DE60225352T2 - METHOD OF ELECTROPLATING METALLIC AND METAL MATRIX COMPOSITE FILMS, COATINGS AND MICROCOMPONENTS - Google Patents

Abstract

The invention relates to a process for forming coatings or free-standing deposits of nanocrystalline metals, metal alloys or metal matrix composites. The process employs drum plating or selective plating processes involving pulse electrodeposition and a non-stationary anode or cathode. Novel nanocrystalline metal matrix composites and micro components are disclosed as well. Also described is a process for forming micro components with grain sizes below 1,000nm.

Description

Field of the invention

The This invention relates to a method of forming coatings of pure metals, metal alloys or metal matrix composites on a workpiece, which is electrically conductive is or an electrically conductive surface layer contains or forming free-standing supports of nanocrystalline metals, Metal alloys or metal matrix composites by use of pulse electro deposition. The method uses a drum plating method for the continuous production of nanocrystalline films of pure Metals, metal alloys or metal matrix composites or a selective plating (brush plating) method, the procedures pulse electro-deposition and a non-stationary anode or cathode. New nanocrystalline metal matrix composites are also disclosed. The invention also relates to a Pulse plating method for the production or coating of microcomponents. The invention also refers to microcomponents with grain sizes 1000 nm.

The new process can be applied to wear-resistant Supports and films 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 other alloying elements selected from C, P, S and Si, and metal matrix composites of pure metals or alloys with particle 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 beads. The selective plating process is particularly suitable for in situ or outdoor applications, such as the repair or reprocessing of nozzles and molds, turbine blades, Steam generating tubes, reactor core head breakthroughs of nuclear power plants and the like. The continuous plating process is particularly suitable for the production of nanocrystalline films, e.g. For magnetic applications. The method can be applied to high strength, equiaxed Microcomponents for use in electronics, biomedicine, telecommunications, used in the automotive, space and consumer applications become.

Description of the Prior Art / Background the invention

Nanocrystalline Materials referred to as ultrafine grained materials , nanophase materials or nanometer-sized materials, which average grain sizes smaller or equal to 100 nm are indicated by a number of known Process, including sputtering, laser ablation, Inert gas condensation, high energy ball milling, sol gel deposition and electro deposition. Electrodeposition provides the ability a big Number of high density metals and metal alloy compositions at high production rates and low capital investment requirements in a single synthesis step.

Of the The prior art primarily describes the use of pulse electrodeposition for the production of nanocrystalline materials.

Erb describes in US 5,352,266 (1994) and in US 5,433,797 (1995) describe a process for producing nanocrystalline materials, in particular nanocrystalline nickel. The nanocrystalline material is electrodeposited on a cathode in an aqueous acidic electrolytic cell by applying a pulsed direct current. The cell optionally also contains voltage lowering means. The products of the invention include abrasion resistant layers, magnetic materials, and hydrogen generation catalysts.

Mori describes in US 5,496,463 (1996) a method and apparatus for composite electroplating of a metallic material comprising 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 contains. The solid particles are introduced into the electrolyte in a fine form.

Adler describes in US 4,240,894 (1980) discloses a drum plater for electrodeposited Cu film production. Cu is plated on a rotating metal drum which is partially immersed and rotates in a copper plating solution. The copper foil is peeled from the drum surface, which emerges from the electrolyte, which is plated with electroformed Cu. The rotational speed of the drum and the current are used to set the desired thickness of the copper foil. The peeled off from the drum surface copper foil is subsequently washed and dried and in a ge suitable coil wound.

Icxi reveals in US 2,961,395 (1960) describe a method for electroplating an article without the need to sink the surface being treated into a plating tank. The hand-operated applicator serves as the anode and supplies chemical solutions to the metal surface of the workpiece to be plated. The workpiece to be plated serves as a cathode. The hand applicator anode with the mesh containing the electrolyte and the workpiece cathode are connected to a DC power source to produce a metal layer on the workpiece by passing a DC current.

Micromechanical Systems (MEMS) are machines that are constructed of small, moving and stationary Parts having an overall dimension ranging from 1 to 1000 μm, e.g. for use in electronics, biomedicine, telecommunications, Automotive, space and consumer technologies.

Such Components are e.g. produced by photoelectrical education, what an additional Method is in which powder is deposited in layers, to the desired Structure, e.g. Laser enhanced electroless plating to build. Lithography, electro-forming and casting (LIGA) and other photolithography related methods are used to obtain aspect ratio (part height to width) to overcome problems in question. Other techniques used include silicon micromachining by mask plating and microcontact printing.

Summary:

It It is an object of the invention to provide a reliable and flexible pulse plating method for forming coatings of freestanding deposits of nanocrystalline metals, metal alloys or metal matrix composites to offer.

It Another object of the invention is to provide microcomponents with clarity improved property-dependent reliability and tailor made desired Properties for to provide improved microsystems in the overall performance.

preferred embodiments of the invention are defined in the respective dependent claims.

The present invention provides a pulse plating method which consists 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 that alternates between cathodal pulses and anodic pulses, may optionally also be used. The cathodic pulses may be inserted into the waveform before, after or between the on pulses 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 "backward pulse" per cycle is always smaller than the cathodic charge (Q _cathodic ).

The An-times of cathodic pulses range from 0.1 to 50 ms (1-50), off-times from 0 to 500 ms (1-100) and anodic pulse times range from 0 to 50 ms, preferably from 1 to 10 ms. The duty cycle, expressed as the cathodic on-times divided by the sum of the cathodic on-times, the off-times and anodic times ranges from 5 to 100%, preferably from 10 to 95%, and more preferably from 20 to 80%. The frequency of the cathodic Pulse ranges from 1 Hz to 1 kHz, and more preferably from 10 Hz to 350 Hz.

• Durchschnittliche Stromdichte (falls bestimmbar, anodisch oder kathodisch): 0,01 bis 20 A/cm², bevorzugt 0,1 bis 20 A/cm², bevorzugter 1 bis 10 A/cm²
• Arbeitszyklus 5 bis 100%
• Frequenz: 0 bis 1000 Hz
• Elektrolytlösungstemperatur: –20 bis 85°C
• Elektrolytlösungsumwälzungs-/Umruhr-Raten: ≤ 10 Liter pro Minute pro cm²
• Anoden- oder Kathodenfläche (0,0001 bis 101/min. cm²)
• Werkstücktemperatur: –20 bis 45°C
• Anodenschwingungsrate: 0 bis 350 Schwingungen/min
• Lineare Geschwindigkeit Anode gegen Kathode: 0 bis 200 m/min (Bürste) 0,003 bis 0,16 m/min (Trommel).

Nanocrystalline coatings or free-standing deposits of metallic materials are obtained by varying process parameters such as current density, duty cycle, workpiece temperature, coating solution temperature, solution recirculation rates, over a wide range of conditions. The following list describes suitable operating parameter ranges for carrying out the invention:

• Average current density (if determinable, anodic or cathodic): 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 1000 Hz
• Electrolytic solution temperature: -20 to 85 ° C
• Electrolyte solution circulation / circulation rates: ≤ 10 liters per minute per cm ²
• Anode or cathode area (0.0001 to 101 / min. Cm ² )
• Workpiece temperature: -20 to 45 ° C
• Anode oscillation rate: 0 to 350 cycles / min
• Linear velocity anode to cathode: 0 to 200 m / min (brush) 0.003 to 0.16 m / min (drum).

The The present invention preferably provides a method for Plating of nanocrystalline metals, metal matrix composites and Microcomponents with deposition rates of at least 0.05 mm / h, preferably from at least 0.075 mm / h, and more preferably at least 0.1 mm / h.

In In the process of the present invention, the electrolyte may be preferred by means of pumps, whirring or ultrasonic excitation with rates of 0 to 750 ml / min / A (ml solution per minute per ampere average current passed), preferably at rates of 0 to 500 ml / min / A.

In The process of the present invention may optionally include a grain refiner or a stress relief agent added to the electrolyte, selected from the group of saccharin, coumarin, sodium lauryl sulfate and Thiourea.

This invention provides a process for plating nanocrystalline metal matrix composites on a permanent or temporary substrate, optionally containing at least 5% by volume of particulate matter, preferably 10% by volume of particulate matter, more preferably 20% by volume. % of particulate matter, more preferably 30 vol% of particulate matter, and most preferably 40 vol% of particulate matter, for applications such as hard topcoats, projectile-truncated armor, valve freshener, valved and valved Rotary tool coatings, energy absorbing armor plates, noise reduction systems, connectors to piping joints, eg used in oil drilling applications, refurbishment of roller bearing axles in the railway industry, computer chips, repair of electric motor and generator parts, repair of grooves in pressure rollers, using tank, drum -, frame, selective (eg Bür cladding) and continuous (eg, drum cladding) plating processes using pulse electrodeposition. The particulate matter may 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 or polymer beads. The average particle size of the particulates is typically below 10 microns, preferably below 1000 nm (1 micron), preferably 500 nm, and more preferably below 100 nm.

The process of this invention optionally offers a process for continuously (drum or belt) plating nanocrystalline films which optionally contain solid particles in solution 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 beads 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 film can be easily and continuously removed.

According to a preferred embodiment of the invention, it is also possible to produce nanocrystalline layers by electroplating without the need to submerge the article to be coated in a coating bath. Brush or tampon plating is a suitable alternative to tank plating, particularly if only a portion of the workpiece is to be plated, without the need to mask areas that are not to be plated. The brush plating apparatus typically uses a dissolving or dimensionally stable anode that is wrapped in an absorbent spacer felt to form the anode brush. The brush is rubbed against the surface to be plated, in a manual or mechanized manner, and an electrolyte solution containing ions of the metal or metal alloys to be plated is injected into the spacer felt. Optionally, this solution also contains solid particles in solution 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 beads to impart desired properties including hardness, wear resistance, lubrication, and the like.

in the Case of Drum, Tape or Brush Plating ranges the relative movement between anode and cathode from 0 to 600 meters per minute, preferably from 0.003 to 10 meters per minute.

In the process of this invention microcomponents for microsystems, including micromes chanic systems (MEMS) and micro-optical systems, with grain sizes equal to or smaller than 1000 nm. The maximum dimension of the microcomponent part is equal to or less than 1 mm, and the ratio between the maximum outer dimension of the microcomponent part and the average grain size is equal to or greater than 10, preferably greater than 100.

The Microcomponents of the present invention may preferably be an equiaxed one Microstructure over having the clad component which is relatively independent of the thickness and the structure the component is.

It Another aspect of the present invention is microcomponents be provided, in which the average grain size a Magnitude smaller than the outer dimension of the part, thereby maintaining a high degree of strength is.

The Microcomponents according to this Invention have a significantly improved property-dependent reliability and improved customized desired Properties of MEMS structures for in their overall performance improved microsystems through preferred equiaxed electrodepositions, which exclude the fine grain of columnar grain transition in the microcomponent, and at the same time reducing the grain size of the deposits below 1000 nm.

Preferred embodiments of the invention:

Other Features and advantages of this invention will become clearer in the following detailed description and examples of the preferred embodiments of the invention, together with the attached schematic drawings, in which:

1 a cross-sectional view of a preferred embodiment of a drum plating device shows;

2 a cross-sectional view of a preferred embodiment of a brush plating device shows; and

3 a top view of a mechanized moving means for generating a mechanized stroke of the anode brush shows.

1 schematically shows a plating tank or container 1 that with an electrolyte 2 is filled, which contains the ions of the metallic material to be plated. Partially immersed in the electrolyte is the cathode in the form of a rotating drum 3 , which are electrically connected to a power source 4 connected is. The drum is rotated by an electric motor (not shown) via a belt drive and the rotational speed is variable. The Ano de 5 may be a plate or conformal anode, as shown, which is electrically connected to the power source 4 connected is. Three different anode arrangements can be used: conformal anodes, as in 1 shown which contour of the submerged portion of the drum 3 Follow, vertical anodes, attached to the walls of the tank 1 are positioned, and horizontal anodes at the bottom of the tank 1 are positioned. In the case of a slide 16 made of metallic material, which is attached to the drum 3 Electrodeposited, the film becomes 16 from the drum surface, which consists of the electrolyte 2 emerges, pulled, which is covered with the electro-formed metallic material.

2 schematically shows a workpiece to be plated 6 connected to the negative output of the power source 4 connected is. The anode 5 includes a handle 7 , with a conductive anode brush 8th , The anode contains channels 9 for supplying the electrolyte solution 2 from a temperature-controlled tank (not shown) to the anode mesh (absorbent spacer) 10 , That of the absorbent spacer 10 Dripping electrolyte is optional in a dish 11 collected and returned to the tank. The absorbent spacer 10 which is the electrolyte 2 contains, the anode brush isolated 8th also electrically from the workpiece 6 and sets the distance between anode 5 and cathode 6 one. The anode brush handle 4 can over the workpiece 6 be moved manually during the plating process, alternatively, the movement may be motorized, as in 3 shown.

3 schematically shows a wheel 12 which is driven by an adjustable speed motor (not shown). A cross-arm 13 can rotate (axis of rotation A) to the rotating wheel 12 at different positions x at a slot 14 be attached with a bushing and an adjusting screw (not shown) to produce a desired stroke or stroke. The stroke length can be one be set by the position x (radius), in which the axis of rotation A of the transversely movable arm at the slot 14 is attached. In

3 is the transversely moving arm 13 shown to be in a non-hub, neutral position with the axis of rotation A in the center of the wheel 12 is. The transversely moving arm 13 has a second pivot axis B which is defined by a bearing (not shown) slidable in a guideway 15 is appropriate. When the wheel 12 turns, causes the rotation of the transversely movable arm 13 about axis A at position x the transversely movable arm 13 , in the guideway 15 to move back and forth and to pivot about axis B. An anode 5 which have the same characteristics as in 2 is shown on the transversely movable arm 13 attached, and moves over the workpiece 6 in a movement that depends on the position x. Usually the movement has the form of the numeral 8th , The anode 5 and the workpiece 6 are respectively connected to positive and negative outputs of the power source (not shown). The kinematic ratio is very similar to that of a steam engine.

These Invention relates to the production of nanocrystalline coatings, Films and microsystem components by pulse electrodeposition. Optionally, solid particles are dissolved in the electrolyte and become inserted into the deposit.

Nanocrystalline Coatings for Abrasion-resistant applications are nowadays aimed at increasing Wear resistance by raising the hardness and reducing the coefficient of friction by Komgrößenverringerung Below 100 nm. It has now been found that a contribution of sufficient Volume fraction of hard particles, the wear resistance of nanocrystalline materials.

The material properties can also be changed by, for example, the addition of lubricants (such as MoS ₂ and PTFE). In general, the particulates selected from the group of metal powders, metal alloy powders and metal oxide powders may be selected from Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; Nitrides of Al, B and Si; C (graphite and diamond), carbides of B, Bi, Si, W; MoS ₂ and organic materials such as PTFE and polymer spheres.

example 1

• Anode/Anodenfläche: Lösliche Anode: Ni-Platte, 80 cm²
• Kathode/Kathodenfläche: Ti oder unlegierter Stahltafel/ca. 5 cm²
• Kathode: fest
• Anode: fest
• Lineare Geschwindigkeit Anode gegen Kathode: nicht zutreffend
• Durchschnittliche kathodische Stromdichte: 0.06A/cm²
• t_an/t_aus: 2ms/6ms
• Frequenz: 125 Hz
• Arbeitszyklus: 25%
• Ablagerungszeit: 1 Stunde
• Ablagerungsrate: 0,09 mm/h
• Elektrolyttemperatur: 60°C
• Elektrolytumwälzrate: kräftiges Umrühren (mechanisches Zweirichtungs-Flügelrad)

Nanocrystalline NiP-B ₄ C nanocomposites were deposited on Ti and unalloyed 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) -Pulsstromversorgung. The following conditions were used:

• Anode / anode area: Soluble anode: Ni plate, 80 cm ²
• Cathode / cathode surface: Ti or unalloyed steel plate / approx. 5 cm ²
• Cathode: firm
• Anode: fixed
• Linear velocity anode to cathode: not applicable
• Average cathodic current density: 0.06A / cm ²
• t _on / t _off : 2ms / 6ms
• Frequency: 125 Hz
• Duty cycle: 25%
• Deposition time: 1 hour
• Deposition rate: 0.09 mm / h
• Electrolyte temperature: 60 ° C
• Electrolyte circulation rate: vigorous stirring (mechanical bidirectional impeller)

• 300 g/l NiSO₄ × 7H₂O
• 45 g/l NiCl₂ × 6H₂O
• 45 g/l H₃BO₃
• 18 g/l H₃PO₄
• 0,5–3 ml/l Grenzflächen-aktiver Stoff zu einer Oberflächenspannung von < 30 Dyn/cm
• 0–2g/l Natriumsaccharinat
• 360 g/l Borcarbid, 5 μm durchschnittlicher Partikeldurchmesser pH 1,5–2,5.

Basic Electrolyte Formulation:

• 300 g / l NiSO ₄ × 7H ₂ O
• 45 g / l NiCl ₂ × 6H ₂ O
• 45 g / l H ₃ BO ₃
• 18 g / l H ₃ PO ₄
• 0.5-3 ml / L of interface active substance to a surface tension of <30 dynes / cm
• 0-2g / l sodium saccharinate
• 360 g / l boron carbide, 5 μm average particle diameter pH 1.5-2.5.

The hardness values of metal matrix composites which have a nanocrystalline matrix structure are typically twice as high as conventional coarsely grained metal matrix composites. In addition, the hardness and wear properties of nanocrystalline NiP-B ₄ C composites containing 5.9 wt% P and 45 vol% B ₄ C are compared with those of pure coarse-grained Ni, pure nanocrystalline Ni and electro-deposited Ni -P of an equivalent chemical composition in the attached table. The material cure is controlled by Hall-Petch grain size enhancement, while the abrasion wear resistance is simultaneously optimized by incorporation of B ₄ C particles. Table: NiP-B ₄ C nanocomposite properties sample Korngöße 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

• Anode/Anodenfläche: lösliche Anode (Co-Platte)/80 cm²
• Kathode/Kathodenfläche: Ti-(oder unlegierter Stahl)-Tafel/ca. 6,5 cm²
• Kathode: fest
• Anode: fest
• Lineare Geschwindigkeit Anode gegen Kathode: nicht zutreffend
• Kathodische Spitzenstromdichte: 0,100 A/cm²
• Anodische Spitzenstromdichte: 0,300 A/cm²
• Kathodische t_an/t_aus /anodische t_an(t_anodisch): 16 ms/0 ms/2 ms
• Frequenz: 55,5 Hz
• Kathodischer Arbeitszyklus: 89%
• Anodischer Arbeitszyklus: 11%
• Ablagerungszeit: 1 h
• Ablagerungsrate: 0,08 mm/h
• Elektrolyttemperatur: 60°C
• Elektrolytumwälzrate: 0,15 Liter/min/cm² Kathodenfläche (kein Pumpenfluss; Umrühren)

Nanocrystalline Co-based nanocomposites were deposited on titanium and unalloyed steel cathodes immersed in a modified Watts bath for cobalt, using a soluble anode made from a cobalt plate, and a Dynatronics (Dynanet PDPR 20-30). 100) -Pulsstromversorgung. The following conditions were used:

• Anode / anode area: soluble anode (co-plate) / 80 cm ²
• Cathode / cathode surface: Ti (or unalloyed steel) panel / approx. 6.5 cm ²
• Cathode: firm
• Anode: fixed
• Linear velocity anode to cathode: not applicable
• Cathodic peak current density: 0.100 A / cm ²
• Anodic peak current density: 0.300 A / cm ²
• Cathodic t _an / t _off / anodic t _an (t _anodic ): 16 ms / 0 ms / 2 ms
• Frequency: 55.5 Hz
• Cathodic duty cycle: 89%
• Anodic duty cycle: 11%
• Deposition time: 1 h
• Deposition rate: 0.08 mm / h
• Electrolyte temperature: 60 ° C
• Electrolyte recirculation rate: 0.15 liter / min / cm ² cathode area (no pump flow; stir)

• 300 g/l CoSO₄ × 7H₂O
• 45 g/l CoCl₂ × 6H₂O
• 45 g/l H₃BO₃
• 2 g/l C₇H₄NO₃SNa Natriumsaccharinat
• 0,1 g/l C₁₂H₂₅O₄SNa Natriumlaurylsulfat (SLS)
• 100 g/l SiC, < 1 μm durchschnittlicher Partikeldurchmesser pH 2,5

Electrolyte Formulation:

• 300 g / l CoSO ₄ × 7H ₂ O
• 45 g / l CoCl ₂ × 6H ₂ O
• 45 g / l H ₃ BO ₃
• 2 g / l C ₇ H ₄ NO ₃ SNa sodium saccharinate
• 0.1 g / l C ₁₂ H ₂₅ O ₄ SNa sodium lauryl sulfate (SLS)
• 100 g / l SiC, <1 μm average particle diameter pH 2.5

In the attached table, hardness and abrasion properties of a nanocrystalline Co-SiC composite containing 22 vol.% SiC are compared with those of pure coarse Co and pure nanocrystalline Co. Hall Petch grain size enhancement controls material hardening, while abrasion wear resistance Resistance is optimized at the same time by the admixture of a material consisting of SiC particles. Table: Co-nanocomposite properties sample grain 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

Continuous plating has been carried out to produce films, for example using drum plating nanocrystalline films optionally containing solid particles in solution selected from pure metals or alloys of pure metals or alloys with particulate additives such as metal powder, metal alloy powder and metal oxide powder 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; and organic materials such as PTFE and polymer beads to impart desired properties including hardness, wear resistance, lubrication, magnetic properties, and the like. Nanocrystalline metal foils were deposited on a rotating Ti drum partially immersed in a plating electrolyte. The nanocrystalline film was cathodically electro-formed on the drum using a soluble anode made of a titanium container filled with an anode metal and using a pulse power supply. For alloy sheet fabrication, a stream of additional cations at a predetermined concentration was continuously added to the electrolyte solution to establish an equilibrium state concentration of the alloying cations in solution. For metal and alloy foil production, containing matrix composites, a stream of the composite additive was added to the plating bath at a predetermined rate to establish an equilibrium content of the additive. Three different anode arrangements may be used: conformal anodes following the contour of the submerged portion of the drum, vertical anodes positioned on the walls of the container, and horizontal anodes positioned at the bottom of the container. Films were made at average cathodic current densities ranging from 0.01 to 5 A / cm ^2, and preferably from 0.05 to 0.5 A / cm ² . The rotational speed was used to adjust the film thickness, and this speed ranged from 0.003 to 0.15 rpm (or 20 to 1000 cm / h), and preferably from 0.003 to 0.05 rpm (or 20 to 330 cm / h).

Example 3: Metal Matrix Composite Drum Plating

• Anode/Anodenfläche: konforme lösliche Anode (Co-Stücke in Ti-Korb)/nicht bestimmt
• Kathode/Kathodenfläche: Ti 600 cm²
• Kathode: drehend
• Anode: fest
• Lineare Geschwindigkeit Anode gegen Kathode: 0,018 Upm
• Durchschnittsstromdichte: 0,075 A/cm²
• Kathodische Spitzenstromdichte: 0,150 A/cm²
• Anodische Spitzenstromdichte: nicht zutreffend
• Kathodische t_an/t_aus/anodische t_an(t_anodisch): 1 ms/1 ms/0 ms
• Frequenz: 500 Hz
• Kathodischer Arbeitszyklus: 50%
• Anodischer Arbeitszyklus: 0%
• Ablagerungszeit: 1 h
• Ablagerungsrate: 0,05 mm/h
• Elektrolyttemperatur: 65°C
• Elektrolytumwälzrate: 0,15 Liter/min/cm² Kathodenfläche (kein Pumpenfluss; Umrühren)

Nanocrystalline Co-based nanocomposites were deposited on a rotating Ti drum as described in Example 3 immersed in a modified Watts bath for cobalt. The nanocrystalline film, 15 cm wide, was cathodically electro-formed on the drum 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:

• Anode / anode area: conformable soluble anode (co-pieces in Ti basket) / not determined
• Cathode / cathode area: Ti 600 cm ²
• Cathode: turning
• Anode: fixed
• Linear velocity anode vs. cathode: 0.018 rpm
• Average current density: 0.075 A / cm ²
• Cathodic peak current density: 0.150 A / cm ²
• Anodic peak current density: not applicable
• Cathodic t _an / t _off / anodic t _an (t _anodic ): 1 ms / 1 ms / 0 ms
• Frequency: 500 Hz
• Cathodic duty cycle: 50%
• Anodic duty cycle: 0%
• Deposition time: 1 h
• Deposition rate: 0.05 mm / h
• Electrolyte temperature: 65 ° C
• Electrolyte recirculation rate: 0.15 liter / min / cm ² cathode area (no pump flow; stir)

• 300 g/l CoSO₄ × 7H₂O
• 45 g/l CoCl₂ × 6H₂O
• 45 g/l H₃BO₃
• 2 g/l C₇H₄NO₃SNa Natriumsaccharinat
• 0,1 g/l C₁₂H₂₅O₄SNa Natriumlaurylsulfat (SLS)
• 5 g/l phosphorige Säure
• 35 g/l SiC, < 1 μm mittlerer Partikeldurchmesser
• .5 g/l Dispersionsmittel
• pH 1,5

Electrolyte Formulation:

• 300 g / l CoSO ₄ × 7H ₂ O
• 45 g / l CoCl ₂ × 6H ₂ O
• 45 g / l H ₃ BO ₃
• 2 g / l C ₇ H ₄ NO ₃ SNa sodium saccharinate
• 0.1 g / l C ₁₂ H ₂₅ O ₄ SNa sodium lauryl sulfate (SLS)
• 5 g / l phosphorous acid
• 35 g / l SiC, <1 μm mean particle diameter
• .5 g / l of dispersant
• pH 1.5

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

Example 4

• Anode/Anodenfläche: konforme lösliche Anode (Ni-Rundstücke in einem Metallkäfig)/unbestimmt
• Kathode/Kathodenfläche: untergetauchte Ti-Trommel/ungefähr 600 cm²
• Kathode: drehend mit 0,018 Upm (oder 120 cm/h)
• Anode: fest
• Lineare Geschwindigkeit Anode gegen Kathode: 120 cm/h
• Durchschnittliche kathodische Stromdichte: 0,07 A/cm²
• t_an/t_aus: 2 ms/2 ms
• Frequenz: 250 Hz
• Arbeitszyklus: 50%
• Herstellungslaufzeit: 1 Tag
• Ablagerungsrate: 0,075 mm/h
• Elektrolyttemperatur: 60°C
• Elektrolytumwälzrate: 0,15 Liter/min/cm² Kathodenfläche
• Elektrolyt-Formulierung:
• 260 g/l NiSO₄ × 7H₂O
• 45 g/l NiCl₂ × 6H₂O
• 12 g/l FeCl₂ × 4H₂O
• 45 g/l H₃BO₃
• 46 g/l Natriumzitrat
• 2 g/l Natriumsaccharinat
• 2,2 ml/l NPA-91
• pH 2,5
• Eisenspeisungs-Formulierung:
• 81 g/l FeSO₄·7H₂O
• 11 g/l FeCl₂·4H₂O
• 13 g/l H₃BO₃
• 9 g/l Natriumcitrat
• 4 g/L H₂SO₄
• 0,5 g/l Natriumsaccharinat
• pH 2,2
• Rate der Beimengung: 0,3 l/h
• Zusammensetzung: 23–27 Gew.% Fe
• Durchschnittliche Korngröße: 15 nm
• Härte: 750 Vickers

Nanocrystalline nickel-iron alloy foils were deposited on a rotating Ti drum which was partially immersed in a modified Watts bath for nickel. The nanocrystalline film, 15 cm wide, was electroformed cathodically on the drum, using a soluble anode made of a titanium wire basket filled with Ni round stock and a Dynatron nics (Dynanet PDPR 50-250-750) pulse power supply. The following conditions were used:

• Anode / anode surface: conformable soluble anode (Ni round pieces in a metal cage) / indefinite
• Cathode / Cathode Area: Submerged Ti-drum / about 600 cm ²
• Cathode: rotating at 0.018 rpm (or 120 cm / h)
• Anode: fixed
• Linear velocity anode to cathode: 120 cm / h
• Average cathodic current density: 0.07 A / cm ²
• t _on / t _off : 2 ms / 2 ms
• Frequency: 250 Hz
• Duty cycle: 50%
• Production time: 1 day
• Deposition rate: 0.075 mm / h
• Electrolyte temperature: 60 ° C
• Electrolyte recirculation rate: 0.15 liter / min / cm ² cathode area
• Electrolyte Formulation:
• 260 g / l NiSO ₄ .7H ₂ O
• 45 g / l NiCl ₂ × 6H ₂ O
• 12 g / l FeCl ₂ × 4H ₂ O
• 45 g / l H ₃ BO ₃
• 46 g / l sodium citrate
• 2 g / l sodium saccharinate
• 2.2 ml / l NPA-91
• pH 2.5
• Iron linefeed formulation:
• 81 g / l FeSO ₄ .7H ₂ O
• 11 g / l FeCl ₂ .4H ₂ O
• 13 g / l H ₃ BO ₃
• 9 g / l sodium citrate
• 4 g / LH ₂ SO ₄
• 0.5 g / l sodium saccharinate
• pH 2.2
• Rate of addition: 0.3 l / h
• Composition: 23-27% by weight Fe
• Average grain size: 15 nm
• Hardness: 750 Vickers

Selective or brush plating is a portable method of selectively plating localized areas on a workpiece without submerging the article in 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 generally unknown. The anodic current density and / or peak current density can be determined, provided that the same anode area is used during the plating operation, eg in the case of flat anodes. In the case out For example, in the case of a shaped anode and a shaped cathode, the "effective" anode area also changes during the plating process. Selective plating is accomplished by moving the anode, which is surrounded with an absorbent spacer braid and containing the electrolyte, back and forth over the workpiece, typically performed by an operator, until the desired total area is coated to the required thickness.

Selective plating techniques are particularly suitable for repairing and refurbishing articles because the brush plating assemblies are portable, easy to operate, and do not require disassembly of the system containing the workpiece to be plated. Brush plating also allows the plating of parts that are too large to be immersed in plating tanks. Brush plating is used to provide coatings for improved corrosion resistance, improved wear, improved appearance (decorative plating), and can be used to recover worn or mis-worked parts. Brush plating systems and plating solutions are commercially available, for example from Sifco Selective Plating, Cleveland, Ohio, which also offers mechanized and / or automated tooling for use in large scale production operations. The plating tools used include the anode ( ^DSA® or soluble) surrounded by an absorbent, an electrically nonconductive material and an insulated handle. In the case of DSA ^® anodes anodes are typically made of graphite or Pt-coated titanium and may contain means for regulating the temperature by means of a heat exchanger system. For example, the electrolyte used may be heated or cooled and passed through the anode to maintain the desired temperature range. The absorbent spacer material contains and distributes the electrolyte solution between the anode and the workpiece (cathode), prevents short circuits between the anode and the cathode, and brushes against the surface of the surface to be plated. This mechanical rubbing or brushing motion applied to the workpiece during the plating process affects the quality and surface finish of the coating and allows for fast plating rates. Selective plating electrolytes are formulated to produce acceptable coatings over a wide temperature range, ranging from low, about -20 ° C to 85 ° C. Since the workpiece is often large compared to the surface being coated, selective plating is often applied to a workpiece at ambient temperature, ranging from low, about -20 ° C to about high 45 ° C. Unlike "typical" electroplating operations, in the case of selective plating, the temperature of the anode, the cathode and the electrolyte can vary significantly. Salting out of electrolyte components can occur at low temperatures and the electrolyte may need to be re-heated periodically or continuously to dissolve any precipitated chemicals.

A Sifco brush plating unit (model 3030-30 A max.) Was set up. The graphite anode tip was inserted into a cotton bag spacer and either attached to a mechanized, transversely movable arm to create the "brushing motion", or manually moved by an operator back and forward over the workpiece, 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 working surface composed of various substrates. A peristaltic pump was used to feed the electrolyte at predetermined rates into the brush plating tool. The electrolyte was allowed to drip from the workpiece into a tray which also served as a "plating solution reservoir" from which it was returned to the electrolyte tank. The anode had flow holes / channels in the bottom surface to ensure good electrolyte distribution and good electrolyte / workpiece contact. The anode was attached to a transversely movable arm and the circular motion was adjusted to allow uniform strokes of the anode with respect to the substrate surface. The rotational speed was adjusted to increase or decrease the relative anode / cathode travel speed as well as the anode / substrate contact time at any single location. Brush plating was normally carried out at a rate of about 35-175 oscillations per minute, at a rate of 50-85 oscillations per minute, which is optimal. Electrical contacts were made on the brush handle (anode) and directly on the workpiece (cathode). Coatings were deposited on a number of substrates including copper, 1018 low carbon steel, 4130 high carbon steel, 304 stainless steel, a 2.5 inch (6.35 cm) outside diameter steel tube, and a weld covered I625 tube. The cathode size was 8 cm ² except for the 2.5 inch (6.35 cm) outer diameter steel tube where a 3 cm wide strip was exposed around the outer diameter and the weld covered I625 tube to which a damage was applied. Repair process was performed.

A Dynatronics Programmable Pulse Plating Power Supply (Dynanet PDPR 20-30-100) was used.

From Sifco provided standard substrate cleaning and activation procedures used.

Example 5:

• Anode/Anodenfläche: Graphit/35 cm²
• Kathode/Kathodenfläche: unlegierter Stahl/8 cm²
• Kathode: stationär
• Anode: mechanisch automatisiert mit 50 Schwingungen pro Minute oszillierend Lineare Geschwindigkeit Anode gegen Kathode: 125 cm/min
• Durchschnittliche kathodische Stromdichte: 0,2 A/cm²
• t_an/t_aus: 8 ms/2 ms
• Frequenz: 100 Hz
• Arbeitszyklus: 80%
• Ablagerungszeit: 1 h
• Ablagerungsrate: 0,125 mm/h
• Elektrolyt-Temperatur: 60°C
• Elektrolyt-Umwälzrate: 10 ml Lösung pro Minute pro cm² Anodenfläche oder 220 ml Lösung pro Minute pro Ampere durchgelassenem durchschnittlichem Strom

Nanocrystalline pure nickel was supported on an 8 cm ² area electrode with a 35 cm ² anode, using the construction described. Usually, the workpiece has a much larger area than the anode. In this example, a workpiece (cathode) was chosen to be substantially smaller than the anode to ensure that the oversized anode, while kept constantly moving, always covered the entire workpiece to allow determination of the cathode current density. Since a non-consumable anode was used, NiCO _{3 was} periodically added to the plating bath to maintain the desired Ni ²⁺ concentration. The following conditions were used:

• Anode / anode surface: graphite / 35 cm ²
• Cathode / cathode surface: unalloyed steel / 8 cm ²
• Cathode: stationary
• Anode: mechanically automated oscillating at 50 oscillations per minute Linear velocity anode to cathode: 125 cm / min
• Average cathodic current density: 0.2 A / cm ²
• t _on / t _off : 8 ms / 2 ms
• Frequency: 100 Hz
• Duty cycle: 80%
• Deposition time: 1 h
• Deposition rate: 0.125 mm / h
• Electrolyte temperature: 60 ° C
• Electrolyte recirculation rate: 10 ml of solution per minute per cm ^{2 of} anode area or 220 ml of solution per minute per amp of average current passed

• 300 g/l NiSO₄ × 7H₂O
• 45 g/l NiCl₂ × 6H₂O
• 45 g/l H₃BO₃
• 2 g/l Natriumsaccharinat
• 3 ml/l NPA-91
• pH 2,5
• Durchschnittliche Korngröße: 19 nm
• Härte: 600 Vickers

Electrolyte Formulation:

• 300 g / l NiSO ₄ × 7H ₂ O
• 45 g / l NiCl ₂ × 6H ₂ O
• 45 g / l H ₃ BO ₃
• 2 g / l sodium saccharinate
• 3 ml / l NPA-91
• pH 2.5
• Average grain size: 19 nm
• Hardness: 600 Vickers

Example 6:

• Anode/Anodenfläche: Graphit/35 cm²
• Kathode/Kathodenfläche: unlegierter Stahl/8 cm²
• Kathode: stationär
• Anode: mechanisch automatisiert mit 50 Schwingungen pro Minute oszillierend
• Lineare Geschwindigkeit Anode gegen Kathode: 125 cm/min
• Durchschnittliche kathodische Stromdichte: 0,10 A/cm²
• t_an/t_aus: 2 ms/6 ms
• Frequenz: 125 Hz
• Arbeitszyklus: 25%
• Ablagerungszeit: 1 h
• Ablagerungsrate: 0,05 mm/h
• Elektrolyt-Temperatur: 65°C
• Elektrolyt-Umwälzrate: 10 ml Lösung pro Minute pro cm² Anodenfläche oder 440 ml Lösung pro Minute pro Ampere durchgelassenem durchschnittlichem Strom

Nanocrystalline Co was deposited using the same structure described under the following conditions:

• Anode / anode surface: graphite / 35 cm ²
• Cathode / cathode surface: unalloyed steel / 8 cm ²
• Cathode: stationary
• Anode: mechanically oscillated with 50 oscillations per minute
• Linear velocity anode to cathode: 125 cm / min
• Average cathodic current density: 0.10 A / cm ²
• t _on / t _off : 2 ms / 6 ms
• Frequency: 125 Hz
• Duty cycle: 25%
• Deposition time: 1 h
• Deposition rate: 0.05 mm / h
• Electrolyte temperature: 65 ° C
• Electrolyte recirculation rate: 10 ml of solution per minute per cm ^{2 of} anode area or 440 ml of solution per minute per amp of average current passed

• 300 g/l NiSO₄ 7H₂O
• 45 g/l NiCl₂ 6H₂O
• 45 g/l H₃BO₃
• 2 g/l Natriumsaccharinat
• 0,1 g/l C₇H₄NO₃Sna Natriumlaurylsulfat (SLS)
• pH 2,5
• Durchschnittliche Korngröße: 13 nm
• Härte: 600 Vickers

Electrolyte Formulation:

• 300 g / l NiSO ₄ .7H ₂ O
• 45 g / l NiCl ₂ 6H ₂ O
• 45 g / l H ₃ BO ₃
• 2 g / l sodium saccharinate
• 0.1 g / l C ₇ H ₄ NO ₃ Sna Sodium Lauryl Sulfate (SLS)
• pH 2.5
• Average grain size: 13 nm
• Hardness: 600 Vickers

Example 7:

• Anode/Anodenfläche/effektive Anodenfläche: Graphit/35 cm²/unbestimmt
• Kathode/Kathodenfläche: 2,5 Inch Außendurchmesser-Stahlröhre, hergestellt aus 2101A1 Kohlenstoffstahl/unbestimmt
• Kathode: rotierend mit 12 Upm
• Anode: stationär
• Lineare Geschwindigkeit Anode gegen Kathode: 20 cm/min
• Durchschnittliche kathodische Stromdichte: unbestimmt
• Durchgelassener Gesamtstrom: 3,5 A
• t_an/t_aus: 2 ms/6 ms
• Frequenz: 125 Hz
• Arbeitszyklus: 25%
• Ablagerungszeit: 1 h
• Ablagerungsrate: 0,05 mm/h
• Elektrolyt-Temperatur: 55°C
• Elektrolyt-Umwälzrate: 0,441 Lösung pro Minute pro durchgelassenem Ampere

Nanocrystalline Ni / 20% Fe was deposited using the previously described build-up. A 1.5 inch wide tape was plated on the outside diameter of a 2.5 inch (6.35 cm) tube by rotating the tube along its longitudinal axis while maintaining a solid anode under the following conditions:

• Anode / anode area / effective anode area: graphite / 35 cm ² / undetermined
• Cathode / Cathode Area: 2.5 inch outer diameter steel tube made from 2101A1 carbon steel / undetermined
• Cathode: rotating at 12 rpm
• Anode: stationary
• Linear velocity anode to cathode: 20 cm / min
• Average cathodic current density: indefinite
• Permitted total current: 3.5 A
• t _on / t _off : 2 ms / 6 ms
• Frequency: 125 Hz
• Duty cycle: 25%
• Deposition time: 1 h
• Deposition rate: 0.05 mm / h
• Electrolyte temperature: 55 ° C
• Electrolyte recirculation rate: 0.441 solution per minute per amp passed

• 260 g/l NiSO₄ × 7H₂O
• 45 g/l NiCl₂ × 6H₂O
• 7,8 g/l FeCl₂ × 4H₂O
• 45 g/l H₃BO₃
• 30 g/l Na₃C₆H₅O₇.2H₂O Natriumzitrat
• 2 g/l Natriumsaccharinat
• 1 ml/l NPA-91
• pH 3,0
• Durchschnittliche Korngröße: 15 nm
• Härte: 750 Vickers

Electrolyte Formulation:

• 260 g / l NiSO ₄ .7H ₂ O
• 45 g / l NiCl ₂ × 6H ₂ O
• 7.8 g / l FeCl ₂ × 4H ₂ O
• 45 g / l H ₃ BO ₃
• 30 g / l Na ₃ C ₆ H ₅ O ₇ .2H ₂ O sodium citrate
• 2 g / l sodium saccharinate
• 1 ml / l NPA-91
• pH 3.0
• Average grain size: 15 nm
• Hardness: 750 Vickers

Example 8:

• Anode/Anodenfläche: Graphit/35 cm²
• Kathode/Kathodenfläche: I625/unbestimmt
• Kathode: stationär
• Anode: mechanisch automatisiert mit 50 Schwingungen pro Minute oszillierend Lineare Geschwindigkeit Anode gegen Kathode: 125 cm/min Durchsc
• hnittliche kathodische Stromdichte: unbestimmt
• t_an/t_aus: 2 ms/6 ms
• Frequenz: 125 Hz
• Arbeitszyklus: 25%
• Ablagerungszeit: 2 h
• Ablagerungsrate: 0,087 mm/h
• Elektrolyt-Temperatur: 55°C
• Elektrolyt-Umwälzrate: 0,441 Lösung pro Minute pro Ampere durchgelassenem
• Durchschnittsstrom

A defect (notch) in a welded tube section was filled with nanocrystalline Ni using the same construction as in Example 1. The notch was about 4.5 cm long, 0.5 cm wide and had an average depth of about 0.175 mm, although the rough finish of the defect made it impossible to determine its exact surface area. The area surrounding the defect was covered and Nano Ni was plated on the defect area until its original thickness was restored.

• Anode / anode surface: graphite / 35 cm ²
• Cathode / Cathode area: I625 / indeterminate
• Cathode: stationary
• Anode: mechanically automated oscillating at 50 oscillations per minute Linear velocity anode to cathode: 125 cm / min
• Average cathodic current density: indefinite
• t _on / t _off : 2 ms / 6 ms
• Frequency: 125 Hz
• Duty cycle: 25%
• Deposition time: 2 h
• Deposition rate: 0.087 mm / h
• Electrolyte temperature: 55 ° C
• Electrolyte recirculation rate: 0.441 solution per minute per amp passed
• Average current

• 300 g/l NiSO₄ × 7H₂O
• 45 g/l NiCl₂ × 6H₂O
• 45 g/l H₃BO₃
• 2 g/l Natriumsaccharinat
• 3 ml/l NPA-91
• pH 3,0
• Durchschnittliche Korngröße: 20 nm
• Härte: 600 Vickers

Electrolyte Formulation:

• 300 g / l NiSO ₄ × 7H ₂ O
• 45 g / l NiCl ₂ × 6H ₂ O
• 45 g / l H ₃ BO ₃
• 2 g / l sodium saccharinate
• 3 ml / l NPA-91
• pH 3.0
• Average grain size: 20 nm
• Hardness: 600 Vickers

Microcomponents having dimensions of less than 1000 μm (1 mm) in all are becoming increasingly important for use in electronic, biomedical, telecommunications, automotive, space and consumer applications. Metallic macrosystem components having a maximum overall dimension of from 1 cm to over 1 m, which contain conventional grain size materials (1-1000 μm) exhibit a ratio of maximum dimension to grain size ranges of 10 to 10 ⁶ . This number reflects the number of grains over the maximum part dimension. When the maximum size of the component is reduced to less than 1 mm using conventional grain size material, the component may potentially be made from only a few grains, or a single grain, and the ratio between the maximum dimension of the microcomponent and the grain size ranges is addressed 1. In other words, a single or a few grains extend along the entire part, which is undesirable. To increase component reliability of microcomponents, the ratio of maximum component size to grain size ranges must be increased above 10 by using a more granular material, as this class of material typically exhibits grain size values 10 to 10,000 times smaller than those of conventional materials.

For conventional LIGA and other plated microcomponents begin electroplating initially with a fine grain size at the Substrate material. With increasing deposition thickness in the growth direction becomes ordinary the transition to columnar grains observed. The thickness of the columnar Grains are enough typically from a few to a few tens of microns while their Some length Can reach hundreds of microns. The consequence of such Structures is the development of anisotropic properties with increasing deposition thickness, and achieving a critical Thickness, in which only a few grains the entire cross section cover the components, with widths below 5 to 10 microns. Another waste in the thickness of a component to a bamboo structure, resulting in a significant loss leads in strength. Therefore, the microstructure of electro-deposited microcomponents, which are currently in use, completely inappropriate regarding property requirements both over the width as well as the thickness of the component based on the grain shape and average grain size.

So far were parts made of conventional grain size materials which were known to have serious reliability issues mechanical properties such as Young's modulus, Limit tensile strength, fatigue strength and to suffer creeping behavior, they are known to be extremely sensitive On processing parameters are related to the structure of these components are connected. Many of the problems encountered were caused by Inappropriate scaling of key microstructure features (i.e., grain size, grain shape, Grain orientation) with the outer size of the component, which is too unusual Property variations resulted, which are usually the same for macroscopic components Material were not observed.

Example 9:

Metal micro-spring fingers are used to make IC chips with high pad count and density, and energy and signals to and from to transport the chips. The feathers offer high value electrical contacts for a variety of interconnect structures, including chip-scaled Semiconductor packages, high density interconnect connectors and sensor contacts. The massive parallel liner structures and assemblies enable High-speed testing of separate integrated circuit components, those on a yielding carrier are fixed, and allow test electronics, in close proximity to the be located to be tested integrated circuit components.

• Anode/Anodenfläche: Ni/4,5 × 10^-3 cm²
• Kathode/Kathodenfläche: goldplattiertes CrMo/ungefähr 1 cm²
• Kathode: stationär
• Anode: stationär
• Lineare Geschwindigkeit Anode gegen Kathode: 0 cm/min
• Durchschnittliche kathodische Stromdichte: 50 mA/cm²
• t_an/t_aus: 10 ms/20 ms
• Frequenz: 33 Hz
• Arbeitszyklus: 33%
• Ablagerungszeit: 120 Minuten
• Ablagerungsrate: 0,05 mm/h
• Elektrolyt-Temperatur: 60°C
• Elektrolyt-Umwälzungsrate: keine

The micro-spring fingers require high resistance to deformation and ductility. A 25 μm thick layer Nanocrystalline Ni was plated on 500 μm gold plated CrMo fingers using the following conditions:

• Anode / anode area: Ni / 4.5 × 10 ^-3 cm ²
• Cathode / Cathode area: gold plated CrMo / about 1 cm ²
• Cathode: stationary
• Anode: stationary
• Linear velocity anode to cathode: 0 cm / min
• Average cathodic current density: 50 mA / cm ²
• t _on / t _off : 10 ms / 20 ms
• Frequency: 33 Hz
• Duty cycle: 33%
• Deposition time: 120 minutes
• Deposition rate: 0.05 mm / h
• Electrolyte temperature: 60 ° C
• Electrolyte recirculation rate: none

• 300 g/l NiSO₄ × 7H₂O
• 45 g/l NiCl₂ × 6H₂O
• 45 g/l H₃BO₃
• 2 g/l Natriumsaccharinat
• 3 ml/l NPA-91
• pH 3,0
• Durchschnittliche Korngröße: 15–20 nm
• Härte: 600 Vickers

Electrolyte Formulation:

• 300 g / l NiSO ₄ × 7H ₂ O
• 45 g / l NiCl ₂ × 6H ₂ O
• 45 g / l H ₃ BO ₃
• 2 g / l sodium saccharinate
• 3 ml / l NPA-91
• pH 3.0
• Average grain size: 15-20 nm
• Hardness: 600 Vickers

The Nanofinger showed a significantly higher contact force compared with fingers "conventional Grain size ".

Claims (27)

A method of cathodic electrodeposition of a selected metallic material on a permanent or temporary substrate in nanocrystalline form having an average grain size of less than 100 nm, using pulse electrodeposition, at a deposition rate of at least 0.05 mm / hr, comprising: providing an aqueous Electrolyte containing ions of the metallic material, maintaining the electrolyte at a temperature in the range of 0 to 85 ° C, providing an anode and a cathode in contact with the electrolyte, passing single or multiple DC cathode current pulses between the anode and cathode at a cathode current pulse frequency in a range between 0 and 1000 Hz at pulsed intervals during which the current flows for a t- _on period in the range of about 0.1 to 50 ms and does not flow for a t _{out time} period in the range of 0 to 500 ms, and passing through one or more at intervals during which the current flows for a t _anodic period in the range of 0 to 50 ms, with a duty cycle in the range of 5 to 100% and a cathodic charge (Q _cathodic ) per interval always greater than an anodic charge (Q _anodic ). The method of claim 1, characterized in that the single or multiple DC cathode current pulses between the anode and the cathode have a peak current density in the range of about 0.01 to 20 A / cm ² . A method according to claim 2, characterized in that the peak current density of the cathode current pulses in the range of about 0.1 to 20 A / cm ² , preferably in the range of 1 to 10 A / cm ² . Method according to one of claims 1 to 3, characterized that the selected metallic material (a) is a pure metal selected from the group consisting of Ag, Au, Cu, Co, Cr, Ni, Fe, Pb, Pd, Rt, Rh, Ru, Sn, V, W, Zn or (b) an alloy consisting of at least one of the elements of group (a) and alloying elements selected from the group consisting of C, P, S and Si. Method according to one of claims 1 to 4, characterized in that t is _at timeperiod in the range of 1 to about 50 msec, the t _off timeperiod in the range of about 1 to 100 msec and the t _anodic -Zeitperi ode in the range of about 1 to 10 ms. Method according to one of claims 1 to 5, characterized that the duty cycle is preferably in the range of 10 to 95%, and more preferably in the range of 20 to 80%. Method according to one of claims 1 to 6, characterized the cathode current pulse frequency ranges from 10 Hz to 350 Hz. Method according to one of claims 1 to 7, characterized the deposition rate is preferably at least 0.075 mm / h and more preferably at least 0.1 mm / h. Method according to one of claims 1 to 8, characterized by stirring of the electrolyte at a stirring speed in the range of 0 to 750 ml / min / A, preferably in the range of 1 to 500 ml / min / A. Method according to one of claims 1 to 8, characterized by stirring the electrolyte at a stirring speed in the range of 0.0001 to 10 l / min / cm ² (liters per minute per cm ² anode or cathode surface). A method according to claim 9 or 10, characterized by stirring of the electrolyte by means of pumps, stirrers or ultrasonic excitation. Method according to one of claims 1 to 11, characterized by a relative movement between the anode and cathode. Method according to claim 12, characterized in that that the speed of relative movement between anode and Cathode from 0 to 600 m / min ranges, preferably from 0.003 to 10 m / min. Method according to claim 12, characterized in that that the relative movement by rotation of the anode and the cathode is achieved relative to each other. A method according to claim 14, characterized by a rotation speed of the rotation of the anode and the cathode relative to each other, which is from 0.003 to 0.15 rpm and preferred from 0.003 to 0.05 rpm. Method according to claim 12 or 13, characterized that the relative motion through a a mechanized movement generating hub of the anode and the cathode is achieved relative to each other. Method according to claim 12 or 16, characterized that the anode is wound in an absorbent spacer. A method according to any one of claims 1 to 17, characterized in that the electrolyte is a voltage-lowering Containing agent or a grain refining agent selected from the group of saccharin, Coumarin, sodium lauryl sulfate and thio-urea. A method according to any one of claims 1 to 18, characterized in that the electrolyte consists of particles additions in the solution contains selected from pure metal powders, metal alloy powders or metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V and Zn, nitrides of Al, B and Si, carbon C (graphite or diamond), carbides of B, Bi, Si, W or organic materials such as PTFE and polymer beads, wherein the electrodeposited metallic material is at least 5% of the Particulate additives contains. Method according to claim 19, characterized that the electrodeposited metallic material is at least 10% containing particulate additives. Method according to claim 19, characterized that the electrodeposited metallic material is at least 20% containing particulate additives. Method according to claim 19, characterized that the electrodeposited metallic material is at least 30% containing particulate additives. Method according to claim 19, characterized that the electrodeposited metallic material is at least 40% containing particulate additives. A method according to any one of claims 19 to 23, characterized in that the average particle size of Particles existing additives below 10 μm preferably less than 1000 nm, more preferably less than 500 nm, and most preferably below 100 nm. Microcomponent produced by a pulse electrodeposition method as in any of the claims 1 to 23, which has a maximum dimension of 1 mm, an average grain size smaller 100 nm, the ratio between the maximum dimension and the average grain size greater than 10 is. Microcomponent according to Claim 25, characterized that the ratio between the maximum dimension of the microcomponent and the average grain size greater than 100 is. Microcomponent according to claim 25 or 26, characterized in that it has an equiaxed microstructure.