EA042591B1 - PRODUCT MANUFACTURING METHOD AND PRODUCT MANUFACTURED BY THE ABOVE METHOD - Google Patents

Description

Cross-reference to related applications

This application claims the benefit of priority of US Provisional Application No. 61/798559, filed March 15, 2013, which is incorporated herein by reference in its entirety.

Technical field

The invention includes articles containing coatings of nanolayered metals and methods for their manufacture.

The essence of the invention

Embodiments of the present disclosure provide methods for manufacturing articles. Such methods include at least two stages. The first stage involves forming the workpiece by additive technology, such as three-dimensional (3D) printing. The preforms are then subjected to electrochemical processes that provide a nano-multilayer metal coating having the desired chemical, physical and/or mechanical properties.

Thus, embodiments of the methods described herein provide the ability to manufacture products that are lightweight relative to similar products made entirely of a material such as metal, ceramic, or composite material, and that can be easily designed to meet specific requirements for a range of applications, including commercial applications. and defense applications. Variants of the implementations of the methods described here can also be applied at various scales and are suitable for both small-scale and high-volume production. Thus, embodiments of the present disclosure provide a method for manufacturing parts that have chemical, physical, and/or mechanical properties that allow them to be used in applications that have typically used metal, ceramic, and/or composite materials.

Detailed Description .0 Definitions.

Additive manufacturing means the manufacture of three-dimensional products by sequentially adding materials. The method includes all types of direct digital manufacturing, including, but not limited to, traditional three-dimensional printing (3D printing), selective laser deposition (sintering) (SLS) or selective laser melting (SLM), molten polymer filament layering modeling (FDM). ) and stereolithography (SLA).

Direct digital manufacturing, rapid prototyping, or rapid prototyping refers to an additive technology or 3D printing method for making a 3D solid product of any shape from a digital model. This method is an additive technology method in which successive layers, ribbons, granules or sections of material are layered into various shapes to form a three-dimensional product.

Selective laser sintering (SLS) refers to a process in which a layer of powder is locally bonded under the action of a laser to form one section of the product at a time.

Fused filament layering (FDM) refers to a method in which a molten material (eg, a thermoplastic material) is applied to form an article of a given shape.

Stereolithography (SLA) refers to a process in which a liquid polymer is locally cured by photoinitiated cross-linking. In this method, light is focused onto the surface of a reservoir of uncured photopolymer and the desired 2D sectional shape is drawn to form a cured 2D pattern. By repeating this method, 3D configurations of the desired shape are obtained.

The manufacture of layered objects (laminated in layers) (LOM) means the application of thin layers cut to shape and bonded together (eg paper, polymer, metal) to form the desired three-dimensional product.

Chemical reduction plating means autocatalytic plating in which the plating bath contains reducing agents ready to react with the substrate, and the catalyst is a deposited metal or metal on the surface of the article placed in the plating bath.

Workpiece means an object or product having such a shape that, after applying a given thickness of the layered material, leads to a part with a given shape and properties.

Here, when compositions or amounts are given in percent, the composition is given in mass percent, unless otherwise indicated.

.0 Description.

2.1 Overview.

In embodiments of the methods described here, nano-layered metallic materials can be applied in a conformal manner to the entire workpiece or part of the workpiece, thus imparting the desired chemical, physical and mechanical (structural) properties to the preformed part with a minimum increase in mass, in particular, in comparison with the product of the same type made of solid metal or ceramic. Such implementations provide

- 1 042591 the possibility of carrying out production processes from raw materials to the final product on a single production line. Moreover, the embodiments described herein can enable fully automated production lines and the production of individual parts without making intermediate castings or forming sheet metal materials. In addition, material can only be placed as needed, thereby further reducing material consumption in the process and reducing the overall weight of the product.

2.2 Methods for the manufacture of blanks and composition of blanks.

The methods described herein may use preforms made from a variety of materials, including metals, ceramics, and polymers (plastics). Preform fabrication can be performed by any additive manufacturing method, including, but not limited to, direct digital manufacturing, three-dimensional printing (3D printing), selective laser deposition (SLS) and/or selective laser melting (SLM), modeling by layering molten polymer filaments (FDM) and stereolithography.

When the blanks are to be made from metal, ceramic or glass, the additive manufacturing process employed will generally be a form of SLS and/or SLM processes. One or more metals can be formed by such methods, including, but not limited to, steels, stainless steels, titanium, brass, bronze, aluminum, gold, silver, cobalt-chromium, lead, tungsten, and tungsten alloys. These methods can also be used to make ceramic preforms such as green sand (for example, a mixture containing: about 75 to about 85% sand (quartz sand (SiO ₂ ), chromite sand (FeCr ₂ O), zircon sand (ZrSiO ₄ ), olivine, staurolite); about 5% to about 11% bentonite, about 2% to about 4% water; 0 to about 1% anthracite, and about 3% to about 5% inert or unidentified materials).

When the preforms are to be made from polymers (eg, thermoplastic materials), methods including SLS and/or SLM and FDM can be used.

Preforms made of polymers and plastics, which can be obtained by additive manufacturing methods, can be broadly divided into two categories: conductive and non-conductive materials. If the preforms are made from non-conductive plastics, at least a portion of the surface to be electrodeposited must be made conductive. This is usually done by applying a layer of metal by chemical reduction plating, although other methods can be used to achieve the desired result. If the plastic used to make the preform is already conductive, the use of chemical reduction plating is not necessary, but may advantageously be used to increase the conductivity of the preform before subjecting it to electrodeposition of the metal-containing composition.

Accordingly, embodiments of the preform may include a non-conductive material such as a polymer or plastic. Such embodiments include a polymer containing, for example, polyetherimide (e.g., Ultem™), polyetherketone ketone, nylon (e.g., Nylon 618), polyvinyl alcohol (PVA), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polylactic acid (PMA), PC/ABS, polymer and wood fiber (eg, LAYWOO-D3™), polyphenylsulfone (PPSU), or a combination of one or more, two or more, or three or more of the above. In other embodiments, the polymer is, for example, polyetherimide, polyetherketone ketone, nylon, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polylactic acid, PC/ABS, polyphenylsulfone, or a combination of one or more, two or more, or three or more of the above.

In other embodiments, the workpiece contains a conductive material. In such embodiments, the conductive material may comprise one or more metals selected from the group consisting of Ag, Al, Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni , Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V, Zn, and Zr. In other embodiments, the conductive material used to make the workpiece may comprise an alloy including, but not limited to, for example, steels, stainless steels, brass, bronze, nickel-cobalt, nickel-chromium, nickel-iron, zinc-iron, cobalt-chromium, tin-based alloys and tungsten alloys.

In other embodiments, the conductive preforms may comprise a conductive or non-conductive polymer and one or more metals or non-metallic conductive materials added to the polymers (eg, before or after curing) that make the composition conductive or more conductive. Examples of conductive non-metallic materials that can be added to polymers to increase conductivity are carbon black, graphene, graphite, carbon nanotubes, carbon nanofibers, or graphite fibers, which can be added to polymers alone or in combination with conductive metal materials.

A number of conductive polymeric materials can be used to make preforms that are conductive, including, but not limited to, polymers containing polyaniline or polypyrrole.

- 2 042591

2.3 The structure of the workpiece.

Workpieces obtained by additive manufacturing may include complex shapes and configurations. In embodiments, the blanks comprise at least one section containing a honeycomb network of, for example, hexagonal prisms, pentagonal prisms, cubes, or triangular prisms (eg, a sheet containing a honeycomb structure of hollow hexagonal prisms). In other embodiments, all or part of the preform may be foamy with pores that are discrete and/or fairly continuous throughout the foam portion of the preform.

In other embodiments, at least a portion of the preform comprises a series of supports extending substantially linearly between the vertices of polyhedral structures that are substantially tetrahedral, icosahedral, dodecahedral, octahedral, or cubic forming part of the preform. The supports may be substantially cylindrical (ie, substantially circular in a plane perpendicular to the two vertices that connect the supports). The supports may also be substantially triangular, square, pentagonal, hexagonal, heptagonal, or octagonal in a plane perpendicular to the two vertices that connect the supports. Such supports may have a width in a plane perpendicular to the two vertices that connect the supports, from about 0.2 to about 1.0 mm, from about 1 mm to about 1 cm, from about 5 mm to about 2 cm, or from about 1 cm up to about 5 cm. Other sizes may be used depending on the size and shape of the structure.

In some embodiments, it may be desirable to introduce parts into the blanks that aid in manufacturing but are not intended to be included in the final product being produced. Accordingly, when it is necessary or desirable to introduce parts necessary or desirable for manufacture but not required in the finished product, such as lugs or wires for suspension and electrodeposition, they can be located in non-structural areas of the product.

In addition, the workpiece geometry can be set so that after electrodeposition of the multilayer coating, a part of the desired final geometry is obtained. For example, workpieces without sharp corners (convex or concave) are less likely to be subjected to highly non-uniform current distributions. Similarly, the workpiece itself may contain areas dedicated solely to influencing the distribution of current, and these areas are intended to be removed immediately after the completion of the manufacture of the part. Such areas can serve either as screens (non-conductive current blockers) or as auxiliary electrodes (conductive current collectors). In addition, the elements of the workpiece can be designed to direct the electrolyte to the surface of the structure, so that both mass transfer and current distribution over the surface of the structure are controlled by non-structural areas of the workpiece.

In addition to their texture, workpieces can have roughness (usually expressed as a Ra value) as well as micropores. The presence of surface roughness and micropores can be advantageous for bonding between the electrodeposited composition(s) (eg, nano-multilayer coating) and the preform. In particular, when the preforms contain a polymer, pores and surface roughness can be introduced into the surface of the polymer prior to deposition of the composition containing any metal by either chemical reduction plating or electrodeposition.

The presence of micropores and the surface roughness of materials can be modified by a number of techniques, including chemical and/or physical processes. In some embodiments, the workpieces may be chemically etched (eg, chromic acid) to modify the surface prior to deposition of a composition containing any metal onto the workpiece.

FDM-deposited polymers can be produced with greater porosity and/or surface area than injection molded preforms of the same material, resulting in greater adhesive strength between coating and preform. The higher porosity and/or surface area inherent in the structure of polymers obtained using the FDM process is a result of their manufacture. The structures obtained by the FDM method have an ordered structure of polymer granules or filaments formed in this way by the FDM apparatus. These granules result in small voids which, while increasing surface area and providing stronger bonding between the preform and coatings applied to the preform, can also trap fluids and contaminants from chemical processes (e.g., chemical reduction plating). The use of ultrasonic agitation provides a new way to remove chemicals and fluids from the structure of an FDM part. Conventional washing and agitation during chemical reduction plating processes does not adequately remove all chemicals and fluids from the structure of FDM parts.

.0 Electrodeposited compositions, and nano-multilayer coatings, and method of applying them.

3.1 Use of chemical reduction plating to impart suitable conductivity to workpieces.

In order to electrodeposit a metal-containing composition onto at least a portion of the workpiece surfaces to which liquids are accessible, these surfaces must be conductive and be

- 3 042591 brought into contact with a bath containing metal salts to be precipitated. To make the surfaces of non-conductive workpieces conductive, it is usually required to subject the surface to chemical reduction plating of a metal such as nickel, cadmium, gold, silver, rhodium, chromium, zinc, tin, or copper. In embodiments, the metal deposited on the workpiece by chemical reduction deposition is nickel.

Preparing preforms for chemical reduction plating, in particular non-conductive plastic/polymer preforms, generally includes the step of etching the surface of the preform. Etching is usually done with a strong oxidizing agent to create microscopic pores or holes in the surface of the plastic. The pores or holes increase the surface area and improve the adhesion of successively deposited metal layers. Some solutions/suspensions of strong oxidants useful as etchants include peroxides (eg, hydrogen peroxide), persulfates, chromic acid, acidic or alkaline permanganate solutions, chromium trioxide solutions or slurries, and sulfuric acid. In embodiments, the preform contains ABS and the etchant is chromic acid or a solution/suspension containing chromium trioxide.

After etching, at least a portion of the etched portion of the preform can be contacted with a composition that deposits the metal catalyst onto the etched surface of the polymer preform. The catalyst is typically palladium, which can be supported using tin as the reducing agent (e.g. Sn ⁺² + Pd ⁺² = Sn ⁺⁴ Pd ⁰ ), however, other catalysts can be used, including noble metal catalysts (e.g. , platinum, rhodium, iridium, nickel, copper, silver, gold). Upon contact with the chemical reduction plating bath, the catalyst causes a layer of metal to form on the surface of the polymer preform exposed to the catalyst and then the bath.

Although the preforms may contain a continuous mass of conductive or non-conductive materials, they may also consist of a series of voids or pores. The voids or pores may be in fluid contact with the surface of the workpiece and provide access to electrolytes used in chemical reduction plating and other operations such as washing. Liquids trapped in these voids, or chemical residues from these liquids, may interfere with subsequent electrodeposition of coatings or remain trapped in the finished part during subsequent electrodeposition.

Before electrodeposition of metal onto the surface of the workpiece, any remaining chemical reduction plating materials must be removed from the workpiece so that they do not interfere with the plating or become trapped in the workpiece. Removal of the components of the electroless plating bath can be accomplished, for example, by immersing the component in a bath or shower of a cleaning solution (eg water) while exposing the preform to ultrasound. Exposure to ultrasound can use sound energy of any effective frequency and amplitude. In some embodiments, the applied frequency is about 18-25 kHz, and in other implementations, the frequency is about 20-23 kHz. In some embodiments, the sonication is performed in a bath with a continuous flow of washing liquid into the bath.

In some embodiments, contacting the chemical reduction plating workpiece with a liquid bath or shower simultaneously with sonication removes more than about 70%, 80%, 90%, 92%, 94%, 96%, 98%, or 99% of the the weight of the chemical reduction plating solution that remained associated with said chemical reduction plating preform after it was removed from the chemical reduction plating solution.

In other embodiments, contacting the chemically reduced plating workpiece with a liquid bath or shower simultaneously with sonication removes more than about 70%, 80%, 90%, 92%, 94%, 96%, 98%, or 99% of the The mass of the component present in the chemical reduction plating solution that remained associated with the electroless plating preform after it was removed from the chemical reduction plating solution.

Prior to electrodeposition of the metal composition (eg, nano-multilayer coating), it may be advantageous to remove liquids and/or volatiles associated with the preforms. Removal of liquids or volatiles from preforms, including from a chemical reduction plating process or exposing the preform to a liquid bath or shower after chemical reduction plating, can be accomplished, for example, by subjecting the preform to reduced pressure (vacuum). In some embodiments, the electroless plating preform is subjected to a reduced gas pressure that is less than 760 mmHg. (1 atm). In other embodiments, the blanks are subjected to pressures less than 500, 400, 300, 200, 100, 50, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.02 , 0.01 mmHg By exposing the preform to reduced gas pressure, more than about 50%, 60%, 70%, 80%, 90%, 92%, 94%, 96%, 98%, or 99% (by weight) of liquids associated with said preform can be removed. exposed to metal

- 4 042591 lyses by chemical reduction.

When chemical reduction plating has been applied to the workpiece and/or when the workpiece has been cleaned by exposure to a liquid, it may be desirable to include small holes (e.g., pinholes or bleed holes) in parts of the workpiece so that chemical reduction plating solutions can be removed from the workpieces. and/or cleaning solutions. Small holes or slots may be included in the preforms in non-structural, low stress and/or visually distinct areas (eg, out of line of sight from the surface). The use of holes located in such areas allows the removal of both chemical reduction plating compositions and liquids used during sonication and/or vacuum treatment described here. Removal of these materials improves the quality of subsequent electrodeposition processes (eg, improving adhesion of the electrodeposited coating) and avoids articles that are potentially contaminated or defective due to the presence of entrapped liquids that can cause or contribute to product deterioration.

3.2 Electrodepositable compositions and nanomultilayer coatings.

Metals, polymers and semiconductors can all be electroplated (electrodeposited) and in most cases this requires or near conventional temperature and pressure conditions. Embodiments of the methods described herein include methods for electrodeposition of a composition containing a metal onto a preform obtained by additive technology, where the process includes:

optionally subjecting all or part of the plating blank to chemical reduction;

providing a bath containing at least one electrodepositable component;

bringing all or part of the preform into contact with the tub;

applying a voltage or current to the preform to deposit at least one electrodepositable component comprising a metal.

In some embodiments, the bath contains at least two, at least three, or at least four electrodepositable components. The electrodepositable components include metal salts from which the metals can be electroplated onto the workpiece, and when the bath contains more than one metal salt as the electrodepositable component, alloys of various compositions can be electrodeposited onto the workpiece depending on the applied current and voltage. .

In some embodiments, the electrodeposition method includes applying a time-varying current density, where the time-varying current density fluctuates for at least two cycles to deposit structure and/or composition modulated material onto the preform. Structurally and/or compositionally modulated materials can be applied so that they have a discontinuous interface or a diffuse interface when the composition changes from the first composition to the second composition over about 3 nm to about 8 nm, from about 5 nm to about 10 nm, from about 7 nm to about 15 nm, or from about 10 nm to about 20 nm. In other embodiments, the discontinuous interface between two layers can be considered as the boundary at which the composition transitions from the composition of the first layer to the composition of the second layer at a distance of less than about 20%, about 15%, about 10%, about 8%, about 5%, about 4% or about 2% of the thickness of the thinner of the first and second layers. In other embodiments, the layers have diffuse interfaces where the compositions change from the first composition to the second composition in a continuous manner. In some embodiments, the diffuse interface changes from the first layer composition to the second layer composition over more than about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, and less than or equal to 50% of the thickness. thinner from the first and second layers.

The composition containing the metal that is electrodeposited onto the workpiece may vary in terms of the metals included in its composition. In some embodiments, the composition contains one or more, two or more, three or more, or four or more different metals independently selected from Ag, Al, Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V, Zn, and Zr, each of these independently selected metals being present in an amount more than 0.1, 0.05, 0.01, 0.005 or 0.001% by weight.

In other embodiments, the composition electrodeposited onto the workpiece contains two or more, or three or more different metals independently selected from Ag, Al, Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo , Nb, Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V, Zn and Zr, each of these independently selected metals is present in an amount of more than 0.1, 0.05, 0.01, 0.005 or 0.001% by weight. In such embodiments, compositions of two or more different metals that can be electrodeposited include, for example, Zn and Fe, Zn and Ni, Co and Ni, Ni and Fe, Ni and Cr, Ni and Al, Cu and Zn or Cu and sn.

In some embodiments, the composition electrodeposited onto the preform contains a mod

- 5 042591 electrodeposited material or composition lyirovanny on structure and/or composition. The structurally and/or compositionally modulated composition may comprise at least one region having a plurality of layers deposited at wavelengths from about 1 nm to about 250 nm, from about 1 nm to about 25 nm, from about 5 nm to about 50 nm , from about 10 nm to about 75 nm, from about 1 nm to about 100 nm, from about 2 nm to about 200 nm, from about 5 nm to about 225 nm, from about 10 nm to about 250 nm.

In other embodiments, the structurally and/or compositionally modulated material has at least one region consisting of a plurality of layers, each of said layers having a thickness in a range independently selected from about 5 nm to about 250 nm, from about 5 nm up to about 25 nm, from about 10 nm to about 30 nm, from about 30 nm to about 60 nm, from about 40 nm to about 80 nm, from about 75 nm to about 100 nm, from about 100 nm to about 120 nm, from about 120 nm to about 140 nm, from about 140 nm to about 180 nm, from about 180 nm to about 200 nm, from about 200 nm to about 225 nm, from about 220 nm to about 250 nm, or from about 150 nm to approximately 250 nm.

As described above, if the electrodeposited material contains two or more layers of different structure and/or composition, these layers may have discontinuous or diffuse interfaces.

In those embodiments in which the electrodeposited material contains two or more layers of different structure and/or composition, the composition may contain a plurality of alternating first layers and second layers. The electrodeposited material coating may consist entirely of alternating first and second layers, which may have discontinuous or diffuse interfaces between the layers. Alternatively, one or more additional layers may be present in the coating between any of the first and second layers.

In those embodiments in which the electrodeposited composition applied to all or part of the preform comprises a plurality of layers (e.g., first layers and second layers, or alternating first and second layers), the electrodeposited composition applied to the preform (e.g., as a conformal coating or partial coverage), may contain two or more, three or more, four or more, six or more, eight or more, ten or more, twenty or more, forty or more, fifty or more, 100 or more, 200 or more , 500 or more, 1000 or more, 1500 or more, or 2000 or more alternating first and second layers independently selected for each multilayer coating.

In some embodiments in which a plurality of first and second layers are present, each first layer contains nickel in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 9092%, 92-93%, 93-94%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%, the rest is cobalt and/or chromium . In such embodiments, every second layer contains chromium and/or cobalt in a range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10-15%, 15-20%, 20 -25%, 25-30% or 30-35%, the rest is nickel.

In some embodiments in which a plurality of first and second layers are present, each first layer contains nickel in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 9092%, 92-93%, 93-94%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%, the rest is aluminum. In such embodiments, every second layer contains aluminum in the range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30% or 30-35%, the rest is nickel.

In some embodiments in which a plurality of first and second layers are present, each first layer contains nickel in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 9092%, 92-93%, 93-94%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%, the rest is aluminum and/or cobalt . In such embodiments, every second layer contains aluminum and/or cobalt in a range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10-15%, 15-20%, 20 -25%, 25-30% or 30-35%, the rest is nickel.

In some embodiments in which a plurality of first and second layers are present, each first layer contains nickel in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 9092%, 92-93%, 93-94%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%, the rest is iron. In such embodiments, every second layer contains iron in the range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30% or 30-35%, the rest is nickel.

In some embodiments in which a plurality of first and second layers are present, each first layer contains zinc in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 9092%, 92-93%, 93-94%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%, the rest is iron. In such embodiments, every second layer contains iron in a range independently selected from

- 6 042591

1-35%, 1-3%, 2-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30% or 30-35%, the rest is zinc.

In some embodiments where multiple first and second layers are present, each first layer contains copper in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20%, 20-30%, 30-40%, 40-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 9092%, 92-93%, 93-94%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%, the rest is zinc and/or tin . In such embodiments, every second layer contains zinc and/or tin in a range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10-15%, 15-20%, 20 -25%, 25-30% or 30-35%, the rest is copper.

In some embodiments where the components of the electrodepositable compositions described above are not fully specified (i.e., less than 100% of the components by weight are specified and/or required), the remainder of these layers may be one or more different elements. In particular, this is the case in embodiments in which the above-described two-component or three-component alloy compositions contain a plurality of layers (eg, first and second layers). Thus, in some embodiments, the electrodepositable compositions may contain one or more elements selected from the group consisting of Ag, Al, Au, Be, C, Cr, Cu, Fe, Hg, In, Ir, Mg, Mn, Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn and Zr. In other embodiments in which the electrodepositable composition comprises one or more of said first and/or second layers, each of the layers may contain one or more, two or more, three or more, or four or more elements independently selected for each first and second a layer from the group consisting of Ag, Al, Au, Be, C, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn and Zr.

.0 Properties of electrodeposited coatings and preformed parts.

Electrodeposited alloys deposited on workpieces (e.g., nano-layer coatings) can be completely or substantially completely dense, with a limited number of pores or cracks, making them suitable as corrosion resistant coatings, in addition to their role as a structural component of finished parts or products.

In those embodiments in which the electrodeposited compositions are composed of multiple layers less than about 20 nm thick (e.g., about 15 nm, 10 nm, 8 nm, or 5 nm), the compositions exhibit increased Hall-Petch/toughness and grain boundary strengthening. The observed increase in hardening occurs due to the localization of grains, and the increase in viscosity occurs due to the reflection of forces in the layered areas. Such coatings tend to follow the Hall-Petch relationship that is commonly used to describe the increase in yield strength in nanocrystalline materials.

In those embodiments in which the electrodeposited compositions comprise multiple layers of hard and soft materials layered together, the electrodeposited composition may exhibit an increase in Couler fracture toughness. This kind of increased fracture toughness is the result of deflection of the incipient crack at the interface due to the different factor. Such articles can thus absorb energy that would normally cause cracking and thereby prevent or substantially minimize bulk material failure and/or prolong the time until such bulk material failure occurs.

In addition to improving the mechanical and physical properties of the preform, the compositions electrodeposited onto the preforms can also change the chemical characteristics. In some embodiments, at least a portion of the composition electrodeposited onto the preform is chemically resistant to the environment and protects the underlying preform (e.g., a metallic coating protects the preform from solvents or UV (ultraviolet) radiation that can damage the preform). In other embodiments, at least a portion of the composition electrodeposited onto the preform is nobler than the underlying preform and acts as a barrier coating in corrosive environments that can damage the underlying preform. In still other embodiments, at least a portion of the composition electrodeposited onto the preform is less noble than the preform and degrades itself in corrosive environments, protecting the preform.

.0 Some implementations.

1. A method of manufacturing a product, including:

production of blanks by additive technology;

optionally subjecting all or part of the preform to chemical reduction plating and electrodeposition onto the preform of a metal-containing composition.

2. The method of Embodiment 1, wherein said preform contains a non-conductive material.

3. The method of Embodiment 2, wherein the non-conductive material is a polymer.

4. The process of Embodiment 3 wherein the polymer contains: Polyetherimide (e.g. Ultem™), Polyetherketone Ketone, Nylon (e.g. Nylon 618), Polyvinyl Alcohol (PVA), Acrylonitrile Butadiene Styrene Copolymer (ABS), Polycarbonate (PC ), polylactic acid (PLA), PC/ABS, wood fiber (e.g. LAYWOO-D3), polyphenylsulfone (PPSU), or a combination of one

- 7 042591 or more, two or more or three or more of the above.

5. The method of Embodiment 4, wherein the polymer is polyetherimide, polyetherketone ketone, nylon, acrylonitrile-butadiene-styrene (ABS) copolymer, polycarbonate (PC), polylactic acid (PLA), PC/ABS, polyphenylsulfone (PPSU), or a combination one or more, two or more, or three or more of the above.

6. The method of Embodiment 2, wherein said preform contains a conductive material.

7. The method of Embodiment 6, wherein said conductive material comprises one or more metals, a non-conductive polymer and one or more metals, and/or a conductive polymer and one or more metals.

8. The method of Embodiment 7, wherein said one or more metals comprise one or more metals selected from the group consisting of Ag, Al, Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn , Mo, Nb, Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V, Zn and Zr.

9. The method of any one of embodiments 6-8, wherein said conductive material comprises a conductive polymer, a non-conductive polymer, and a conductive non-metallic material, and/or a conductive polymer and a conductive non-metallic material.

10. The method of Embodiment 9, wherein said conductive polymer comprises polyaniline or polypyrrole.

11. The method of embodiment 9 or 10, wherein said conductive non-metallic material comprises carbon black, graphene, graphite, carbon nanotubes, carbon nanofibers, or graphite fibers.

12. The method of any one of embodiments 1-11, wherein prior to said electrodeposition, all or part of said preform is contacted with a chemical reduction plating solution to form an electroreduction metallized preform, and then removing said electroreduction metallized preform from contact with said solution. for metallization by chemical reduction.

13. The method of embodiment 12, further comprising contacting said chemical reduction metallized preform with a bath or shower of liquid while being exposed to ultrasound.

14. The method of Embodiment 13, wherein contacting said ER-plated preform with a bath or shower of liquid when subjected to sonication removes more than about 90%, 92%, 94%, 96%, 98%, or 99% by weight an electroreduction plating solution associated with said electroreduction plating preform after said removal of said electroreduction plating preform from contact with said electroreduction plating solution.

15. The method of Embodiment 13, wherein contacting said ER-metallized preform with a bath or shower of liquid while sonicated removes more than about 70%, 80%, 90%, 92%, 94%, 96%, 98 % or 99% by weight of a component present in the chemical reduction plating solution associated with said chemical reduction plating preform after said removal of said electroreduction metallized preform from contact with said chemical reduction plating solution.

16. The method of any one of embodiments 12-15, wherein prior to said electrodeposition, said chemical reduction metallized preform is subjected to a reduced gas pressure of less than 760 mmHg. (1 atm), 100, 50, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01 mmHg

17. The method of Embodiment 16 wherein said ER-plated preform is subjected to said reduced gas pressure for a period of time to remove more than about 50%, 60%, 70%, 80%, 90%, 92%, 94% , 96%, 98%, or 99% by weight of any liquid associated with said metallized chemical reduction preform prior to subjecting it to said reduced pressure.

18. The method of any one of embodiments 1-17, wherein said preform is manufactured by a process comprising direct digital manufacturing or additive manufacturing (eg, FDM, SLS, SLA, or LOM).

19. The method of any one of embodiments 1-18, wherein electrodeposition of a metal-containing composition comprises:

providing a bath containing at least one electrodepositable component;

bringing all or part of the preform into contact with the tub; and applying a voltage or current to the preform to deposit at least one electrodepositable metal-containing component.

20. The method of embodiment 19, comprising providing a bath containing at least

- 8 042591 at least two, at least three or at least four electrodepositable components.

21. The method of embodiment 19 or 20, further comprising applying a time-varying current density, said time-varying current density fluctuating for at least two cycles to deposit structure and/or composition modulated material onto said preform.

22. The method of any one of embodiments 1-21, wherein electrodeposition of a composition containing a metal comprises electrodeposition of a composition containing one or more, two or more, three or more, four or more different metals independently selected from Ag, Al, Au , Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V , Zn and Zr, each of the independently selected metals being present in an amount of more than 0.1, 0.05, 0.01, 0.005 or 0.001 wt.%.

23. The method of any one of embodiments 1-21, wherein electrodeposition of a composition containing a metal comprises electrodeposition of a composition containing two or more different metals independently selected from Ag, Al, Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V, Zn and Zr, each of these independently selected metals is present in an amount of more than 0.01 wt.%.

24. The method of Embodiment 23, wherein said two or more different metals comprise Zn and Fe, Zn and Ni, Co and Ni, Ni and Fe, Ni and Cr, Cu and Zn, or Cu and Sn.

25. The method of any one of embodiments 21-24, wherein the structurally and/or compositionally modulated material comprises at least one region with multiple layers deposited at wavelengths from about 1 nm to about 250 nm, from about 1 nm to about 25 nm, from about 5 nm to about 50 nm, from about 10 nm to about 75 nm, from about 1 nm to about 100 nm, from about 2 nm to about 200 nm, from about 5 nm to about 225 nm, from about 10 nm to about 250 nm.

26. The method of any one of embodiments 21-24, wherein the structurally and/or compositionally modulated material comprises at least one region consisting of a plurality of layers, each of said layers having a thickness in a range independently selected from about 5 nm to about 250 nm, from about 5 nm to about 25 nm, from about 10 nm to about 30 nm, from about 30 nm to about 60 nm, from about 40 nm to about 80 nm, from about 75 nm to about 100 nm , from about 100 nm to about 120 nm, from about 120 nm to about 140 nm, from about 140 nm to about 180 nm, from about 180 nm to about 200 nm, from about 200 nm to about 225 nm, from about 220 nm up to about 250 nm or from 150 nm to about 250 nm.

27. The method of any one of embodiments 1-26, wherein said metal-containing composition comprises a plurality of first layers and second layers, which may have discontinuous or diffuse interfaces between the first and second layers, and which may be arranged in alternating first layers. and second layers.

28. The method of embodiment 27, wherein said plurality of alternating first layers and second layers comprises two or more, three or more, four or more, six or more, eight or more, ten or more, twenty or more, forty or more , fifty or more, 100 or more, 200 or more, 500 or more, 1000 or more, 1500 or more, or 2000 or more alternating first and second layers independently selected for each coating.

29. The method of any one of embodiments 27-28, wherein each said first layer contains nickel in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20% , 20-30%, 3040%, 40-50%, 50-55%, 55-60%, 60-65% 65-70%, 70-75%, 75-80%, 80-85%, 85- 90%, 90-92% 92-93%, 9394%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%.

30. The method of any one of embodiments 27-29, wherein every second layer contains cobalt and/or chromium in a range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10 -15%, 15-20%, 2025%, 25-30% and 30-35%.

31. The method of embodiment 29 or 30, wherein each said first layer contains nickel in a range independently selected from 1-5%, 5%-7%, 7%-10%, 10-15%, 15-20% , 20-30%, 30-40%, 40-50%, 50-55%, 55-60%, 60-65% 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 90-92% 92-93%, 93-94%, 9495%, 95-96%, 96-97%, 97-98% or 98-99%, and the rest in the layer is cobalt and /or chrome.

32. The method of embodiment 30 or 31, wherein every second layer contains cobalt and/or chromium in a range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10-15 %, 15-20%, 20-25%, 25-30% and 30-35%, and the rest in the layer is nickel.

33. The method of any one of embodiments 27-32, wherein one or more of said first and/or second layers comprise one or more, two or more, three or more, or four or more elements independently selected for each first and second a layer from the group consisting of Ag, Al, Au, Be, C, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn and Zr.

34. The method of any one of embodiments 27-33, wherein each said first layer contains nickel in a range independently selected from 1-5%, 5-7%, 7-10%, 10-15%, 15-20% , 20-30%, 30

- 9 042591

40%, 40-50%, 50-55%, 55-60%, 60-65% 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 90-92 % 92-93%, 9394%, 94-95%, 95-96%, 96-97%, 97-98% or 98-99%, and the rest in the layer is iron.

35. The method of any one of embodiments 27-34, wherein every second layer contains iron in a range independently selected from 1-35%, 1-3%, 2-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30% or 30-35%, and the rest in the layer is nickel.

36. The product obtained by the method according to any of the implementation options 1-35.

37. The article of embodiment 36, wherein said article has a property selected from the group consisting of hardening and/or toughness that is greater than said billet.

38. The article of Embodiment 36, wherein said electrodeposited composition contains NiCo and has a microhardness of about 400 to about 500 Vickers measured according to ASTM (American Society for Testing and Materials) E384-11e1.

39. The article of Embodiment 36, wherein said electrodeposited composition contains nickel and chromium and has a microhardness of about 500 to about 600 Vickers measured according to ASTM E384-11e1.

40. The article of embodiment 36, wherein said electrodeposited composition comprises a plurality of layers and exhibits increased Hall-Patch strength relative to a uniform electrodeposited composition having the same average composition and substantially the same thickness as said plurality of layers.

41. The article of embodiment 36 or 40, wherein said electrodeposited composition comprises a plurality of layers and exhibits increased grain boundary strengthening relative to a uniform electrodeposited composition having the same average composition and substantially the same thickness as said plurality of layers.

42. The article of embodiment 36, wherein said electrodeposited composition comprises a plurality of layers and exhibits increased Coiler fracture toughness relative to a homogeneous electrodeposited composition having the same average composition and substantially the same thickness as said plurality of layers.

6.0 EXAMPLES.

Example 1. Additive technology of wrenches with nickel-iron nano-layer coating.

Wrenches were made from ABS blanks obtained using the FDM process. Wrenches were made at two different FDM print densities, with the first set of wrenches having a smaller FDM bead size than the second set. The blanks were subjected to chromate etching and subjected to plating by chemical reduction of Nickel to impart conductivity to the blanks. A 100 µm thick nano-layered Ni-Fe coating was electrodeposited with alternating layers of 70% Ni-30% Fe and 90% Ni-10% Fe (about 100 nm each). The coated articles obtained by this method had a glossy surface which proved to be self leveling and had good adhesion. Wrenches with a larger grain structure in the printed blank were larger and more rigid, but the larger grains prevented effective impregnation of the plastic blank.

Example 2. Additive manufacturing of wrenches and parts of complex shape with a nickel-iron nano-multilayer coating.

FDM made ABS blanks into wrenches, an unmanned aerial vehicle propeller and wing, a honeycomb speaker cover, corrugated products and plastic structures with teeth, and small air ducts for aircraft. Plastic dome-shaped blanks with an internal rod system were made from Ultem™. The workpieces were etched with chromate and subjected to plating by chemical reduction of Nickel to impart conductivity. A 100 µm thick nano-layered Ni-Fe coating was applied by electrodeposition with alternating layers of 70% Ni-30% Fe and 90% Ni-10% Fe (about 100 nm each). The coated articles obtained by this method had a glossy surface which proved to be self leveling and had good adhesion. Wrenches with a larger grain structure in the printed blank were larger and more rigid, but the larger grains prevented effective impregnation of the plastic blank. These articles demonstrated the complexity of the parts that could be produced and the efficient coverage and adhesion of nano-multilayer coatings to preforms. The dome, wing and propeller show the uniformity of the coating on surfaces of complex shape.

Example 3: Additive Technology of Nano-Multilayer Nickel-Iron-Coated Wrenches.

Two models of wrenches were obtained from ABS blanks obtained using FDM. The blanks were subjected to chromate etching and subjected to plating by chemical reduction of Nickel to impart conductivity to the blanks. A coating of a target thickness of 100 μm was applied by electrodeposition of nano-multilayer Ni-Fe with alternating layers of the composition 70% Ni-30% Fe and 90% Ni-10% Fe (about 100 nm each). As in Example 1, the coated articles obtained by this method had a glossy surface which proved to be self leveling and had good adhesion. Gaech

-

Claims (15)

Keys with a larger grain structure in the printed blank were larger and more rigid, but the larger grains prevented efficient impregnation of the plastic blank. Both models of wrenches were tested for their ability to withstand torque compared to uncoated ABS blanks. Both models of Nano-Multilayer Ni-Fe Coated Wrenches resulted in less destructive mechanical stresses than uncoated plastic blanks. This lower destructive stress has been attributed to plastic embrittlement during nickel chemical reduction, the inability to achieve full plating thickness, and other factors including the metal's inability to penetrate (weave) the ABS workpiece weave. Example 4. Additive technology of rod and honeycomb structures with nano-multilayer nickel-iron coating. Stereolithography was used to rapidly prototype honeycomb structures and blank structures from a combination of nylon-11 and nylon-12 with and without the addition of graphite. Both graphite-containing and non-graphite blanks were subjected to chromate etching and electroless nickel plating to impart conductivity to the blanks. A 100 µm thick nano-layered Ni-Fe coating was applied by electrodeposition with alternating layers of 70% Ni-30% Fe and 90% Ni-10% Fe (about 100 nm each). The fabrication of these products has demonstrated that preforms suitable for electrodeposition of nano-multilayer alloys can be fabricated by stereolithography. The bar structure has also demonstrated that localized strength properties and localized tensile properties can be developed or imparted to parts with minimal compromises in terms of surface area. The use of rapid prefabrication in the method allows adjustments in response to improve part performance based on test results without having to completely rework and reshape the plastic substrate. Example 5. Additive manufacturing of an I-profile with a nickel-iron nano-multilayer coating. Stereolithography was used to fabricate a blank for the I-profile support and wire holders from graphite-filled nylon-12. The blanks were subjected to chromate etching and subjected to plating by chemical reduction of Nickel to impart conductivity to the blanks. A 100 µm thick nano-layered Ni-Fe coating was applied by electrodeposition with alternating layers of 70% Ni-30% Fe and 90% Ni-10% Fe (about 100 nm each). The fabrication of these products has demonstrated that stereolithography can be used to fabricate blanks. CLAIM 1. A method for applying a multilayer coating to a substrate, including: electrodeposition on the workpiece of a multilayer coating containing two or more metals, while the multilayer coating contains a plurality of layers, which includes alternating first and second layers, each of the first layers and each of the second layers contains the above two or more metals, while each of the first layers independently contains Nickel in a concentration in the range from 1% to 99% by weight, and the rest is cobalt and/or chromium; each of the second layers independently contains cobalt and/or chromium in a concentration in the range from 1% to 35% by weight, and the rest is Nickel; wherein the preform includes a polymer; and wherein (A) the preform includes a conductive material, or (B) the preform is subjected to chemical reduction plating, comprising: obtaining a chemical reduction plating preform by contacting all or part of the preform with a chemical reduction plating solution prior to said electrodeposition; and removing the chemical reduction plating preform from contact with the chemical reduction plating solution. 2. The method of claim 1, wherein the plurality of layers further includes third layers between adjacent first and second layers. 3. The method of claim 1 wherein the polymer comprises polyetherimide, polyetherketone ketone, nylon, polyvinyl alcohol (PVA), acrylonitrile butadiene styrene copolymer (ABS), polycarbonate (PC), polylactic acid (PLA), PC/ABS, wood fiber, polyphenylsulfone (PPS) or a combination of at least one of the above polymers. 4. The method of claim 1, further comprising, following removing the ER-plated preform from contact with the ER-plated solution, removing more than about 80% by weight of the ER-plated solution associated with the ER-plated preform by contact - 11 042591 a chemically reduced metallized preform with a bath or shower of liquid while exposing the preform to ultrasound. 5. The method according to claim 1, in which before electrodeposition metallized chemical recovery workpiece is subjected to a reduced gas pressure of less than 760 mmHg. (1 atm) for a period of time sufficient to remove more than about 80 wt.% of any liquid associated with metallized chemical reduction of the workpiece before it is subjected to reduced pressure. 6. The method according to claim 1, further comprising the preparation of the workpiece using additive technology. 7. The method of claim 6, wherein the additive technology includes direct digital manufacturing. 8. The method of claim 1, wherein the electrodeposition comprises providing a bath comprising said two or more metals, contacting all or part of the workpiece with the bath, and depositing said two or more metals by applying a voltage or current to the workpiece. 9. The method of claim 8, wherein the electrodeposition comprises applying a time-varying current density that fluctuates over at least two cycles to deposit the multilayer coating on the workpiece. 10. The method of claim 9, wherein at least one area of the multilayer coating includes layers deposited at wavelengths ranging from about 1 nm to about 250 nm. 11. A coated substrate, comprising: polymer blank; and a multilayer coating containing two or more metals on a polymer preform, wherein the multilayer coating comprises a plurality of layers that includes alternating first and second layers, each of the first layers and each of the second layers contains the said two or more metals, each of the first layers independently contains nickel in a concentration in the range from 1% to 99% by weight, and the rest is cobalt and/or chromium; each of the second layers independently contains cobalt and/or chromium in a concentration in the range from 1% to 35% by weight, and the rest is Nickel; and wherein (A) the polymer preform includes a conductive material, or (B) the coated polymer preform includes a metal layer between the polymer preform and the multilayer coating. 12. The coated substrate of claim 11, wherein the plurality of layers further includes third layers between adjacent first and second layers. 13. The coated substrate of claim 11, wherein the portion of the polymer preform includes a honeycomb network. 14. The coated substrate according to claim 13, wherein the multilayer coating is made of NiCo and has a microhardness of 400-500 Vickers measured according to ASTM (American Society for Testing and Materials) E384-1 lei, or the multilayer coating is made of NiCr and has a microhardness of 500-600 Vickers units, measured according to ASTM E384-1 lei. 15. The coated substrate of claim 11, wherein the multilayer coating exhibits increased Hall-Petch or grain boundary strengthening relative to a uniform electrodeposited composition having the same average composition and substantially the same thickness as said plurality of layers; or wherein the multilayer coating exhibits increased Couler fracture toughness relative to a homogeneous electrodeposited composition having the same average composition and substantially the same thickness as said plurality of layers. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2