals of metals selected from the group consisting of elements and metal oxide powders, metal alloy powders and metal 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 metal-based composite materials made of alloys or pure metals containing particulate additives such as PTFE and organic materials such as polymer spheres. In particular, the partial plating process is suitable for field use, such as retrofitting die and molds, turbine plates, steam generator tubes, and core reactor head penetrations in nuclear power plants. Continuous plating processes are particularly suitable for producing nanocrystalline foils, for example for magnetic applications. Continuous plating processes can be applied to high strength, equiaxed microcomponents used in electronics, biomedical, telecommunications, automotive, aerospace and consumer applications.

Nanocrystalline materials, also called ultra-fine particle materials, nanophase materials, or nanometer-sized materials and exhibiting an average particle size of less than 100 nm, are known as sputtering, laser cutting, inert gas condensation, and high energy ball milling. It is known to synthesize by many methods including milling, sol-gel deposition and electrodeposition. Electrodeposition provides the ability to yield large numbers of fully dense metal and metal alloy composites with high production rates and low capital investment in one synthesis step.

The prior art mainly describes pulse electrodeposition to produce nanocrystalline materials.

Elb discloses a process for producing nanocrystalline materials, in particular nanocrystalline nickel, in US Pat. No. 5,352,266 (1994) and US Pat. No. 5,433,797 (1995). The nanocrystalline material is electrodeposited by applying a pulsed direct current to a cathode of an aqueous acidic electrolyzer. The electrolyzer may optionally include a stress reliever. Workpieces of this invention include antiwear coatings, magnetic materials, and hydrogen generating catalysts.

Mori is described in US Pat. No. 5,496,463 (1996) in SiC, BN, Si 3 N 4 , WC, TiC, TiO 2 , Al 2 O 3 , ZnB 3 , diamond, CrC, MoS 2 , coloring materials, PTFE A process and apparatus for composite electrodeposition of a metal composite material containing polytetrafluoroethylene and microcapsules are disclosed. Solid particles are injected into the electrolyte in a fine form.

Adler discloses a drum plater for the production of Cu foils deposited in US Pat. No. 4,240,894 (1980). Cu is plated in a rotating metal drum that is partially immersed in a Cu plating solution and rotated. The Cu foil is peeled off the surface of the floating drum from the electrolyte while covered with electroformed Cu. The rotational speed of the drum and the current density are used to adjust the desired thickness of the Cu foil. The Cu foil peeled from the drum surface is wound with a suitable coil after washing and drying.

Icxi discloses a process of electroplating a workpiece without the need to submerge the surface to be treated in US Pat. No. 2,961,395 (1960). A manually-operated applicator acts as an anode and applies the chemical solution to the metal surface of the workpiece to be plated. The workpiece to be plated acts as a cathode. The passive applicator positive electrode and the workpiece negative electrode having a wick containing electrolyte are connected to a direct current power source to allow a direct current to create a metal coating on the workpiece.

Micromechanical systems (MEMS) are, for example, machines that are used in the fields of electronics, biomedical, telecommunications, automotive, aerospace, consumer goods, and consist of small moving and stationary parts with overall dimensions in the range of 1 to 1,000 μm.

Such component parts are manufactured by, for example, photo-electroforming, which comprises a powder layered to form a desired structure by laser enhanced electroless plating or the like. Is an additional process that is deposited. Lithography, electroforming and molding (LIGA) and other optical lithography related processes are used to solve problems related to aspect ratio (part height to width). Another technique used is silicon micromachining using mask plating and microcontact printing.

It is an object of the present invention to provide a reliable and flexible pulse plating method for forming a coating or free deposit of a nano crystalline metal, metal alloy or metal based composite material.                 

It is a further object of the present invention to provide microcomponents with improved and tailored desired properties and significantly improved property-dependent reliability for microsystems with improved overall performance.

Preferred embodiments of the invention are defined in the corresponding dependent claims.

The present invention provides a pulse plating process consisting of multiple application times with one cathode application time or different current density per cycle, and one or multiple non-application times. Periodic pulse reversal, bipolar waveforms alternately between negative and positive pulses, may optionally be used. The bipolar pulse may be inserted in waveform before, after or between the on pulse and / or before, after or within the non-applied time. The anode pulse current density is usually greater than or equal to the cathode current density. The positive charge (Q positive ) of the "reverse pulse" per cycle is always less than the negative charge (Q negative ).

Cathode pulse application time is 0.1-50 msec (1-50), unapplication time is 0-500 msec (1-100), anode pulse time is 0-50 msec, Preferably it is 1-10 msec. The duty cycle represented by dividing the cathode application time by the sum of the cathode application time, unapplied time and anode time is in the range of 5 to 100%, preferably in the range of 10 to 95%, more preferably 20 To 80%. The frequency of the cathode pulses is in the range of 1 Hz to 1 kHz, more preferably in the range of 10 Hz to 350 Hz.

Nanocrystalline coatings or free deposits of metallic materials are obtained by varying process parameters such as current density, duty cycle, workpiece temperature, plating solution temperature, solution circulation rate over a wide range of states. The list below describes implementation parameter ranges suitable for practicing the present invention.

Average current density (anode or cathode, if defined): 0.01 to 20 A / cm 2 , preferably 0.1 to 20 A / cm 2 , more preferably 1 to 10 A / cm 2

Duty cycle: 5 to 100%

Frequency: 0 to 1,000 Hz

Electrolytic solution temperature: -20 to 85 ° C

Electrolytic Solution Circulation / Wave Rate: 10 liters or less per cm 2 of anode or cathode area (0.0001 to 10 l / min.cm 2 )

Workpiece temperature: -20 to 45 ℃

Anode Vibration Rate: 0 to 350 Vibration / min

Positive to negative linear velocity: 0 to 200 meter / min (brush), 0.003 to 0.16 m / min (drum)

The present invention provides a method of plating nanocrystalline metals, metal based composites and microcomponents at deposition rates of at least 0.05 mm / h, preferably at least 0.075 mm / h, more preferably at least 0.1 mm / h. .                 

In the process of the invention, the electrolyte is preferably 0 to 750 ml / min / A (1 ampere applied and 1 ml solution per minute), preferably 0 to 500, by means of a pump, agitator or ultrasonic agitation. Stir at a rate of ml / min / A.

In the method of the present invention, optionally, particle tablets or stress removers selected from the group of saccharin, coumarin, sodium lauryl sulfate and thiourea may be added to the electrolyte.

The present invention provides a process for plating a nanocrystalline metal based composite material onto a permanent or temporary substrate, the substrate optionally containing at least 5% of particulate material, preferably at least 10% by volume. Contains particulate matter, more preferably at least 20% particulate matter, still more preferably at least 30% particulate matter, most preferably at least 40% particulate matter It contains. The process of the present invention uses a tank, barrel, rack, partial plating (brush plating) process using pulse electrodeposition and a continuous plating (drum plating) process to hard face and blast the projectiles. Pipe fittings used in projectile blunting armor, valve refurbishment, valve and machine tool coatings, energy absorbing armor panels, acoustic damping systems, crude oil extraction plants, retrofitting roller bearing shafts in the railway industry, computer chips, It is used for repairing electric motors and generator parts, repairing scratches on printing rolls, and the like. The particulate material may be Al, Co, Cu, In, Mg, Ni, Si, Sn, V and Zn metal oxide powder, metal alloy powder and metal powder; Nitrides of Al, B and Si; C (graphite or diamond); Carbides of B, Cr, Bi, Si, W; MoS 2 ; And organic materials such as PTFE and polymer spheres. The average particle size of this particulate material is usually less than 10 μm, preferably less than 1,000 nm (1 μm), more preferably 500 nm and even more preferably less than 100 nm.

The method of the present invention includes metal oxide powders, metal alloy powders and metal 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 a process of continuous (drum or belt) plating nanocrystalline foil optionally containing solid particles in suspension state selected from organic materials such as PTFE and polymer spheres. The drum or belt provides a temporary substrate on which the plated foil can be easily and continuously removed.

According to a preferred embodiment of the present invention, the nanocrystalline coating may be prepared by electroplating without having to dip the workpiece to be coated into the plating bath. Particularly in the case where only a part of the workpiece is plated, brush plating or tampon plating is a suitable alternative to solution bath plating without covering the unplated portions. Brush plating apparatus generally employs a soluble or dimensionally stable anode surrounded by an absorbent separator felt to form an anode brush. The brush is rubbed manually or mechanically against the surface to be plated, and the electrolytic solution containing the metal or metal alloy ions to be plated is injected into the separator felt. Optionally, this solution is a metal oxide powder, metal alloy powder and metal of Al, Co, Cu, In, Mg, Ni, Si, Sn, V and Zn to provide the desired properties including hardness, wear resistance, lubrication, etc. powder; Nitrides of Al, B and Si; C (graphite or diamond); Carbides of Bi, Si, W; MoS 2 ; And solid particles in a suspension state selected from organic materials such as PTFE and polymer spheres.

In the case of drums, belts or brushes, the relative motion between the anode and the cathode is in the range of 0 to 600 meters per minute, preferably in the range of 0.003 to 10 meters per minute.

By the process of the present invention, microcomponents up to 1,000 nm in particle size for microsystems including micromechanical systems (MEMS) and micro-optical-systems can be produced. The maximum size of the micro component parts is 1 mm or less, and the ratio between the maximum external dimension and the average particle size of the micro component parts is at least 10, preferably at least 100.

The microcomponents of the present invention preferably have an equiaxed microstructure over the plated component, irrespective of the thickness and structure of the component.

According to yet another aspect of the present invention, there is provided a micro component in which the average particle size is at least one order of magnitude smaller than the external size of the part, thereby maintaining a high level of strength.

The microcomponents according to the invention preferably have improved and tailored desired properties and significantly improved property-dependent reliability of micromechanical systems (MEMS) for microsystems whose overall performance is improved by equiaxed electrical deposits, The transition from particles to columnar grains is eliminated and the particle size of the deposit is reduced to 1,000 nm or less.

Other features and advantages of the present invention will become more apparent from the following detailed description of the invention and examples of the preferred embodiments in conjunction with the illustrative drawings.

1 is a cross-sectional view of a preferred embodiment of a drum plating apparatus.

2 is a cross-sectional view of a preferred embodiment of the brush plating apparatus.

3 is a plan view of a mechanical motion device for generating a mechanical stroke of the anode brush.

1 shows diagrammatically a plating bath or plating vessel 1 filled with an electrolyte solution 2 containing ions of a metal material to be plated. The negative electrode in the form of a rotating drum 3 electrically connected to the power supply 4 is partially submerged in the electrolyte. The drum is rotated by an electric motor with a belt drive (not shown) and the rotational speed is variable. The positive electrode 5 may be a plate or a positive electrode formed in a coincidence shape as shown, and is electrically connected to the power supply device 4. Three different anode arrangements can be used. One is of a conforming type along the shape of the locked part of the drum 3 as shown in FIG. 1, the other is a vertical anode located on the wall of the plating bath 1, and the other is of the plating bath 1. It is a horizontal anode located at the bottom. In the case of the metal material foil 16 electrodeposited to the drum 3, the foil 16 is obtained from the drum surface covered with the electroformed metal material emerging from the electrolyte 2.

2 shows diagrammatically a plated workpiece 6 connected to the negative connection of the power source 4. The anode 5 consists of a handle 7 with a conductive anode brush 8. The anode comprises a conduit 9 which feeds an electrolytic solution 2 from a temperature control tank (not shown) to an anode wick (absorbent separator) 10. Optionally, the electrolyte falling from the absorbent separator 10 can be collected in the tray 11 and recycled to the tank. The absorbent separator 10 containing the electrolyte solution 2 also electrically insulates the positive electrode brush 8 from the workpiece 6 and controls the space between the positive electrode 5 and the negative electrode 6. The anode brush handle 7 may be manually moved over the workpiece during the plating operation, or the movement of the handle may be motorized as shown in FIG. 3.

3 shows diagrammatically a wheel 12 driven by an adjustable motor (not shown). The through arm 13 can be rotatably attached (rotating axis A) to the rotating wheel 12 with a set screw (not shown) and bushing (not shown) at the variable position x of the slot 14. The stroke length can be adjusted by the position x at which the axis of rotation A of the penetrating arm is mounted in the slot 14. In FIG. 3 the through arm 13 is not in a stroke movement but in a neutral position with the axis of rotation A in the center of the wheel 12. The through arm 13 has a second pivot axis B which is defined by a bearing (not shown) and which is slidably mounted on the track 15. As the wheel 12 rotates, the through arm 13 rotates about axis A at position x so that the through arm 13 reciprocates in track 15 and with respect to axis B. The pivot will rotate. An anode 5 having the same characteristics as shown in FIG. 2 is attached to the through arm 13 and moves over the workpiece 6 by movement according to position x. The movement usually shows the shape of the number eight. The positive electrode 5 and the workpiece 6 are connected to the positive and negative connection portions of a power supply (not shown), respectively. The appearance of the movement is very similar to the steam engine.

This invention is for producing nanocrystalline coatings, foils and micro system components by pulse electrodeposition. Optionally, solid particles may be suspended in the electrolyte and included in the deposit.

Nanocrystalline coatings for abrasion resistant applications have thus far been focused on increasing wear resistance by reducing particle size below 100 nm to reduce friction coefficient and increase hardness. It has been found that the wear resistance of nanocrystalline materials can be further improved by including hard particulates in sufficient volume fractions.

Material properties can also be modified by including lubricants (such as MoS 2 and PTFE), for example. Generally, the fine particles are Al, Co, Cu, In, Mg, Ni, Si, Sn, V and Zn metal oxide powder, metal alloy powder and metal powder; 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.

Example 1

Watts bath for nickel with nanocrystalline NiP-B 4 C nanocomposite modified using soluble anodes in nickel plate and Dynatronix (Dynanet PDPR 20-30-100) pulsed power supply Deposited on Ti and mild steel cathodes. The conditions used were as follows:

Anode / anode area: Soluble Anode: Ni plate, 80 cm 2

Cathode / cathode area: Ti or mild steel sheet / approx. 5 cm 2

Cathode: fixed

Anode: fixed

Anode-to-cathode linear rate: N / A

Average Cathode Current Density: 0.06 A / cm 2

t on / t off : 2 msec / 6 msec

Frequency: 125 Hz

Duty cycle: 25%

Deposition time: 1 hour

Deposition Rate: 0.09 mm / hr

Electrolyte Temperature: 60 ℃

Electrolyte circulation rate: Strongly agitated (2-way mechanical impeller)

Basic electrolyte composition

NiSO 4 .7H 2 O 300 g / l

NiCl 2 .6H 2 O 45 g / l

H 3 BO 3 45 g / l

H 3 PO 4 18 g / l

Surfactant with surface tension of less than 30 dyne / cm 0.5-3 ml / l

Sodium Saccharinate 0-2 g / l

Boron carbide 360 g / l, average particle diameter 5 μm

pH 1.5-2.5

Hardness values for metal matrix composites with nanocrystalline matrix structures are generally twice as high as for ordinary coarse-grained metal matrix composites. Also, P a 5.9 wt.%, B 4 to 45% by volume of C containing nanocrystalline NiP-B 4 C hardness and wear properties of the composite material is in the table below, the chemical composition of the equivalent that has the electrodeposited NiP, pure nanocrystalline that It is compared with the hardness and wear characteristics of Ni and pure coarse Ni. Material hardening is controlled by Hall-Petch particle size enhancement, and wear resistance is simultaneously optimized by including B 4 C particles.

NiP-B 4 C Nanocomposite Properties  Sample  Particle size Vickers Hardness [VHN]                                          Taber Wear Index [TWI]  Pure Ni 90 μm                                          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


Example 2

Nanocrystalline cobalt-based nanocomposites were fabricated in a modified cobalt Watts bath using a soluble anode made of cobalt plate and a Dynatronix (Dynanet PDPR 20-30-100) pulse power supply. It was deposited on immersed Ti and mild steel cathodes. The conditions used are as follows:

Anode / anode area: soluble anode (Co plate) / 80 cm 2

Cathode / cathode area: Ti (or mild steel) sheet / approximately 6.5 cm 2

Cathode: fixed

Anode: fixed

Anode-to-cathode linear rate: N / A

Peak Cathode Current Density: 0.100 A / cm 2

Peak Anode Current Density: 0.300 A / cm 2

Cathode t on / t off / Anode t on (t anode ): 16 msec / 0 msec / 2 msec

Frequency: 55.5 Hz

Cathode Duty Cycle: 89%

Anode Duty Cycle: 11%

Deposition time: 1 hour

Deposition Rate: 0.08 mm / hr

Electrolyte Temperature: 60 ℃

Electrolyte circulation rate: 0.15 litres / min / cathode area cm 2 (no pump flow; agitated)

Electrolyte Composition

CoSO 4 .7H 2 O 300 g / l

CoCl 2 .6H 2 O 45 g / l

H 3 BO 3 45 g / l

Saccharin Sodium C 7 H 4 NO 3 SNa 2 g / l

Sodium Lauryl Sulfonate (SLS) C 12 H 25 O 4 SNa 0.1 g / l

SiC 100 g / l, average particle diameter less than 1 micrometer

pH 2.5                 

In the following table, the hardness and wear characteristics of the nanocrystalline CoSiC composites containing 22% by volume of SiC are compared with the hardness and wear characteristics of pure nanocrystalline Co and pure coarse grain Co. Material hardening is controlled by Hall-Petch particle size enhancement, and wear resistance is simultaneously optimized by the inclusion of SiC particulates.

Co nano composites properties  Sample  Particle size Vickers Hardness [VHN]                                          Taber Wear Index [TWI]  Pure Co 5 μm                                          270 32.0  Pure Co 14 nm                                          538 38.0  Co-22SiC 15 nm                                          529 7.1


Metal oxide powders, metal alloy powders, and metal powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn to provide desired properties including hardness, wear resistance, lubrication, magnetic properties, and the like; Nitrides of Al, B and Si; C (graphite or diamond); Carbides of B, Bi, Si, W; And nanocrystalline foils optionally containing solid particulates in a suspension state selected from alloys or pure metals comprising particulate additives such as PTFE and organic materials such as polymer spheres, for example using a drum plating method. Plating was achieved. Nanocrystalline metal foil was deposited on a rotating Ti drum partially immersed in the plating electrolyte. The nanocrystalline foil was electrocast to the drum on the cathode side using a soluble anode in a titanium container filled with anode metal and a pulsed power supply. For the preparation of the alloy foil, a flow of additional cations of a predetermined concentration was continuously applied to the electrolytic solution to maintain a steady state concentration of the alloy cations in the solution. In order to produce metal and alloy foils containing known composite materials, a flow of composite material additives was applied to the plating bath at a predetermined rate so that the additives contained in steady state. Three different anode arrangements can be used. One is a matching anode in the form of a locked part of the drum, the other is a vertical anode located at the wall of the plating bath, and the other is a horizontal anode located at the bottom of the bath. The foil was produced in the average cathode current density range of 0.01 to 5 A / cm 2 , preferably in the average cathode current density range of 0.05 to 0.5 A / cm 2 . Rotational speeds were used to adjust the foil thickness, the speeds ranging from 0.003 to 0.15 rpm (or 20 to 1000 cm / hr), preferably 0.003 to 0.05 rpm (or 20 to 330 cm / hr) Was in.

Example 3: Metal-Based Composite Drum Plating

Nanocrystalline cobalt-based nanocomposites were deposited on a rotating Ti drum while immersed in a modified cobalt Watts bath. Using a soluble cobalt anode in a Ti wire basket and a Dynanet PDPR 20-30-100 pulsed power supply, 15 cm wide nanocrystalline foil was electroformed into the drum on the cathode side. The conditions used are as follows:

Anode / Anode Area: Matched Fusible Anode (Co Piece in Ti Basket) / Undefined                 

Cathode / cathode area: Ti / 600 cm 2

Cathode: rotating

Anode: fixed

Anode-to-cathode linear speed: 0.018 rpm

Average current density: 0.075 A / cm 2

Peak Cathode Current Density: 0.150 A / cm 2

Peak Anode Current Density: N / A

Cathode t on / t off / Anode t on (t anode ): 1 msec / 1 msec / 0 msec

Frequency: 500 Hz

Cathode Duty Cycle: 50%

Anode Duty Cycle: 0%

Deposition time: 1 hour

Deposition Rate: 0.05 mm / hr

Electrolyte Temperature: 65 ℃

Electrolyte circulation rate: 0.15 litres / min / cathode area cm 2 (no pump flow; agitated)

Electrolyte Composition

CoSO 4 .7H 2 O 300 g / l

CoCl 2 .6H 2 O 45 g / l

H 3 BO 3 45 g / l

Saccharin Sodium C 7 H 4 NO 3 SNa 2 g / l

Sodium Lauryl Sulfonate (SLS) C 12 H 25 O 4 SNa 0.1 g / l

Phosphorous Acid 5 g / l

SiC 35 g / l, average particle diameter less than 1 μm

Dispersant 0.5 g / l

pH 1.5

The Co / P-SiC foil had a particle size of 12 nm and a hardness of 690 VHN, containing 1.5% of P and 22% by volume of SiC.

Example 4

Nanocrystalline nickel-iron alloy foil was deposited on a rotating Ti drum partially immersed in a modified cobalt Watts bath. Using a soluble anode in a titanium basket filled with Ni primitives and a Dynanet PDPR 20-30-100 pulsed power supply, 15 cm wide nanocrystalline foil was electroformed into the drum on the cathode side. The conditions used are as follows:

Anode / anode area: matched fusible anode (Ni rounds in metal cage) / undefined

Cathode / cathode area: immersed Ti drum / approx. 600 cm 2

Cathode: rotates at a rate of 0.018 rpm (or 120 cm / hr)                 

Anode: fixed

Anode-to-cathode linear speed: 120 cm / hr

Average Cathode Current Density: 0.07 A / cm 2

t on / t off : 2 msec / 2 msec

Frequency: 250 Hz

Duty cycle: 50%

Manufacture implementation time: 1 day

Deposition Rate: 0.075 mm / hr

Electrolyte Temperature: 60 ℃

Electrolyte circulation rate: 0.15 liters / minute / cathode area cm 2

Electrolyte Composition

NiSO 4 .7H 2 O 260 g / l

NiCl 2 .6H 2 O 45 g / l

FeCl 2 .4H 2 O 12 g / l

H 3 BO 3 45 g / l

Sodium Citrate 46 g / l

Saccharin Sodium 2 g / l

NPA-91 2.2 ml / l                 

pH 2.5

Iron supply composition

FeSO 4 .7H 2 O 81 g / l

FeCl 2 .4H 2 O 11 g / l

H 3 BO 3 13 g / l

Sodium Citrate 9 g / l

H 2 SO 4 4 g / l

Sodium Saccharinate 0.5 g / l

pH 2.2

Addition rate: 0.3 l / hr

Composition: Fe 23-27 wt%

Average particle size: 15 nm

Hardness: 750 Vickers

The partial or brush plating method is a plating method which can be carried out by carrying out a selective plating of a local part of the workpiece without dipping the workpiece into the plating bath. There is a significant difference between the use of selective plating and the use of plating baths and plating baths. In the case of the partial plating method, it is difficult to accurately define the cathode region, and thus the cathode current density and / or the peak current density are variable and generally unknown. For example, in the case of flat anodes, if the same anode area is used during the plating operation, the anode current density and / or the peak current density can be determined. In the case of shaped anodes the anode area cannot be accurately determined, for example in the case of shaped anodes and shaped cathodes the "effective" anode area also changes during the plating operation. Partial plating is performed by moving the anode, covered with an absorbent separator wick, and containing the electrolyte back and forth over the workpiece, generally by the operator until the desired overall area is coated to the thickness required.

Partial plating techniques are particularly suitable for repair or refurbishment of workpieces because brush plating facilities are portable, easy to operate and do not require dismantling of the system including the workpiece to be plated. Brush plating also allows plating of parts that are too large to immerse in the bath. Brush plating is used to provide a coating that improves corrosion resistance, abrasion resistance, and appearance (decoration plating), and can also be used to protect worn or mismachined parts. Brush plating systems and plating solutions can be purchased from Sifco Selective Plating, Cleveland, Ohio, which also provides mechanization and / or automation equipment for high volume manufacturing operations. . The plating equipment used includes an anode (DSA or soluble) covered with an absorbent, an electrically nonconductive material and an insulated handle. In the case of a DSA anode, the anode is typically made of graphite or titanium coated with Pt, and may comprise means for temperature control by a heat exchanger system. For example, the electrolyte used can be passed through the anode to heat or cool and maintain the desired temperature range. The absorbent separator material contains the electrolytic solution to distribute the electrolytic solution between the anode and the workpiece (cathode), to prevent short circuit between the anode and the cathode and to sweep the surface of the area to be plated. This mechanical scrubbing or rubbing action on the workpiece during the plating process affects the quality of the coating and the surface finish and allows the plating to be done at a high speed. The partially plated electrolyte has a composition that allows for the production of coatings that meet the criteria over a wide temperature range of -20 ° C to 85 ° C. Partial plating is often applied to workpieces at ambient temperatures of -20 ° C to 45 ° C because the workpieces are often larger than the areas to be coated. Unlike "normal" electroplating operations, the temperature of the anode, cathode and electrolyte can be essentially different for partial plating. Salting of electrolyte components may occur at low temperatures, and it may be necessary to reheat the electrolyte periodically or continuously to dissolve the precipitated chemical components.

A Sifco brush plating device (model 3030-30A Max) was installed. A graphite anode tip was inserted into the cotton pouch separator and attached to a mechanized through arm or moved back and forth over the workpiece by an operator to generate a "brushing motion". The anode assembly was immersed in the plating solution, and the coating was deposited by rubbing the plating tool into a working area filled with a cathode made of other substrates. Peristaltic pumps were used to supply the electrolyte to the brush plating tool at a predetermined rate. The electrolyte dropped from the workpiece to a tray that also served as a "plating solution storage container" and was recycled from the tray to the electrolyzer. The anode portion has flow holes / conduits at the bottom to facilitate electrolyte distribution and electrolyte / workpiece contact. The anode is fixed to the penetrating arm and the periodic movement is adjusted to provide a uniform stroke of the substrate surface of the anode. The rotation speed is adjusted to increase or decrease the relative anode / cathode movement speed as well as the anode / substrate contact time at any particular location. Brush plating was typically performed at a speed of about 35 to 175 frequencies per minute, with a speed of 50 to 85 frequencies per minute being optimal. Electrical connection is made to the brush handle (anode) and direct electrical connection to the workpiece (cathode). The coating can be deposited on a number of substrates including copper, 1018 low carbon steel, 4130 high carbon steel, 304 stainless steel, external 2.5 inch steel pipes and welddlad I625 pipes. The cathode size was 8 cm 2 except for an outer diameter 2.5 inch steel pipe with a 3 cm wide strip exposed around the outer diameter and a welded Clad I625 pipe where a defect repair procedure was performed.

Dynatron's programmable pulse plating power supply (Dynanet PDPR 20-30-100) was used.

Standard substrate cleaning and operating procedures provided by Sifco were used.

Example 5

Nanocrystalline pure nickel was deposited as an anode with an area of 8 cm 2 and the anode was 35 cm 2 and the equipment described above was used. Typically, the area of the workpiece is essentially larger than the anode. In this example, the large anode will move constantly, but the workpiece (cathode) was chosen to be essentially smaller than the anode in order to always cover the entire workpiece so that the cathode current density can be determined. Since non-consumable anodes were used, NiCO 3 was periodically added to the plating bath to maintain the desired Ni 2+ concentration. The conditions used are as follows:

Anode / anode area: graphite / 35 cm 2

Cathode / cathode area: mild steel / 8 cm 2

Cathode: fixed

Anode: Automatically mechanical vibration at 50 frequencies per minute

Anode-to-cathode linear speed: 125 cm / min

Average Cathode Current Density: 0.2 A / cm 2

t on / t off : 8 msec / 2 msec

Frequency: 100 Hz

Duty cycle: 80%

Deposition time: 1 hour

Deposition Rate: 0.125 mm / hr

Electrolyte Temperature: 60 ℃

Electrolyte circulation rate: solution 10 ml / min / cathode area cm 2 or solution 220 ml / min / average applied current A

Electrolyte Composition                 

NiSO 4 .7H 2 O 300 g / l

NiCl 2 .6H 2 O 45 g / l

H 3 BO 3 45 g / l

Sodium Saccharinate 2 g / l

NPA-91 3 ml / l

pH 2.5

Average particle size: 19 nm

Hardness: 600 Vickers

Example 6

Nanocrystalline Co was deposited under the following conditions using the same equipment as described above.

Anode / anode area: graphite / 35 cm 2

Cathode / cathode area: mild steel / 8 cm 2

Cathode: fixed

Anode: Automatically mechanical vibration at 50 frequencies per minute

Anode-to-cathode linear speed: 125 cm / min

Average Cathode Current Density: 0.10 A / cm 2

t on / t off : 2 msec / 6 msec

Frequency: 125 Hz

Duty cycle: 25%

Deposition time: 1 hour

Deposition Rate: 0.05 mm / hr

Electrolyte Temperature: 65 ℃

Electrolyte circulation rate: Solution 10 ml / min / cathode area cm 2 or Solution 440 ml / min / average applied current A

Electrolyte Composition

CoSO 4 .7H 2 O 300 g / l

CoCl 2 .6H 2 O 45 g / l

H 3 BO 3 45 g / l

Sodium Saccharinate C 7 H 4 NO 3 SNa 2 g / l

Sodium Lauryl Sulfonate (SLS) C 12 H 25 O 4 SNa 0.1 g / l

pH 2.5

Average particle size: 13 nm

Hardness: 600 Vickers

Example 7

Nanocrystalline Ni / 20% Fe was deposited using the equipment described above. A 1.5 inch wide band was plated on the outer diameter (OD) of the 2.5 inch pipe, which was done by rotating the pipe along its longitudinal axis while maintaining a fixed anode under the following conditions.

Anode / anode area / effective anode area: graphite / 35 cm 2 / undefined

Cathode / cathode area: 2.5 inch outer diameter steel pipe made of 210A1 carbon steel / undefined

Cathode: rotates at 12 rpm

Anode: fixed

Cathode to anode linear speed: 20 cm / min

Average Cathode Current Density: Undefined

Total applied current: 3.5 A

t on / t off : 2 msec / 6 msec

Frequency: 125 Hz

Duty cycle: 25%

Deposition time: 1 hour

Deposition Rate: 0.05 mm / hr

Electrolyte temperature: 55 ℃

Electrolyte circulation rate: solution 0.44 l / min / applied current A

Electrolyte Composition                 

NiSO 4 .7H 2 O 260 g / l

NiCl 2 .6H 2 O 45 g / l

FeCl 2 .4H 2 O 7.8 g / l

H 3 BO 3 45 g / l

Sodium citrate Na 3 C 6 H 5 O 7 2H 2 O 30 g / l

Sodium Saccharinate 2 g / l

NPA-91 1 ml / l

pH 3.0

Average particle size: 15 nm

Hardness: 750 Vickers

Example 8

Using the same equipment as in Example 1, the defects (grooves) of the weld clad pipe section were filled with nanocrystalline Ni. The groove is impossible to determine the exact surface area due to the rough finish of the defect, but is about 4.5 cm long, 0.5 cm wide and about 0.175 mm in average depth. Nano Ni is plated in the defect area until the area surrounding the defect is peeled off and the original thickness is restored.

Anode / anode area: graphite / 35 cm 2

Cathode / cathode area: I625 / not determined                 

Cathode: fixed

Anode: Automatically mechanical vibration at 50 frequencies per minute

Anode-to-cathode linear speed: 125 cm / min

Average Cathode Current Density: Undefined

t on / t off : 2 msec / 6 msec

Frequency: 125 Hz

Duty cycle: 25%

Deposition time: 2 hours

Deposition Rate: 0.087 mm / hr

Electrolyte temperature: 55 ℃

Electrolyte circulation rate: 0.44 l / min solution / average applied current A

Electrolyte Composition

NiSO 4 .7H 2 O 300 g / l

NiCl 2 .6H 2 O 45 g / l

H 3 BO 3 45 g / l

Sodium Saccharinate 2 g / l

NPA-91 3 ml / l

pH 3.0

Average particle size: 20 nm                 

Hardness: 600 Vickers

Micro components with an overall size of less than 1,000 μm (1 mm) are becoming increasingly important for applications in the electronics, biomedical, telecommunications, automotive, aerospace and consumer applications. Metal macro system components having a maximum overall dimension of 1 cm to 1 m or larger containing normal particle size materials (1-1,000 μm) indicate the ratio between the maximum dimension and the particle size range ranging from 10 to 10 6 . This number represents the number of particles over the largest part dimension. When the maximum component size using ordinary particle size materials is reduced to less than 1 mm, the component can be made of one or several particles and the ratio between the maximum microcomponent dimensions and the particle size range approaches 1 do. That is, one or only a few particles extend over the whole part, which is undesirable. In order to increase the component reliability of microcomponents, small particle materials should be used to increase the ratio between the maximum part dimension and the particle size range to 10 or more, and this kind of material has a particle size of 10 to 10,000 times smaller than ordinary materials Indicates a value.

For conventional LIGA and other plated microcomponents, electrodeposition initially begins with the fine particle size of the substrate material. However, as the deposition thickness increases in the growth direction, transition to columnar particles is generally observed. The thickness of the columnar particles is usually in the range of several to tens of micrometers, but their length can reach several hundred micrometers. As a result of such a structure, as the deposition thickness increases, anisotropic properties develop and only a few particles reach a critical thickness covering the entire cross-section of the component, which is less than 5-10 microns in width. Further reduction in the thickness of the component creates a bamboo structure, greatly reducing the strength. Therefore, the microstructure of the electrodeposited microcomponents currently in use does not meet the property requirements at all, both in the width and thickness of the component, based on the particle shape and the average particle size.

To date, parts made of conventional particle sized materials known to have serious reliability problems with regard to mechanical properties such as Young modulus, yield strength, tensile strength, fatigue strength and creep behavior have been described in detail. It has been found to be extremely sensitive to the processing parameters involved. Many of the problems encountered are due to the fact that important microstructural properties (ie particle size, particle shape, particle orientation) are not proportional to the external size of the component, which is a strange property that is not usually observed in the visible component of the same material. Make a difference.

Example 9

Metal microspring fingers are used to contact the pad count and dense IC chips and to transfer power and signals to and from the chips. The springs provide high pitch compliant electrical contacts for various connection structures including chip scale semiconductor packages, high density interposer connectors and probe contactors. The large number of parallel interface structures and assemblies permits high speed testing of isolated integrated circuit devices attached to a compliant carrier and allows the test electronics to be placed in close proximity to the integrated circuit device under test.                 

The micro spring fingers require high yield strength and ductility. A 25 μm thick nanocrystalline Ni layer was plated on a 500 μm long gold-coated CrMo finger under the following conditions.

Anode / anode area: Ni / 4.5 × 10 -3 cm 2

Cathode / cathode area: CrMo coated with gold / about 1 cm 2

Cathode: fixed

Anode: fixed

Anode-to-cathode linear speed: 0 cm / min

Average Cathode Current Density: 50 mA / cm 2

t on / t off : 10 msec / 20 msec

Frequency: 33 Hz

Duty cycle: 33%

Deposition time: 120 minutes

Deposition Rate: 0.05 mm / hr

Electrolyte Temperature: 60 ℃

Electrolyte Circulation Speed: None

Electrolyte Composition

NiSO 4 .7H 2 O 300 g / l

NiCl 2 .6H 2 O 45 g / l

H 3 BO 3 45 g / l

Sodium Saccharinate 2 g / l

NPA-91 3 ml / l

pH 3.0

Average particle size: 15-20 nm

Hardness: 600 Vickers

The nano-finger exhibits significantly higher contact compared to "traditional particle size" fingers.

Claims (88)

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  54. A method of cathodic electrodeposition of a selected metallic material on a permanent or temporary substrate in the form of nanocrystalline having an average grain size of less than 100 nm at a deposition rate of at least 0.05 mm / h,
    Providing a water-soluble electrolyte containing ions of the metallic material;
    Stirring the electrolyte at a stirring rate ranging from 0.0001 to 10 l / min.cm 2 (liter per minute per cm 2 of anode or cathode area) or a stirring rate ranging from 1 to 750 ml / min / A,
    Passing one or a plurality of cathodic-current pulses between the anode and the cathode.
  55. 55. The method of claim 54, wherein the duty cycle is in the range of 5 to 100%.
  56. The cathode electrodeposition method of claim 54 or 55, wherein the frequency of the cathode-current pulse is in the range of 0 to 1000 Hz.
  57. 55. The method of claim 54, wherein the one or more cathode-current pulses between the anode and the cathode have a peak current density in the range of 0.01 to 20 A / cm 2 .
  58. 59. The method of claim 57, wherein the peak current density of the cathode-current pulse is in the range of 0.1 to 20 A / cm 2 .
  59. 59. The method of claim 58, wherein the peak current density of the cathode-current pulse is in the range of 1-10 A / cm 2 .
  60. 55. The method of claim 54, wherein the selected metal material is selected from the group consisting of (a) Ag, Au, Cu, Co, Cr, Ni, Fe, Pb, Pd, Rt, Rh, Ru, Sn, V, W, Zn. Or (b) an alloy containing at least one of an alloying element selected from the group consisting of C, P, S and Si and an element of the group (a).
  61. 55. The method of claim 54, wherein the t cathode-on period is in the range of 0.1 to 50 msec, the t cathode-off period is in the range of 0 to 500 msec, and the t anode-on period is in the range of 0 to 50 msec. Cathode electrodeposition method characterized in that.
  62. The method of claim 55, wherein the duty cycle is in the range of 10 to 95%.
  63. 63. The method of claim 62, wherein the duty cycle is in the range of 20 to 80%.
  64. 55. The cathode electrodeposition method of claim 54, wherein the deposition rate is at least 0.075 mm / h.
  65. 65. The method of claim 64, wherein the deposition rate is at least 0.1 mm / h.
  66. 55. The method of claim 54, comprising stirring the electrolyte at a stirring rate in the range of 1 to 500 ml / min / A.
  67. 55. The method of claim 54, comprising stirring the electrolyte by a pump, a stirrer, or by ultrasonic agitation.
  68. 55. The method of claim 54, wherein there is a relative movement between the anode and the cathode.
  69. 69. The method of claim 68, wherein the rate of relative movement between the anode and the cathode is in the range of 0 to 600 m / min.
  70. 70. The method of claim 69, wherein the rate of relative movement between the anode and the cathode is in the range of 0.003 to 10 m / min.
  71. 69. The method of claim 68, wherein the relative movement is by rotation of the anode and cathode relative to each other.
  72. 72. The method of claim 71, wherein the relative rotational speeds of the positive and negative electrodes relative to each other are in the range of 0.003 to 0.15 rpm.
  73. 73. The method of claim 72, wherein the rotational speed of rotation of the anode and cathode relative to each other is in the range of 0.003 to 0.05 rpm.
  74. 69. The method of claim 68, wherein the relative motion is by mechanized motion that generates strokes of the anode and cathode with respect to each other.
  75. 69. The method of claim 68, wherein the anode is enclosed in an absorbent separator.
  76. 55. The method of claim 54, wherein the electrolyte is a grain refining agent or stress relieving agent selected from the group of saccharin, coumarin, sodium lauryl sulfate, and thiourea a cathode electrodeposition method comprising a stress relieving agent).
  77. The method of claim 54,
    The electrolyte solution is Al, Co, Cu, In, Mg, Ni, Si, Sn, V and Zn metal oxide powder, metal alloy powder or pure metal powder; Nitrides of Al, B and Si; C (graphite or diamond); Carbides of B, Bi, Si, W; Or in suspension state particulate additive selected from organic materials such as PTFE and polymer spheres,
    The electrodeposited metallic material contains at least 5% of the particulate additive.
  78. 78. The method of claim 77 wherein the electrodeposited metallic material contains at least 10% of the particulate additive.
  79. 78. The method of claim 77 wherein the electrodeposited metallic material contains at least 20% of the particulate additive.
  80. 78. The method of claim 77 wherein the electrodeposited metallic material contains at least 30% of the particulate additive.
  81. 78. The method of claim 77 wherein the electrodeposited metallic material contains at least 40% of the particulate additive.
  82. 78. The method of claim 77, wherein the average particle size of the particulate additive is less than 10 μm.
  83. 83. The method of claim 82, wherein the average particle size of the particulate additive is less than 1000 nm.
  84. 84. The method of claim 83, wherein the average particle size of the particulate additive is less than 500 nm.
  85. 85. The method of claim 84, wherein the average particle size of the particulate additive is less than 100 nm.
  86. A micro component manufactured by the cathode electrodeposition method according to claim 54,
    A microcomponent having a maximum dimension of 1 mm, an average particle size of 1000 nm or less, and a ratio between the maximum dimension and the average particle size of greater than 10.
  87. 87. The microcomponent of claim 86, wherein the ratio between the largest dimension and the average particle size is greater than 100.
  88. 87. The microcomponents of claim 86, having an equiaxed micro structure.
KR1020047021188A 2002-06-25 2002-06-25 Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents KR100890819B1 (en)

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