EA041389B1 - METHODS FOR PRODUCING MULTILAYER COATINGS ON WORKPIECES AND THE PRODUCTS MADE BY THEM - Google Patents

Description

Technical field

The present invention generally relates to the creation of multilayer coatings on blanks using electroplating methods such as drum plating, vibrating basket plating, oscillating vessel plating, or other non-suspension methods that involve moving the plating blanks in a container device, as well as to products, done in such ways. Embodiments of such methods include mass transfer modulation to create compositionally modulated coatings.

Background of the invention

Electroplating is regarded as an inexpensive way to form a dense coating or cladding on a variety of electrically conductive materials, including metals, alloys, conductive polymers, and the like. Electroplating has also been successfully used to deposit nanolaminate coatings on non-conductive materials such as non-conductive polymers by incorporating suitable materials into the non-conductive polymer to render it sufficiently conductive, or by treating the surface to make it conductive, such as electroless plating of nickel, copper, silver, cadmium, and etc., in a variety of technical applications. Electroplating has also been shown to be an effective means of producing multi-layer and nanolaminate coatings, claddings, materials and products, in which individual laminate layers can vary in metal, ceramic, organometallic composition and/or microstructure characteristics.

While electrodeposition techniques are known, there remains a need in the art for methods of electrodepositing multilayer coatings on preforms that are not economically viable or structurally unsuitable with known suspension or rail plating techniques. The present invention provides this and the advantages associated with it.

The essence of the invention

The present invention provides, among other things, methods for plating a batch of preforms using suspensionless systems, such as plating in a drum and a vibrating basket, to create multilayer (including nanolayer, so-called nanolaminate) coatings on them and products made by such methods.

In embodiments, the present invention provides a method for producing a plurality of products by electroplating a batch of blanks, comprising bringing at least a portion of the batch of blanks into contact with an electrodeposition bath in contact with at least a portion of a container device, the electrodeposition bath comprising at least first and second electrodepositable materials; moving part of the batch of blanks by driving the container device in a given mode of movement; electrodeposition of the first identifiable layer onto at least a portion of the preforms in the batch by applying a first electrical current for a first amount of time through at least two cathode contacts that create at least intermittent electrical contact with a portion of the batch of preforms, the first identifiable layer comprising at least first and second electrodepositable materials; and electrodeposition of the second identifiable layer on a portion of the blanks in the batch by applying a second electric current for a second amount of time through the cathode contacts, the second identifiable layer containing at least the first and second electrodepositable materials, and the composition, grain size, structure or thickness or combination thereof of the second identifiable layer are different from those of the first identifiable layer.

In additional embodiments, the present invention provides a method for forming a plurality of articles by forming a nanolaminate coating on a plurality of blanks, comprising bringing at least a portion of the plurality of blanks into contact with an electrodeposition bath in contact with the interior of the drum, the electrodeposition bath comprising at least first and second electrodepositable materials. , while the blanks, each independently, have the longest dimension, and the drum has a length and a radius; drum rotation; electrodeposition of the first identifiable layer on at least a part of the plurality of blanks by supplying the first electric current for the first amount of time through at least two cathodes with the ends located inside the internal volume of the drum, separated from each other by a distance, the first identifiable layer contains at least the first and the second electrodeposited materials; and electrodeposition of the second identifiable layer on a part of the plurality of blanks by applying a second electric current for a second amount of time through said at least two cathodes, wherein the second identifiable layer contains at least the first and second electrodepositable materials, wherein at least one of the composition, size grains, structure and thickness, or combinations thereof, of the second identifiable layer differs from those of the first identifiable layer.

In other additional embodiments, the implementation of the present invention provides an article made according to the method according to the invention. In other embodiments, the present invention provides an article of manufacture comprising a nanolaminate coating, wherein the nanolaminate coating contains

- 1 041389 lives the first identifiable layer having a thickness in the range from about 150 to about 20000 nm, in one or more places on the product, and the first identifiable layer contains at least the first and second components, and the first identifiable layer has the first composition, the first grain size and first grain structure; a second identifiable layer having a thickness in the range of about 150 to about 20,000 nm at one or more locations on the article, the second identifiable layer having first and second components, the second identifiable layer having a second composition, a second grain size, and a second grain structure, wherein at least one of the second composition, the second grain size and the second grain structure or combinations thereof differs from the first composition, the first grain size and the first grain structure; and one or more inhomogeneities characterized by an inwardly directed deformation of the first and second identifiable layers towards the surface of the substrate.

Embodiments of the methods provided herein include plating a batch of preforms to produce identifiable nanolaminate coating layers on a plurality of preforms in the batch. For example, some embodiments include at least first and second identifiable layers. The embodiments presented herein include a batch of preforms having identifiable nanolaminate coating layers on a plurality of preforms in the batch.

Embodiments of the suspensionless methods described herein involve mass transfer modulated nanolaminate coating processes. In such processes, the compositions of the alloys in the individual layers of the nanolaminate coating can be varied by modulating the electrochemical deposition frequency between different current densities. In embodiments, current densities and other deposition parameters are matched to those of the particular plating method employed in order to achieve modulation of the composition of the nanolaminate layers having the desired properties.

In embodiments, the layers contain one, two, three, four or more elements independently selected from the group consisting of Ag, Al, Au, B, Be, C, Co, Cr, Cu, Fe, Hg, In, Ir, Mg , Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn, and Zr, each of the independently selected metals being present in amounts over 0.1 wt.%. In additional embodiments, each of the independently selected metals is present in amounts greater than 0.05, 0.01, 0.005, or 0.001% by weight. Within the scope of such embodiments of this invention are coating layers containing a variety of elements including Ni, Zn, Co, Al, and Fe. Within the scope of such embodiments are corrosion resistant coatings containing Zn and Ni, where nickel is from 11 to 17% by weight, and the remaining weight percentage of the coating, i.e. the rest contains Zn.

In embodiments, the first identifiable layer in the multilayer coatings in the plurality has a thickness at one or more locations on the article that is at least about 200 nm. In other embodiments, the first identifiable layer in the multilayer coatings in the plurality has a thickness at one or more locations on the article that is at least about 250 nm. In additional embodiments, the implementation of the first identifiable layer in the multilayer coatings in the set has a thickness in one or more places on the product, which is up to 1 micron. In other additional embodiments, the implementation of the first identifiable layer in the multilayer coatings in the set has a thickness in one or more places on the product, which is greater than 1 micron.

In embodiments, the second identifiable layer likewise also has a thickness of at least about 200 nm at one or more locations on the article. In other embodiments, the implementation of the second identifiable layer in the multilayer coatings in the set is about 250 nm in one or more places on the product. For example, the second layer has a thickness of from about 200 to about 400 nm at one or more locations on the article.

In embodiments, at one or more locations on the article, the second identifiable layer is substantially the same thickness as, or thinner than, the first layer. In other embodiments, at one or more locations on the product, the second layer is thicker than the first layer. For example, the first layer may have a thickness in the range of about 200 to about 400 nm, and the second layer may have a thickness in the range of about 600 to about 1000 nm. In other embodiments, at one or more locations on the article, the second layer is significantly thinner than the first layer. For example, the second layer may have a thickness in the range of about 200 nm to about 400 nm at one or more locations on the article, and the first layer may have a thickness greater than about 600 nm at one or more locations on the article. In some such embodiments, the first layer has a thickness in the range of about 600 to about 1000 nm (or more) at one or more locations on the article. In embodiments, the thickness is measured for comparison purposes on a threadless surface.

In embodiments, nanolaminate-coated articles have a plurality of corrosion-resistant coatings. In embodiments, nanolaminate coatings provide at least 1,000 to over 15,000 hours before first red rust appears when tested under ASTM-B-117-11 salt spray conditions.

- 2 041389

The multilayer coatings of this invention, and in particular the nanolayer metals of this invention, are of interest for a wide variety of applications including structural, thermal, and corrosion resistant applications due to their unique properties of fracture toughness, fatigue strength, heat resistance, wear resistance, abrasion resistance, and chemical properties. . Methods for producing such nanolaminate coatings by the fabrication methods described here, and multilayer (eg, nanolaminate) coated articles produced by the methods described here, are of interest due to their low cost fabrication and impressive material properties. Therefore, electrodeposition by the methods described here is an effective means of obtaining multilayer (for example, nanolaminate) materials and coatings in which identifiable, individual laminate layers can vary in composition (for example, the concentration of metals in the alloy, etc.) or structure (for example , microstructure, morphology, layer thickness, layer density, etc.) of the deposited components. In addition, the fabricated nanolaminate coatings can have reproducible wavelengths that can be substantially continuous over portions of the workpiece surface. In some embodiments, the implementation of the coating is a cladding.

Brief description of some views in the drawings

Fig. 1A-1E illustrate examples of some of the different preforms that can be coated (eg, roll plated) as described herein and show the various surfaces where coatings can be applied and measured.

Fig. 2A-2C are scanning electron microscope cross-sectional images of nanolaminate coatings in accordance with embodiments of this invention.

Fig. 3A and 3B are schematic illustrations of one embodiment of a drum plating configuration that can be used to create nanolaminate coatings as described herein.

Fig. 4 illustrates the region of interest in the stirring experiment described in Example 4.

Fig. 5 illustrates the drum configuration for experimental jitter determination as described here and in Example 5.

Fig. 6 is a plot of the average current measured over time during the jitter experiment as described here in Example 5.

Fig. 7 is a graph of the average current measured for various combinations of drum plating parameters as described in Example 5.

Fig. 8 shows nuts and washers in which the ratio of zinc to nickel concentration varies in adjacent layers obtained using a bath containing zinc and nickel salts as described in Example 6.

Detailed description

This invention relates to the application of coatings to a batch of preforms by using non-suspension plating methods such as drum plating, vibratory plating, or other plating methods in which multilayer coatings are applied to the preforms. Such methods may be useful, for example, for plating a number of small workpieces that may be difficult or too labor-intensive to plate on a hanger. The embodiments described herein also provide for mass transfer modulated processes in which the composition of the laminate layers is modulated by variations in current density, other process parameters during the plating process, or both.

Before describing this invention in more detail, for a better understanding, it may be helpful to define some of the terms used herein. Additional definitions are set forth throughout this description.

Electroplating or electrodeposited refers to a process or product, respectively, in which electrolysis is used to deposit a coating on a workpiece. In other words, the workpiece is brought into contact with (e.g., partially immersed or completely immersed in) an electrolyte solution containing one or more ions (e.g., metal, ceramic, etc.), while the workpiece and the electrolyte solution pass an electric current, leading to the deposition of a thin coating on the surface of the workpiece.

For the purposes of this invention, coatings include thin layers that are electrodeposited onto the surface of a workpiece. Therefore, the coatings used herein include claddings that are composed of a succession of thin electrodeposited layers on the surface of the mandrel, the mandrel being removed after the formation of the electrodeposited layers. The claddings, once formed, are usually attached to another product as a protective layer.

For the purposes of this invention, the term multi-layer or laminate refers to materials (eg, coatings) that contain two or more layers. Nanolaminate coatings in the sense of this invention are coatings containing two or more layers, in which each of

- 3 041389 individual layers have a thickness of less than 10,000 nm (ie 10 μm). In other words, the term nanolaminate in nanolaminate coatings in this specification refers to the thickness of the layers in the coating and not to the entire thickness of the coating consisting of individual layers. The processes described here are particularly suitable for creating nanolaminate coatings, but they can certainly be used also for the manufacture of products in which the individual layers are thicker than 10 microns.

The term wavelength refers to the thickness of two adjacent layers that are formed in a single deposition cycle in those embodiments where the current density is a periodic function.

The term periodic layer refers to an individual layer of a sequence of two or more (eg, three or more, or four or more) non-identical layers (types of electrodeposited layers) that are repeatedly deposited on a workpiece. Sequences of non-identical layers that are repeatedly deposited have variations in at least one of composition, grain size, metal composition and/or structure relative to other types of electrodeposited layers that are repeatedly deposited in such a sequence. In some embodiments, sequences of non-identical layers are deposited in alternating first and second layers.

Fully dense means that the electrodeposited material is substantially free of pinholes, cavities, and cracks that would expose the substrate to corrosive agents (corrosive agents) in contact with the coatings or claddings described herein.

The term workpiece covers any object with a surface on which a coating is electrodeposited. The blanks include substrates, which are those objects that are coated, and mandrels, which are substrates from which the coating is removed after formation. The preforms can be formed from a conductive material (for example, metal), formed from a mixture of conductive and non-conductive materials (for example, a polymer-metal mixture), or coated with a conductive material (for example, a non-conductive material coated with a metal layer by chemical reduction deposition, i.e. . non-electrochemical deposition).

The blank used in the embodiments of the present invention may be any suitable blank. In embodiments, the workpiece is made of metal or a metal alloy. In some embodiments, the workpiece is made from a steel alloy. In certain embodiments, the implementation of the steel alloy includes C and Fe; C, Fe and Mo or C, Fe, Mo and Co. In other embodiments, the blank is made of plastic or polymeric material. In some embodiments, the plastic or polymer material includes arylamides, acrylamides, polybenzimidazole (PBI), polyetherimide, polyether ketone (PEKK), polyether ether ketone (PEEK), polyamide, polyimide, polyamidimides, polyphenylene oxide (PPO), polystyrene (PS), polyphenylene oxide (PPO) and polystyrene (PS), polyphthalamide (PPA), polyvinyl alcohol (PVA), acrylonitrile butadiene styrene copolymer (ABS), polycarbonate (PC), polylactic acid (PLA), PC/ABS, cellulose fiber, polyphenylsulfone (PPSU), thermoset polymers , PBI-PEEK, urea, epoxides, cyanate esters, polyurethanes, or any combination thereof.

Product describes a finished product from a preform that has been coated in the manner described here. Therefore, the product is a preform with a multilayer, nanolaminate or microlaminate coating or cladding after the mandrel has been removed.

The embodiments provided herein provide for a batch of metal products having identifiable nanolaminate coating layers on a plurality of products in the batch. In such processes, the set of items may include all of the items in the lot, or may include a subset selected from all of the items in the lot. In other words, not all of the articles in a batch may be provided with the desired nanolaminate coating and/or have the desired characteristics of one or more of the embodiments described herein. If less than all items in a lot have the desired characteristics of a particular embodiment, then the set referred to herein will include those items within the lot that are determined (after examination, measurement, and/or testing, if necessary) to be nanolaminate coated according to the methods described herein, or having the desired characteristics described here.

As used herein, the abbreviation ASTM means (ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA, 19428-2959). Where reference is made in this specification to an ASTM standard having more than one version and no version number is given, the reference is to be understood as referring to the ASTM standard in effect at the time of filing of the earliest priority document in the patent family.

The term roughly has the meaning typically assigned to it by one of ordinary skill in the art when used in connection with a stated numerical value or range, i.e. denoting a little more than or a little less than the specified value or range, within the range of ±20% of the specified value; ±19% of the specified value;

- 4 041389 ±18% of the specified value; ±17% of the specified value; ±16% of the specified value;

±15% of the specified value; ±14% of the specified value; ±13% of the specified value;

±12% of the specified value; ±11% of the specified value; ±10% of the specified value;

±9% of the specified value; ±8% of the specified value; ±7% of the specified value;

±6% of the specified value; ±5% of the specified value; ±4% of the specified value;

±3% of the specified value; ±2% of the specified value or ±1% of the specified value.

The term has the practical meaning normally assigned to it by one of ordinary skill in the art when used to describe a physical characteristic of an item, i.e. indicating that the item has a specified characteristic to a significant extent, for example, within a range of ±20% of the specified characteristic; ±19% of the specified characteristic; ±18% of the specified characteristic; ±17% of the specified characteristic; ±16% of the specified characteristic; ±15% of the specified characteristic; ±14% of the specified characteristic; ±13% of the specified characteristic; ±12% of the specified characteristic; ±11% of the specified characteristic; ±10% of the specified characteristic; ±9% of the specified characteristic; ±8% of the specified characteristic; ±7% of the specified characteristic; ±6% of the specified characteristic; ±5% of the specified characteristic; ±4% of the specified characteristic; ±3% of the specified characteristic; ±2% of specification or ±1% of specification. For example, an object may be considered substantially round if any two measurements of the object's diameter are within the range of ±20, ±19; ±18; ±17; ±16; ±15; ±14; ±13; ±12; ±11; ±10; ±9; ±8; ±7; ±6; ±5; ±4; ±3; ±2 or ±1% of each other.

When used in connection with the object of comparison (eg, the first coating is significantly thicker than the second coating), the concept is significantly used to mean that the difference is at least ±20% of the specified characteristic; ±19% of the specified characteristic;

±18% of the specified characteristic; ±17% of the specified characteristic; ±16% of the specified characteristic;

±15% of the specified characteristic; ±14% of the specified characteristic; ±13% of the specified characteristic;

±12% of the specified characteristic; ±11% of the specified characteristic; ±10% of the specified characteristic;

±9% of the specified characteristic; ±8% of the specified characteristic; ±7% of the specified characteristic;

±6% of the specified characteristic; ±5% of the specified characteristic; ±4% of the specified characteristic;

±3% of the specified characteristic; ±2% of specification or ±1% of specification.

Terms or concepts used in the context of the description of the invention in the singular (especially in the context of the following claims) should be construed as covering both the singular and the plural (i.e. one or more), unless otherwise stated here or specifically denied by the context. The value ranges given here are intended to serve as a method of shortening references individually to each specific value that falls within the range. As used herein, any concentration range, percentage range, ratio range, or integer range is to be understood to include the value of any integer within the specified range and, if appropriate, its fractions (such as one tenth and one hundredth of an integer) if not otherwise stated. In addition, any numerical range specified herein referring to any physical property, such as size or thickness, should be understood to include any integer within the specified range, unless otherwise noted. Unless otherwise stated here, each individual value is included in the description as if it were specified here separately.

The use of an alternative (eg, or) should be understood to mean one, both, or any combination of alternatives. The various embodiments described above may be combined to create additional embodiments. The groupings of alternative elements or embodiments of the invention described herein are not to be construed as limitations. Each member of the group may be listed and claimed individually or in any combination with other members of the group or other elements found here. The union or used here in the specification and in the claims is to be understood to mean either or both of the elements thus combined, i.e. elements that are present together in some cases and present separately in other cases. Multiple elements listed with or must be interpreted in the same way, i.e. one or more of the elements thus combined. Other elements may optionally be present other than the elements specifically specified with the conjunction or, whether or not they are related to those specifically specified elements. Thus, as a non-limiting example, reference to A or B, when used in connection with non-limiting terminology such as containing or including, may mean in one embodiment only A (optionally including elements other than B), in yet another embodiment, only B (optionally including other elements than A), in yet another additional embodiment, both A and B (optionally including other elements), etc.

The expression and/or used here in the description and in the claims is to be understood

- 5 041389 as meaning either or both of the elements thus combined, i.e. elements that are present together in some cases and present separately in other cases. Multiple items listed with and/or should be construed in the same way, i.e. one or more elements combined in this way. Other elements may optionally be present other than the elements specifically specified with the conjunction and/or whether or not they are related to those specifically specified elements. Thus, as a non-limiting example, reference to A and/or B, when used in connection with non-limiting terminology such as containing or including, may mean in one embodiment only A (optionally including elements other than B), in yet another embodiment - only B (optionally including other elements than A), in yet another additional embodiment - both A and B (optionally including other elements), etc.

Used here in the description and in the claims, the expression at least one with reference to a list of one or more elements should be understood as meaning at least one element selected from any one or more elements in the list of elements, but optionally including at least one from each and every element specifically listed within the list of elements and not excluding any combination of elements from the list of elements. This definition also allows that elements other than the elements specifically specified within that list of elements to which the expression at least one refers may optionally be present, whether or not they are related to those specifically specified elements. Thus, as a non-limiting example, at least one of A and B (or equivalently at least one of A or B, or equivalently at least one of A and/or B) may refer in one embodiment to to at least one A, optionally including more than one A, without the presence of B (and optionally including elements other than A), in another embodiment, to at least one B, optionally including more than one B, without the presence of A (and optionally including elements other than A), in yet another further embodiment, at least one A, optionally including more than one A, and at least one B, optionally including more than one B (and optionally including other elements), etc.

In the context of this description, the words process and method are synonymous. It should also be understood that, unless expressly stated otherwise, the processes described herein and claimed below may include steps in addition to the steps indicated, and the order of steps or process steps is not necessarily limited to the order in which those steps or process steps are specified.

Each embodiment disclosed herein may contain, consist essentially of, or consist of the specified element, step, ingredient, or component. The term contain or contains means includes, but is not limited to and allows the inclusion of unspecified elements, steps, ingredients or components, even in significant amounts. The expression consisting of excludes any element, step, ingredient, or component that is not specifically stated. The expression consisting essentially of limits the scope of the embodiment to the specified elements, steps, ingredients or components, and those that do not significantly affect the basic and new characteristics of the claimed invention.

In the claims, as well as in its description, all transitive expressions, such as containing, composed of, including, bearing, having, containing, containing, holding, composed of something, etc., should be understood as non-limiting, i.e. .e. including, but not limited to. Only transitional expressions consisting of and consisting essentially of shall be understood as closed or semi-closed transitional expressions, respectively, as set out in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

The present invention provides container devices that can be used to deposit nanolaminate coatings on preforms. In use, at least a portion of such container devices (eg, a basket or drum) contains one or more preforms, allowing at least a portion of the preforms to be in contact with the electrodeposition bath. It also shows methods for metallizing blanks using container devices.

Drum plating.

In drum plating processes, the workpieces to be coated are placed in a container device (ie, an electroplating drum) made of plastic or other material that does not conduct electrical current. The electroplating drum (hereinafter referred to as the drum) has openings around its circumference (for example, openings formed in the wall of the drum, or sections of mesh or perforated screen), so that when the drum is placed in an electroplating bath containing an electrolytic solution, this solution can pass through the holes made along the circumferential periphery into the inner part of the drum and come into contact with the workpieces to be coated. Typically, the cathode (for example, the cathode in the form of a flexible electrode or pendant, so called because it is usually connected through a flexible conduit) is passed through a hole in each end of the drum. The cathode enters and remains inside the drum as the drum rotates about its horizontal axis of rotation. There are one or more anodes in the electrolytic solution on the outside of the drum.

During operation, the drum is at least partially immersed in a plating bath and rotates. Current is applied between the anode(s) outside the drum and the cathode(s) in the drum. As the drum rotates, one or more workpieces in the drum may alternately contact each other and at least one of the cathodes, thereby completing a circuit between the cathode(s) and the conductive articles. When a circuit is initiated or closed, the work(s) in the circuit become(are) negatively charged and attract positively charged ions from the anode or in the electrolytic solution. Positively charged ions from the anode, from the electrolytic solution, or both, capable of reaching the negatively charged workpiece(s) in a closed circuit, are deposited on the workpiece(s). As a rule, more positively charged ions reach those preforms that are on or near the metalizing surface of the drum, which is the area near the outer periphery of the drum. On the plating surface of the drum, there are fewer obstacles for ions to reach and deposit on the surface of negatively charged workpieces. In principle, plating tends to occur on those workpieces that are in the outer part of the drum, since this is where the attraction is strongest.

Any type of drum may be used in accordance with this invention. Drums are available from a variety of manufacturers (eg Sterling Systems) in various lengths, diameters and general shapes (eg round or octagonal). For example, drums come in a variety of sizes such as 18" x 36", 24" x 60", 3" x 5", 4" x 6", 6" x 6", 6" x 9", 6" x 12". inches or 10 inches by 18 inches.

To intensify mixing, drums that do not have a circular cross section in a plane perpendicular to the axis of rotation can be used. For example, drums that have a hexagonal or octagonal cross section can be used. Similarly, drums with surface features (eg, ribs) on the inner wall(s) can be used to encourage mixing. One exemplary drum, electrolyte, and anode configuration is shown in FIG. 3A and 3B.

The cathodes may be of any shape, size, or configuration as will be appreciated by one of ordinary skill in the art. In embodiments, the cathodes are designed or modified to better remain substantially centered along the axis of rotation in the drum. In those embodiments where cathodic flexible electrodes are used, flexible electrode holders are provided to keep them placed closer to the axis of rotation of the drum. In embodiments, such holders may include a non-conductive material, such as polyvinyl chloride (PVC) tubing or other non-conductive plastic tubing, that at least partially covers the flexible portion of the flexible electrode. Such holders can also serve to protect flexible electrodes from damage by metallized blanks.

Typically, two cathodes will be used. In some such embodiments, the lengths of the cathodes (e.g., cathode flexible electrodes) are such that, when fully extended to the center of the drum, the cathodes are separated from each other by a distance that is greater than the longest dimension of any of the preforms being plated, so that a single preform could not create a connection between the cathodes. A longer distance can help provide more uniform coverage as more of the billets in the drum can be energized during the process. In other embodiments, the cathodes, being fully extended to the center of the drum, are separated from each other by a distance that is less than or the same as the longest dimension of any of the preforms to be plated. However, during operation, when the loaded drum rotates, the downward weight of the blanks in the drum may cause the cathodes to tilt slightly downward, thereby lengthening the distance between the ends of the cathodes. Therefore, during plating, shorter separation distances can actually be increased.

Embodiments of drum plating processes described herein include, for example:

(i) providing a drum plating system including:

(a) a drum having a length and a radius;

(b) at least two cathodic flexible electrodes disposed in the drum, the at least two cathodic flexible electrodes having a length at which, being completely extended into the center of the drum, the ends of the flexible electrodes are separated from each other by a distance (i.e. the sum of the lengths of these at least two cathode flexible electrodes is less than the length of the drum);

(c) an electrodeposition bath containing one or more electrodepositable ions; and (d) at least one anode in an electrodeposition bath outside the drum;

(ii) bringing at least a portion of the batch of preforms to be coated placed in the drum into contact with the electrodeposition bath, the preforms having the longest dimension;

- 7 041389 (iii) drum rotation;

(iv) electrodepositing a first identifiable layer onto at least a portion of the preforms in the batch by applying a first electrical current (e.g., a first constant current or a first time varying waveform) for a first amount of time across the cathodes, the first identifiable layer comprising at least first and second electrodepositable ions of said one or more electrodepositable ions;

(vii) electrodepositing a second identifiable layer onto a portion of the preforms in the batch by applying a second electrical current (e.g., a second constant current or a second time varying waveform) for a second amount of time through the flexible electrodes, the second identifiable layer comprising at least the first and the second electrodeposited ions, and the composition, grain size, structure (eg, microstructure or morphology) or thickness of the second identifiable layer differs from those of the first layer; and (viii) optionally, electrodeposition of an additional layer on a portion of the preforms in the batch by applying additional electrical current through the cathodes, wherein the additional layer contains at least the first and second electrodepositable ions, and the composition, grain size, structure (e.g., microstructure or morphology), or thickness additional layer differs from those of the immediately preceding layer.

In some embodiments, the first layer has a thickness at one or more locations on the article in the range of about 150 nm to about 20,000 nm, the second layer has a thickness at one or more locations on the article in the range of about 150 nm to about 20,000 nm, or both. . In additional embodiments, the implementation of the additional layer has a thickness in one or more places on the product in the range from about 150 to about 20,000 nm.

Additional embodiments of the drum plating processes described herein include, for example:

(i) providing a drum with a batch of coated metal products, and the drum has a length and radius, with each of the products has the longest dimension;

(ii) placing at least part of the drum and metal products in a tank containing an electrodeposition bath containing one or more electrodepositable metal ions;

(iii) providing at least one anode in the electrodeposition bath on the outside of the drum;

(iv) providing at least two cathode flexible electrodes extending into opposite ends of the drum, and being completely extended into the center of the drum, the ends of the flexible electrodes are separated from each other by a distance;

(v) rotating the drum;

(vi) applying a first electric current (e.g., a first constant current or a first time varying waveform) for a first amount of time through the flexible electrodes, thereby causing the first identifiable metal layer to be electrodeposited onto the metal products in the batch, the first layer having thickness in one or more places on the product in the range from about 150 to about 20,000 nm and contains at least the first and second metal components;

(vii) applying a second electrical current (eg, a second constant current or a second time varying waveform) for a second amount of time through the flexible electrodes, thereby causing electrodeposition of a second identifiable metal layer on the metal products in the batch having a thickness of one or more places on the product in the range from about 150 to about 20,000 nm and containing at least the first and second metal components, and the composition, grain size and / or structure (for example, microstructure or morphology) of the second layer differs from those of the first layer, and additionally, the second layer may also differ in thickness from the first layer; and (viii) optionally, applying one or more additional electrical currents through the flexible electrodes to cause the electrodeposition of additional metal layers on the metal products in the batch, each having a thickness at one or more locations on the product in the range of about 150 nm to about 20,000 nm. and contains at least one of the first and second metal components, and at the same time at least one feature selected from the group consisting of the composition, grain size and/or structure (for example, microstructure or morphology) of each such additional metal layer differs in from at least one of the features of the immediately preceding layer.

In some embodiments, the implementation of the thickness of the coating varies in different areas of the product. For example, the thickness of the coating may vary in the threaded areas of the product. Therefore, for comparison purposes, it may be easier and more favorable to measure and compare the thickness at the target surface in the threadless region of the product. Such a target surface can be designated as a significant surface, i.e. the surface on which coating thickness determinations are made and may be chosen, for example, because it is a surface on which corrosion can be expected. In other embodiments, it is more favorable to measure

- 8 041389 and comparison of the thickness in the threaded area of the product.

In drum plating systems, as the drum rotates about its axis of rotation (i.e., its longitudinal axis), the workpieces in the drum move and roll within the drum. The movement of the workpieces is a function of the displacement amplitude of the container system, the size of the workpiece and/or the ratio of the share of the load to the size of the drum. The load share is the ratio of the volume loaded into the drum blanks (ie displaced volume) to the volume of the drum.

At times during the rotation of the drum, the preform may be in the interior of the drum near its center, where it is unlikely to become metallized, even if it is charged, due to competition with other preforms in the drum, which block ions from reaching the preform. At other times, the preform will be closer to the outer surface of the drum (ie, the plating surface), where ions can easily be deposited on the preform if it is charged. At other times, the workpiece is somewhere between the center of the drum and the plating surface. The movement of the workpieces in the drum and the frequency with which the workpieces appear on and away from the plating surface during the plating process is referred to here as agitation.

The agitation rate can be approximated by the degree of agitation, which is the number of occurrences of a preform on a plated surface within a batch that could be plated over 50 drum revolutions divided by the number of drum revolutions (ie, 50). The higher the degree of agitation, the greater is the number of times a product blank within a batch will appear on the plating surface of the drum where it can be plated. In other words, as the degree of agitation increases, more of a particular preform in the batch will be coated. The degree of agitation can be determined empirically, for example by introducing differently colored labeled preforms into the interior of the drum and observing the number of occurrences of the labeled preforms on the plating surface over fifty revolutions of the drum, as described below in Example 4.

Similarly, as the drum rotates, the group of workpieces in the drum can simultaneously come into contact with each other and with the cathode(s), forming or completing a circuit between the cathodes and thereby creating a current between the cathode(s) that flows through each workpiece in the group and charges it. At such times, the group of preforms becomes negatively charged and deposition will occur on those negatively charged preforms in the group that are on or near the plating surface. At other times, the group of blanks in the drum is not simultaneously in contact with each other and with the cathodes, and therefore the circuit between the cathodes is open. When there is no current between the cathodes, charging and plating on the workpieces do not occur. As discussed here, this deviation from a steady or closed circuit (when plating occurs) to an open circuit (when plating does not occur) is referred to here as jitter.

One formula that can be used to experimentally measure the magnitude of such jitter during drum plating is the absolute value of the applied signal minus the average value of the measured signal, i.e.:

Jitter = |featured signal - average value of the measured signal|.

The challenge is to create a system in which the jitter is as close to zero as possible. However, systems where jitter is low but the standard deviation of the measured signal is greater than 20% of the applied signal may generate too much noise to provide the desired plating results.

Jitter can be determined experimentally by making measurements for any particular drum, load (including, for example, load fraction, length fraction, and product types), voltage, rpm, and current. The ratio of the longest size of metal products in the batch to the radius of the drum is a fraction of the length. Stirring can be experimentally determined in a similar manner as described above.

By comparing jitter and agitation among the many potential combinations of drums, loads (e.g., quantities, sizes, and constituents), RPM, input currents, voltages, and other parameters discussed here, one can vary the parameters of different systems to find and optimize parameter combinations. , which can provide metallization conditions leading to the desired multi-layer and nanolaminate coatings (see, for example, Examples 4 and 5 below).

The embodiments described here that minimize jitter and maximize agitation also give better results in terms of improved plating uniformity across multiple items in a batch, as the blanks will both charge more frequently and move closer to the plating surface of the drum where they can be plated. The embodiments described herein may provide the preforms in the drum with a multi-layer coating comprising at least two identifiable layers of electrodeposited coatings in which the composition, grain size and/or grain structure (e.g., microstructure or morphology) of the first electrodeposited layer is different from the composition, grain size and /or grain structure (for example, microstructures or

- 9 041389 morphology) of the second electrodeposited layer. In other embodiments, the implementation described here, the method can give products, including from 3 to 20 layers. In additional embodiments, the method described herein may produce articles comprising at least three identifiable layers, at least four identifiable layers, five to ten identifiable layers, ten to fifteen identifiable layers, fifteen to twenty identifiable layers, or more than twenty identifiable layers. layers. Each identifiable layer of these differs in one or more features selected from composition, grain size and/or grain structure (eg, microstructure or morphology), and potentially also in thickness, from immediately adjacent layers. Regardless of the number of layers identified, the layers can be deposited using a uniform composition bath by varying one or more of current/voltage, waveform, agitation speed, and temperature. Alternatively, it is possible to change the composition of the bath in situ, or move the drum or batch of blanks to another bath during the process to apply coating layers that differ in their composition, grain size and/or grain structure (eg, microstructure or morphology).

Vibratory plating in a basket.

Other alternatives to hanging plating can be used according to this invention, for example vibratory plating in a basket, in which the preforms to be coated are placed within the container system of the vibratory plating apparatus. In some embodiments, the container system includes a basket placed around a central shaft. The basket contains points of electrical contact, such as small disc electrodes, placed symmetrically around the bottom of the basket to provide a cathodic connection, which are connected to a power source. In some embodiments, the basket is porous (i.e., has one or more holes, or includes mesh or perforated screen sections) such that when the container system is placed in the plating bath, the electrolyte solution can flow through the holes into the container system when it is immersed in the electrolytic solution when it comes into contact with the workpieces, and flow out when it is removed from the solution. The basket may include bevels, deflectors, or other structural elements that help move the workpieces within the basket.

The vibratory plating device includes a frequency generator and a plate vibrator that vibrate the basket at a given frequency and amplitude, which causes the plate vibrator to twist back and forth, in turn causing the workpieces in the basket to slide and move around the central shaft of the basket.

In some embodiments, the implementation of the basket can move around the Central shaft with a given number of revolutions per minute (RPM), for example, from 5 to 20 rpm. In further embodiments, the basket may move around the central shaft at 5 to 10 rpm, 10 to 15 rpm, or 15 to 20 rpm.

In operation, the basket is loaded with preforms to be coated and at least partially immersed in an electrolytic solution. The anode can be placed in the bath solution on the outside of the basket. In some embodiments, the implementation of the anode is placed under the basket. In further embodiments, two or more anodes are placed outside the basket. Because the basket is porous, the electrolytic solution is able to flow into the basket and contact the workpieces. The basket vibrates at a predetermined frequency, rotates around a central shaft at a predetermined RPM, or both, while current is applied to electrical contact points, such as small disk electrodes. As the basket moves, the workpieces slide across the surface of the basket towards each other and come into contact with electrical contact points where they become negatively charged and metallized. The basket advantageously enables almost uniform mixing and sliding of the workpieces during the plating process.

In some embodiments of the vibratory system, the basket is connected to a motor or similar system through a central shaft, which causes the basket to move by a displacement distance (x) with a frequency (p), where p is set to provide electrodeposition of one full layer by applying the first current and a second full layer by applying the second current, leading to the formation of the intended layered structure on the part of the blanks inside the container system. The offset distance, x, and the periodicity, p, are determined in part by the level of current variation (ie, jitter) measured for any given combination of system parameters (eg, billet length fraction, load fraction, and average degree of agitation). The variables x and p are chosen to minimize the measured system jitter. In such embodiments, the processes may produce a plurality of articles in which the weight percent of the first component in any article of the plurality does not differ by more than a predetermined amount, such as 6 wt.% or less, from the weight percent of the same metal component in another article of the plurality. .

Other non-suspension methods of metallization with container devices.

Alternatively, according to this invention, other non-suspended metallization methods can be used to create nanolaminate coatings, as well as modulated

- 10 041389 mass transfer processes for applying such coatings. For example, nanolaminate coatings can be created by plating processes that involve moving the preforms to be coated within a container device that provides intermittent contact of the preforms to be coated with an electrical power source. In other embodiments, nanolaminate coatings can be created through plating processes that involve moving the preforms to be coated within a container device that provides substantially continuous contact of the preforms to be coated with an electrical power source.

For example, an oscillating-type plating system could be designed in which the workpieces to be coated are held in a container system including a basket having a conductive (eg, metal) mesh bottom, which may be flat or shaped, eg, arcuate. In embodiments, the sides of the basket may be coated with a non-conductive coating, or made of a non-conductive material. In operation, the basket may be at least partially immersed in the electrodeposition bath and current is applied to the conductive mesh bottom. One or more anodes may be placed in the bath on the outside of the basket. In some embodiments, the implementation of the anode is placed under the basket. In embodiments, the basket is connected to rocker arms which, when applied, pump the basket. The basket can be rocked back and forth in an arc-shaped motion around the longitudinal axis of rotation, which would cause the workpieces to roll or move along the bottom of the basket, practically maintaining contact with the conductive mesh and providing dosed exposure of the coated surface, depending on the frequency of swings. The longitudinal axis of rotation can typically be outside the electrodeposition bath. In other embodiments, the basket tilts in one direction for a period of time and then tilts in the opposite direction for a period of time. In further embodiments, the basket tilts in a first direction for a period of time, tilts in a second direction for a period of time, and tilts in a third direction for a period of time. In other additional embodiments, the implementation of the basket moves in a circular motion around the Central shaft, deviating away from the Central shaft.

This method of plating in a oscillating vessel can be an acceptable replacement for the non-suspended plating of small workpieces. In some embodiments, the oscillating vessel plating device provides substantially continuous electrical contact with the workpiece(s) to be plated, without the need for each part to be physically connected to an electrical circuit. For example, such a method could be used for plating studs (ie, threaded cylindrical blanks), given their ability to roll along the mesh bottom. Such a method could provide the additional benefit of minimizing damage during the plating process caused by violent collisions between large workpieces, which can occur in processes such as drum plating. Therefore, such a method could also be advantageously used to plate heavier workpieces (eg, pins) that cannot be plated in the drum due to collision damage that can occur in the drum during drum coating. For example, studs weighing more than 0.1 kg, more than 0.2 kg, more than 0.25 kg, more than 0.5 kg, more than 1 kg, more than 1.5 kg, more than 2 kg or more than 2 kg, with significantly less damage to the coating than equivalent stud plating using the traditional drum plating method.

In such oscillating systems, the basket can be subdivided into compartments or lanes using non-conductive baffles, which themselves can be movable or removable (e.g., like dividers in a refrigerator), to facilitate the loading of workpieces of varying sizes from batch to batch and from run to run. to another. For example, a rectangular basket could have four dividers to create five compartments or lanes within the basket. The preforms to be coated can then be placed along the conductive bottom with sufficient spacing in each compartment or each track to allow the preforms to roll or move along the conductive mesh floor when the basket is rocked. The compartments or tracks may be sized to promote substantially linear rolling motion of the blanks and to minimize any twisting of the blanks that would interfere with rolling. For example, the width of each lane could be only slightly wider than the length of the blanks, thereby allowing the blanks to be stacked side by side and then allowing the blanks to roll freely in the direction of the arcuate or oblique motion, but preventing the blanks from twisting within the lane.

In embodiments, the mesh bottom provides substantially continuous electrical contact with the blanks in the basket. The supply of electrical power to the mesh bottom could be accomplished in any of a number of ways, as would be understood by one of ordinary skill in the art. For example, the coated wire(s) could pass directly to the contact points on the mesh bottom on the outside of the tub. Alternatively, the rocker arms can be conductive and in contact with the basket, so that the rocker arms conduct current from outside the tub to the mesh bottom in the tub.

- 11 041389 no. In such embodiments, the portion of the basket to be immersed in the bath (eg, the sides) would then be coated with a dielectric, such as plastic, to render such areas non-conductive. In embodiments, the plating device in the oscillating vessel is a circular rotating wheel (like a Ferris or squirrel wheel) which, when partially submerged in the electrodeposition bath and rotated, provides one or more continuous tracks for rolling the preforms to be coated.

In embodiments, the basket is connected to a motor or similar system that causes the basket to move a displacement distance (x) at a frequency (h), where h is set to allow electrodeposition of one full layer by applying the first current and a second full layer by applying the second current, resulting in the formation the intended layered structure on the part of the metal blanks inside the container system. The offset distance, x, and frequency, h, are determined in part by the level of current variation (ie, jitter) measured for any given combination of system parameters (eg, billet length fraction, load fraction, and average degree of agitation). The variables x and h are chosen to minimize the altered system jitter. The rocker arms can rock or tilt back and forth, for example in an arcuate, linear, or tilted circular motion, so as to cause the preforms to roll along the screen bottom. In embodiments where the preform is a pin, the pin can be rolled back and forth so that it is continuously in contact with the mesh bottom while maintaining a substantially constant motion that can help create a substantially uniform layer of laminate and help prevent overgrowth. hairpins and fastenings with the mesh bottom.

As with the aforementioned drum plating and vibratory basket plating methods, embodiments of the oscillating tank plating systems also include mass transfer modulation, as discussed above, to modulate the composition of the nanolaminate layers. This mass transfer modulation can take into account basket movement, which also contributes to the mass transfer modulation effects described above.

Waveform, voltage, current and mass transfer frequency.

The non-suspension methods described herein involve mass transfer modulated processes for creating nanolaminate coatings. In such processes, the compositions of the alloys in the individual layers of the nanolaminate coating can be varied by modulating the electrochemical deposition frequency between different current densities. In embodiments, current densities and other deposition parameters are matched to those of the particular plating method employed in order to achieve compositional modulation of nanolaminate layers having the desired compositions.

The characteristics of the nanolaminate coatings deposited by the various plating methods described herein, including the thickness and stress of the layers, can be controlled, among other things, by controlling the electrical voltage and current during the electrodeposition process. The current can be applied uniformly and continuously to each type of layer (periodic layer) by being applied to the workpiece. The current may also be applied in a predetermined mode, such as a waveform, to electrodeposit one or more periodic layer(s). In particular, the wave signal may be applied continuously or discontinuously (pulsed) to facilitate the electrodeposition process of each periodic layer. The stepwise inversion of the current applied during the electrodeposition (pulse inversion) can be used to improve the quality of the electrodeposited material (for example, promoting the formation of fully dense layers), change the grain size and/or change the internal mechanical stress in the electrodeposited material. Suitable waveforms include sine waves, square waves, sawtooth waves, triangular waves, or combinations thereof, applied either sequentially or overlapping (overlapping).

In one embodiment, the displacement of a sine wave or sine wave-like function due to superimposed bias current and a sine wave or sine-wave-like function can be used to deposit a corrosion resistant coating comprising one or more periodic layers, where the coating has a mechanical stress that is less than 400 MPa, less than 300 MPa, less than 200 MPa, less than 100 MPa, less than 50 MPa, less than 20 MPa, less than 10 MPa, or not measurable.

Voltage, current and/or current density and wave period may vary. In embodiments, the voltage ranges from 1 to about 10 V, for example, the voltage can range from 2 to 9 V or from 3 to 8 V. In embodiments, the voltage ranges from about 3 to about 8 V. In some embodiments, the voltage ranges from 3 to 4V, 3 to 5V, 3 to 6V, 3 to 7V, 4 to 5V, 4 to 6V, 4 to 7V, 4 to 8V, 4 to 9 V, 5 to 7 V, 5 to 8 V, 5 to 9 V, 6 to 7 V, 6 to 8 V, 6 to 9 V, 7 to 8 V, or 7 to 9 V. In embodiments, the voltage for deposition of the second layer may be at least twice as high as that used for deposition of the first layer. Depending on bath chemistry and pH, voltages below about 3.3 V may not be sufficient to achieve proper results.

- 12 041389 plating, and voltages above about 8 V can produce unacceptable plating of metals such as nickel, as well as noise and jitter levels that are too high to obtain the desired plating results.

In embodiments, the first electric current that is applied to deposit the first layer is, for example, from about 10 to about 180 A. In other embodiments, the first electric current is in excess of 180 A. In further embodiments, the first electric current is in the range of about 10 to about 20 A, about 20 to about 30 A, about 30 to about 40 A, about 40 to about 50 A, about 50 to about 60 A, about 60 to about 70 A, about 70 to about 80 A, about 80 to about 90 A, about 90 to about 100 A, about 100 to about 110 A, about 110 to about 120 A, about 120 to about 130 A, about 130 to about 140 A, from about 140 to about 150 A, from about 150 to about 160 A, from about 160 A to 170 A, from about 170 to about 180 A, or greater than 180 A. In embodiments, the first electric current is in the range of about 40 A. about 140 A. In such embodiments, the first electric current may range from about 40 to about 60 A, from about 60 to about 80 A, from about 80 to about 110 A, from about 100 to about 140 A, from about 70 to 80 A, about 80 to about 90 A, about 90 to about 100 A, about 100 to about 110 A, about 110 to about 120 A, about 120 to about 130 A, and about 130 to about 140 A.

In some embodiments where the preforms are pucks that are being nanolaminated, the first electric current is in the range of about 60 to about 70 A. In specific embodiments where the preforms are pucks, the first electric current is about 64 A. In some embodiments, where the preforms are pucks. In embodiments where the blanks are nuts that are being nanolaminated, the first electrical current is in the range of about 40 to about 60 A. In specific embodiments, where the blanks are nuts, the first electrical current is about 50 A. In some embodiments, the first electrical current is about 50 A. where the preforms are pins that are being nanolaminated, the first electric current is in the range of about 20 to about 30 A. In particular embodiments where the preforms are pins, the first electric current is about 25 A.

In embodiments, the second electrical current that is supplied to deposit the second layer is, for example, from about 10 to about 180 A. In other embodiments, the second electrical current is in excess of 180 A. In further embodiments, the second electrical current is in the range of about 10 to about 20 A, about 20 to about 30 A, about 30 to about 40 A, about 40 to about 60 A, about 40 to about 50 A, about 50 to about 60 A, about 60 to about 70 A, about 70 to about 80 A, about 80 to about 90 A, about 90 to about 100 A, about 90 to about 110 A, about 100 to about 110 A, about 110 to about 120 A, from about 120 to about 130 A, from about 130 to about 140 A, from about 140 to about 150 A, from about 150 to about 160 A, from about 160 A 170 A, from about 170 to about 180 A or more 180 A. In variants implemented and the second electric current, which is supplied for the deposition of the second layer, is about twice the current that is supplied for the deposition of the first layer. In other embodiments, the second electrical current that is applied to deposit the second layer is significantly more than twice the current that is applied to deposit the first layer.

In embodiments where the preforms are hairpins that are being nanolaminated, the second electric current is in the range of about 40 to about 60 A. In specific embodiments where the preforms are hairpins, the second electric current is about 50 A. In some embodiments, embodiments where the blanks are nuts that are being nanolaminated, the second electric current is in the range of about 90 to about 110 A. In specific embodiments where the blanks are nuts, the first electric current is about 100 A. In some embodiments, where the preforms are pucks that are being nanolaminated, the first electric current is in the range of about 120 to about 135 A. In particular embodiments where the preforms are pucks, the first electric current is about 128 A.

In embodiments where one or more additional electrical currents are applied to deposit one or more additional layers, each additional electrical current may be the same as the first and/or second electrical current. In other embodiments, each additional electric current is from 10 to 180 A. In further embodiments, each additional current is independently in the range of 10 to about 20, about 20 to about 30, about 30 to about 40, about 40 to about 60, about 40 to about 50, about 50 to about 60, about 60 to about 70,

- 13 041389 about 70 to about 80, about 80 to about 90, about 90 to about 100, about 90 to about 110, about 100 to about 110, about 110 to about 120, about 120 to about 130, about 130 to about 140, about 140 to about 150, about 150 to about 160, about 160 to about 170, about 170 to about 180, or greater than about 180 A.

In embodiments, the first and second electric currents are repeated several times (for the same length of time as the first and second times) until the desired number of layers and/or total coating thickness is achieved.

In some embodiments, the implementation of the current density may vary continuously or discretely in the range from about 0.5 to about 200 mA/cm ² . In drum plating embodiments, using current density as a parameter is generally a less accurate measure of current due to the ever-changing surface area of the workpieces being plated. However, current density can become a valid measure if the drum plating equipment used requires a current density value as an input parameter.

In embodiments, current densities used are in the range of about 1 to about 5 mA/cm ² , about 5 to about 10 mA/cm ² , about 10 to about 20 mA/cm ² , about 20 to about 40 mA /cm ² from about 40 to about 60 mA/cm ² from about 60 to about 80 mA/cm ² from about 80 to about 100 mA/cm ² from about 100 to about 150 mA/cm ² or from about 150 to about 200 mA/cm ² . In embodiments, higher current densities are used.

In some embodiments, the frequency of the waveforms may be from about 0.01 to about 50 Hz. In other embodiments, the implementation of the frequency may be from about 0.5 to about 10 Hz; from about 0.02 to about 1 Hz; from about 2 to about 10 Hz; or from about 1 to about 5 Hz.

Electric currents will typically be applied for periods on the order of minutes to deposit a given layer on all or a significant portion of the preforms in a batch. In embodiments, the step of applying a first electric current for a first amount of time is carried out over a period of several minutes ranging from about 0.5 to about 25 minutes. In other embodiments, the first electrical current is applied for more than 25 minutes. In additional embodiments, the first electrical current is applied for a first amount of time in the range of from about 0.5 to about 1 minute, from about 1 to about 3 minutes, from about 1 to about 4 minutes, from about 1 to about 5 minutes, from about 2 to about 4 minutes, from about 2 to about 5 minutes, from about 2 to about 6 minutes, from about 3 to about 6 minutes, from about 3 to about 7 minutes, from about 4 to about 6 minutes, from about 4 to about 7 minutes, from about 4 to about 8 minutes, from about 5 to about 8 minutes, from about 5 to about 9 minutes, from about 5 to about 10 minutes, from about 6 to about 8 minutes, from about 6 to about 9 minutes, about 6 to about 10 minutes, about 8 to about 12 minutes, about 10 to about 15 minutes, about 15 to about 20 minutes, about 20 to about 25 minutes, or longer than about 25 minutes.

In embodiments, the step of applying a second electric current for a second amount of time is carried out over a period of several minutes ranging from about 0.5 to about 25 minutes. In other embodiments, the second electrical current is applied for more than 25 minutes. In further embodiments, the second electrical current is applied for a second amount of time ranging from about 0.5 to about 1 minute, from about 1 to about 3 minutes, from about 1 to about 4 minutes, from about 1 to about 5 minutes, from about 2 to about 4 minutes, from about 2 to about 5 minutes, from about 2 to about 6 minutes, from about 3 to about 6 minutes, from about 3 to about 7 minutes, from about 4 to about 6 minutes, from about 4 to about 7 minutes, from about 4 to about 8 minutes, from about 5 to about 8 minutes, from about 5 to about 9 minutes, from about 5 to about 10 minutes, from about 6 to about 8 minutes, from about 6 to about 9 minutes, about 6 to about 10 minutes, about 8 to about 12 minutes, about 10 to about 15 minutes, about 15 to about 20 minutes, about 20 to about 25 minutes, or longer than about 25 minutes.

In embodiments where one or more additional electrical currents are applied to deposit one or more additional layers, the step of applying each additional electrical current may be carried out for the same number of minutes as for the first and/or second layers. In embodiments, each additional electrical current is applied over a number of minutes ranging from about 0.5 to about 25 minutes. In other embodiments, each additional electrical current is delivered for more than 25 minutes. In further embodiments, each additional electrical current is applied for an amount of time ranging from about 0.5 to about 1 minute, from about 1 to about 3 minutes, from about 1 to about 4 minutes, from about 1 to about 5 minutes. , from about 2 to about 4 minutes, from about 2 to about 5 minutes, from about 2 to about 6 minutes, from about 3 to about 6 minutes, from about 3 to about 7 minutes, from about 4 to about 6 minutes, from about 4 to about 7 minutes, from about 4

- 14 041389 up to about 8 minutes, from about 5 to about 8 minutes, from about 5 to about 9 minutes, from about 5 to about 10 minutes, from about 6 to about 8 minutes, from about 6 to about 9 minutes, from about 6 to about 10 minutes, about 8 to about 12 minutes, about 10 to about 15 minutes, about 15 to about 20 minutes, about 20 to about 25 minutes, or longer than about minutes.

In embodiments, the optional step of applying additional current includes repeating the first electric current for a first amount of time an additional number of times. In the present invention, the first electric current is applied for the first amount of time 1 time, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times , 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times or more than 20 times. In embodiments, the optional step of applying additional current comprises repeating the second electric current for a second amount of time an additional number of times. In some embodiments, the second electrical current is applied for a second amount of time 1 time, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times or more than 20 times.

In embodiments, the optional step of electrodepositing additional layers includes applying a current that is the same as the first or second electrical current for a period of time that is the same as either the first or second amount of time. In other embodiments, the optional step of electrodeposition of additional layers includes the behavior of a current that is the same as the first or second electrical current for a period of time that is different from the first or second amount of time. In embodiments, the optional step of electrodepositing further layers includes applying a current that is different from the first or second electrical current for a period of time that is the same as the first or second amount of time. In embodiments, the optional step of electrodepositing additional layers includes applying a current that is different from the first or second electric current for a period of time that is different from either the first or second amount of time. Again, depending on the parameters discussed above, including voltage, current, and desired layer thickness, the amount of deposition time for each such additional layer is likely to be on the order of minutes, such as from about 0.5 to about 1 minute, from about 1 to about 2 minutes, from about 2 to about 3 minutes, from about 3 to about 4 minutes, from about 4 to about 5 minutes, from about 5 to about 6 minutes, from about 6 to about 7 minutes, from about 7 to about 8 minutes, about 8 to about 9 minutes, about 9 to about 10 minutes, about 10 to about 11 minutes, about 11 to about 12 minutes, about 12 to about 14 minutes, about 14 to about 16 minutes, from about 16 to about 18 minutes, about 18 to about 20 minutes, about 20 to about 25 minutes, or longer than about 25 minutes.

In embodiments, the power supply for the plating process is designed to minimize noise. Illustrative power supply manufacturers include Dynatronix, American

Plating Power and Kepco.

Electrolytes and optional post-treatments.

The electrodeposition of coatings, including individual layers, can be carried out using an electrolyte (electroplating bath) containing(s) liquid/solvent and ions of the material(s) to be electrodeposited. Such baths are well known in the art. The liquid/solvent may be water, an organic solvent, an ionic liquid, a molten salt, or a combination thereof. In addition to the liquid/solvent, the plating bath may contain various salts (eg metal salts) which will be reduced at the cathode to form the electrodeposited metal(s). The bath may additionally contain metalloids, polymers, ceramic or ceramic-like materials, which may be present, for example, in the form of particles that are subjected to electrophoretic deposition. During the deposition process, the components of the bath will be depleted and therefore need to be monitored and replenished as needed, depending on the lifetime of the bath.

A variety of ionic liquids are known that can be used in the electrodeposition of the coatings and claddings described here. Suitable ionic liquids include those listed in Table. 1, where

EMIM - 1-ethyl-3-methylimidazolium,

PMIM - 1-propyl-3-methylimidazolium,

BMIM - 1-butyl-3-methylimidazolium,

HMIM - 1-hexyl-3-methylimidazolium,

DMIM - 1-decyl-3-methylimidazolium, b-diMIM - 1-butyl-2,3-dimethylimidazolium,

OMIM - 1-methyl-3-octylimidazolium,

BZMIM - 1-benzyl-3-methylimidazolium and

- 15 041389

P14 ⁺ - phosphorus cation.

Table 1

Cation Anion [EM1M] ⁺ [bf ₄ ]· [(CF ₃ SO ₂ ) ₂ N]- [RM1M] ⁺ [bf ₄ ]· [(CF ₃ SO ₂ ) ₂ N]' [VM1M] ⁺ [bf ₄ ]· [ _PF6 ]- [TFO]- [(CF ₃ SO ₂ ) ₂ N]' [ _SbF6 ]- [CF ₃ SO ₃ ]' [NM1M] ⁺ [(CF ₃ SO ₂ ) ₂ N]- [0M1M] ⁺ [bf ₄ ]· [RRb]' [(CF ₃ SO ₂ ) ₂ N]- [DMIM] ⁺ [(CF ₃ SO ₂ ) ₂ N] [b-AMIM] ⁺ [bf ₄ ]· [(CF ₃ SO ₂ ) ₂ N]' [BZMIM] ⁺ [(CF ₃ SO ₂ ) ₂ N]' [OH(CH ₂ ) ₂ -MIM] ⁺ [(CF ₃ SO ₂ ) ₂ N]' [Rm]' [(CF ₃ SO ₂ ) ₂ N]' n-butylammonium [SCN]' sec-butylammonium [SCN]' dipropylammonium [SCN]' ethylammonium [ _NO3 ]' n-propylammonium [ _NO3 ]' tributylammonium [ _NO3 ]' tetrabutylammonium [CHES]' tetrapropylammonium [CHES]' tetrapentylammonium [(CF ₃ SO ₂ ) ₂ N]-

The coatings may be subjected to an auxiliary treatment, such as chromate, carbonate, or heat treatment, using methods known to the person skilled in the art, to increase the corrosion resistance, hardness, or some other property of the coating.

Other parameters that affect metallization.

Additional parameters of the plating process can affect the results of plating. As discussed earlier, embodiments that maximize agitation and minimize jitter tend to give better results in terms of improved plating uniformity across multiple items in a batch.

Furthermore, in addition to varying the applied electric current as discussed above, one or more of the electrolyte temperature, the pH value, the concentration of additives in the electrolyte, or the agitation of the electrolyte can be varied individually to obtain periodic layers that are variable in composition or microstructure. or in combination with changes in the input current, to obtain one or more coating layers.

For drum plating, one example of such a parameter is the ratio of the longest dimension of the preforms to be coated to the radius of the drum, i.e. fraction of the length. In embodiments, the ratio is less than about 1.5, less than about 1.3, less than about 1.1, less than about 1.0, less than about 0.9, less than about 0.8, less than about 0.75, less than about 0.7, less than about 0.6, less than about 0.5, less than about 0.45, less than about 0.4, less than about 0.35, less than about 0.3, less than about 0.25, or less than about 0, 2. In other embodiments, this ratio is in the range of about 0.1 to about 1.5. In some embodiments, this is from about 0.2 to about 0.3, from about 0.2 to about 0.6, from about 0.3 to about 0.4, the ratio is from about from about about

0.2 to about 0.4, 0.2 to about 0.7, 0.3 to about 0.5, from from from about 0.1 about 0.2 about 0.2 about 0.3 to up to up to about about about

0.2

0.5

0.8

0.6

- 16 041389 from about 0.3 to about 0.7, from about 0.3 to about 0.8, from about 0.4 to about 0.5, from about 0.4 to about 0.6, from about 0 .4 to about 0.7, from about 0.4 to about 0.8, from about 0.5 to about 0.6, from about 0.5 to about 0.6, from about 0.5 to about 0, 7, from about 0.5 to about 0.8, from about 0.6 to about 0.7, from about 0.6 to about 0.75, from about 0.6 to about 0.8, from about 0, 6 to about 0.9, about 0.7 to about 0.8, about 0.7 to about 0.9, about 0.7 to about 1.0, about 0.8 to about 1.0, about 0.8 to about 1.1, about 0.8 to about 1.2, about 0.9 to about 1.1, about 0.9 to about 1.2, about 0.9 to about 1.3, from about 1.0 to about 1.1, from about 1.0 to about 1.2, from about 1.0 to about 1.3, from about 1.0 to about 1.4, from about 1, 1 to about 1.2, from about 1.1 to about 1.3, from about 1.1 to about 1.4, from about 1.1 to about 1.5, about 1.2 to about 1.3, about 1.2 to about 1.4, or about 1.2 to about 1.5. In some embodiments of the methods disclosed herein, a length fraction ranging from about 0.6 to about 0.75 provides an acceptable result. In additional embodiments, a length fraction of about 0.67 may provide acceptable results (see Example 1 below).

In other embodiments, the system parameters are adjusted to allow the plating of articles having a higher length fraction. In such embodiments, the length fraction can be up to about 1.1 or about 1.3. In further such embodiments, the length fraction may be greater than 1.3. Changing parameters, such as the loading rate and/or the composition of the types of workpieces in the drum, as well as other parameters, such as the number of revolutions per minute and current, may allow higher length fractions to be successfully applied.

Load volume fraction, which is the ratio of the stuffing volume of the preforms to the volume of that part of the container device that holds the preforms to be coated, such as the drum, vibrating basket, or oscillating vessel, is another parameter that can be adjusted to modify the plating results. In the case of solid billets, the volume fraction of the load will be the same as the fraction of the load (ie the ratio of the volume of the billets to the volume of the container device). The stuffing volume is the volume of the workpiece if it were considered as a geometric solid body. For example, in the case of a washer, the packing volume would not account for the hole in the washer. Thus, the stuffing volume would be larger than the displaced volume. Accordingly, in the case of blanks that are not solid objects (eg washers or nuts), a packing volume should be used (as different from the displaced volume).

In drum plating embodiments, if the loading ratio is too high, then jitter will be reduced, but mixing will also be reduced, potentially resulting in reduced plating uniformity among products in a batch, including when depositing multiple layers. Conversely, if the load fraction is too low, mixing will be improved but jitter will be increased, again potentially resulting in reduced plating uniformity among the products in the batch.

In embodiments, the load fraction is less than a predetermined value, such as less than about 0.7 (i.e., 70%), less than about 0.6, less than about 0.5, less than about 0.4, less than about 0, 35, less than about 0.3, less than about 0.25, less than about 0.2, less than about 0.15, or less than about 0.1. In embodiments, the processes herein have load shares, for example, in the range of from about 0.05 to about 0.10, from about 0.05 to about 0.15, from about 0.05 to about 0.20, from about 0, 05 to about 0.25, about 0.05 to about 0.3, about 0.05 to about 0.35, about 0.05 to about 0.4, about 0.10 to about 0.15 , from about 0.10 to about 0.20, from about 0.10 to about 0.25, from about 0.10 to about 0.3, from about 0.1 to about 0.35, from about 0.1 up to about 0.4, from about 0.15 to about 0.20, from about 0.15 to about 0.25, from about 0.15 to about 0.30, from about 0.15 to about 0.35, about 0.15 to about 0.40, about 0.15 to about 0.45, about 0.20 to about 0.25, about 0.20 to about 0.30, about 0.20 to about 0.35, from about 0.20 to about 0.40, from about 0.20 to about 0.45, from about 0.25 to about 0.30, from about 0.25 to about 0.35, from approximately 0.25 to about 0.40, about 0.25 to about 0.45, about 0.30 to about 0.35, about 0.30 to about 0.40, about 0.30 to about 0 .45, from about 0.30 to about 0.50, from about 0.35 to about 0.40, from about 0.35 to about 0.45, from about 0.35 to about 0.50, from about 0 35 to about 0.60, about 0.40 to about 0.50, about 0.40 to about 0.60, or about 0.50 to about 0.60. Generally speaking, loading fractions ranging from about 0.05 to about 0.4 can provide acceptable plating results, depending on other parameters of the particular drum plating system discussed here. In some embodiments, the loading fraction is in the range of about 0.2 to about 0.4.

The load fraction can be used to determine the volume of blanks loaded into a container device such as a drum, vibrating basket or oscillating container.

Another measure of loading is apparent loading, which is the experimentally determined ratio (i) of the number of blanks, such as fasteners, nuts, washers, etc., that are actually loaded into a drum, basket, or other container device, to (ii) the number of items, such as fasteners, nuts, washers, etc., that can be physically loaded into that drum, basket, or other container device.

In some embodiments where apparent loading is used to determine loading, apparent loading percentages ranging from about 10% to about 80% are used. In further embodiments, apparent loading percentages greater than about 10% are used. In some embodiments, apparent loadings range from about 10% to about 20%, from about 10% to about 30%, from about 10% to about 40%, from about 15% to about 25%, from about 15% to about 35%, from about 15 to about

45%, about 20 to about 30%, about 20 to about 40%, about 25 to about

35%, about 25% to about 45%, about 25% to about 55%, about 25% to about

65%, about 25% to about 75%, about 30% to about 40%, about 30% to about

50%, about 30% to about 60%, about 30% to about 70%, about 40% to about

50%, about 40% to about 60%, about 40% to about 70%, about 40% to about

80%, about 50% to about 60%, about 50% to about 70%, or about 50% to about 80%. It should be noted that apparent load values may have some variability, since this value is experimentally derived from the actual loading of blanks into a drum, basket, or other container device, and therefore may vary due to the packing of blanks in any given attempt to determine how many blanks can be be loaded.

Metallization results can also be affected by the types and geometric shapes of the workpieces to be metallized. For example, one set of parameters may give acceptable results when the same type of work piece is plated, such as studs or bolts of the same size. A different set of parameters may give acceptable results when multiple types of workpieces are plated, such as studs along with nuts and washers. This is because the presence of smaller pieces can facilitate mixing of larger pieces in a drum, basket or other container device so that a higher load fraction or length fraction can be used. Additionally or alternatively, items such as stainless steel balls may be added to the container device to aid in better mixing among the preforms.

Another parameter that can affect plating results is the number of revolutions per minute (RPM) of the drum, vibrating basket, or other container device. In embodiments, the container device is rotated during the application of the first and second currents at a predetermined rpm, eg at least 3 rpm. In some embodiments, the container device is rotated at an RPM in the range of about 3 to about 20 RPM. In some embodiments, the container device is rotated at an RPM in the range of about 3 to 4 rpm, about 3 to 5 rpm, about 3 to about 6 rpm, about 3 to about 7 rpm. about 4 to about 5 rpm, about 4 to about 6 rpm, about 4 to about 7 rpm, about 4 to about 8 rpm, about 5 to about 6 rpm about 5 to about 7 rpm, about 5 to about 8 rpm, about 5 to about 9 rpm, about 5 to about 10 rpm, about 6 to about 7 rpm about 6 to about 8 rpm, about 6 to about 9 rpm, about 6 to about 10 rpm, about 7 to about 8 rpm, about 7 to about 9 rpm about 7 to about 10 rpm, about 8 to about 9 rpm, about 8 to about 10 rpm, about 8 to about 11 rpm, about 8 to about 12 rpm min, from about 10 to about 12 rpm, from about 10 to about 15 rpm, about 15 to about 18 rpm, about 15 to about 20 rpm, or greater than about 20 rpm. Generally speaking, for drum plating embodiments, rotation speeds ranging from about 3 to about 8 rpm can produce acceptable plating results, depending on other parameters of the particular drum plating system discussed here. Generally speaking, for plating in a vibrating basket, rotation speeds ranging from about 6 to about 20 rpm can provide acceptable plating results, again depending on other parameters of the particular vibrating basket system. When other parameters in the system have been set, the RPM can be varied to improve the overall plating results, for example by improving the shake and agitation in the drum plating system.

Therefore, in drum plating embodiments, a number of parameters can be tested and adjusted to achieve a drum plating system in which nanolaminate coatings can be produced on a desired batch of preforms or multiple preforms in a batch. For example, length fraction, load fraction, rpm, and type(s) of preforms being plated can all influence the results of plating. The amount of jitter and mixing can also be experimentally determined by making measurements on any particular drum system.

- 18 041389 plating, including load (eg load fraction, length fraction and product types), voltage, rpm and current.

Similarly, in vibration or wobble embodiments, a number of parameters can be tested and adjusted to achieve a plating system in which nanolaminate coatings can be produced on multiple preforms in a batch. For example, length fraction, load fraction, rpm, and type(s) of preforms being plated can all influence the results of plating.

Thicknesses of layers and coatings.

In embodiments of the processes described herein, the first and second layers in the articles of the plurality are thicker than about 150 nm, eg, in the range of from about 150 to about 5000 nm. In additional embodiments, the first and second layers in the articles of the plurality have a thickness, for example, independently ranging from about 200 to about 500 nm, from about 200 to about 500 nm, from about 200 to about 300 nm, from about 300 to about 400 nm, about 400 to about 500 nm, about 500 to about 750 nm, about 500 to about 1000 nm, about 500 to about 600 nm, about 600 to about 700 nm, about 700 to about 800 nm , from about 800 to about 900 nm, from about 900 to about 1000 nm, from about 1000 to about 1250 nm, from about 1000 to about 1500 nm, from about 1250 to about 1500 nm, from about 1500 to about 2000 nm, from about 2000 to about 2500 nm, from about 2500 to about 3000 nm, from about 3000 to about 4000 nm, from about 4000 to about 5000 nm, or above 5000 nm. In embodiments, the first and second layers have a minimum thickness of at least about 200 nm. In embodiments, the first and second layers have a minimum thickness of at least about 250 nm. In specific embodiments, the implementation of the first and/or second layer has a thickness in the range from about 200 to about 400 nm. In other embodiments, the first and/or second layer has a thickness ranging from about 250 to about 350 nm.

In embodiments, the second layer is significantly thicker than the first layer. For example, the thickness of the first layer may be in the range of about 200 to about 400 nm, and the thickness of the second layer may be in the range of about 600 to about 1000 nm. In embodiments, the thickness of the second layer is approximately a multiple of the thickness of the first layer, eg, approximately two times (2x), three times (3x), or four times (4x) the thickness of the first layer. For example, if the first layer is about 250 nm thick, then the second layer may be about 500 nm thick, or about 750 nm thick. In embodiments, the thickness of the second layer is in the range of about 400 to about 600 nm. In further embodiments, the thickness of the first layer is in the range of about 200 to about 300 nm and the thickness of the second layer is in the range of about 600 to about 900 nm. In embodiments, individual layer thicknesses are up to 5000 nm. In other embodiments, the implementation of the thickness of the individual layers are more than 5000 nm.

Typically, one or more additional layers will be applied, and each additional layer may independently have a thickness of at least about 150 nm, eg, independently ranging from about 150 to about 5000 nm. In embodiments, each additional layer has a thickness of, for example, about 200 to about 500, about 200 to about 300, about 300 to about 400, about 400 to about 500, about 500 to about 750, about 500 to about 1000, about 500 to about 600, about 600 to about 700, about 700 to about 800, about 800 to about 900, about 900 to about 1000, about 1000 to about 1250, about 1000 to about 1500, about 1250 to about 1500, about 1500 to about 2000, about 2000 to about 2500, about 2500 to about 3000, about 3000 to about 4000, about 4000 to about 5000, or greater than about 5000 nm. As with the first and second layers, said one or more additional layers will typically have a minimum thickness of at least about 200 nm. In other embodiments, said one or more additional layers will typically have a minimum thickness of at least about 250 nm. For example, the first and/or second layer may have a thickness independently ranging from about 200 to about 400 nm, or from about 250 to about 350 nm.

Generally speaking, it may be desirable to form coatings with an overall thickness in the range of about 5 to about 15 microns. In some embodiments, it is desirable that the total coating thickness be in the range of about 6 to about 10 microns, about 6 to about 12 microns, about 8 to about 10 microns, about 8 to about 12 microns, about 10 to about 12 µm, or about 12 to about 15 µm. The total, or cumulative, thickness of the electrodeposited layers (ie, coating thickness) on a plurality of articles may be at least about 300 nm. In other embodiments, the coating thickness is in the range of about 300 to about 50 microns. In further embodiments, the coating thickness is

- 19 041389 in the range from about 500 to about 50 microns. In other additional embodiments, the coating thickness is greater than about 50 microns. The total thickness of the coating may range from about 400 to about 500 nm, from about 500 to about

750 nm, from about 500 to about 1000 nm, from about 750 to about 1000 nm, from about 500 to from to from to about 600 nm, from about 600 to about 700 nm, from about 700 to about 800 nm, about 800 up to about 900 nm, from about 900 to about 1000 nm, from about 1000 to about 1500 nm, from about 1500 to about 2000 nm, from about 2000 to about 3000 nm, from about 3000 to about 4000 nm, from about 4000 to about 5000 nm , from about 5000 to about 6000 nm, from about 6000 to about 7000 nm, from about 7000 to about 8000 nm, from about 8000 to about

9000 nm, from about 9000 to about 10000 up to up to up to up to about about about about about about

11000

13000

15000

17000

19000

25000 nm, nm, nm, nm, nm, nm, from from from from from about about about about about about

11000

13000

15000

17000

19000

25000 up to up to up to up to about about about about about about

12000

14000

16000

18000

20000

30,000 nm, nm, nm, nm, nm, nm, nm, from about from from from from to about 40,000 nm, from about 40,000 to about 50,000 nm, or more about about about about about about about about

10000

12000

14000

16000

18000

20000

30000

50000 nm. In embodiments, the combined thickness of the layers on a plurality of articles may range from about 200 nm to about 50,000 nm. In some embodiments, the combined thickness of the layers on a plurality of articles may range from about 5,000 to about 15,000 nm (about 5 to about 15 microns), or from about 8,000 to about 12,000 (about 8 to about 12 microns).

In the case where the workpieces to be plated are threaded, the coating thickness is typically about 12 microns or less, for example, the coating thickness may be in the range of about 6 to about 12 microns. In some embodiments where the workpieces to be plated are threaded, the thickness of the coating is in the range of about 8 to about 10 microns. Depending on the desired total thickness and the desired thickness of the individual layers, a total number of layers in the range of 10 to 18 may be desirable. In some embodiments, a total of 12 to 15 layers may be deposited.

One consideration for coating threaded workpieces such as nuts, bolts and studs is the potential for significant variation in composition and deposition rate between threadless surfaces and threads. Where workpieces are exposed to corrosive conditions and therefore must be coated for corrosion resistance, generally threadless surfaces may be more susceptible to corrosive conditions than threaded surfaces and thus may be selected as target surfaces for coverage estimates.

Examples of various workpiece surfaces where measurements can be made, including significant surfaces, are shown in FIG. 1A-1E. As shown, for a nut or washer, the significant surface can be defined as the face of the nut or washer. For a bolt, the significant surface can be defined as the top of the bolt head, and for a stud, the significant surface can be defined as the threadless end of the stud (as shown). Such threadless surfaces are also more accessible to electrolyte and current than threads and as a result exhibit higher deposition rates on average. However, thread crests act as sharp bumps during deposition and the associated current focusing on these surfaces results in higher local deposition rates and may also affect higher proportions of one or more components. For example, in the case where a ZnNi-e coating is to be applied, the nickel percentage may be higher in the thread area. On the other hand, at the root of the thread profile, coating is much more difficult because the current is diverted to the crest of the thread. The result of this is that thread root thicknesses can be thinner than threadless surfaces or thread crests. Therefore, the systems and parameters used in the plating process must be optimized to ensure that the target surfaces satisfy the target composition and thickness without leaving the coating at the root of the thread too thin or the coating at the top of the thread too thick. With this variation in mind, in practice, the system and parameters can be designed to coat one or more threadless surfaces of a workpiece to be coated having composition and thickness within predetermined ranges. The process and parameters will typically be controlled so that the thickness of the coatings in the threads is not so great as to render the surfaces incapable of mating with the corresponding threaded surfaces. As noted above, threadless surfaces are usually a good place to measure and compare nanolaminate coating thickness and composition across products in a batch due to the greater uniformity of deposition on such surfaces. Generally speaking, when comparing the thickness and composition of a coating among two or more articles in a batch, it is preferable to compare the thickness and/or composition at the same location on each of the articles. Such comparisons can also be made at multiple locations on the metallized products in a batch, again comparing the thickness and/or composition of the coating at each location on the same product (for example, the top or bottom of a middle thread section, or the top or bottom of an end section). threads) with the thickness and/or composition of the coating in the same places on another product.

Depending on several parameters, including the contour geometry of the threadless surface, and the service life and composition of the bath, deposition rates can range from less than 1 µm/h to more than 10 µm/h. In various embodiments, the deposition rates are less than 0.5 µm/h, or are in the range of about 0.5 to about 1 µm/h, about 1 to about 2 µm/h, about 1 to about 3 µm/h , from about 1 to about 4 µm/h, from about 1 to about 5 µm/h, from about 2 to about 3 µm/h, from about 2 to about 4 µm/h, from about 2 to about 5 µm/h , about 2 to about 6 µm/h, about 2 to about 7 µm/h, about 2 to about 8 µm/h, about 2 to about 9 µm/h, about 2 to about 10 µm/h , about 3 to about 4 µm/h, about 3 to about 5 µm/h, about 3 to about 6 µm/h, about 3 to about 7 µm/h, about 3 to about 8 µm/h , about 3 to about 9 µm/h, about 3 to about 10 µm/h, about 4 to about 5 µm/h, about 4 to about 6 µm/h, about 4 to about 7 µm/h , from about 4 to about 8 µm/h, from about 4 to about 9 µm/h, from example but 4 to about 10 µm/h, about 5 to about 6 µm/h, from about 5 to about 7 µm/h, from about 5 to about 8 µm/h, from about 5 to about 9 µm/h, from about 5 to about 10 µm/h, about 6 to about 7 µm/h, from about 6 to about 8 µm/h, from about 6 to about 9 µm/h, from about 6 to about 10 µm/h, from about 7 to about 8 µm/h, about 7 to about 9 µm/h, from about 7 to about 10 µm/h, from about 8 to about 10 µm/h, from about 9 to about 10 µm/h, from about 10 to about 15 microns/hour, or from about 15 to about 20 microns/hour.

Nanolaminate coating.

By adjusting the plating parameters discussed above, preforms in a batch can be coated with identifiable layers. As used herein, the term identifiable layers means distinguishable layers that differ in composition and/or structure from adjacent layers. Identifiable layers can be visualized using any procedure that is appropriate, as would be understood by a person skilled in the art. In one procedure, the product is first cut with a diamond saw to expose the cross section. The cut section of the article to be visualized is then protected, for example by encapsulating the cut material in epoxy resin. The cut material is then sanded and polished with sandpaper and aluminum oxide in preparation for etching. The resulting material is then chemically etched with a slowly etching etchant, such as Nital etchant, and examined with a scanning electron microscope (SEM) using a backscatter detector.

Such etching techniques reveal that the metallized articles of this invention will have nanolaminate coatings that include identifiable layers. In addition, in the case of embodiments of drum plating, the coatings are distinguishable from nanolaminate coatings obtained by plating on a hanger.

The interface between individual layers may be discrete or diffuse. An interface between adjacent layers is considered discrete if the composition between the first layer and the second layer changes over a distance that is less than about 20% of the thickness of the thinner of the two layers. In embodiments, an interface between adjacent layers is considered discrete if the composition between the first and second layers varies by a distance that is less than about 15%, about 10%, about 8%, about 5%, about 4%, or about 2%. the thickness of the thinner layer.

In embodiments, the interface is diffuse if the change in composition between the first layer and the second layer occurs over more than 20% of the thickness of the thinner of the two layers. In embodiments, an interface between adjacent layers is considered diffuse if the composition varies between the first layer and the second layer by a distance that is greater than about 15%, about 10%, about 8%, about 5%, about 4%, or about 2%. the thickness of the thinner layer.

In embodiments, the diffuse interface has a change in composition between the first layer and the second layer over a thickness ranging from about 0.5 to about 5 nm. In some embodiments, the diffuse interface has a thickness in the range of about 0.5 to about 3 nm, about 1 to about 4 nm, or about 2 to about 5 nm. In additional embodiments, the diffuse interface has a thickness in the range of about 0.5 to about 1 nm, about 1 to about 2 nm, about 2 to about 3 nm, about 3 to about 4 nm, or about 4 to about 5 nm.

As shown in FIG. 2A-2C, drum-plated nanolaminate coatings will include one or more random damage-induced discontinuities in the coating that result from collisions between items in the drum as they roll over each other.

- 21 041389 to a friend during the plating process. As shown in FIG. 2A-2C, these damage-induced discontinuities can typically take the form of an inward notch, dent, or inward deformation from the surface of the nanolaminate coating toward the surface of the workpiece. The nanolaminate coating layers on one side of the damage-induced inhomogeneity are again deformed along the direction of the notch, dent, or deformation, typically towards the surface of the substrate. As also seen in FIG. 2A and 2B, damage-induced discontinuities may include a crack or split that extends to or near the substrate surface and may extend in a direction that is substantially perpendicular to the coating surface. As shown in FIG. 2C, the damage-induced discontinuity may not have a crack or split in the coating, but rather only an indentation in the coating layer, which may be further overcoated with metal. Fig. 2C shows an example of a dent that is topped (closed). However, in other embodiments, such dents are not covered from above, for example, if they were formed shortly before the end of the drum plating cycle. As also shown in FIG. 2A-2C, the damage-induced discontinuity also typically contains material deposited within the discontinuity itself. That is, having been formed during the plating process, the inhomogeneity is then usually closed in subsequent stages of plating. It should be noted that the practically pure, vertical inhomogeneities in Figs. 2A and 2B, which appear as uniform breaks from the surface to the substrate without being overplated, or the deformation of the layers inward from the coating surface to the substrate surface, is most likely caused by the preparation of the surface for etching, and not by the drum plating process.

In practice, the methods disclosed herein can produce a batch of articles in which a plurality of articles have the desired distribution of characteristics. That is, within the ranges, the array may be substantially completely dense (having no pinholes or cracks that extend from the surface of the coating to the surface of the product), and may have a desired number of layers, a desired total coating thickness, and desired layer compositions in one or more places on products, for example, on a non-threaded surface. Depending on the desired characteristics and ranges, when adjusting the parameters discussed here, the plurality can be the majority of the products in the batch, for example, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 97%.

For example, in embodiments, a plurality of metallized articles made according to this invention may have a total nanolaminate coating thickness at one location on the article that is within 6 µm or less of the average nanolaminate coating thickness at the same location on other articles in the plurality, which are the same size and shape. In other embodiments, a plurality of metallized articles produced according to this invention may have a total nanolaminate coating thickness at one location on the article that is within 5 µm or less of the average nanolaminate coating thickness at the same location on other articles in the plurality that are the same size and shape. In additional embodiments, a plurality of metallized articles made according to this invention may have a total nanolaminate coating thickness at one location on the article that is within 4 µm or less of the average nanolaminate coating thickness at the same location on other articles in the plurality that are the same size and shape. In other additional embodiments, a plurality of metallized articles made according to this invention may have a total nanolaminate coating thickness at one location on the article that is within 3 µm or less of the average nanolaminate coating thickness at the same location on other articles in the plurality, which are the same size and shape. In still other further embodiments, a plurality of metallized articles produced according to this invention may have a total nanolaminate coating thickness at one location on the article that is within 2 µm or less of the average nanolaminate coating thickness at the same location on other articles in the plurality. that are the same size and shape. In still further embodiments, a plurality of metallized articles produced according to this invention may have a total nanolaminate coating thickness at one location on the article that is within 1 µm or less of the average nanolaminate coating thickness at the same location on other articles in the plurality, which are the same size and shape.

Furthermore, in embodiments, a plurality of metallized articles made according to this invention have total nanolaminate coating thicknesses at two different locations on the article that are within 6 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality. that are the same size and shape. In embodiments, a plurality of metallized articles made according to this invention have total nanolaminate coating thicknesses at two different locations on the article that are within 5 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality that have the same size and shape. In other embodiments, a plurality of metallized products obtained according to this invention

- 22 041389 shade, has total nanolaminate coating thicknesses at two different locations on the product that are within 4 µm or less of the average nanolaminate coating thickness at the same locations on other products in the set that are the same size and shape. In some embodiments, a plurality of metallized articles made according to this invention have total nanolaminate coating thicknesses at two different locations on the article that are within 3 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality that are are the same size and shape. In additional embodiments, a plurality of metallized articles made according to this invention have total nanolaminate coating thicknesses at two different locations on the article that are within 2 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality that are are the same size and shape. In still further embodiments, a plurality of metallized articles made according to this invention have total nanolaminate coating thicknesses at two different locations on the article that are within 1 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality, which are the same size and shape.

Further, in embodiments, a plurality of metallized articles produced by the methods of this invention have total nanolaminate coating thicknesses at three different locations on the article that are within 6 µm or less of the average nanolaminate coating thickness at the same locations on other articles in that article. set that are the same size and shape. In some embodiments, a plurality of metallized articles produced by the methods of this invention have total nanolaminate coating thicknesses at three different locations on the article that are within 5 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality, which are the same size and shape. In additional embodiments, a plurality of metallized articles produced by the methods of this invention have total nanolaminate coating thicknesses at three different locations on the article that are within 4 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality, which are the same size and shape. In some embodiments, a plurality of metallized articles produced by the methods of this invention have total nanolaminate coating thicknesses at three different locations on the article that are within 3 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality, which are the same size and shape. In additional embodiments, a plurality of metallized articles produced by the methods of this invention have total nanolaminate coating thicknesses at three different locations on the article that are within 2 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality, which are the same size and shape. In still further embodiments, a plurality of metallized articles produced by the methods of this invention have total nanolaminate coating thicknesses at three different locations on the article that are within 1 µm or less of the average nanolaminate coating thickness at the same locations on other articles in the plurality. that are the same size and shape.

Similarly, in embodiments, a plurality of plated articles produced by the methods of this invention will have a first electrodepositable component (e.g., metal) in the first layer of any article in the plurality that differs by less than a predetermined amount from the mass percent of the same electrodepositable component in another item in this set. In some embodiments, the weight percent of the first electrodepositable component in the first layer of any of the articles in the array differs from the weight percent of the same electrodepositable component in the other article in the array by less than 6 weight percent. In additional embodiments, the weight percent of the first electrodepositable component in the first layer of any of the articles in the array differs from the weight percent of the same electrodepositable component in the other article in the plurality by less than 5 wt%. In additional embodiments, the weight percent of the first electrodepositable component in the first layer of any of the articles in the array differs from the weight percent of the same electrodepositable component in the other article in the plurality by less than 4 wt%. In some embodiments, the weight percent of the first electrodepositable component in the first layer of any of the articles in the array differs from the weight percent of the same electrodepositable component in the other article in the plurality by less than 3 wt%. In still further embodiments, the weight percent of the first electrodepositable component in the first layer of any of the articles in the plurality differs from the weight percent of the same electrodepositable component in the other article in the plurality by less than 2 wt%. In specific embodiments, the weight percent of the first electrodepositable component in the first layer of any of the articles in the plurality differs from the weight percent of the same electrodepositable component in the other article in the plurality by less than 1 wt%.

- 23 041389

Measurements and/or tests may be required to determine if the plated products in a batch have the desired characteristics. Any suitable methods may be used, as will be appreciated by one of ordinary skill in the art. For example, X-ray fluorescence (XRF) analysis can be used to determine the composition and thickness of a particular coating. XRF measurements can be supported by energy dispersive X-ray spectroscopy (EDS) and inductively coupled plasma (ICP) analysis.

Coating compositions.

The composition of each electrodeposited layer, which is applied to metal blanks in a batch, can be variable in its constituent elements. In embodiments, the composition of the nanolaminate coating at one or more locations on the article includes at least one (e.g., one or more, two or more, three or more, four or more, etc.) of various elements independently selected from Ag , Al, Au, B, Be, C, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pb, Pd, Pt, Re, Rh, Sb, Sn , Ta, Ti, W, V, Zn and Zr, A^, SiO2, TiO2, BN, CrN, GaN, MO2N, NbN, TiN, VN, W2N, Fe2O ₃ , MgO, Cr ₃ C ₂ , Cr7C ₃ , Cr ₂₃ C ₆ , Mo ₂ C, SiC, WC, ZrC, diamond, epoxy, polyurethane, polyaniline, polyethylene, polyether ether ketone (PEEK), copolymers of polyether ether ketone, polyether ketone (PEKK), copolymers of polyether ketone ketone, polypropylene and other polymers, including conductive polymers such as poly(3,4-ethylenedioxythiophene) or polystyrenesulfonate. In some embodiments, the electrodeposited elements are selected from silver (Ag), aluminum (Al), gold (Au), boron (B), beryllium (Be), carbon (C), cobalt (Co), chromium (Cr), copper ( Cu), iron (Fe), mercury (Hg), indium (In), iridium (Ir), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), neodymium (Nd), nickel ( Ni), phosphorus (P), palladium (Pd), platinum (Pt), rhenium (Re), rhodium (Rh), antimony (Sb), silicon (Si), tin (Sn), lead (Pb), tantalum ( Ta), titanium (Ti), tungsten (W), vanadium (V), zinc (Zn), and zirconium (Zr). In embodiments, each of the independently selected elements is present in an amount of at least 0.1, 0.05, 0.01, 0.005, or 0.001% by weight. In additional embodiments, each of the independently selected elements is present in an amount greater than 0.1, 0.05, 0.01, 0.005, or 0.001% by weight. In some embodiments, each of the independently selected elements is present in an amount independently ranging from about 1 to about 99 wt%.

In such embodiments, the amount of each element present can be from about 1 to about 5 wt.%, from about 5 to about 7 wt.%, from about 7 to about 10 wt.%, from about 10 to about 15 wt.%, from about 15 to about 20 wt.%, from about 20 to about 30 wt.%, from about 30 to about 40 wt.%, from about 40 to about 50 wt.%, from about 50 to about 55 wt.%, from about 55 to about 60 wt.%, from about 60 to about 65 wt.%, from about 65 to about 70 wt.%, from about 70 to about 75 wt.%, from about 75 to about 80 wt.%, from about 80 to about 85 wt.%, from about 85 to about 90 wt.%, from about 90 to about 92 wt.%, from about 92 to about 93 wt.%, from about 93 to about 94 wt.%, from about 94 to about 95 wt.%, from about 95 to about 96 wt.%, from about 96 to about 97 wt.%, from about 97 to about 98 wt.%, or from about 98 to about 99 wt.%. As one skilled in the art would appreciate, the percentages of elements that are electrodeposited in a given layer will add up to 100%. Embodiments with two or more, three or more, or four or more different electrodepositable elements (e.g., metals) that can be co-electrodeposited include, for example, at least two or more elements independently selected from the group consisting of Zn , Cr, Fe, Co and Ni. In such embodiments, one or more additional elements that may be included with such combinations include Ag, Al, Au, B, Be, C, Cu, Hg, In, Mg, Mn, Mo, Nb, Nd, Pd, Pt , Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V, and Zr. In some embodiments, one or more additional elements that can be introduced with such combinations, including P, Al, Si, and B, can be introduced with two or more metals independently selected from the group consisting of Zn, Cr, Fe, Co and Ni. In some such embodiments, one or more additional elements are selected from the subgroup consisting of P, Al, Si, and B. Examples of such combinations include NiCr, NiFe, NiCo, NiCrCo, NiAl, NiCrAl, NiFeAl, NiCoAl, NiCrCoAl, NiMo, NiCrMo, NiFeMo, NiCoMo, NiCrCoMo, NiW, NiCrW, NiFeW, NiCoW, NiCrCoW, NiNb, NiCrNb, NiFeNb, NiCoNb, NiCrCoNb, NiTi, NiCrTi, NiFeTi, NiCoTi, NiCrCoTi, NiCrP, NiCrAl, NiCoP, NiCoAl, NiFeP, NiFeAl, NiCrSi, NiCrB, NiCoSi, NoCoB, NiFeSi, NiFeB, ZnCr, ZnFe, ZnCo, ZnNi, ZnCrP, ZnCrAl, ZnFeP, ZnFeAl, ZnCoP, ZnCoAl, ZnNiP, ZnNiAl, ZnCrSi, ZnCrB, ZnFeSi, ZnFeB, ZnCoSi, ZnCoB, ZnNiSi, ZnNiB, CoCr, CoFe, CoCrP, CoFeP, CoCrAl, CoFeAl, CoCrSi, CoFeSi, CoCrB, CoFeB, CoAl, CoW, CoCrW, CoFeW, CoTi, CoCrTi, CoFeTi, CoTa, CoCrTa, CoFeTa, CoC, CoCrC, CoFeC, FeCr, FeCrP, FeCrAl, FeCrSi and FeCrB.

In other embodiments, the implementation of one or more layers of the coating contain a variety of elements, including Ni, Zn, Co, Al and Fe. Within the scope of such embodiments are corrosion resistant coatings containing Zn and Ni, where nickel is from about 11 to about 17 wt.%, and the remaining wt.% of the composition, i. the rest contains zinc.

Throughout this description, where percentages of coating components are given

- 24 041389 ty, they are indicated as a percentage by weight (mass percent), unless otherwise indicated. In those examples where the rest of the coating is mentioned, this should be understood as an indication of the remaining weight percent in the coating, the composition of which is not otherwise specifically indicated. Thus, for example, the above indication that the balance contains zinc only means that the remainder of the weight percentage in the composition of the layer includes zinc, but is not limited to zinc, and may also include other components.

In this description, the elements listed in the combination of elements are not listed in order from the most present element to the least present element. For example, the above combination of NiCr means a combination of the metals Ni and Cr, in which either Ni or Cr may be the predominant element.

Other embodiments with two or more, three or more, or four or more different elements that are co-electroplated include, for example, at least two or more elements independently selected from C, Cr, Mo, W, Nb, Fe , Ti, Al, V and Ta. In some embodiments, these at least two or more elements are independently selected from the group consisting of C, Cr, Mo, W, Nb, Fe, Ti, Al, V, and Ta. In embodiments, one or more additional elements that are introduced with such combinations include Ag, Al, Au, B, Be, Co, Cu, Hg, In, Mg, Mn, Ni, Nd, Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Zn and Zr.

Illustrative alloys that can be used in one or more coating layer(s) include Zn and Fe; Zn and Ni; Co and Ni; Ni, Co and Mo; Ni and Fe; Ni and Cr; Cu and Zn; Cu and Sn; Ni, Co and P; Ni, Co, W and P; Ni, Co and W; Ni and W; Ni, W and P; Ni, Co and B; Ni, Co, W and B or Ni, W and B. In specific embodiments, the alloy used in the nanolaminate coating layer includes Ni and Fe; or Ni and Co. In still further embodiments, the nanolaminate coating layer comprises three or more, four or more, or five or more of Co, Cr, Mo, W, Fe, Si, Mn, and Ni.

In embodiments, the first layer and the second layer of the nanolaminate coating comprise a first alloy and a second alloy, respectively, that contain the same first and second metals. In some embodiments, the difference between the concentrations of the first metal in the first alloy and the first metal in the second alloy is less than about 10%, about 20%, about 30%, or about 50%. In additional embodiments, the difference between the concentrations of the first metal in the first alloy and the first metal in the second alloy is greater than about 1%, about 2%, about 5%, or about 10%.

Other substances may be coprecipitated or entrained along with any of the above elements and combinations of elements. Such other materials include, for example, Al ₂ O ₃ , Fe ₂ O ₃ , MgO, P, Si, SiO ₂ , TiN, TiO ₂ , diamond, epoxide, polyurethane, polyaniline, polyethylene, polyether ether ketone (PEEK), polyether ether ketone copolymers, polyether ketone ketone (PEKK), polyetherketone ketone copolymers, and polypropylene, any of which may be present in particulate form. In some embodiments, the particles have a largest size that is less than the size of the applied individual layers (eg, one tenth or less, one quarter or less, or less than half the thickness of the layer).

In some embodiments, the implementation of the first and second identifiable layers in one or more places on the product (for example, on a non-threaded surface) may contain from 1 to 99 wt.% Ni. In additional embodiments, Ni is present in the first and second identifiable layers

V one or more places on product in quantity, regardless component in the range from approximately 1 to about 5 wt.%, from approximately 5 to about 7 wt.%, from about 7 before approximately 10 wt%, from approximately 10 before approximately 15 wt%, from approximately 15 before approximately 20 wt%, from approximately 20 before approximately thirty wt%, from approximately thirty before approximately 40 wt%, from approximately 40 before approximately 50 wt%, from approximately 50 before approximately 55 wt%, from approximately 55 before approximately 60 wt%, from approximately 60 before approximately 65 wt%, from approximately 65 before approximately 70 wt%, from approximately 70 before approximately 75 wt%, from approximately 75 before approximately 80 wt%, from approximately 80 before approximately 85 wt%, from approximately 85 before approximately 90 wt%, from approximately 90 before approximately 92 wt%, from approximately 92 before approximately 93 wt%, from approximately 93 before approximately 94 wt%, from approximately 94 before approximately 95 wt%, from approximately 95 before approximately 96 wt%, from approximately 96 before approximately 97 wt%, from approximately 97

up to about 98 wt.% or from about 98 to about 99 wt.%. The remainder (i.e. the remainder of the composition) of the first and second identifiable layers at one or more locations on the article, such as a threadless surface, may contain Co and/or Cr, as well as additional elements or electrodepositable substances, where cobalt and/or chromium make up most of the rest. In some embodiments, Co and/or Cr are present in an amount of at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, at least 95 wt. %, at least 97 wt.%, at least 99 wt.%, at least 99.9 wt.% or 100% of the rest.

In embodiments, the implementation of the second(s) layer(s) contain chromium and/or cobalt in an amount ranging from 1 to 35 wt.%. In some embodiments, the implementation of the second(s) layer(s) contain chromium and/or cobalt in an amount independently ranging from 1 to 3 wt.%, from 2 to 5 wt.%, from 5 to 10 wt. .%, 10 to 15 wt.%, 15 to 20 wt.%, 20 to 25 wt.%, 25 to 30 wt.% or 30 to 35 wt.%. The balance of the second layer(s) in such embodiments contains Ni. In such embodiments, the remainder of the second layer(s) may also contain additional elements or electrodepositables. In some such embodiments, Ni makes up most of the remainder, such as at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, at least 95 wt. .%, at least 97 wt.%, at least 99 wt.%, at least 99.9 wt.% or 100 wt.% of the rest.

In some embodiments, the implementation of the first and second identifiable(my) layer(s) in one or more places on the product (eg, threadless surface) contain Ni in the range from about 1 to about 99 wt.%. In additional embodiments, the implementation of the first and second identifiable(my) layer(s) in one or more places on the product contain Ni in the amount

ranging from about 1 to about 5 wt.%, from about 5 to about 7 wt.%, from about 7 before approximately 10 wt%, from approximately 10 before approximately 15 wt%, from approximately 15 before approximately 20 wt%, from approximately 20 before approximately thirty wt%, from approximately thirty before approximately 40 wt%, from approximately 40 before approximately 50 wt%, from approximately 50 before approximately 55 wt%, from approximately 55 before approximately 60 wt%, from approximately 60 before approximately 65 wt%, from approximately 65 before approximately 70 wt%, from approximately 70 before approximately 75 wt%, from approximately 75 before approximately 80 wt%, from approximately 80 before approximately 85 wt%, from approximately 85 before approximately 90 wt%, from approximately 90 before approximately 92 wt%, from approximately 92 before approximately 93 wt%, from approximately 93 before approximately 94 wt%, from approximately 94 before approximately 95 wt%, from approximately 95 before approximately 96 wt%, from approximately 96 before approximately 97 wt%, from approximately 97 up to about 98 wt.% or from about 98 to about 99 wt.%. The rest (i.e. the remainder composition) in the lane

The first and second identifiable layers at one or more locations on the article, such as a threadless surface, may contain aluminum (eg deposited by ionic liquid deposition) as well as additional elements or electrodepositable materials. In some such embodiments, Al makes up most of the rest. In some embodiments, Al is, for example, at least about 75 wt.%, at least about 80, at least about at least about wt.%, at least about 90 wt.% .%, wt.%, wt.%, at least about 99 wt.%, at least about 99.9 wt.% or about 100 wt.% of the rest. In embodiments, the implementation of the second(s) layer(s) contain Al in an amount in the range from about 1 to about 35 wt.%. In some embodiments, the implementation of the second(s) layer(s) contain Al in an amount ranging from about 1 to about 3 wt.%, from to to about 2 to about 5 wt.%, from about 5 to about 10 wt. %, from about 10 to about 15 wt.%, from about 15 to about 20 wt.%, from about 20 to about 25 wt.%, from about 25 to about 30 wt.%, or from about 30 to about 35 wt.%. In some such embodiments, the remainder of the second layer comprises

Ni. In some embodiments, the rest of the second layer also contains additional elements or electrodepositables, with Ni making up most of the rest. In some embodiments, Ni is, for example, at least about at least about about wt %, wt %, wt %, at least about at least about .%, wt.%, wt.%, wt.%, at least about 99.9 wt.% or about 100 wt.% of the rest.

In some embodiments, the implementation of the first and second identifiable(my) layer(s) in one or more places on the product, for example, on a non-threaded surface, contain Nickel in the range from 1 to 99 wt.%. In some embodiments, the implementation of the first and second identifiable(my) layer(s) in one or more places on the product contain nickel in an amount, regardless of

schem in the range from about 1 up to about 5 wt.%, from about 5 up to about 7 wt.%, from approximately 7 before approximately 10 wt%, from approximately 10 before approximately 15 wt%, from approximately 15 before approximately 20 wt%, from approximately 20 before approximately thirty wt%, from approximately thirty before approximately 40 wt%, from approximately 40 before approximately 50 wt%, from approximately 50 before approximately 55 wt%, from approximately 55 before approximately 60 wt%, from approximately 60 before approximately 65 wt%, from approximately 65 before approximately 70 wt%, from approximately 70 before approximately 75 wt%, from approximately 75 before approximately 80 wt%, from approximately 80 before approximately 85 wt%, from approximately 85 before approximately 90 wt%, from approximately 90 before approximately 92 wt%, from approximately 92 before approximately 93 wt%, from approximately 93 before approximately 94 wt%, from approximately 94 before approximately 95 wt%, from approximately 95 before approximately 96 wt%, from approximately 96 before approximately 97 wt%,

- 26 041389 from about 97 to about 98 wt.% or from about 98 to about 99 wt.%. In embodiments, the remainder of the first and second identifiable layers at one or more locations on the article, such as a threadless surface, contains Al and/or Co, as well as additional elements or electrodepositables, where Al and/or Co make up most of the remainder. In some embodiments

Al and/or Co are, for example, at least about 75 at at least at least about about about wt.%, wt.%, wt.%, at least at least about about about wt.%, wt.%, wt.%, wt.%, at least about 99.9 wt.% or about 100 wt.% of the rest. In embodiments, the implementation of the second(s) layer(s) contain Al and/or Co in an amount independently ranging from about 1 to about 35 wt.%. In some embodiments, the implementation of the second(s) layer(s) contain Al and/or Co in an amount independently ranging from about 1 to about 3 wt.%, from 2 to about 5 wt.%, from about 5 to about 10 about 10 to about 15 wt%, about 15 to about 20 wt%, about 20 to about 25 wt%, about 25 to about 30 wt%, or about 30 to about 35 wt. wt%; the rest of the second layer in such embodiments contains Ni. In some such embodiments, the rest of the second layer also contains most of the additional elements or electrodepositables, with Ni making up the remainder. In some embodiments, at least about at least about about wt.%, wt.%, wt.%, at least about 99 wt.%, according to the implementation of Ni is, for example, less than at least least about about about wt.%, wt.%, wt.%, at least about 99.9 wt.% or about 100 wt.% the rest.

In embodiments, the first and second identifiable layer(s) at one or more locations on the article, such as a threadless surface, contain nickel in the range of 1 to 99% by weight. In some embodiments, the implementation of the first and second identifiable(s) layer(s) in one or more places on the product contain nickel in an amount ranging from about 1 to about 5 wt.%, from about 5 to about 7 wt.%, from about 7 to about 10 wt.%, from about 10 to about 15 wt.%, from about 15 to about 20 wt.%, from about 20 to about 30 wt.%, from about 30 to about 40 wt.%, from about 40 to about 50 wt.%, from about 50 to about up to up to up to about about about about about about about wt.%, wt.%, wt.%, wt.%, wt.%, wt.% , wt.%, from about from from from from from to about 98 about about about about about about to up to to to about about about about about about about about about wt.%, from about wt.%, wt.%, wt.%, wt.%, wt.%, wt.%, from from from from from from wt.% or from about 98 to about 99 wt.% on about about about about about about about about about weight. In some embodiments, the rest of the first and second identifiable layers at one or more locations on the article, such as a threadless surface, contains iron, as well as additional elements or electrodeposits of the rest.

substances. In some such embodiments, Fe makes up a majority of at least some of about about about about about about about about about about about about embodiments.

Fe by wt.%, wt.%, wt.%, at least at least about, for example, wt.%, wt.%, wt.%, at least about 99 wt.%, at least about 99.9 wt.% or about 100 wt.% the rest. In embodiments, the implementation of the second(s) layer(s) contain Fe in the range from about 1% to about 35%. In some embodiments, the implementation of the second(s) layer(s) contain iron in an amount in the range from about 1% to about 3 wt.%, from about 2 to about 5 wt.%, from about 5 to about 15 to about wt. %, wt.%, from about 10 to about 15 about 20 to about 25 wt.%, wt.%, from about 25 to about 30 wt.% or from about 30 to about 35 wt.%. The balance of the second layer in such embodiments contains Ni. In some embodiments, the rest of the second layer also contains additional elements or electrodepositables, with Ni making up most of the rest. In some embodiments, Ni is, for example, at least about 75 wt.%, at least about 80 wt.%, at least about 85 wt.%, at least about 90 wt.%, at least about 95 wt.%, at least about 97 wt.%, at least about 99 wt.%, at least about 99.9 wt.% or about 100 wt.% of the rest.

In some embodiments, the implementation of the first and second identifiable layers in one or more places on the product, for example, on a non-threaded surface, contain Zn in the range from about 1 to about 99 wt.%. In some embodiments, the first and second identifiable layers at one or more locations on the article contain Zn in the range of 1 wt% to about 5 wt%, about 5 wt% to about 7 wt%, about 7 wt% to about 10 wt%. .%,

from approximately 10 before approximately 15 wt%, from approximately 15 before approximately 20 wt%, from approximately 20 before approximately thirty wt%, from approximately thirty before approximately 40 wt%, from approximately 40 before approximately 50 wt%, from approximately 50 before approximately 55 wt%, from approximately 55 before approximately 60 wt%, from approximately 60 before approximately 65 wt%, from approximately 65 before approximately 70 wt%, from approximately 70 before approximately 75 wt%, from approximately 75 before approximately 80 wt%, from approximately 80 before approximately 85 wt%, from approximately 85 before approximately 90 wt%, from approximately 90 before approximately 92 wt%, from approximately 92 before approximately 93 wt%, from approximately 93 before approximately 94 wt%, from approximately 94 before approximately 95 wt%, from approximately 95 before approximately 96 wt%, from approximately 96 before approximately 97 wt.%, from about 97 before about 98 wt% or

from about 98 to about 99 wt.% by weight. The remainder of the first and second layers at one or more locations on the article, such as a threadless surface, contains Fe as well as additional elements or electrodepositables, with Fe making up most of the remainder. In some embodiments, the implementation of Fe is, for example, at least about 75 wt.%, at least about 80 wt.%, at least about 85 wt.%, at least about 90 wt.%, at least about 95 wt.%, at least about 97 wt.%, at least about 99 wt.%, at least about 99.9 wt.% or about 100 wt.% of the rest. In embodiments, the implementation of the second(s) layer(s) contain Fe in the range, independently selected from from about 1 to about 35 wt.%. In some embodiments, the second(s) layer(s) contain Fe in the range of from about 1 to about 3 wt.%, from about 2 to about 5 wt.%, from about 5 to about 10 wt.%, from about 10 to about 5 wt.%, from about 15 to about 20 wt.%, from about 20 to about 25 wt.%, from about 25 to about 30 wt.%, or from about 30 to about 35 wt.% by weight. The remainder of the second layer in such embodiments contains zinc. In yet another embodiment, the remainder of the second layer also contains additional elements or electrodepositables, with Zn making up most of the remainder. In some embodiments, the implementation of Zn is, for example, at least about 75 wt.%, at least about 80 wt.%, at least about 85 wt.%, at least about 90 wt.%, at least about 95 wt.%, at least about 97 wt.%, at least about 99 wt.%, at least about 99.9 wt.% or about 100 wt.% of the rest.

In some embodiments, the implementation of the first and second layers in one or more places on the product, for example, on a non-threaded surface, contain Zn in the range, independently selected from from about 1 to about 99 wt.%. In some embodiments, the implementation of the first and second layers in one or more places on the product contain Zn in the range from about 1 to about 5 wt.%, from about 5 to about 7 wt.%, from about 7 to about 10 wt.%, from about 10 to about 15 wt.%, from about 15 to about 20 wt.%, from about 20 to about 30 wt.%, from about 30 to about 40 wt.%, from about 40 to about 50 wt.%, from about 50 to about 55 wt.%, about 55 to about 60 wt.%, from about 60 to about 65 wt.%, from about 65 to about 70 wt.%, from about 70 to about 75 wt.% , from about 75 to about 80 wt.%, from about 80 to about 85 wt.%, from about 85 to about 90 wt.%, from about 90 to about 92 wt.%, from about 92 to about 93 wt.%, from about 93 to about 94 wt.%, about 94 to about 95 wt.%, from about 95 to about 96 wt.%, from about 96 to about 97 wt.%, from about 97 to about 98 wt.%, or from about 98 to about 99 wt%. The remainder (residue of composition) of the first and second layers at one or more locations on the article, such as the threadless surface, contains Fe as well as additional elements or electrodepositables, with Fe making up most of the remainder.

by by by

In some embodiments, the implementation of Fe is, for example, at least about wt.%, at least about 80 wt.%, at least about 85 wt.%, at least at least about 90 to about 97 wt.%, by wt. %, at least about 95 to about 99 wt.%, wt.%, at least about 99.9 wt.%, or about 100 wt.% of the rest. In embodiments, the implementation of the second(s) layer(s) independently contain Ni in the range from about 1 to about 35 wt.%. In embodiments from to to to about about about about the second(s) wt.%, wt.%, wt.%, from from layer(s) independently from about about about to to contain Ni in about about about the range from about wt. %, wt.%, wt.%, from from about about to about 30 wt.% or from about 30 to about 35 wt.%. The balance of the second layer in such embodiments contains Zn. In some embodiments, the rest of the second layer also contains additional elements or electrodepositable substances, with Zn making up most of the rest, for example, at least about 75 wt.%, at least about 80 wt.%,

- 28 041389 at least about 85 wt.%, at least about 90 wt.%, at least about wt.%, at least about 97 wt.%, at least about 99 wt.%, at least about 99.9 wt.% or about 100 wt.% the rest.

ZnNi embodiments contemplated herein are embodiments where the first and second layers comprise combinations of Zn and Ni, wherein the Zn component at one or more locations on the product, such as a threadless surface, is from about 80 to about 90 wt.%. the first and second layers, and nickel is from about 10 to about 20 wt.% of the first and second layers. Within such embodiments, at one or more locations on the article, such as a threadless surface, the nickel in the nanolaminate coating can be from about 10 to about 17 wt.%, from about 13 to about 15 wt.%, from about 13 to about 16 wt.%, from about 13 to about 17 wt.%, about 14 wt.%, from about 14 to about 16 wt.%, from about 14 to about 17 wt.%, from about 14.5 to about 16 .5 wt.%, from about 11 to about 16 wt.%, from about 12 to about 16 wt.%, or from about 12 to about 15 wt.%, with Zn constituting at least about 97 wt.% of the rest. In some embodiments, the implementation of Zn is at least about 99 wt.%, at least about 99.9 wt.%, or about 100 wt.%. Such embodiments may further include repetitive first and second layers, wherein the first layer has a thickness of about 200 to about 300 nm, about 200 to about 400 nm, about 250 to about 300 nm, about 250 to about 350 nm, or about 250 nm, and the second layer has a thickness of from about 600 to about 900 nm, from about 650 to about 850 nm, from about 700 to about 800 nm, or about 750 nm. Such embodiments may further include a total number of first and second layers in the range of 12 to 15 layers and have a total coating thickness in the range of about 5 to about 11 microns, or about 8 to about 12 microns. In some embodiments, the coating thickness is in the range of about 8 to about 10 microns on at least some surfaces of the articles.

In some embodiments, the implementation of the first(s) layer(s) in one or more places on the product, for example on a non-threaded surface, independently contain Cu in the range from 1 to 99 wt.%. In some embodiments, the implementation of the first layer in one or more places on the product contains

Cu ranging from about 1 to about 5 wt.%, from about 5 up to about 7 wt%, from about 7 up to about 10 wt.%, from about 10 to about 15 wt%, from about 15 up to about 20 wt.%, from about 20 to about 30 wt%, from about 30 up to about 40 wt.%, from about 40 to about 50 wt%, from about 50 up to about 55 wt.%, from about 55 to about 60 wt%, from about 60 up to about 65 wt.%, from about 65 to about 70 wt%, from about 70 up to about 75 wt.%, from about 75 to about 80 wt%, from about 80 up to about 85 wt.%, from about 85 to about 90 wt%, from about 90 up to about 92 wt.%, from about 92 to about 93 wt%, from about 93 up to about 94 wt.%, from about 94 to about 95 wt%, from about 95 up to about 96 wt.%, from about 96 to about 97 wt%, from about 97 to about 98 wt.% or from about 98 to about 99 wt.%. The rest of the first and

the second layer in one or more places on the product, for example, on a threadless surface, contains Zn and/or Sn, as well as additional elements or electrodepositable substances, with Zn and/or Sn

is a big part of the rest for example, at least about 75 wt%, By lesser measure approximately 80 wt%, By lesser measure approximately 85 wt%, By lesser measure approximately 90 wt%, By lesser measure approximately 95 wt%, By lesser measure approximately 97 wt%, By lesser measure approximately 99 wt%,

Zn and/or Sn in the range of at least about 99.9 wt.% or about 100 wt.% the rest.

In embodiments, the second layer(s) independently comprise from from about about about about 35 to about up to about up to about about wt.%, including from about 1 to about 3 wt.%, wt.% , from about 5 to about 10 wt.%, from about 15 to about 20 wt.%, wt.%, wt.%, from about 25 to about 30 wt.%, or from about 30 to about 35 wt.%. The rest of the second layer in such embodiments contains Cu. In some embodiments, the rest may also contain additional elements or electrodepositables, with Cu making up most of the rest. In some embodiments, Cu is, for example, at least about at least about about wt.%, wt.%, wt.%, at least about at least about at least about .%, wt.%, wt.%, wt.%, at least about 99.9 wt.% or about 100 wt.% of the rest.

In embodiments, the electrodeposited layers at one or more locations on the article, for example, on a threadless surface, contain metal from fine to granular or from ultrafine to

- 29 041389 granular, including a metal or metal alloy having an average grain size of from 1 to 5000 nm (for example, from about 1 to about 20 nm, from about 1 to about 100 nm, from about 5 to about 50 nm, from about 5 up to about 100 nm, from about 5 to about 200 nm, from about 10 to about 100 nm, from about 10 to about 200 nm, from about 20 to about 200 nm, from about 20 to about 250 nm, from about 20 to about 500 nm, about 50 to about 250 nm, about 50 to about 500 nm, about 100 to about 500 nm, about 200 to about 1000 nm, about 500 to about 2000 nm, or about 1000 to about 5000 nm ), based on grain size measurements in micrographs. In such embodiments, the fine grained metal or alloy at one or more locations on the article, such as a threadless surface, may contain one or more, two or more, three or more, or four or more elements independently selected from the group consisting of Ag , Al, Au, B, Be, C, Co, Cr, Cu, Fe, Hg, In, Ir, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Si , Sn, Pb, Ta, Ti, W, V, Zn and Zr, each of the independently selected metals being present in amounts greater than 0.001 wt%. In some embodiments, each of the independently selected metals is present in amounts of greater than about 0.1 wt%, greater than about 0.05 wt%, greater than about 0.01 wt%, or greater than about 0.005 wt%. In other embodiments, the independently selected metal is present in an amount ranging from about 1 to about 99 wt%.

In additional embodiments, an independently selected metal is present in an amount ranging from about 1 to about 5 wt.%, from about 5

before approximately 7 wt%, from approximately 7 before approximately 10 wt%, from approximately 10 before approximately 15 wt%, from approximately 15 before approximately 20 wt%, from approximately 20 before approximately thirty wt%, from approximately thirty before approximately 40 wt%, from approximately 40 before approximately 50 wt%, from approximately 50 before approximately 55 wt%, from approximately 55 before approximately 60 wt%, from approximately 60 before approximately 65 wt%, from approximately 65 before approximately 70 wt%, from approximately 70 before approximately 75 wt%, from approximately 75 before approximately 80 wt%, from approximately 80 before approximately 85 wt%, from approximately 85 before approximately 90 wt%, from approximately 90 before approximately 92 wt%, from approximately 92 before approximately 93 wt%, from approximately 93 before approximately 94 wt%, from approximately 94 before approximately 95 wt%, from approximately 95 before approximately 96 wt%, from approximately 96

to about 97 wt.%, from about 97 to about 98 wt.% or from 98 to about 99 wt.%.

Although the plating according to this invention will typically be carried out in a single bath, it is possible to apply different nanolaminate layers to articles using separate baths. In practice of such embodiments, one electroplating bath would be used to deposit one layer. The drum, basket, tumbler, or other container device would then be removed from this bath, washed, and then immersed in a second bath, and the plating process continued. Additional layers could be obtained using different baths.

In embodiments, the coefficient of thermal expansion of the nanolaminate coating layers is within 20% (e.g., less than 20%, 15%, 10%, 5%, or 2%) of the preform in a direction parallel to the movement of the preform (i.e., in the plane of the preform and parallel to the direction of movement of the preform). ).

Corrosion resistance.

In embodiments, nanolaminate-coated articles are provided with corrosion-resistant coatings in a plurality. As one skilled in the art would understand, corrosion includes wear, spalling, crevice corrosion, intergranular corrosion, stress corrosion cracking (SCC), blistering, embrittlement, hydrogen sulfide stress cracking (SSC), and corrosion fatigue.

In embodiments, depending on coating composition and thickness, nanolaminate coatings at one or more locations on a product, such as a threadless surface, provide at least 1000 hours before first red rust when tested in salt spray according to ASTM-B117-11 . For example, embodiments with ZnNi coatings as described herein having a thickness of at least 10 microns will provide such corrosion resistance. Other embodiments provide at least 2000 hours to first red rust when tested in salt spray according to ASTM-B117-11, and other embodiments provide at least 3000 hours to first red rust when tested in salt spray according to ASTM-B117-11 standard. Still other embodiments provide resistance for at least 4000 hours, at least 5000 hours, at least 6000 hours, at least 7000 hours, at least 8000 hours, at least 9000 hours, at least 10000 hours, at least 12,500 hours and at least 15,000 hours to first red rust when tested in salt spray according to ASTM-B117-11. The embodiments of the coating methods here also produce coatings that are considered non-brittle according to ASTM F519-12a.

- 30 041389

In embodiments, nanolaminate-coated articles are provided with corrosion-resistant coatings in a plurality. Embodiments of such corrosion resistant coatings may comprise at least first and second metals (and optionally one or more additional metals) independently selected for each layer from the group consisting of Zn, Cr, Fe, Co, and Ni, and optionally may also include at least one additional element selected from P, Al, Si, or B. Examples of such combinations include NiCr, NiFe, NiCo, NiCrCo, NiAl, NiCrAl, NiFeAl, NiCoAl, NiCrCoAl, NiMo, NiCrMo, NiFeMo, NiCoMo, NiCrCoMo, NiW, NiCrW, NiFeW, NiCoW, NiCrCoW, NiNb, NiCrNb, NiFeNb, NiCoNb, NiCrCoNb, NiTi, NiCrTi, NiFeTi, NiCoTi, NiCrCoTi, NiCrP, NiCrAl, NiCoP, NiCoAl, NiFeP, NiFeAl, NiCrSi, NiCrB, NiCoSi, NoCoB, NiFeSi, NiFeB, ZnCr, ZnFe, ZnCo, ZnNi, ZnCrP, ZnCrAl, ZnFeP, ZnFeAl, ZnCoP, ZnCoAl, ZnNiP, ZnNiAl, ZnCrSi, ZnCrB, ZnFeSi, ZnFeB, ZnCoSi, ZnCoB, ZnNiSi, ZnNiB, CoCr, CoFe, CoCrP, CoFeP, CoCrAl, CoFeAl, CoCrSi, CoFeSi, CoCrB, CoFeB, CoAl, CoW, CoCrW, CoFeW, CoTi, CoCrTi, CoFeTi, CoTa, CoCrTa, CoFeTa, CoC, CoCrC, CoFeC, FeCr, FeCrP, FeCrAl, FeCrSi and FeCrB. As noted above, in the above list, the elements listed in the combination of elements are not listed in order from the most present element to the least present element. Other embodiments of such corrosion resistant coatings may include at least first and second layers containing Ni as electrodeposits and one or more, two or more, three or more, or four or more elements independently selected for each nanoscale layer from the group, consisting of C, Co, Cr, Mo, W, Nb, Fe, Ti, Al, V and Ta.

Examples

The following examples illustrate embodiments of this invention.

EXAMPLE 1 Preparation of Zn-Ni nanolaminate coatings by drum plating.

This example describes the production in a drum of a multi-layer coating comprising nano-sized layers of zinc-nickel alloy, in which the concentration of nickel varies in adjacent layers. In this example, 200 pins having a diameter of 5/8 inches and a length of 3.25 inches are loaded into a drum having a diameter of 10 inches and a length of 18 inches, resulting in a drum loading fraction of 0.12. The proportion of the length of the pins relative to the radius of the drum is 0.676. The drum consists of two flexible electrodes having a total area of approximately 20 cm ² .

The composition of the bath is described in table. 2. The bath is maintained within the temperature range of 6973°F throughout the drumming process.

table 2

Composition of Zn-Ni bath

Material Concentration (g/l) NaOH 117 Ni 1.3 Zn 7.7

The drum may be rotated at 8 rpm and a square wave signal is applied with a current density of about 2 mA/cm ² for about 4 minutes and a second current density of about 4 mA/cm ² for about 8 minutes. . The drum processes for approximately 3.5 hours.

A list of thicknesses and compositions of four samples randomly selected from a batch of 200 studs is shown in Table 1 below. 3. The resulting laminate flooring looks shiny and has a uniform finish.

Table 3

ASTM B117-11 Nanolaminated Zn-Ni Stud Results

start date Sample number Thickness (µm) Composition (%Ni) expiration date 1st red rust (hours) 6/8/2014 113.018.01 7.0 15.4 no data no data ⁽⁵ ) 113.018.02 19.2 14.9 no data no data! ⁵ ) 113.019.01 9.3 15.2 no data >190000) 113.019.02 24.7 15.8 no data no data ⁽⁵ )

⁽⁵⁾ The test is still ongoing, with no signs of rust after 19,000 hours.

Example 2 Comparative Corrosion Test.

This example illustrates the comparative results of ASTM B117-11 testing of various types of anti-corrosion coatings on studs, nuts and washers, including samples from a batch that was plated with zinc and nickel in a manner similar to that described in Example 1.

- 31 041389

Table 4

ASTM B117-11 Test Results for Nanolaminated Zn-Ni Studs, Nuts and Washers

Coating system Minimum Thickness (µm) Salt Spray Test Result (ASTM B117-11) (hours) 1st red rust (RR) 5%RR 10%RR (defeat) No coverage no data no data 16 36 Cadmium 4.3 no data 536 736 Electrolytic galvanizing ⁽⁴ ) 1.7 48 168 329 hot dip galvanizing by immersion (HDG) 13.1 no data 245 677 Polytetrafluoroethylene (PTFE) 4.5 48 563 840 Inflicted in the drum Zn-Ni-oe coating 4.7 no data® no data® no data® Drum Coated Zn-Ni-oe Coating + Finish Coat® 4.7® no data® no data® no data®

¹¹¹ No recordable injury after 4000 h (test duration).

⁽²⁾ Finigard 460 finish applied after metallization.

⁽³⁾ Coating thickness only.

⁽⁴⁾ Electrodeposited zinc coating.

Example 3 Hydrogen Embrittlement (astm f519).

To evaluate ZnNi-coated articles obtained from a 10x18 inch drum coating process like that described in Example 1 for susceptibility to hydrogen embrittlement, a test was performed in accordance with ASTM F519-12a.

Products were tested for sensitivity to hydrogen embrittlement according to ASTM F519-12A Mechanical Hydrogen Embrittlement Evaluation of Plating/Coating Processes and Service Environments. After applying the metalizing coatings, the samples were annealed at 275°F for 24 hours in accordance with ASTM B850.

A hydrogen embrittlement test was then carried out according to ASTM F 519-12A. Each specimen was subjected to a continuous load of 75% notched fracture resistance (NFS) for 235 hours or until failure. The plating method was then evaluated under the assumption that if two or more specimens from the same selected batch failed during the test, then the method was considered brittle.

Test results.

None of the annealed specimens failed within the required 200.0 h of long-term stress (Table 4). According to ASTM F519-12a, the coating method is considered non-embrittling.

Table 4

ASTM B117-11 Test Results for Nanolaminated Zn-Ni Studs, Nuts and Washers

Sample No. Destruction (yes/no) Load time (hour) Place of destruction Heat treatment Suitable / unsuitable 1 No 235 no data 24 hours at 275°F fit 2 No 235 no data 24 hours at 275°F fit 3 No 235 no data 24 hours at 275°F fit 4 No 235 no data 24 hours at 275°F fit

EXAMPLE 4 Drum Metalization Stirring Experiment.

As noted above, the agitation rate in drum plating can be approximated by the degree of agitation, which describes the number of occurrences on the plated surface of a preform within a batch that can be plated in fifty (50) drum revolutions divided by the number of drum revolutions (i.e. 50). In this example, the degree of mixing of several hairpins is investigated. Studs come in 3/8x2.0, 5/8x3.25" and 1/2x2.5" sizes. Each of the studs has an aspect ratio of 5:1. Two octagonal Sterling drums (6x6 inches and 6x9 inches) were used, each with two flexible stainless steel electrodes. For the mixing study, mixing was roughly modeled by adding three preforms that could be monitored during the mixing process. These three blanks were wrapped in reflective tape of different colors, and their ends were dipped in plastisol for protection. The preforms are measured optically so that one mark is made on the sheet of paper each time the preform is visible inside the grating from areas on the drum that are considered best for plating. Such areas are shown by way of example in FIG. 4, and as shown, these regions are numbered 1-6.

The appearance of each marker in one of the six grids shown in FIG. 4 is recorded for a measurement time coinciding with 50 revolutions. Only new occurrences in each sector are noted, and only measurements in these six sectors are recorded. Blanks that appear again in the same sector, or blanks that appear in unnumbered sectors, do not count. The average of the occurrences for the three markers can then be determined to obtain the experimental shuffling value for that operating cycle. Even very small numbers of blanks fill all six sectors during rotation, with the blanks layered on the front side of the drum as it moves up.

Various work cycles were carried out and various parameters were varied to determine combinations of parameters, including, for example, length fraction, load fraction and rpm, which provide the highest mixing ratios. Multiple operating cycles at any given combination of parameters may be carried out to better determine the appropriate mixing for any given combination of a set of parameters. Generally speaking, when all other parameters are held constant, the degree of agitation can be experimentally observed to decrease with increasing load fraction or as length fraction increases beyond a certain value. Similarly, when all other parameters are held constant, the degree of agitation can be experimentally observed to decrease slightly at RPM above a certain value, such as above 5.

Such experiments can be similarly carried out for different types of drums and different types of loads and parameters.

EXAMPLE 5 Jitter experiment with drum plating.

A drum set similar to that described in Example 4 is used. The drum is additionally equipped with a shake monitor as shown in FIG. 5. The flexible electrodes are positioned so that they are separated from each other by one workpiece length for each part size. The flexible electrodes are initially pressed against the bottom of the drum and blanks are randomly added to the drum. A 480 mA current signal is passed through the flexible electrode wires to simulate noise in the current signal (like jitter). During this test procedure, those marked blanks described in Mixing Example 4 are replaced by three conventional non-marked blanks. During operation, the drum rotates at a variable number of revolutions per minute, load fractions and workpiece sizes. The current is monitored in 0.5 second intervals for 25 min = 3001 measurements. Deviations from the applied signal are noise, due to the fact that the workpieces between the flexible electrodes create noise, or jitter, in the signal. This noise mimics anode/cathode noise during plating. The instrument cannot detect more than 610 mA.

The resulting jitter data is shown in FIG. 6. The applied signal and the calculated average value of the measured signal are shown. The average current for that particular drum is then calculated for various combinations of length fraction, load fraction, average degree of agitation, and rpm and plotted as shown in FIG. 7 to see if one or more combinations of parameters can be found that can provide acceptable deposition of nanolaminates as described here. As shown in FIG. 7, in this particular drum with these particular preforms, the combination of a length fraction of 0.67, a load fraction of about 0.20 to 0.25, and a speed of 5 rpm appears to be a combination that can provide an acceptable application of nanolaminates as described here.

Example 6 Zn-Ni Coatings

A. Application of Zn-Ni nanolaminate coatings.

A multi-layer coating comprising nanoscale layers of zinc and nickel was formed on 200 threaded steel tie bolts (studs), nuts and washers, in which the ratio of zinc to nickel concentrations varies in adjacent layers, during the preparation using a bath containing salts of zinc and nickel , see FIG. 8. The coating was applied using a pulsed wave signal to deposit alternating layers of a Zn-Ni coated alloy having a total composition of 86.5% Zn and 13.5% Ni. The analysis showed that the coating varied along the length of the bolt with a thickness of 4.7 µm (average three threads); 7.7 (end three threads); an average thickness of 19.4 microns.

B. Corrosion test.

Threaded bolts (5/8" fully threaded studs per ASTM A193 B7), nuts (5/8" thick hex nuts per ASTM A194 2H), and washers (5/8" per ASTM F436), prepared as follows , as described in Section A of this example, were subjected to an accelerated corrosion test according to ASTM B117-11. One set of bolts, nuts and washers was prepared as described in Section A with the addition of a Finigard 460 finish applied according to the manufacturer's data sheet. In addition, control bolts, nuts and washers were prepared, which were otherwise identical.

- 33 041389 used in Section A, but one set was uncoated, others were electroplated with cadmium (6.6-15.5 µm), zinc hot dip galvanized (14.122.5 µm), PTFE (32.0 microns, Teflon) or zinc electroplating (1.7-7.1 microns, electrolytic zinc plating). Test bolts, nuts and washers were tested in parallel with the bolts described in

Section A. The time of occurrence of red rust is given in table. 5.

Table 5

Nanolaminate coating Time to observed appearance of red rust (hours) Nickel-zinc No signs of corrosion after 4000 hours of exposure ¹ coating (Section A) Control Coatings Without cover hot dip galvanizing hot dip galvanizing Time to observed appearance of red rust (hours) 5% red rust was observed after 4 pm; 10% red rust was observed in 36 hours. 5% red rust was observed after 245 hours; 10% after 677 hours Initial red rust was observed after 48 hours; 5% red rust observed in 168 hours and 10% red rust in 329 hours Cadmium plating 5% red rust in 53 hours; 10% red rust in 736 hours PTFE coating Initial rust in 48 hours; 5% red rust in 563 hours, and 10% in 840 hours

Test completed.

C. Cyclic corrosion test and subsequent hydrogen embrittlement tensile test.

Three sets of 5/8" x 3.25" threaded bolts (studs), nuts and washers were Zn-Ni plated to a thickness of 19.4 µm average thickness (4.7 µm (middle three threads); 7.7 (end three threads) threads)) as described in Section A of this example. The coating contained 86.5±0.54% zinc by weight. Additional test bolts, nuts and washers were prepared which were otherwise identical to those used in Section A, but one set was uncoated, others were electroplated with cadmium (6.6-15.5 µm), zinc with hot dip galvanizing (14.1-22.5 µm), PTFE (32.0 µm, Teflon) or zinc plated (1.7-7.1 µm, electro zinc plated). The test and control bolts were placed in a cylindrical ring and tightened with nuts to 227 ft-lbs, 187 ft-lbs, or 176 ft-lbs of torque to stretch the bolts prior to cyclic corrosion testing as prescribed by General Motors Worldwide Engineering Standard GMW 14872 (accelerated corrosion test by General Motors). The time for the appearance of red rust on bolts in tension is given in Table. 6.

Table 6

Cyclic corrosion and subsequent hydrogen embrittlement_______

Nanolaminate coating Nickel-zinc coating (Section A) without stretch Nickel-zinc coating (Section A) at each stretch level Control samples Time to Observed Red Rust in ASTM B117-11 Accelerated Corrosion Test No signs of corrosion (red rust) after more than 4000 hours No signs of corrosion (red rust) after more than 1000 hours (42 cycles) Time to observable appearance of red rust Without cover Red rust after 672 hours hot dip galvanizing immersion (zinc) Red rust after 672 hours Electrolytic zinc plating (zinc) Red rust after 672 hours Cadmium Red rust after 672 hours PTFE coating Red rust after 672 hours

Embodiments

The following embodiments are included within the scope of this invention.

1. A method for drum plating a batch of metal products to provide a nanolaminate metal coating on a plurality of products in a batch, including the steps:

providing a drum with a batch of coated metal products, and the drum has a length and radius, with each of the products has the longest dimension;

placement of at least part of the drum and metal products in a tank containing

- 34 041389 bath electrodeposition, including one or more electrodepositable metal ions;

providing at least one anode in the electrodeposition bath, the anode being on the outside of the drum;

providing at least two cathode flexible electrodes in the electrodeposition bath, wherein the at least two flexible electrodes extend into opposite ends of the drum, the ends of the flexible electrodes extending into the drum being separated from each other by a distance;

drum rotation;

applying a first electric current for a first amount of time through the flexible electrodes, thereby causing the first identifiable metal layer to be electrodeposited onto the metal articles in a plurality, the first metal layer having a thickness at one or more locations on the article between 150 and 20,000 nm and containing at least first and second metal components;

applying a second electric current for a second amount of time through the flexible electrodes, thereby causing the electrodeposition of a second identifiable metal layer onto the metal articles in a plurality, the second metal layer having a thickness at one or more locations on the article between 150 and 20,000 nm and containing at least one of the first and second metal components, and wherein at least one feature in the second layer selected from the group consisting of composition, grain size, and grain structure (e.g., microstructure or morphology) differs from at least one of the features in first layer;

optionally, applying one or more additional electrical currents through the flexible electrodes, causing electrodeposition of additional identifiable metal layers onto the metal articles in a plurality, each of the additional identifiable layers having a thickness at one or more locations on the article between 150 and 20,000 nm and containing at least one of the first and second metal components, wherein for each such additional layer, at least one feature selected from the group consisting of composition, grain size, and grain structure (e.g., microstructure or morphology) differs from at least one of the features immediately preceding metal layer.

2. The drum plating method of embodiment 1, wherein each identifiable metal layer has a thickness of at least 200 nm at one or more locations on the product.

3. The method of drum plating according to option 1 or 2, and the ratio of the longest size of the metal products in the batch to the radius of the drum is less than 1.3.

4. The method of drum plating according to option 1 or 2, and the ratio of the longest size of the metal products in the batch to the radius of the drum is less than 1.1.

5. The method of drum plating according to option 1 or 2, and the ratio of the longest size of the metal products in the batch to the radius of the drum is less than 0.9.

6. The method of drum plating according to option 1 or 2, and the ratio of the longest size of the metal products in the batch to the radius of the drum is less than 0.7.

7. The method of drum plating according to any of options 1-6, and the following ratio of the stuffing volume of the products loaded into the drum to the volume of the drum is less than 70%.

8. The method of drum plating according to option 7, and the ratio of the volume of products loaded into the drum to the volume of the drum is less than 50%.

9. The method of drum plating according to option 7, and the ratio of the volume of products loaded into the drum to the volume of the drum is between 10 and 40%.

10. The drum plating method according to any one of embodiments 1-9, wherein in a plurality of drum metallized articles in a batch, the weight percentage of the first metal component at one or more locations on any of the plurality of articles does not differ by more than 6 wt.% from the mass percent of that the same metal component in one or more places of another item from the set.

11. The drum plating process according to any one of embodiments 1-10, wherein in a plurality of drum metallized articles in a batch, the weight percent of the second metal component at one or more locations on any one of the plurality of articles does not differ by more than 6 wt.% from the mass percent of that the same metal component in one or more places of another item from the set.

12. The method of drum plating according to any one of options 1-11, and the drum rotates during the summing of the first and second currents at a speed of 4-10 rpm.

13. The drum plating method according to any one of embodiments 1-12, wherein the first and second amounts of time are each from 2 to 10 minutes.

14. The drum plating process of embodiment 13 wherein the first amount of time is 2 to 6 minutes.

15. The drum plating method according to option 13 or 14, and the first amount of time is from 5 to 10 minutes.

16. The method of drum metallization according to any of options 1-15, and the first electric

- 35 041389 the current is between 20 and 70 A.

17. The drum plating method according to any one of options 1-16, wherein the second electric current is between 40 and 140 A.

18. The drum plating method according to any one of embodiments 1-17, wherein the voltage associated with the first or second electric current, or both, is between 3 to 8 V.

19. A drum plating method according to any one of embodiments 1-18, wherein the first identifiable layer in the articles in said plurality has a thickness of 200 to 500 nm at one or more locations on the article.

20. The drum plating method of embodiment 19, wherein the first identifiable layer in the articles in said plurality has a thickness of 200 to 350 nm at one or more locations on the article.

21. A drum plating method according to any one of embodiments 1-20, wherein the second identifiable layer in the articles in said plurality has a thickness of 400 to 1000 nm at one or more locations on the article.

22. The drum plating method of embodiment 21, wherein the second layer in the articles in said plurality has a thickness of 650 to 850 nm at one or more locations on the article.

23. The drum plating method of any one of embodiments 1-22, comprising applying one or more additional electrical currents through flexible electrodes, each such additional electrical current being applied for an amount of time sufficient to cause an additional identifiable metal layer to be formed by electrodeposition in one or more locations on a plurality of metal products.

24. The drum plating method of embodiment 23, comprising applying additional currents through flexible electrodes to deposit 6 to 15 additional identifiable layers at one or more locations on a plurality of metal products.

25. The drum plating method according to any one of embodiments 1-24, wherein the total thickness in nanometers of the electrodeposited metal layers at one or more locations on each of the plurality of articles is between 6 and 14 microns.

26. The drum plating method of any one of embodiments 1-24, wherein the total nanometer thickness of the electrodeposited metal layers at one or more locations on each of the plurality of articles is between 8 and 10 microns.

27. The drum plating method according to any one of options 1-26, and the first and second metal components in the set contain at least two elements selected from the group consisting of Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn, Co, Pb, Al, Ti, Mg, W, Rh and Cr.

28. The drum plating method according to any one of options 1-27, and in a variety of products, the first identifiable metal layer, the second identifiable metal layer, or both of them contain at least two metals selected from the group consisting of Ni and Zn, Ni and Co , Ni and Cr, and Zn and Fe.

29. The drum plating method of any one of embodiments 1-28, wherein at one or more locations on the articles in the plurality, the first identifiable metal layer, the second identifiable metal layer, or both contain 13 to 17% Ni.

30. The drum plating method of embodiment 29, wherein at one or more locations on the articles in the plurality, the first identifiable metal layer, the second identifiable metal layer, or both contain 83 to 87% Zn.

31. A drum plating method according to any one of embodiments 1-30, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 1000 hours before first red rust appears when tested in salt spray according to ASTM-B117. -eleven.

32. The drum plating method of any one of embodiments 1-30, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 3,000 hours before first red rust appears when tested in salt spray according to ASTM-B117. -eleven.

33. The drum plating method of any one of embodiments 1-30, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 5,000 hours before first red rust appears when tested in salt spray according to ASTM-B117. -eleven.

34. The drum plating method according to any one of embodiments 1-33, wherein any article in the set has a total thickness of the nanolaminate coating at the first location on the article that is within 6 μm of the average thickness of the nanolaminate coating at the same location on the other articles in the set. .

35. The drum plating method according to any one of embodiments 1-33, wherein any article in the plurality has a total thickness of the nanolaminate coating at a first location on the article that is within 3 µm of the average thickness of the nanolaminate coating at the same location on the other.

- 36 041389 many products.

36. The drum plating method of embodiment 34 or 35, wherein any article in the plurality has a total thickness of the nanolaminate coating at a second location on the article that is within 6 µm of the average thickness of the nanolaminate coating at the same location on the other articles in the plurality.

37. The drum plating method according to option 34 or 35, wherein any item in the set has a total thickness of the nanolaminate coating at the second location on the item, which is within 3 microns of the average thickness of the nanolaminate coating at the same location on the other item in the set.

38. The drum plating method according to any one of embodiments 1-37, wherein the plurality includes a majority of the same shaped items in the batch, and the majority being at least 70% of the total number of the same shaped items in the batch.

39. A drum plating method according to any one of embodiments 1-37, wherein the plurality includes a majority of the same shaped items in the batch, and the majority being at least 90% of the total number of the same shaped items in the batch.

40. The drum plating method according to any one of embodiments 1-37, wherein the plurality includes a majority of the same shaped items in the batch, and the majority being at least 95% of the total number of the same shaped items in the batch.

41. A drum plating method according to any one of embodiments 1-40, wherein one or more locations includes a threaded surface.

42. A drum plating method according to any one of embodiments 1-41, wherein one or more locations includes a threadless surface.

43. A plurality of drum-metallized metal products made by the method of any one of embodiments 1-42.

44. Drum-plated metal product in a plurality, made by the method according to any of options 1-42.

45. A combination including a drum and a plurality of metal products metallized in the drum according to option 41.

46. A metal product with a nanolaminate coating, and the coating contains:

a first identifiable metal layer having a thickness between 150 and 20,000 nm at one or more locations on the article, the first metal layer comprising at least first and second metal components;

a second identifiable metal layer having a thickness between 150 and 20,000 nm at one or more locations on the articles, the second metal layer comprising first and second metal components;

wherein at least one feature in the second layer selected from the group consisting of composition, grain size, and grain structure (eg, microstructure or morphology) is different from at least one of the features in the first layer;

moreover, the metal product optionally contains one or more additional, identifiable metal layers having a thickness between 150 and 20000 nm, in one or more places on the product, and the additional identifiable metal layer also contains at least one of the first and second metal components, while for each such additional layer, at least one feature selected from the group consisting of composition, grain size, and grain structure (e.g., microstructure or morphology) differs from at least one of the features in the immediately preceding metal layer, and wherein the nanolaminate coating contains one or more inhomogeneities characterized by inwardly directed deformation of the nanolaminate coating towards the substrate surface, wherein the layers of the nanolaminate coating on either side of the inhomogeneity are deformed along the inhomogeneity and in the direction from the coating surface and towards the substrate surface.

47. The nanolaminate coated metal article of embodiment 46, wherein each identifiable metal layer is at least about 200 nm thick at one or more locations on the article.

48. Nanolaminate coated metal article of embodiment 46 or 47, wherein the first identifiable metal layer is between 225 and 500 nm thick at one or more locations on the article.

49. The nanolaminate coated metal article of embodiment 48, wherein the first identifiable metal layer is between 225 and 350 nm thick at one or more locations on the article.

50. The nanolaminate coated metal article of any one of embodiments 46-49, wherein the second identifiable metal layer is between 400 and 1000 nm thick at one or more locations on the article.

51. The nanolaminate coated metal article of embodiment 50, wherein the second identifiable metal layer is between 650 and 850 nm thick at one or more locations on the article.

- 37 041389

52. The nanolaminate coated metal article of any one of embodiments 46-51, wherein the article comprises 6 to 20 identifiable metal layers at one or more locations on the article.

53. The nanolaminate coated metal article of any one of embodiments 46-52, wherein the total nanometer thickness of the electrodeposited metal layers is between 6 and 14 microns at one or more locations on the article.

54. The nanolaminate coated metal article of any one of embodiments 46-52, wherein the total nanometer thickness of the electrodeposited metal layers is 8 to 10 microns at one or more locations on the article.

55. The nanolaminate coated metal article of any one of embodiments 46-54, wherein the first and second metal components comprise at least two elements selected from the group consisting of Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn, Co, Pb, Al, Ti, Mg, W, Rh and Cr.

56. The nanolaminate coated metal article of any one of embodiments 46-55, wherein the first identifiable metal layer, the second identifiable metal layer, or both contain at least two metals selected from the group consisting of Ni and Zn, Ni and Co, Ni and Cr, and Zn and Fe.

57. The nanolaminate coated metal article of any one of embodiments 46-56, wherein the first identifiable metal layer, the second identifiable metal layer, or both contain 13 to 17% Ni at one or more locations on the article.

58. The nanolaminate coated metal article of any one of embodiments 46-57, wherein the first identifiable metal layer, the second identifiable metal layer, or both contain 83 to 87% Zn at one or more locations on the article.

59. The nanolaminate coated metal product of any one of embodiments 46-58, wherein at one or more locations on the product the nanolaminate coating resists corrosion and provides at least 1000 hours before first red rust appears when tested in salt spray according to ASTM-B117. -eleven.

60. The nanolaminate coated metal product of any one of embodiments 46-58, wherein at one or more locations on the product the nanolaminate coating resists corrosion and provides protection for at least 2000 hours before first red rust appears when tested in salt spray ASTM- B117-11.

61. The nanolaminate coated metal product of any one of embodiments 46-58, wherein at one or more locations on the product, the nanolaminate coating resists corrosion and provides protection for at least 3,000 hours before first red rust occurs when tested in an ASTM-Salt Spray Test. B117-11.

62. The nanolaminate coated metal product of any one of embodiments 46-58, wherein at one or more locations on the product, the nanolaminate coating resists corrosion and provides protection for at least 5,000 hours before first red rust occurs when tested in an ASTM-Salt Spray Test. B117-11.

63. The metal article of any one of 46-62, wherein one or more locations includes a threaded surface.

64. The metal article of any one of 46-62, wherein one or more locations includes a threadless surface.

65. A plurality of metal articles as in any one of embodiments 46-64, wherein the weight percentage of the first metal component in the coating on any article in the plurality does not differ by more than 6% by weight from the weight percent of the same metal component in the coating on another article in the plurality.

66. A plurality of metal articles as in any one of embodiments 46-64, wherein the weight percentage of the first metal component in the coating on any article in the plurality does not differ by more than three weight percent from the weight percent of the same metal component in the coating on another article in the plurality.

67. A plurality of metal articles as in any one of embodiments 46-66, wherein the weight percentage of the second metal component in the coating on any article in the plurality does not differ by more than 6% by weight from the weight percent of the same metallic component in the coating on another article in the plurality.

68. A plurality of metal articles as in any one of embodiments 46-66, wherein the weight percent of the second metal component in the coating on any article in the plurality does not differ by more than three weight percent from the weight percent of the same metal component in the coating on another article in the plurality.

69. A plurality of metal articles as in any one of embodiments 46-68, wherein any article in the plurality has a total thickness of the nanolaminate coating at the first location on the article that is within 3 μm of the average thickness of the nanolaminate coating at the same location on the other articles of the plurality. .

- 38 041389

70. A plurality of metal articles as in any one of embodiments 46-68, wherein any article in the plurality has a total thickness of the nanolaminate coating at the first location on the article that is within 6 µm of the average thickness of the nanolaminate coating at the same location on the other articles of the plurality. .

71. A plurality of metal articles as in any one of embodiments 69 or 70, wherein any article in the plurality has an overall nanolaminate coating thickness at second locations on the article that is within 6 μm of the average nanolaminate coating thickness at the same location on the other articles in the plurality. .

72. A plurality of metal articles as in any one of embodiments 69 or 70, wherein any article in the plurality has an overall nanolaminate coating thickness at a second location on the article that is within 3 µm of the average nanolaminate coating thickness at the same location on the other articles in the plurality. .

73. A plurality of metal products according to any one of embodiments 65-72, wherein one or more locations includes a threadless surface.

74. A plurality of metal articles as in any one of embodiments 65-72, wherein one or more locations includes a threaded surface.

75. A combination comprising a plating drum and a plurality of metal products according to any one of options 65-74.

76. A method for non-suspension plating of a batch of products in an electrodeposition bath to provide a nanolaminate metal coating on a plurality of products in a batch, wherein the products are placed in a container device, and at least a portion of the container device is capable of moving inside the bath so as to cause movement of the products inside the container device, wherein the method includes the steps:

introduction of a batch of coated products into a container device;

placing at least a portion of the container device containing the articles into a reservoir containing an electrodeposition bath, the electrodeposition bath containing one or more electrodepositable metal ions;

providing at least one anode in the electrodeposition bath outside the container device;

providing at least two cathodic connections providing substantially continuous or discontinuous contact with the batch of metal articles within the container device;

driving the container device in a predetermined mode of motion, thereby causing the articles to move within the container device;

applying a first electrical current for a first amount of time, thereby causing a first identifiable metal layer to be electrodeposited onto the metal products in the batch, having a thickness at one or more locations on the product between 150 and 20,000 nm and containing at least first and second metal components;

applying a second electric current for a second amount of time, thereby causing the electrodeposition of a second identifiable metal layer on the metal products in the batch, having a thickness at one or more locations on the product between 150 and 20,000 nm and containing at least the first and second metal components, when wherein at least one feature selected from the group consisting of composition, grain size, and grain structure (eg, microstructure or morphology) of the second layer differs from those of the first layer, and additionally, the second layer may also differ in thickness from the first layer; and optionally, applying one or more additional electrical currents for one or more additional amounts of time to cause one or more additional identifiable metal layers to be electrodeposited onto metal products in the batch, each independently having a thickness at one or more locations on the product between 150 and 20000 nm and contains at least one of the first and second metal components, and for each such additional layer, at least one feature selected from the group consisting of composition, grain size and grain structure differs from at least one of the same features in the immediately preceding metal layer, and additionally may have a thickness that is the same as or different from the thickness of either the first and/or second layers.

77. The method of embodiment 76, wherein the container device is selected from the group consisting of a drum plating device, a vibrating basket plating device, and a rocking vessel plating device.

78. The method according to option 76 or 77, wherein at least one parameter selected from the group consisting of first current, first time, second current, second time, optional one or more additional electric currents, and optional one or more additional times, is determined based at least in part on one or more parameters that are applicable to the container device, wherein the parameters applicable to the container device are selected from the group consisting of load fraction, load volume fraction, apparent load, length fraction,

- 39 041389 stuffing volume, rpm, frequency, amplitude, container device movement speed, jitter and mixing speed.

79. The method of embodiment 78, wherein the parameters applicable to the container device are selected from amplitude and frequency.

80. The method of any one of embodiments 76-79, wherein each identifiable metal layer is at least 200 nm thick at one or more locations on the article.

81. The method of plating according to any one of options 1-6, and the following ratio of the stuffing volume of the products loaded into the container device to the volume of the container device is less than 70%.

82. The method according to option 81, wherein the ratio of the volume of products loaded into the container device is less than 50%.

83. The method of embodiment 81, wherein the ratio of the volume of articles loaded into the container device to the volume of the container device is between 10 and 40%.

84. A plating method according to any one of options 76-83, and in a plurality of products in a batch, the mass percentage of the first metal component in one or more places in any product from the set does not differ by more than 6 wt.% from the mass percent of the same metal component in one or more places in another product from the set.

85. The method of any one of embodiments 76-84, wherein, in a plurality of articles in a batch, the weight percent of the second metal component at one or more locations in any article of the plurality does not differ by more than 6 wt.% from the weight percent of the same metal component in one or more places in another product from the set.

86. The method of any one of embodiments 76-85, wherein the container device is rotated during the application of the first and second currents at a speed of 4-10 rpm.

87. The method of any one of embodiments 76-86, wherein the first and second amounts of time are each from 2 to 10 minutes.

88. The method of embodiment 87, wherein the first amount of time is 2 to 6 minutes.

89. The method according to option 87 or 88, and the first amount of time is from 5 to 10 minutes.

90. The method of any one of embodiments 76-89, wherein the first electrical current is between 20 and 70 A.

91. The method of any of embodiments 76-90, wherein the second electric current is between 40 and 140 A.

92. The method of any one of embodiments 76-91, wherein the voltage associated with the first or second electrical current, or both, is between 3 and 8 volts.

93. The method of any one of embodiments 76-92, wherein the first identifiable layer in the articles in the plurality has a thickness of 200 to 500 nm at one or more locations on the article.

94. The method of embodiment 93, wherein the first identifiable layer in the articles in the plurality has a thickness of 200 to 350 nm at one or more locations on the article.

95. The method of any one of embodiments 76-94, wherein the second identifiable layer in the articles in the plurality has a thickness of 400 to 1000 nm at one or more locations on the article.

96. The method of embodiment 95, wherein the second layer in the articles in the plurality has a thickness of 650 to 850 nm at one or more locations on the article.

97. The method of any one of embodiments 76-96, comprising applying one or more additional electrical currents, each such additional electrical current being applied for an amount of time sufficient to cause an additional identifiable metal layer to be formed by electrodeposition at one or more locations on the many metal products.

98. The method of embodiment 97, comprising applying additional currents to deposit 6 to 15 additional identifiable layers at one or more locations on a plurality of metal products.

99. The method of any one of embodiments 76-98, wherein the total nanometer thickness of the electrodeposited metal layers at one or more locations on each article in the plurality is between 6 and 14 microns.

100. The method of any one of embodiments 76-98, wherein the total nanometer thickness of the electrodeposited metal layers at one or more locations on each article in the plurality is 8 to 10 microns.

101. The method according to any one of options 76-100, and the first and second metal components in the set contain at least two elements selected from the group consisting of Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn, Co, Pb, Al, Ti, Mg, W, Rh and Cr.

102. The method of any one of embodiments 76-101, wherein in a plurality of articles, the first identifiable metal layer, the second identifiable metal layer, or both contain at least two metals selected from the group consisting of Ni and Zn, Ni and Co, Ni and Cr, and Zn and Fe.

103. The method according to any of the options 76-102, and in one or more places on the products in many

- 40 041389 the first identifiable metal layer, the second identifiable metal layer, or both contain 13 to 17% Ni.

104. The method of embodiment 103, wherein at one or more locations on the articles in the plurality, the first identifiable metal layer, the second identifiable metal layer, or both contain 83 to 87% Zn.

105. The method of any one of embodiments 76-104, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 1000 hours before first red rust appears when tested in salt spray according to ASTM-B117-11 .

106. The method of any one of embodiments 76-104, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 3,000 hours before first red rust appears when tested in salt spray according to ASTM-B117-11 .

107. The method of any one of embodiments 76-104, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 5,000 hours before first red rust appears when tested in salt spray according to ASTM-B117-11 .

108. The method of any one of embodiments 76-107, wherein any article in the plurality has a total thickness of the nanolaminate coating at the first location on the article that is within 6 microns of the average thickness of the nanolaminate coating at the same location on the other articles in the plurality.

109. The method of any one of embodiments 76-107, wherein any article in the plurality has an overall nanolaminate coating thickness at a first location on the article that is within 3 μm of the average nanolaminate coating thickness at the same location on other articles in the plurality.

110. The method of embodiment 108 or 109, wherein any article in the plurality has an overall nanolaminate coating thickness at a second location on the article that is within 6 μm of the average nanolaminate coating thickness at the same location on the other articles in the plurality.

111. The method of embodiment 108 or 109, wherein any article in the plurality has an overall nanolaminate coating thickness at a second location on the article that is within 3 μm of the average nanolaminate coating thickness at the same location on the other articles in the plurality.

112. The method of any one of embodiments 76-111, wherein the plurality includes a majority of the same shaped articles in the lot, and the majority being at least 70% of the total number of like shaped articles in the lot.

113. The method of any one of embodiments 76-111, wherein the plurality includes a majority of the same shaped articles in the lot, and the majority being at least 90% of the total number of like shaped articles in the lot.

114. The method of any one of embodiments 76-111, wherein the plurality includes a majority of the same shaped articles in the lot, and the majority being at least 95% of the total number of like shaped articles in the lot.

115. The method of any one of embodiments 76-114, wherein one or more locations includes a threadless surface.

116. The method of any one of embodiments 76-115, wherein one or more locations includes a threaded surface.

117. The method of any one of embodiments 76-116, wherein the plurality includes pins, and wherein the container device is a plating device in a rocking container.

118. The method of embodiment 117, wherein the plurality includes pins weighing at least 0.25 kg.

119. The method of embodiment 117, wherein the plurality includes pins weighing at least 0.5 kg.

120. Many metal products made by the method according to any of options 76-120.

121. A metal product in a plurality of metal products, made by the method of any one of options 76-120.

122. A combination including a container device and a plurality of metal products according to option 120.

123. Combination including a vibratory plating device and a plurality of metal products according to option 120.

124. A combination including a plating device in a rocking container and a variety of metal products according to option 120.

125. A method for producing a plurality of articles by plating a batch of blanks, comprising bringing at least a portion of the batch of blanks into contact with an electrodeposition bath in contact with a part of a container device, the electrodeposition bath containing at least first and second electrodepositable materials;

moving part of a batch of blanks by setting the container device in motion in a given mode of motion;

electrodeposition of the first identifiable layer onto at least a portion of the preforms in the batch by applying a first electric current for a first amount of time through at least two cathode contacts that create at least intermittent electrical contact with a portion of the batch of preforms, the first identifiable layer comprising at least first and second electrodepositable materials; and electrodepositing a second identifiable layer on a portion of the preforms in the batch by applying a second electric current for a second amount of time through the cathode contacts, wherein the second identifiable layer comprises at least the first and second electrodepositable materials, and the composition, grain size, structure or thickness, or a combination thereof , the second identified layer differs from those of the first identified layer.

126. The method of embodiment 125, wherein the container device is a drum plating device, a vibrating basket plating device, or a rocking vessel plating device.

127. The method according to option 125 or 126, further comprising electrodeposition of an additional layer on a part of the blanks in the batch by supplying additional electric current through the cathode contacts, the additional layer containing at least the first and second electrodepositable materials, and the composition, grain size, structure (for example, microstructure or morphology) or the thickness of the additional layer differs from that of the immediately preceding layer.

128. The method of any one of embodiments 125-127, wherein at least one parameter selected from the group consisting of first current, first time, second current, and second time is determined based at least in part on one or more parameters, which are applicable to the container device, wherein the parameters applicable to the container device are selected from the group consisting of load fraction, load volume fraction, apparent load, length fraction, stuffing volume, rpm, frequency, amplitude, container device travel speed, jitter, and mixing speed.

129. The method of any one of embodiments 125-128, wherein the ratio of the stuffing volume of articles loaded into the container device to the volume of the container device is less than 70%.

130. The method of any one of embodiments 125-129, wherein the ratio of the volume of articles loaded into the container device to the volume of the container device is from about 10% to about 40%.

131. The method of any one of embodiments 125-130, wherein in a plurality of articles obtained, the mass percent of the first electrodepositable material at one or more locations on any one of the plurality of articles does not differ by more than 6 wt.% from the mass percent of the same electrodepositable material at one or more locations in another article of the plurality, or wherein in a plurality of articles in a batch, the mass percent of the second electrodepositable material at one or more locations on any article of the plurality does not differ by more than 6 wt.% from the mass percent of the same electrodepositable material in one or more more places in another product from the set.

132. The method of any one of embodiments 125-131, wherein the first and second amounts of time are each in the range of about 2 to about 10 minutes.

133. The method of any one of embodiments 125-132, wherein the first electrical current is in the range of about 20 to about 70 A, or wherein the second electrical current is in the range of about 40 to about 140 A.

134. The method of any one of embodiments 125-133, wherein the voltage associated with the first electrical current, the second electrical current, or both is in the range of about 3 to about 8 volts.

135. The method of any one of embodiments 125-134, wherein the total thickness of the electrodeposited layers at one or more locations on each article in the plurality is independently 6 to 14 microns.

136. The method according to any one of options 125-135, wherein the first and second electrodepositable materials in a variety of products contain at least two elements selected from the group consisting of Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn , Co, Pb, Al, Ti, Mg, W, Rh and Cr.

137. The method according to any one of options 125-136, and in a variety of products, the first identifiable layer, the second identifiable layer, or both of them contain at least two metals selected from the group consisting of Ni and Zn, Ni and Co, Ni and Cr , and Zn and Fe.

138. The method according to any of the options 125-137, and in one or more places on the products in the set, the first identifiable layer, the second identifiable layer, or both of them contain from 13 to 17 wt.% Ni or moreover, in one or more places on the products in the plurality, the first identifiable layer, the second identifiable layer, or both contain from 83 to 87 wt.% Zn.

139. The method of any one of embodiments 125-138, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 1000 hours before first red rust appears when tested in salt spray according to ASTM-B117-11 .

- 42 041389

140. The method of any one of embodiments 125-139, wherein any article in the plurality has a total nanolaminate coating thickness at a first location on the article that is within µm of the average nanolaminate coating thickness at the same location on another article in the plurality.

141. The method of any one of embodiments 125-140, wherein any article in the plurality has an overall nanolaminate coating thickness at a second location on the article that is within 6 µm of the average nanolaminate coating thickness at the same location on another article in the plurality.

142. The method of any one of embodiments 125-141, wherein the plurality of articles includes a majority of articles having the same shape, with the majority accounting for at least 70% of the total number of articles.

143. The method of any one of embodiments 125-142, wherein one or more locations includes a threadless surface.

144. The method of any one of embodiments 125-143, wherein the plurality of articles include studs, and wherein the container device is a plating device in an oscillating vessel.

145. The method of any one of embodiments 125-144, wherein the plurality of articles comprise studs weighing at least 0.25 kg.

146. The method of any one of embodiments 125-145, wherein the at least two cathode contacts make at least substantially continuous contact with a portion of the batch of preforms.

147. A method for producing a plurality of products by forming a nanolaminate coating on a plurality of blanks, including bringing at least a portion of the plurality of blanks into contact with an electrodeposition bath in contact with the internal volume of the drum, the electrodeposition bath containing at least first and second electrodepositable materials, while the blanks, each independently, have the longest dimension, and the drum has a length and a radius;

drum rotation;

electrodeposition of the first identifiable layer on at least a part of the plurality of workpieces by supplying the first electric current for the first amount of time through at least two cathodes with ends located inside the internal volume of the drum, separated from each other by a distance, and the first identifiable layer contains at least the mentioned first and second electrodepositable materials; and electrodeposition of the second identifiable layer on a part of the plurality of blanks by applying a second electric current for a second amount of time through said at least two cathodes, wherein the second identifiable layer contains at least the first and second electrodepositable materials, wherein at least one of the composition, size grains, structure or thickness, or combinations thereof, of the second identifiable layer is different from those of the first identifiable layer.

148. The method according to option 147, further comprising electrodeposition of an additional identifiable layer on a part of a plurality of blanks by supplying additional electric current through said at least two cathodes, and the additional layer contains at least first and second electrodepositable materials, while at least one of the composition , grain size, structure and thickness, or combinations thereof, the additional layer differs from those of the adjacent layer.

149. The method of embodiments 147 or 148, wherein the first electrical current is a first time varying waveform or the second electrical current is a second time varying waveform.

150. The method according to any one of the options 147-149, and the first identifiable layer has a thickness in one or more places on the workpiece, which is in the range from about 150 to about 20,000 nm; or wherein the second identifiable layer has a thickness at one or more locations on the preform ranging from about 150 nm to about 20,000 nm.

151. The method of any one of embodiments 147-150, wherein the ratio of the longest dimension of the plurality of preforms to the drum radius is less than 1.3.

152. The method of any one of embodiments 147-151, wherein the ratio of the stuffing volume of the plurality of blanks loaded into the drum to the internal volume of the drum is less than 70%.

153. The method of any one of embodiments 147-152, wherein the ratio of the volume of the plurality of preforms loaded into the drum to the volume of the drum is in the range of about 10% to about 40%.

154. The method according to any one of options 147-153, and in a plurality of products, the mass percentage of the first electrodepositable material in one or more places in any product from the plurality does not differ by more than 6 wt.% from the mass percent of the same electrodepositable material in one or more locations in another article of the plurality, or wherein, in the plurality of articles, the mass percent of the second electrodepositable material at one or more locations in any article of the plurality does not differ by more than 6% by weight from the mass percent of the same electrodepositable material in one

- 43 041389 or more places in another product from the set.

155. The method of any one of embodiments 147-154, wherein the drum is rotated during the application of the first and second currents at a speed of 4-10 rpm.

156. The method of any one of embodiments 147-155, wherein the first and second amounts of time are each in the range of about 2 to about 10 minutes.

157. The method of any one of embodiments 147-156, wherein the first electrical current is in the range of about 20 to about 70 A.

158. The method of any one of embodiments 147-157, wherein the second electric current is in the range of about 40 to about 140 A.

159. The method of any one of embodiments 147-158, wherein the voltage associated with the first electrical current, the second electrical current, or both is in the range of about 3 to about 8 volts.

160. The method of any one of embodiments 147-159, wherein the total nanometer thickness of the electrodeposited layers at one or more locations on each preform in the plurality is in the range of about 6 microns to about 14 microns.

161. The method according to any one of options 147-160, wherein the first and second electrodepositable materials contain at least two elements selected from the group consisting of Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn, Co, Pb, Al, Ti, Mg, W, Rh and Cr.

162. The method according to any one of options 147-161, and the first identifiable layer, the second identifiable layer, or both of them contain at least two metals selected from the group consisting of Ni and Zn, Ni and Co, Ni and Cr, and Zn and Fe.

163. The method according to any one of the options 147-162, and in one or more places on the products in the set, the first identifiable layer, the second identifiable layer, or both of them contain from about 13 to about 17 wt.% Ni, or moreover, in one or more places on articles in the plurality, the first identifiable layer, the second identifiable layer, or both contain from about 83 to about 87 wt.% Zn.

164. The method of any one of embodiments 147-163, wherein one or more locations on the articles in the plurality comprise a corrosion resistant nanolaminate coating that provides at least 1000 hours before first red rust appears when tested in a salt spray according to ASTM-B117-11 .

165. The method of any one of embodiments 147-164, wherein any article in the plurality has a total nanolaminate coating thickness at a first location on the article that is within 6 µm of an average nanolaminate coating thickness at the same location on other articles in the plurality; or wherein any article in the plurality has an overall nanolaminate coating thickness at a second location on the article that is within 6 μm of the average nanolaminate coating thickness at the same location on the other articles in the plurality.

166. The method of any one of embodiments 147-165, wherein the plurality of articles comprise a majority of articles having the same shape, and the majority being at least 70% of the total number of articles in the plurality.

167. The method of any one of embodiments 150-166 wherein one or more locations includes a threadless surface.

168. Metallized product, made by the method according to any of the options 125-167.

169. A product with a nanolaminate coating containing a first identifiable layer having a thickness in the range from about 150 to about 20,000 nm, in one or more places on the product, and the first identifiable layer contains at least the first and second components, and the first identifiable layer has a first composition, a first grain size, and a first grain structure;

a second identifiable layer having a thickness in the range of about 150 to about 20,000 nm at one or more locations on the article, the second identifiable layer having first and second components, the second identifiable layer having a second composition, a second grain size, and a second grain structure, wherein at least one of the second composition, the second grain size and the second grain structure is different than the first composition, the first grain size and the first grain structure; and one or more inhomogeneities characterized by an inwardly directed deformation of the first and second identifiable layers towards the surface of the substrate.

170. The product according to option 169, further comprising an additional identifiable layer having a thickness in the range from about 150 to about 20,000 nm, in one or more places on the product, and the additional identifiable layer contains at least one of the first and second components, and moreover the additional identifiable layer has at least one feature selected from the group consisting of composition, grain size, and grain structure (eg, microstructure or morphology) that differs from at least one of the features of the immediately preceding layer.

- 44 041389

171. The product according to options 169 or 170, and the first identifiable layer has a thickness in the range from about 225 to about 500 nm in one or more places on the product.

172. An article of any one of embodiments 169-171, wherein the second identifiable layer has a thickness in the range of about 400 nm to about 1000 nm at one or more locations on the article.

173. The article of any one of embodiments 169-172, wherein the article includes at least 6 layers at one or more locations on the article.

174. The article of any one of embodiments 169-173, wherein the combined thickness of the layers is 6 to 14 microns at one or more locations on the article.

175. The product according to any one of options 169-174, and the first and second components contain Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn, Co, Pb, Al, Ti, Mg, W, Rh or Cr .

176. The article of any one of embodiments 169-175, wherein the first identifiable layer, the second identifiable layer, or both contain Ni and Zn, Ni and Co, Ni and Cr, or Zn and Fe.

177. The article according to any one of options 169-176, wherein the first identifiable layer, the second identifiable layer, or both of them contain from about 13 to about 17 wt.% Ni in one or more places on the product, or wherein the first identifiable layer, the second identifiable layer or both of them contain from about 83 to about 87 wt.% Zn in one or more places on the product.

178. The article of any one of embodiments 169-178, wherein at one or more locations on the article the nanolaminate coating resists corrosion and provides at least 1000 hours before first red rust when tested in salt spray according to ASTM-B117-11.

179. The product according to any one of options 169-177, and one or more places include a threadless surface.

180. The article of any one of 169-179, wherein one or more locations include a threaded surface.

181. The article of any one of embodiments 169-180, wherein the first and second components are electrodeposited.

182. A plurality of articles according to any one of embodiments 169-181, wherein the weight percentage of the first electrodeposited component in the coating on any article in the plurality does not differ by more than 6% by weight from the weight percent of the same component in the coating on another article in the plurality; or wherein the weight percent of the second electrodeposited component in the coating on any article in the plurality does not differ by more than 6% by weight from the weight percent of the same component in the coating on another article in the plurality.

183. A plurality of articles as in any one of embodiments 169-182, wherein any article in the plurality has an overall nanolaminate coating thickness at the first location on the article that is within 6 μm of the average nanolaminate coating thickness at the same location on the other articles in that plurality. .

184. A plurality of articles as in any one of embodiments 169-183, wherein any article in the plurality has an overall nanolaminate coating thickness at a second location on the article that is within 6 μm of the average nanolaminate coating thickness at the same location on the other articles in that plurality. .

185. A plurality of articles as in any one of embodiments 169-184, wherein one or more locations include a non-threaded surface.

186. A plurality of products according to option 184, with the first or second places including a threadless surface.

The above descriptions of exemplary embodiments of methods for forming nanolaminate coatings are illustrative only, and thus the invention disclosed herein is not intended to be limited to the specific embodiments described above. Modifications and variations that are obvious to those skilled in the art upon reading the above description are intended to be covered by this disclosure. Moreover, those skilled in the art will understand, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments described herein. Such equivalents are intended to be covered by the following claims.

The various embodiments described above may be combined to create additional embodiments. All of the U.S. Patents, U.S. Patent Application Publications, U.S. Patent Applications, Foreign Patents, Foreign Patent Applications, and Non-Patent Publications cited in this specification and/or listed in the Application Information Sheet, including U.S. Patent Application No. 62/385,071, are incorporated herein by reference. links in their entirety. Aspects of the embodiments may be modified, if necessary, to use concepts from various patents, applications, and publications while providing other additional embodiments.

These and other changes may be made to the embodiments in light of the above detailed description. In general, the inventions used in the following claims

Claims (23)

These terms are not to be construed as limiting the claims to the specific embodiments disclosed in the description and claims, but are to be considered as including all possible embodiments along with the full scope of equivalents to which such claims fall. Accordingly, the claims are not limited to the above disclosure. CLAIM 1. A method for applying a nanolaminate electroplating coating on a plurality of substrates, including loading said plurality of substrates into a container device, wherein the loading fraction of said plurality of substrates in the container device is in the range from 0.6 to 0.7 and the proportion of the length of said plurality of substrates in the container device is in the range from 0.1 to 1.5, and the load share and length share are controlled so that the measured percentage of jitter is less than 6.25% in order to obtain uniform coverage among the substrates in the said set; placing the container device in the electrodeposition bath to bring at least a portion of said plurality of substrates in the container device into contact with the electrolyte in the electrodeposition bath, the electrolyte comprising at least first and second electrodepositable materials, the container device comprising at least two cathode contacts, and openings allowing the electrolyte to flow into the container device and contact with said at least a portion of said plurality of substrates; moving a portion of said plurality of substrates by driving the container device in a predetermined mode of motion; electrodeposition of a first layer onto at least a portion of the substrates in said plurality by applying a first electrical current for a first amount of time through said at least two cathode contacts that create at least intermittent electrical contact with a portion of said plurality of substrates, the first layer comprising at least least the first and second electrodepositable materials; and electrodepositing a second layer on a portion of the substrates in said plurality by applying a second electric current for a second amount of time through said at least two cathode contacts, wherein the second layer comprises at least first and second electrodepositable materials, and the composition, grain size, structure, or thickness or their combination of the second layer is different from those of the first layer; and repeatedly applying the first and second electric currents for a first amount of time and a second amount of time, respectively, until the required number of alternating first and second layers is electrodeposited, the load share being defined as the ratio of the volume of said plurality of substrates to the volume of the container device, the length fraction being defined as the ratio of the longest size of each substrate of said plurality of substrates to the radius of the container device, with the changed jitter percentage being given by the following formula: jitter percentage = ((|current signal applied - average value of the measured current signal|)/current signal applied) x 100%. 2. Method according to claim 1, wherein the container device is a drum plating device, a vibrating basket plating device, or a rocking vessel plating device. 3. The method according to claim 1 or 2, wherein at least one parameter selected from the group consisting of first current, first time, second current, and second time is determined based at least in part on one or more parameters that applicable to the container device, wherein the parameters applicable to the container device are selected from the group consisting of load fraction, load volume fraction, apparent load, length fraction, stuffing volume, rpm, frequency, amplitude, container device travel speed, jitter, speed mixing or combinations thereof. 4. Method according to any one of claims 1 to 3, wherein said plurality of substrates comprises pins, and wherein the container device is a plating device in a rocking vessel. 5. A method according to any one of claims 1 to 4, wherein said plurality of substrates comprises pins weighing at least 0.25 kg. 6. A method according to any one of claims 1 to 5, wherein said at least two cathodic contacts make at least substantially continuous contact with a portion of said plurality of substrates. 7. The method according to any one of claims 1 to 6, wherein the container device is an electroplating drum, and the movement of a part of said plurality of substrates is carried out by rotating the electroplating drum. - 46 041389 8. The method according to any one of claims 1 to 7, further comprising electrodeposition of an additional layer on a part of said plurality of substrates by applying an additional electrical current through said at least two cathode contacts, wherein the additional layer comprises at least first and second electrodepositable materials, wherein at least one of the composition, grain size, structure and thickness of the additional layer is different from those of the adjacent layer. 9. The method according to claim 7 or 8, wherein the first electric current is a first time varying waveform or where the second electric current is a second time varying waveform. 10. The method according to any one of paragraphs.7-9, and the first layer has a thickness in one or more places on the substrate, component in the range from about 150 to about 10,000 nm; or wherein the second layer has a thickness at one or more locations on the substrate ranging from about 150 nm to about 10,000 nm. 11. The method according to any one of claims 7 to 10, wherein the length fraction is less than 1.3. 12. A method according to any one of claims 1 to 11, wherein in said plurality of substrates, the weight percent of the first electrodepositable material at one or more locations in any one of said plurality of substrates does not differ by more than 6 wt.% from the mass percent of the same electrodepositable material in one or more locations in another substrate from said plurality, or wherein, in said plurality of substrates, the mass percent of the second electrodepositable material at one or more locations in any substrate of said plurality does not differ by more than 6 wt.% from the mass percent of the same electrodepositable material in one or more places in another substrate from the above set. 13. The method according to any one of claims 1 to 12, wherein the plating drum is rotated during the application of the first and second currents at a speed of from 4 to 10 rpm, and each of the first and second amounts of time is in the range from about 2 to about 10 minutes; moreover, the voltage associated with the first electric current, the second electric current, or both of them, is in the range from about 3 to about 8 V; or both. 14. The method of any one of claims 1-13, wherein the first electrical current is in the range of about 20 to about 70 A, or wherein the second electrical current is in the range of about 40 to about 140 A. 15. The method of any one of claims 1-14, wherein the combined thickness of the first and second layers at one or more locations on each of said plurality of substrates is in the range of about 6 micrometers to about 14 micrometers. 16. The method according to any one of claims 1 to 15, wherein the first and second electrodepositable materials independently contain at least two elements selected from the group consisting of Ni, Zn, Fe, Cu, Au, Ag, Pd, Sn, Mn, Co, Pb, Al, Ti, Mg, W, Rh and Cr. 17. The method according to any one of claims 1 to 16, wherein the first layer, the second layer, or both of them independently contain at least two metals selected from the group consisting of Ni and Zn, Ni and Co, Ni and Cr, and Zn and Fe. 18. The method according to any one of claims 1 to 17, wherein at one or more locations on the substrates of said plurality, the first layer, the second layer, or both of them independently contain from about 13 to about 17 wt.% Ni, or moreover, in one or more places on the substrates of the above set of the first layer, the second layer or both of them, independently, contain from about 83 to about 87 wt.% Zn. 19. A method according to any one of claims 1 to 18, wherein one or more locations on said plurality of substrates comprise a corrosion resistant nanolaminate coating that provides at least 1000 hours before first red rust when tested in salt spray according to ASTM-B117 -eleven. 20. A method according to any one of claims 1 to 19, wherein any substrate of said plurality has a total nanolaminate coating thickness at the first location on the substrate that is within 6 µm of the average nanolaminate coating thickness at the same location on the other substrates of said sets; or wherein any substrate of said plurality has an overall nanolaminate coating thickness at a second location on the substrate that is within 6 µm of the average nanolaminate coating thickness at the same location on other substrates of said plurality. 21. A method according to any one of claims 1 to 20, wherein said plurality of substrates constitute a majority of substrates having the same shape, and wherein the majority constitute at least 70% of the total number of substrates in said plurality. 22. A method according to any one of claims 10, 12, 15, 18, or 19, wherein one or more locations comprise a non-threaded surface. 23. A coated substrate containing a nanolaminate coating on the surface of the substrate -