Electrodeposition using ultrashort duration pulses

Abstract

The present disclosure relates to a method including, providing an apparatus that has an anode and a cathode, coupled to each other through a power supply and providing, in contact with the anode and the cathode, a liquid comprising a substrate and a material and providing 10 to 1000 nanosecond electric pulses between the cathode and the anode, wherein the material is electrodeposited onto a surface of the substrate, and wherein the substrate acts as either a cathode or an anode in the liquid. The electric pulses may be from 1 to 100,000 volts and for a period of 0.001 to 10,000 Hz. Also disclosed is a system for providing the electric pulses for electrodeposition onto a substrate.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a Bypass Continuation of International Application No. PCT / US2024 / 048303, filed Sep. 25, 2024, which claims priority to U.S. Provisional Application No. 63 / 585,386 filed Sep. 26, 2023. The entire contents of each of these prior applications are hereby incorporated by reference in their entirety.FIELD OF THE INVENTION

[0002] The present disclosure relates to the electrodeposition of materials onto electrically conductive surfaces.BACKGROUND OF THE INVENTION

[0003] Electrodeposition involves the coating of a charged substrate with a charged material and has typically been performed using low power direct current (DC) either continuously applied to a substrate or applied to a substrate in long pulses for minutes or seconds. This disclosure addresses the issues and limitations with conventional DC or longer duration pulsed electrodeposition. The present disclosure overcomes these and other limitations.SUMMARY OF THE INVENTION

[0004] In an aspect, disclosed is a method including providing an apparatus including an anode and a cathode, coupled to each other through a power supply; providing, in contact with the anode and the cathode, a liquid including a substrate and a material; and providing 10 to 1000 nanosecond electric pulses between the cathode and the anode wherein the material is electrodeposited onto a surface of the substrate, wherein the substrate acts as either a cathode or an anode in the liquid.

[0005] In an example, the electric pulse has a period of about 0.001 Hz to 10,000 Hz. In another example, the electric pulse has a period of about 0.001 to 0.01 Hz. In still another example, the electric pulse has a period of about 0.01 to 0.1 Hz. In yet another example, the electric pulse has a period of about 0.1 to 1 Hz. In a further example, the electric pulse has a period of about 1 to 2 Hz. In still a further example, the electric pulse has a period of about 2 to 4 Hz. In yet a further example, wherein the electric pulse has a period of about 5 to 10 Hz. In an example, the electric pulse has a period of about 10 to 100 Hz. In another example, the electric pulse has a period of about 100 to 1000 Hz. In still another example, the electric pulse has a period of about 1000 to 2000 Hz. In yet another example, the electric pulse has a period of about 2000 to 3000 Hz. In a further example, the electric pulse has a period of about 2000 to 3000 Hz. In still a further example, the electric pulse has a period of about 3000 to 4000 Hz. In yet a further example, the electric pulse has a period of about 4000 to 5000 Hz. In an example, the electric pulse has a period of about 5000 to 6000 Hz. In another example, the electric pulse has a period of about 6000 to 7000 Hz. In still another example, the electric pulse has a period of about 7000 to 8000 Hz. In yet another example, the electric pulse has a period of about 8000 to 9000 Hz. In a further example, the electric pulse has a period of about 9000 to 10,000 Hz.

[0006] In an example, the electric pulse has one or more period. In another example, the electric pulse is from about 1 to about 12 volts. In still another example, the electric pulse is from about 12 to about 24 volts. In a further example, the electric pulse is from about 24 to about 36 volts. In still a further example, the electric pulse is from about 36 to about 48 volts. In yet a further example, the electric pulse is from about 48 to about 100 volts. In an example, the electric pulse is from about 100 to 200,000 volts. In another example, the electric pulse is from about 100 to 500 volts. In still another example, the electric pulse is from about 500 to 1,000 volts. In yet another example, the electric pulse is from about 1,000 to 2,000 volts. In a further example, the electric pulse is from about 2,000 to 3,000 volts. In still a further example, wherein the electric pulse is from about 3,000 to 4,000 volts. In still a further example, the electric pulse is from about 4,000-5,000 volts. In yet a further example, the electric pulse is from about 5,000 to 6,000 volts. In an example, the electric pulse is from about 6,000 to 7,000 volts. In another example, the electric pulse is from about 7,000 to 8,000 volts. In still another example, the electric pulse is from about 8,000 to 9,000 volts. In yet another example, wherein the electric pulse is from about 9,000 to 10,000 volts. In a further example, the electric pulse is from about 10,000 to 20,000 volts. In still a further example, the electric pulse is from about 20,000 to 50,000 volts. In yet a further example, wherein the electric pulse is from about 50,000 to 100,000 volts. In an example, the electric pulse is from about 100,000 to 200,000 volts.

[0007] In an example, the total electric pulse count is about 10 to 100,000,000. In another example, the total electric pulse count is about 10 to 1,000. In still another example, the total electric pulse count is about 1,000 to 5,000. In yet another example, the total electric pulse count is about 5,000 to 10,000. In a further example, the total electric pulse count is about 10,00 to 100,000. In still a further example, a total electric pulse count is about 100,00 to 500,000. In yet a further example, the total electric pulse count is about 500,00 to 1,000,000. In an example, a total electric pulse count is about 1,000,000 to 10,000,000. In another example, a total electric pulse count is about 10,000,000 to 100,000,000.

[0008] In an example, the electric pulse is from about 10 to 10,000 amps. In another example, the electric pulse is from about 100 to 200 amps. In still another example, the electric pulse is from about 200 to 300 amps. In yet another example, the electric pulse is from about 300 to 400 amps. In a further example, the electric pulse is from about 400 to 500 amps. In still a further example, the electric pulse is from about 500 to 600 amps. In yet a further example, the electric pulse is from about 500 to 600 amps. In an example, the electric pulse is from about 600 to 700 amps. In another example, the electric pulse is from about 700 to 800 amps. In still another example, the electric pulse is from about 800 to 900 amps. In yet another example, the electric pulse is from about 1,000 to 2,000 amps. In a further example, the electric pulse is from 2,000 to 3,000 amps. In still a further example, the electric pulse is from about 3,000 to 4,000 amps. In yet a further example, the electric pulse is from about 4,000 to 5,000 amps. In an example, the electric pulse is from about 5,000 to 6,000 amps. In another example, the electric pulse is from about 6,000 to 7,000 amps. In still another example, the electric pulse is from about 7,000 to 8,000 amps. In yet another example, the electric pulse is from about 8,000 to 9,000 amps. In a further example, the electric pulse is from about 9,000 to 10,000 amps.

[0009] In an example, the electric pulse creates a current density in the substrate from about 1 to 2,000 amps / cm2. In another example, wherein the electric pulse creates a current density in the substrate from about 1 to 10 amps / cm2. In still another example, the electric pulse creates a current density in the substrate from about 10 to 100 amps / cm2. In yet another example, the electric pulse creates a current density in the substrate from about 100 to 200 amps / cm2. In a further example, the electric pulse creates a current density in the substrate from about 200 to 300 amps / cm2. In still a further example, the electric pulse creates a current density in the substrate from about 300 to 400 amps / cm2. In yet a further example, the electric pulse creates a current density in the substrate from about 400 to 500 amps / cm2. In an example, the electric pulse creates a current density in the substrate from about 500 to 600 amps / cm2. In another example, the electric pulse creates a current density in the substrate from about 600 to 700 amps / cm2. In still another example, the electric pulse creates a current density in the substrate from about 700 to 800 amps / cm2. In yet another example, the electric pulse creates a current density in the substrate from about 900 to 1,000 amps / cm2. In a further example, the electric pulse creates a current density in the substrate from about 1,000 to 2,000 amps / cm2.

[0010] In an example, the electrodeposited material covers less than 1% of the surface of the substrate. In another example, the electrodeposited material covers about 1% of the surface of the substrate. In still another example, the electrodeposited material covers about 1 to 5% of the surface of the substrate. In yet another example, the electrodeposited material covers about 5 to 10% of the surface of the substrate. In a further example, the electrodeposited material covers about 10 to 20% of the surface of the substrate. In still a further example, the electrodeposited material covers about 20 to 30% of the surface of the substrate. In yet a further example, the electrodeposited material covers about 30 to 40% of the surface of the substrate. In an example, the electrodeposited material covers about 40 to 50% of the surface of the substrate. In another example, the electrodeposited material covers about 50 to 60% of the surface of the substrate. In still another example, the electrodeposited material covers about 60 to 70% of the surface of the substrate. In yet another example, the electrodeposited material covers about 70 to 80% of the surface of the substrate. In a further example, the electrodeposited material covers about 80 to 90% of the surface of the substrate. In still a further example, the electrodeposited material covers about 90 to 100% of the surface of the substrate.

[0011] In an example, the electrodeposited material thickness variation is less than about 1%. In another example, the electrodeposited material thickness variation is less than about 5%. In still another example, the electrodeposited material thickness variation is less than about 10%. In yet another example, the electrodeposited material thickness variation is less than about 15%. In a further example, the electrodeposited material thickness variation is less than about 20%.

[0012] In an example, the electrodeposited material thickness is less than 1 nanometer. In another example, the electrodeposited material thickness is about 1 nanometer. In still another example, the electrodeposited material thickness is about 5 to 10 nanometers. In yet another example, the electrodeposited material thickness is about 10 to 50 nanometers. In still a further example, the electrodeposited material thickness is about 50 to 100 nanometers. In a further example, the electrodeposited material thickness is about 100 to 500 nanometers. In still a further example, the electrodeposited material thickness is about 500 to 1000 nanometers. In yet a further example, the electrodeposited material is about 1000 to 10,000 nanometers.

[0013] In an example, the liquid is aqueous. In another example, the liquid is a solvent. In still another example, the liquid is aprotic. In yet another example, the electrodeposited material thickness is controlled by electric pulse duration. In a further example, the electrodeposited material thickness is controlled by the total number of electric pulses. In still a further example, the electrodeposited material thickness is controlled by the concentration of the electrolyte. In yet a further example, electrodeposited material thickness is controlled by voltage.

[0014] In an example, the electrodeposited material thickness is in relation to a number of nucleation sites created on the surface of the substrate wherein the number of nucleation sites is controlled by the voltage. In another example, the electrodeposited material thickness is in relation to a number of nucleation sites created on the surface of the substrate wherein the number of nucleation sites is controlled by the electric pulse duration. In still another example, the electrodeposited material thickness is in relation to a number of nucleation sites created on the surface of the substrate wherein the number of nucleation sites is controlled by the solution concentration. In yet another example, the electrodeposited material is crystalline in structure. In a further example, the electrodeposited material is amorphous in structure. In an example, the electrodeposited material is semi-crystalline in structure. In another example, the material is dissolved in the liquid. In still another example, the material is partially dissolved in the liquid. In yet another example, an additional component is added to the liquid to adjust conductivity of the liquid. In still another example, an additional component is added to the liquid to adjust the pH of the liquid. In yet another example, further including adding one or more additional material to the liquid wherein the one or more additional material is electrodeposited onto the surface of the substrate. In a further example, further including changing the liquid to electrodeposit an additional one or more material onto the surface of the substrate. In still a further example, further including one or more changing the liquid to electrodeposit one or more additional materials onto the surface of the substrate.

[0015] In an example, an orientation of the electrodeposited material can be controlled by the electric pulse, a voltage and a concentration of the liquid. In another example, the electrodeposited material is silica. In still another example, the electrodeposited material is silica and the substrate is stainless steel. In yet another example, the electrodeposited material is silica and the substrate is stainless steel and the liquid is an aqueous solution.

[0016] In an example, the electrodeposited material deposition thickness can be determined by scanning electron microscopy. In another example, the electrodeposited material coverage percentage can be determined by scanning electron microscopy. In still another example, the electrodeposited material microstructure can be determined by spectrometry. In a further example, wherein the electric pulse has one or more of electric pulse range, electric pulse frequency, electric pulse duration or any combination thereof.

[0017] In an example, disclosed is a device including an apparatus comprising an anode and a cathode, coupled to each other through a power supply; wherein the anode and the cathode contact a liquid comprising a substrate and a material; and wherein the power supply is configured to provide 10 to 1000 nanosecond electric pulses between the cathode and the anode such that the material is electrodeposited onto a surface of the substrate wherein the substrate contacts either a cathode or an anode in the liquid.BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the disclosure and together with the detailed description herein, serve to explain the principles of the disclosure. The drawings are only for purposes of illustrating preferred embodiments and are not to be construed as limiting the disclosure. It is emphasized that, in accordance with the standard practice in the industry, various features are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion. The foregoing and other objects, features and advantages of the disclosure are apparent from the following detailed description taken in conjunction with the accompanying drawings in which:

[0019] FIG. 1 shows a non-limiting example of a device or system used for electrodeposition, in accordance with an aspect of the present disclosure;

[0020] FIG. 2 shows a non-limiting example of a scanning electron microscope (SEM) image of stainless-steel substrate without an electrodeposition material on the surface, in accordance with an aspect of the present disclosure;

[0021] FIG. 3 shows a non-limiting example of an SEM Image of calcium phosphate (CaP) electrodeposition on stainless-steel, in accordance with an aspect of the present disclosure;

[0022] FIG. 4 shows a non-limiting example of a uniform layer of calcium phosphate (CaP) electrodeposited on a silica wafer, in accordance with an aspect of the present disclosure;

[0023] FIG. 5 shows a non-limiting example of an SEM image of silica electrodeposition on a stainless-steel washer, in accordance with an aspect of the present disclosure;

[0024] FIG. 6 shows a non-limiting example of an SEM image of silver (Ag) electrodeposition on a stainless-steel substrate, in accordance with an aspect of the present disclosure;

[0025] FIG. 7 shows a non-limiting example of an SEM image of silver doped calcium phosphate electrodeposition on a stainless-steel substrate, in accordance with an aspect of the present disclosure;

[0026] FIG. 8 shows a non-limiting example of an SEM image of zinc oxide (ZnO) electrodeposition on a stainless-steel washer, in accordance with an aspect of the present disclosure;

[0027] FIG. 9 shows a non-limiting example of an SEM image of zinc oxide (ZnO) electrodeposition on a stainless-steel washer, in accordance with an aspect of the present disclosure;

[0028] FIG. 10 shows a non-limiting example of amorphous calcium phosphate electrodeposition on a 316L stainless-steels washer, in accordance with an aspect of the present disclosure;

[0029] FIG. 11 shows a non-limiting example of an SEM image of crystalline calcium phosphate electrodeposition on a 316L stainless-steels washer, in accordance with an aspect of the present disclosure;

[0030] FIG. 12 shows a non-limiting example of amorphous calcium phosphate electrodeposition on a 316L stainless-steels washer, in accordance with an aspect of the present disclosure; and

[0031] FIG. 13 shows a non-limiting example of an SEM image of crystalline calcium phosphate electrodeposition on a 316L stainless-steels washer, in accordance with an aspect of the present disclosure.DETAILED DESCRIPTION FOR CARRYING OUT THE INVENTION

[0032] Electrodeposition involves the flow of electrical current through the deposition liquid, due to a difference in electrical potential between two electrodes. One electrode is commonly attached to the substrate or component which is to be coated. Often the substrate acts as the electrode. Electrodeposition has conventionally been done with direct current voltages of less than 100 volts. Electrodeposition has been performed using pulses of direct current where the pulses last many minutes down to seconds. Traditional electrodeposition techniques that utilize low power for long periods of time, suffer from multiple problems that may lead to uneven coating thickness. Low power density may lead to fewer nucleation sites resulting in fewer points of contact of the coating material to build up on the substrate. Lack of control of nucleation site formation may lead to uneven coating of the deposition material. The evenness of the coating may be further inhibited by the effect of localized charge buildup. Localized charge buildup can be especially dramatic on objects with complex geometry such as finer features, like edges, having higher charge than large flat regions. Efforts to achieve uniform thickness of the deposition material in traditional systems led to the introduction of turbulent flow of the deposition liquid. The turbulent flow of the deposition liquid may create a steady stream of ions being directed at the charged substrate thereby reducing regions with high ion concentration buildup due to the constant movement of ions. Applying high DC power in a traditional electrodeposition system may result in the creation of excessive bubbles in the deposition solution and on the deposition substrate surface. This may be due to hydrolysis of the electrodeposition solution. Hydrolysis of the deposition solution typically becomes problematic as the power in the system increases.

[0033] The disclosed systems and methods of electrodeposition may be carried out using a power supply connected to electrodes in a conductive liquid, electrolyte or solution. The electrodeposition system includes an anode and cathode, where the substrate to be coated is electrically connected to either the anode or the cathode. The electrodeposition substrate may act as either the anode or the cathode. The counter electrode, the electrode not electrically connected to the substrate, is electrically connected to the deposition liquid (see FIG. 1). In an example, a power supply is connected to a pulse generator such that electric pulses are provided to electrodes which are electrically connected to the substrate and the liquid and the charged substrate attracts material of the opposite charge in the liquid which is electrodeposited on the surface.

[0034] The duration and amplitude of the pulses used to deposit material onto the substrate surface are in a range of 1 to 200,000 volts with a duration of 10 to 1,000 nanoseconds with a period of 0.001 to 10,000 hertz. Some embodiments utilize voltage in the range of 100 to 200,000 volts and may be called high voltage examples as the voltages used are high compared to traditional electrodeposition. The disclosed systems and methods allow for more controllable electrodeposition of materials onto the surfaces of electrically conductive substrates. The short duration of the pulses also reduces the burden on electrical components in the system compared to similar voltages and currents in a DC system. Adjusting the parameters of the voltage, pulse duration, deposition liquid concentration, pulse frequency and total electrodeposition pulse number allow for control over the electrodeposition of material onto a substrate including the thickness, nanoscale morphology, nanoparticle size, the number of nucleation sites, deposition geometry and combinations thereof. In embodiments, the high voltage used in the disclosed systems and methods (100 to 200,000 volts) allows for new materials to be electrodeposited on substrates that could not be electrodeposited using traditional methods of less than 100 volts. It should be recognized that the methods and systems disclosed will operate at lower voltages, such as less than 1 volt and 1 to 100 volts. In some instances, 50 to 100 volts may be used. Many of the examples demonstrate the use of voltages, amperage and power previously not possible with direct current electrodeposition systems. The disclosed systems and methods include electrodeposition of materials at the nanoscale.

[0035] The electrodeposition of materials on substrates at the nanoscale allows for precise uniformity of coating. The uniformity in coating of a material on a substate may be the uniformity in coverage of the substrate with the electrodeposition material. The uniformity in coating may be in the strength of adhesion of the material to the substrate. The uniformity in the coating may be in the thickness of the material on the substrate. The uniformity may be in the nanoscale morphology of the material on the substrate. The uniformity in the coating may be any combination of thickness, nanoscale morphology, adhesive strength and percent of substrate coated. The electrodeposition of material may be less than a nanometer thick per pulse of electricity. The electrodeposition of material may be on the molecular scale with the electrodeposition of single molecules on the substrate per electric pulse.

[0036] The total number of pulses may allow the uniformity of thickness to achieve hundreds, thousands, tens of thousands, hundreds of thousands or millions of nanometers in thickness. The total pulse number may be selected to achieve a desired thickness of electrodeposition material. The total electric pulse number may include a total electric pulse number for one or more electrodeposition material and another total electric pulse number for another one or more electrodeposition material. The total number of pulses may be different or the same for two or more electrodeposition materials. Another advantage of the precise control of electrodeposition of material on the nanometer scale with the disclosed systems and methods is that new material properties are exhibited with materials electrodeposited on the nanoscale.

[0037] Materials behave differently at the nanoscale. The disclosed systems and methods allow for the ability to control surface properties in a uniform manner through controlled electrodeposition of material at the nanoscale. The nanoscale morphology of material nanostructures directly defines their optical, catalytic, magnetic and electronic properties and even small morphological changes can cause significant property variations. The disclosed electrodeposition methods allow for the deposition of materials in crystalline, semi-crystalline and amorphous nanoscale morphology which can be controlled.

[0038] The electrodeposition material may form nanoparticles on the surface of the substrate. These nanoparticles may be characterized by their nanoscale morphology, size, optical, electrical, adhesive, magnetic, catalytic activity, hardness and other physical properties. The electrodeposition of nanocrystals allows for the introduction of new properties to substrates. Nanocrystals may exhibit superior properties to their bulk coarse grained material counterparts because of the reduced sizes, diverse nanoscale morphologies, and controllable exposed crystal facets. Nanomaterials are materials sized from 1 to 1000 nm in at least one dimension. Nanoparticles may be as small as the atom and molecular in scale. There are different nanoscale morphologies of nanoparticles: amorphous, semi-crystalline or crystalline, and nanocrystals may be the semi-crystalline or crystalline form of nanoparticles. Nanoparticles of electrodeposition material may be regarded as a unique material state to some degree and may be different from the solid, liquid, and gaseous states of the bulk coarse grained material. Surface effects and quantum effects are the two primary properties of nanomaterials that make them show significantly different characteristics from bulk materials. Surface effect refers to the change in properties of nanomaterials caused by the sharp increase of the ratio of surface atoms to total atoms as the particle size decreases. At the nanoscale, van der waals forces may have a substantial effect on the surface properties like surface adhesion to the substrate. The crystal field environment and binding energy of surface atoms are different from those of internal atoms. Surface atoms lack adjacent atoms and have many suspended bonds. They are unsaturated and easy to combine with other atoms to stabilize. Therefore, they show positive chemical and catalytic activity. The surface effect influences chemical reactivity, catalytic, mechanical, thermal, adhesive, optical, electrical, and magnetic properties of nanomaterials. These activities may differ based on size, nanoscale morphology, material composition, thickness and uniformity of coating of the electrodeposition material.

[0039] The electrodeposition of nanoparticles allows for new properties to be added to substrates. For example, films of electrodeposited nanoscale material may be added to the surface of substrates. The modified substrates may be useful in a variety of applications. For example, nanocrystalline and amorphous metals and alloys are generally regarded as advanced structural materials, because as a materials class they tend to exhibit high strength, high abrasion resistance, high hardness, and other desirable structural and functional properties. An amorphous metal (also known as metallic glass) is a solid metallic material with disordered atomic-scale structure. Most metals are crystalline in their solid state, which means they have a highly ordered arrangement of atoms. Amorphous metals are non-crystalline and have a glass-like structure. But unlike common glasses which are typically electrical insulators, amorphous metals have good electrical conductivity and can show metallic luster. Metal glasses are traditionally formed using alloys, but the described system and methods may produce amorphous or glass metal using a single metal or with alloys. Amorphous metals may have superior properties such as higher elasticity, strength, and biocompatibility than their crystalline counterparts. Amorphous metals also have isotropic behavior since they have the same material properties in all directions. Amorphous metals may have low temperature ductility, which means that they are excellent for use in applications with extremely low temperatures and they retain their properties.

[0040] Nanocrystalline materials show exceptional mechanical properties relative to their microcrystalline varieties. The nanocrystalline metals are characterized by superior yield and fracture strength, improved wear resistance and super plasticity observed at relatively low temperatures and high strain rates as compared with their microcrystalline counterparts. Nanocrystalline materials show novel properties compared to their microcrystalline counterparts and are the focus of significant research and development.

[0041] The ability to control the nanoscale morphology and size of the electrodeposition material allow for the control of the physical properties of the electrodeposition material. In an example, a nanoparticle of material may be electrodeposited having an amorphous, semi-crystalline or crystalline nanoscale morphology. In an example, the nanoparticle size may be controlled. In an example, the nanocrystal size can be controlled. In another example, the electrodeposited nanocrystals are deposited in uniform layer and post processing the electrodeposition material may modify the crystal orientation, structure, size and combinations thereof of the deposited nanocrystals. In an example, post processing of crystalline calcium phosphate modifies the crystal shape such that the crystals are epitaxial to the substrate. This can be seen in the crystals standing vertically on the substrate surface. In an example, the nanocrystals may be electrodeposited to be foliated or flat on the surface of the substrate. In another example, the nanocrystal is electrodeposited in a granular morphology on the substrate. It is thought that the surface of the substrate interacts with the electrodeposition material through a layer of ions at the substrate surface.

[0042] Without being bound by theory, in surface science, a double layer (DL), also called an electrical double layer (EDL), is a structure that appears on the surface of an object when it is exposed to a fluid. In an example, the object is a substrate in a deposition liquid. The DL refers to two parallel layers of charged ions surrounding the substrate. The first layer, the surface charge (either positive or negative), consists of ions which are adsorbed onto the substrate due to chemical interactions. The second layer is composed of ions attracted to the surface charge via the Coulomb force or electrostatic force, electrically screening the first layer. This second layer is loosely associated with the substrate. It is made of free ions that move in the fluid under the influence of electric attraction and thermal motion rather than being firmly anchored. It is thus called the diffuse layer. The double layer of ions is believed to consist of a stable layer of counter ions that shield the substrate surface preventing the formation of nucleation sites of the desired coating material. In electrodeposition the nanoscale morphology, structure, size and properties of the electrodeposited material deposits may be determined by the initial stages of the electrochemical nucleation and growth process. Thus, the ability to control nucleation allows for precise control of the properties and characteristics of the electrodeposition materials. The disclosed systems and methods allow for control of the nucleation process of the electrodeposition materials onto substrates.

[0043] Traditionally, voltages less than 100 volts were used to charge the substrate because if the voltage was too high, the electrodes would produce gas, oxygen at the anode and hydrogen at the cathode, disrupting the liquid at the surface of the substrate and inhibiting nucleation. The disclosed systems and methods demonstrate the use of high voltage (100-200,000 volts) with minimal gas bubble formation. Traditionally, higher voltages created bubbles on the substrate that may have disrupted or impeded electrodeposition. In an example, small transient bubbles form on the substrate surface using the disclosed systems and methods but do not inhibit electrodeposition of material on the substrate. In another example, bubbles do not form on the substrate using the disclosed systems and methods. In an example, the bubble formation can be controlled using the disclosed parameters. The ability to use higher voltages with minimal bubble formation may result in new changes in the electric double layer. The nanosecond electric pulse may create high surface charges on the substrate which may momentarily break the DL to allow the formation of more nucleation sites. The high voltage of the nanosecond pulses may create a compressed high energy double layer (C-HEDL) at the surface of the substrate-liquid interface compared to low voltage DC systems. As the substrate is charged the EDL may rearrange to form a double layer in reaction to the charged state of the substrate. Since this rearrangement only lasts nanoseconds, this movement of ion species may allow for breaks in the EDL allowing more nucleation sites to occur on the substrate. The electric pulse may disrupt the DL followed by reformation of the DL when the electric pulse is off. This continuous cycle may allow charged ions of the material to contact the substrate and form nucleation sites.

[0044] The control of the nucleation of the electrodeposition material has resulted in the ability to control the nanoscale morphology, thickness, and size of the electrodeposition material. The electrodeposition material may be referred to as the deposition material, deposited material, deposited layer, material and combinations thereof in this disclosure. Control of nucleation may lead to control over the nanoscale morphology of the deposition material such that the electrodeposition may be crystalline, semi-crystalline, amorphous or any combination thereof. The degree of crystal formation may be controlled. This may be controlled by increasing or decreasing the percentage of crystalline nanoparticles electrodeposited. The degree of crystal formation may be controlled by increasing or decreasing the percentage of amorphous nanoparticles that are electrodeposited. Nanoparticles with both amorphous and crystalline nanoscale morphology may be semi-crystalline. The properties of semi-crystalline polymers are determined not only by the degree of crystallinity, but also by the size and orientation of the molecular chains. The electrodeposition material nanoscale morphology may also be controlled by electric pulse number, electric pulse duration, voltage, pulse frequency, total electric pulse time, ionic concentration of the electrodeposition liquid, concentration of material in liquid and combinations thereof. The control of the electrodeposition material may be seen in the type of nanoscale morphology that is electrodeposited onto the substrate. In an example, a combination of voltage, pulse duration, pulse frequency, ionic concentration of the liquid and material concentration of the liquid results in the electrodeposition of material that is crystalline in nanoscale morphology. In an example, a combination of voltage, pulse duration, pulse frequency, ionic concentration of the liquid and material concentration of the liquid results in the electrodeposition of material that is semi-crystalline in nanoscale morphology. In another example, a combination of voltage, pulse duration, pulse frequency, ionic concentration of the liquid and material concentration of the liquid results in the electrodeposition of material that are amorphous in nanoscale morphology. In an embodiment, the voltage, pulse duration, pulse frequency, ionic concentration of the liquid and material concentration of the liquid allow for the electrodeposition of an amorphous material and then when desired any one or more of the conditions are changed to then electrodeposit crystalline material. In another embodiment, the voltage, pulse duration, pulse frequency, ionic concentration of the liquid and material concentration of the liquid allow for the electrodeposition of a crystalline material and then when desired any one or more of the conditions are changed to then electrodeposit amorphous material. These examples demonstrate the ability to control the percentage or degree of crystallization of an electrodeposited material. In an embodiment, the nanoscale morphology of the electrodeposited material is further modified after electrodeposition to modify the nanoscale morphology such as reacting the electrodeposited material with one or more acid, base, salt or any combination thereof. In an embodiment, calcium is electrodeposited onto stainless-steel, in a crystalline or semicrystalline form, and then reacted with a strong base, sodium hydroxide, to modify the nanoscale morphology to be amorphous in nature. In another embodiment, an electrodeposited material is heat annealed on the surface of the substrate modifying the nanoscale morphology of the material. Post and pretreatments treatments include one or more heating, cooling, annealing, cryogenics, exposure to acid, exposure to base, exposure to UV light, exposure to laser light, exposure to solvents or any combination thereof.

[0045] In an example, the disclosed systems and methods allow for surface electrodeposition of materials not previously possible with low voltages. This may be due to the high voltage in the disclosed systems and methods producing high concentrations of energy on the surface of the substrate allowing new electrochemical reactions to take place. The high voltages and short pulses may disrupt the electric double layer and allow chemical bonds to form between the material and substrate that require a higher level of energy input, which is not possible with conventional electrodeposition. The disclosed systems and methods may result in charged materials that interact with the EDL in novel ways that allows for strong uniform attachment of an electrodeposition material. The repeated disruption of the DL for nanosecond intervals may allow for a new range of materials to be electrodeposited that previously could not overcome the screening effect of the DL at the surface of the substrate.

[0046] The electrodeposition of new material may include materials that are of low solubility in the electrodeposition liquid. New materials may include materials of a weaker charge than previously possible for electrodeposition. New materials may include materials that require higher energy to ionize than previously possible. New materials may include materials with higher electronegativities. New materials include materials capable of electrodeposition using the described systems and methods that were not capable of electrodeposition using traditional methods. The disclosed systems and methods may be used to electrodeposit material by using chemistries with low solubility or where insoluble products are near the interface of the conductive electrode where the short pulse of high energy assist the low soluble material to bind to the charged substrate. An example of this capability is the aqueous electrodeposition of SiO2 onto a stainless-steel substrate (see FIG. 5). The high voltage pulses being applied for the nanosecond duration may allow for more energy at the substrate surface to form interconnected bonds of the silica. The short pulse duration minimizes the formation of gas at the electrodes in an aqueous deposition liquid allowing electrodeposition to occur on the substrate. Conventional electrodeposition may suffer from increasing gas formation at the electrodes as the voltages or the amperage increases. Gas bubble formation at the electrodes in aqueous deposition liquid may destabilize the substrate surface and interfere with the electrodeposition of materials.

[0047] High voltage electric pulses for nanosecond intervals may result in higher deposition energy at the surface of the substrate creating more nucleation sites. The more nucleation sites may result in a stronger surface adhesion of the electrodeposited material. Control over electrodeposition parameters allows for precise control over nucleation sites and the size of the electrodeposited material and thus control the characteristics of the coating material such as adhesive strength.

[0048] The disclosed systems and methods allow control over the strength of bonding or adhesive strength of the electrodeposited materials to the surface of the substrate. Conventionally electrodeposited micron thick coatings are weakly adhered to the substrate surface. This weak adherence may be a result of fewer nucleation sites, differences in mechanical properties between substrate and coating, uneven dissolution of the coating, and the presence of multiple phases of electrodeposition material on the substrate. Additionally, micron thick coatings may expand and contract relative to the substrate causing delamination of the coating. The material property differences of the electrodeposited coating and the substrate may be more pronounced with micron thick coatings which may also result in a weaker bond between the coating and substrate. The electrodeposition of material, as nanometer thin layers or nanoparticles onto the substrate surface exhibit stronger interactions with the surface. This may be based on Van der Waals forces, electrostatic forces, more free bonding atoms in nanoscale material, more nucleation sites directly attached to the surface of the substrate or any combination thereof. Larger particulates deposited onto the surface may be dominated by the material properties of the coating material. Larger particles have been demonstrated to show lower adhesion energy than nanoscale particles as described in Influences of Substrate Adhesion and Particle Size on the Shape Memory Effect of Polystyrene Particles, Cox et al. 2016, incorporated in its entirety herein by reference. In some embodiments, the electrodeposition of nanoparticles creates a stronger adhesive force to the substrate. The electrodeposition of material on the nanometer scale may result in a significantly higher number of nucleation sites compared to the electrodeposition of material on the micrometer scale. The large increase in nucleation sites may result in a much higher adhesion force. The electrodeposition of nanometer scale material may result in more atoms available in the material to form bonds with the substrate forming a tighter bond resulting in higher adhesive strength. Coating a substrate with high adhesive strength coatings may have many commercial benefits such as coatings with higher durability. The ability to modify substrate surfaces through controlled electrodeposition allows for the modification of many properties, such as optical luster, wettability with various liquids, coefficient of friction and corrosion resistance, hardness and wear resistance that depend on the surface morphologies of materials, metals and alloys.

[0049] In some substrates traditional electrodeposition coatings cannot remain adhered due to the stresses and forces exerted to the surface of the substrate. Substrates that have been a challenge to traditional electrodeposition include orthopedic applications where a substrate experiences significant mechanical stress. Other examples of substrates where coatings do not adhere include substrates that have a high degree of flexibility such as shape memory alloys, and super elastic metals. Additional substrates that could benefit from strong adhesive coating include thin gauge stainless-steel and nitinol which is used in various industries, including medical orthopedic applications. The disclosed systems and methods allow for coatings with higher adhesive strength, that last longer and can perform in orthopedic applications, where traditional electrodeposition materials have performed poorly. The stronger adhesion of the nanolayer or nanoparticles or the electrodeposition material may allow thinner coatings with improved durability or entirely new coatings with new properties.

[0050] It has been observed that the thickness of electrodeposited material is directly related to the concentration of the ions in the electrodeposition liquid. It is believed the short high energy electric pulses attract ions only a few micrometers away to attach to the substrate. The higher the ionic concentration the more ions present within the few micrometers that can be electrodeposited onto the surface. Thus, the ability to control the ionic concentration of the liquid and the duration and frequency of the electric pulses allow for fine control of the electrodeposition process. It has been observed that electrodeposition using lower concentration ionic solution of the deposition fluid results in less material being deposited in a single pulse. In an example, lowering the concentration of the electrodeposition liquid resulted in finer nanocrystals being electrodeposited onto the substrate. In an example, increasing the concentration of the liquid resulted in coarser, larger nanocrystals. Controlling the concentration of the material to be electrodeposited in the liquid allows control of electrodeposition. Control over electrodeposition thickness in complex structures of substrates has been a challenge for traditional electrodeposition.

[0051] The disclosed nanosecond pulses allow for a more uniform electrodeposition of material onto the substrate including complex geometries. The nanosecond pulses of electricity may result in a more uniform distribution of charge on the substrate being coated. This may be the result of an even distribution of the current, voltage, charge or combinations thereof. The short duration electric pulses may prevent high current regions from having time to form and influence coating uniformity. Ions of the electrodeposition material may orient in solution with the voltage field applied but may move through the liquid based on the current flowing through the system. The current may flow through the system for such a brief period of time between pulses that ions of material cannot form regions of high density or concentration on the substrate.

[0052] It has been noted in conventional direct current electrodepositing that edges and tips of substrates have a higher current density that may result in ions in liquid drifting to these locations of higher current concentration leading to high localized ion concentrations in the deposition liquid. The high localized ion concentration may then create regions of the substrate where the electrodeposition is thicker compared to other regions of the substrate. The problem of nonuniform electrodeposition using traditional electrodeposition systems using continuous voltage or long pulse times, minutes to seconds, is particularly evident in substrates with complex geometries. It has been observed that three-dimensional printed substrates and substrates such as screws with threads have regions where the current density is greater leading to thicker electrodeposition on these regions of the substrate. Conventional electrodeposition has problems with evenness of the coating thickness due to ions drifting to points of higher field strengths. The unevenness in conventional electrodeposition is made worse with the difficulty creating nucleation sites on the substrate. The difficulty in nucleation is conventionally helped with adding turbulence in the deposition liquid to encourage nucleation by providing a bulk flow of ions toward the substrate surface in addition to the electrical current induced movement of the ions. The need for turbulence can make complex geometry even more difficult to coat uniformly with traditional electrodeposition as the flow of liquid is nonuniform. Removing the need for turbulent flow simplifies the number of variables in electrodeposition manufacturing. Though a turbulent flow of electrodeposition liquid is unnecessary in the disclosed systems and methods to achieve uniform coating and uniform thickness it may be used in some embodiments.

[0053] The disclosed short duration pulses may not lead to high current density regions on the substrate but instead may form a brief uniform charge that results in uniform electrodeposition even on complex geometries. The pulses are short enough that the ions in solution may only travel a few micrometers. This may prevent the localized formation of high ion concentrations near current dense regions as the ions do not have time to drift in response to the electric field or electric current in the liquid. Even where geometry features are prone to generate high current densities the short pulse may only draw ions from a few micrometers away where the deposition liquid does not have time to form high ion concentration regions which may result in even uniform electrodeposition of material on the substrate. Since the ions travel a short distance in the high voltage nanosecond electric pulses this may allow an overall smaller volume of electrodeposition liquid to be used for electrodeposition. This may reduce the cost of coating a substrate where a coating material is expensive or only available in small quantities.

[0054] The concentration of the electrodeposition liquid may be modified to control the electrodeposition material characteristics. In an example, decreasing the concentration of the material in the liquid reduces the ion concentration of the material resulting in more uniform electrodeposition of smaller nanoparticles of material. In an embodiment, a lower concentration of material in the electrodeposition liquid might be preferred for electrodepositing a material onto a substrate with a complex geometry. In an embodiment, lowering the concentration of the material in the liquid reduced the nanoparticle size of the electrodeposited material. In an embodiment, lowering the concentration of the material in the liquid increases the percentage of crystallization in the electrodeposited nanoparticles. In an embodiment, increasing the concentration of the material in the liquid increases the percentage of the amorphous electrodeposited nanoparticles. In an embodiment, the concentration of material in the liquid is changed to alter the nanoscale morphology of the electrodeposited nanoparticles. In another example, the concentration of material in the liquid is altered one or more times. In another example, a relatively uniform substrate may benefit from a high concentration of material in the electrodeposition liquid to increase the amount of material electrodeposited with each electric pulse, particularly if the desired coating thickness was high for a particular application.

[0055] In an embodiment, controlling electrodeposition characteristics such as thickness, strength of adhesion, number of nucleation sites, nanoscale morphology of electrodeposited material may be accomplished modifying one parameter while the other parameters remain constant. In an example, the total number of pulses may be modified by increasing or decreasing the total number of pulses to achieve a desired characteristic of electrodeposition material. The pulse duration may be modified by increasing or decreasing the duration. The voltage may be modified by increasing or decreasing voltage. The concentration of the material in the liquid may be modified by increasing or decreasing the concentration of the material in the liquid. The ionic concentration of the liquid may be modified by increasing or decreasing one or more salts or one or more electrodeposition materials or combinations thereof. The total pulse time may be modified by increasing or decreasing the total time electrodeposition is performed on a substrate.

[0056] In some embodiments, the electrodeposition characteristics may be controlled by modifying more than one parameter of voltage, pulse duration, material concentration in the liquid, liquid ionic concentration, total pulse time and pulse number. In an example voltage and pulse duration are modified. The voltage and material concentration in the liquid may be modified. The voltage and liquid ionic concentration may be modified. The voltage and pulse number may be modified. The pulse duration and the concentration of the material in the liquid may be modified. The pulse duration and the ionic concentration of the liquid may be modified. The pulse duration and the number of pulses may be modified. The concentration of material in the liquid and the number of pulses may be modified. The concentration of material in the liquid and the pulse duration may be modified. The number of pulses and the voltage may be modified. The number of pulses and the pulse duration may be modified. The number of pulses and the liquid concentration may be modified. In other embodiments, the voltage may be modified, the pulse duration may be modified, the concentration of the material in the liquid may be modified, ionic concentration of the liquid may be modified, the total pulse number may be modified, total pulse duration or any combination thereof. The precise modification of the various electrodeposition parameters allows for precise control or tuning of the electrodeposition of a desired material onto a desired substrate.

[0057] The total number of pulses may be modified to control the thickness of the electrodeposition material. In an example, a single pulse only deposits material a molecule thick and the additional hundreds or thousands of such pulses would result in an electrodeposition material thickness of hundreds or thousands of times thicker. In an example a single pulse my deposit material less than a nanometer thick. In an example, the concentration of the material in the liquid is optimized along with the pulse duration, ionic concentration of the liquid and the voltage to achieve electrodeposition of a uniform nanometer thickness of material on the substrate and the final thickness is determined by the total number of pulses applied.

[0058] The electrodeposition of material in a single pulse may result in a small percentage of the surface area of the substate being covered. In an embodiment, the first electric pulse may result in much less than 1% of the surface area of a substrate being coated. In an example, additional pulses may build on to the previously deposited material and create new nucleation sites. The level of material build up on the substrate may be controlled. In an example, less than the entire surface of a substrate is to be coated to achieve a desired surface property of the substrate. The percentage of coating may change the optical characteristics, electrical characteristics, magnetic characteristics, conductive characteristics, electric characteristics, binding characteristics and combinations thereof.

[0059] The pulse duration may be modified to control the electrodeposition thickness, nanoscale morphology, nanoparticle size or combinations thereof. Modification of the pulse duration includes increasing or decreasing the pulse duration as desired. A ten-nanosecond pulse may be so brief that very few materials are electrodeposited as compared to a one hundred nanosecond pulse that allows more materials to be electrodeposited onto the substrate. Thus, the pulse duration can be modified to control the electrodeposition rate and thus the total thickness of the electrodeposition material onto the substrate. Where the pulse duration is longer the total number of pulses required may be fewer to reach the desired coating thickness on the substrate. A longer pulse duration may allow for weaker ions of a material to form nucleation sites on a substrate. Modifying the pulse duration may allow a range of voltages not possible using conventional electrodeposition or electroplating. Voltages in hundreds to hundreds of thousands of volts may be possible using pulses in nanoseconds. In an example, ten thousand or twenty thousand volts may be possible with pulse durations of tens of nanoseconds. In another example ten or twenty thousand volts may be possible using pulse durations of one hundred nanoseconds. In another embodiment, one hundred thousand or two hundred thousand volts may be used with nanosecond pulses. In an embodiment, the voltage may increase as the substrate size increases. In another embodiment, the amperage may increase as the substrate size increases. In an example, one million volts may be used. In another example, ten million volts may be used.

[0060] The voltage may be modified by increasing or decreasing the voltage to achieve the desired electrodeposition characteristics such as nanoscale morphology, nanoparticle size, thickness and combinations thereof. Increasing the voltage may allow for the electrodeposition of material that traditionally would not have enough energy to become bound to the substrate. In an example materials of poor solubility can be electrodeposited to the surface of a substrate. In an example, silica is electrodeposited onto stainless-steel in an aqueous solution as the high voltage imparts enough surface energy into the substate to electrodeposit silica. Increasing the voltage may increase the formation of nucleation sites. Increasing the voltage may increase the electrostatic attraction to nearby charged material. Increasing the voltage may more significantly disrupt the DL allowing new material to form bonds with the substrate. In some embodiments, a substrate with complex geometry, with many points or edges and larger regions of flat surfaces, may require lower voltages to mitigate the creation of high current densities on these regions of the substrate. In an example, increasing the voltage may increase the size of the electrodeposition nanoparticle. In an example increasing the voltage may decrease the size of the electrodeposition nanoparticle. In an embodiment, reducing the voltage lowers the rate of nucleation formation. In an embodiment, increasing the voltage increases the rate of nucleation formation.

[0061] The substrate may include one or more masked regions where electrodeposition will be excluded. Masking the substrate may include covering the surface of the substrate with a nonconductive material such that the electrodeposition material cannot contact the substrate surface. The controlled coverage of the surface area of a substrate may be controlled by masking the areas of the substrate where electrodeposition is not desired. Thus, with masking the substrate the percentage of the surface area coated with electrodeposition material is possible to control. Masking of the substrate may include shapes, decorations, images, patterns or any combination thereof. In an example, a substrate is masked such that the electrodeposition material coats the material in a pattern. In an example, a mask allows for the electrodeposition of a pattern with unique optical properties. In another example, a material is electrodeposited on a substrate to modify the optical properties of the substrate. The optical properties may include fluorescence, luminescence, UV absorption or reflections, pigmentation, light reflection, mirrored surface, and combinations thereof. The masking may allow for specific areas of electrodeposition on the substrate such as the electrodeposition of thin films, nanoparticles, nanocrystals, and combinations thereof. In an example, a thin film seals the surface of a substrate from releasing ions into the environment while the unsealed region of substrate releases ions into the environment. In another example, a thin film provides mechanical wear resistance in a specific region of a substrate. In an embodiment, one or more 3D masks are used on the surface of the substrate. In another embodiment, one or more masks are used for a first one or more electrodeposition material and a second one or more masks are used for a second one or more electrodeposition materials and this process is repeated as many times as desired. In an example, one or more electrodeposition materials are electrodeposited in a specific region followed by one more electrodeposition materials being electrodeposited in another specific region to create a three-dimensional structure on the substrate where the structure is configured to have unique electrical properties, optical properties, magnetic properties, physical properties or combinations thereof.

[0062] The substrate may have one or more processes, treatments and pretreatments done prior to electrodeposition of the material or after electrodeposition of material and may have cycles of electrodeposition of one or more material with one or more processing steps repeated as many times as desired. The substrate may receive one or more pretreatments prior to electrodeposition of material on to the surface of the substrate or after electrodeposition of material. Pretreatments, treatments and processes include, but are not limited to, ultrasonic IPA cleaning, plasma cleaning, light acid etching, chemical bonding of materials, non-chemical bonding of materials, electropolishing, chemical polishing, physical polishing, laser ablation, polishing with slurries, evaporative deposition of materials, ultraviolet light treatment, contact with acid, contact with base, contact with solvent or any combination thereof. In an example, one or more material is bonded to a substrate prior to the electrodeposition of one or more materials. In a further example, an abrasive such as diamond, polycrystalline diamond (PCD), cubic boron nitride (cBN), and polycrystalline cubic boron nitride (PCBN), zirconia or any combination thereof is bonded to a substrate prior to electrodeposition.

[0063] In an example, electrodeposition takes place in a non-conductive container that holds the fluid or liquid and a power generator is connected to a pulse generator which is connected to one or more anode and cathode that are contacting the fluid and the substrate acts as either one or more cathode or anode and the nanosecond pulses of electricity causes negatively charged ions (anions) to move to the anode and positively charged ions (cations) to transfer to the cathode where a desired material or the ion of the material are coated on to the substrate. The electrodeposition material, the charged electrodeposition material, the ionic electrodeposition material may be referred to as the material, electrodeposition material and deposition material. In an example, one or more substrate is submerged in a plastic container where the electric pulses generate a brief electrical current and the material of the opposite charge of the substrate is coated onto the substate. In another example, a substrate is partially submerged in the liquid and the submerged portion has material electrodeposited onto the surface. In another example, one surface of a substrate contacts the liquid and has material electrodeposited thereon. Those skilled in the art of electrodeposition or electroplating will appreciate many sizes and shapes of containers, vessels, holders, baths and similar devices can be used to hold or retail the liquid while containing the electric field and electric current within such vessel. Additionally, it should be appreciated that a variety of pulse generators and power generators could be used. In another example, one or more substrate is anodic and one or more different substrate is cathodic in the liquid, and material of different charges is electrodeposited on the different charged substrates.

[0064] The electrodeposition characteristics such as thickness, surface coverage, thickness variation, nanoscale morphology, nanoparticle size, optical properties, chemical properties, electrical properties, magnetic properties, physical properties and combinations thereof may be determined using a variety of methods. In an example, a scanning electron micrograph image of the substrate is used to determine electrodeposition characteristics of the material electrodeposited onto the surface of the substrate. In an example, electrodeposition may be monitored using light absorption, reflection or combinations thereof.

[0065] The electrodeposition liquid, also referred to as liquid, electrolyte or solution herein, may be any suitable liquid that is conductive. Electrodeposition is commonly carried out in aqueous fluids but is not limited to aqueous systems. For example, electrodeposition liquid can include molten salts, solvents, gels, alcohols, acids, bases and combinations thereof. The electrodeposition liquid may include additional salts. The additional salts may provide additional conductivity to the deposition liquid while not playing an active role in the deposition chemistry. An electrodeposition liquid that lacks conductivity may become conductive with additional salts. Salts may be used to increase or decrease the ionic concentration of the liquid. Salts and ionic compounds may be included in the liquid to increase or decrease the ionic concentration of the liquid. Salts and ionic compounds are well known in the art, any of which may be suitable for use in the liquid. In an example, one or more ionic compound may be used for electrodeposition material. The concentration of the electrodeposition material may increase or decrease the ionic concentration of the liquid. The electrodeposition material, salts, additives or any combination thereof may be used to increase or decrease the ionic concentration of the liquid. Additives may include acids, bases, alcohols, solvents, buffers, salts, ionic compounds, polymers, antioxidants, gels, oxidants, doping compounds and combinations thereof. Any one or more material disclosed herein may be used as a doping compound. In example, the liquid is a gel. In another example, the liquid is a gel with an additional electrolyte.

[0066] The electrodes include one or more cathode and one or more anode. The cathode may be characterized by a negative charge. The anode may be characterized by a positive charge. The electrodes may be of the same material or different material. The electrodes may be alloys of two or more materials such as metals. The electrodes can be made of any suitable conductive material such as metal or a semiconductor. The materials that may be used for electrodes may also be used for substrates and for electrodeposition materials. An electrode may have a positive or negative charge. A counter electrode may be referred to as an electrode of opposite charge to the reference electrode. In an example, one or more electrode is referred to by its charge, positive or negative. In an example, a cathode is an electrode from which the current exits a polarized electrical device and an anode is an electrode from which a current enters into a polarized electrical device. In an example, one or more electrode is referred to as positive or negative as opposed to cathode or anode.

[0067] Examples of materials for electrodes and substrates include but are not limited to stainless steel (SS), SS 316, SS 316L, SS 304, SS304L, SS 303, SS 321, SS 347, SS 410, SS 416, SS 440C, SS 2205, SS 2207, SS 13-8, SS 15-5, SS 17-4, 17-4PH and combinations and alloys thereof. Graphite and carbon nanotubes may be used for electrodes and substrates. In another example, silica may be an electrode or a substrate. Inconel, monel, brass, and bronze may be electrodes and substrates.

[0068] Metals may be used for electrodeposition materials, substrates and electrodes. Examples of metals that may be used for electrodes, substrates, electrodeposition materials and combinations thereof include but are not limited to Lithium (Li), Beryllium (Be), Sodium (Na), Magnesium (Mg), Aluminum (Al), Potassium (K), Calcium (Ca), Scandium (Sc), Titanium (Ti), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Gallium (Ha), Rubidium (Rb), Strontium (Sr), Yttrium (Y), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Technetium (Tc), Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Silver (Ag), Cadmium (Cd), Indium (In), Tin (Sn), Cesium (Cs), Barium (Ba), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium (Ir), Platinum (Pt), Gold (Au), Mercury (Hg), Thallium (TI), Lead (PB), Bismuth (Bi), Polonium (Po), Francium (Fr), Radium (Ra), Actinium (Ac), Thorium (Th), Protactinium (Pa), Uranium (U), Neptunium (Np), Plutonium (Pu), Americium (Am), Curium (Cm), Berkelium (Bk), Californium (Cf), Einsteinium (Es), Fermium (Fm), Mendelevium (Md), Nobelium (No), Lawrencium (Lr), Rutherfordium (Rf), Dubnium (Db), Seaborgium (Sg), Bohrium (Bh), Hassium (Hs), Meitnerium (Mt), Darmstadtium (Ds), Roentgenium (Rg), Copernicium (Cn), Ununtrium (Uut), Flevorium (Fl), Livermorium (Lv) and alloys and combinations thereof. Alloys may include the combination of two or more metals.

[0069] Electrodeposition materials, electrodes and substrates include alloys including but not limited to Nickel (Ni) and Tungsten (W); Iron (Fe) and Molybdenum (Mo); Iron (Fe) and Tungsten (W); Nickel (Ni) and Molybdenum (Mo); Nickel (Ni) and Phosphorous (P); Nickel (Ni), Tungsten (W) and Boron (B); Iron (Fe), Nickel (Ni) and Carbon (C); Iron (Fe), Chromium (Cr), Phosphorous (P) and Carbon (C); Cobalt (Co) and Tungsten (W); Chromium (Cr) and Phosphorous (P); Copper (Cu) and Silver (Ag); Copper (Cu) and Zinc (Zn); Cobalt (Co), Zinc (Zn), carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl) and nihonium (Nh), alloys and combinations thereof.

[0070] Electrodeposition materials, substrates, additives or combinations thereof may include one or more semiconductor material. Examples of semiconductor materials include silicon (Si), germanium (Ge), silicon germanium alloys (SiGe), silicon carbide (SiC), silicon germanium carbide (SiGeC), III-V compound semiconductors or II-VI compound semiconductors. III-V compound semiconductors are materials that include at least one element from Group III of the Periodic Table of Elements and at least one element from Group V of the Periodic Table of Elements. II-VI compound semiconductors are materials that include at least one element from Group II of the Periodic Table of Elements and at least one element from Group VI of the Periodic Table of Elements. For example, Group II-VI compound semiconductors include Group IIB (Cd, Zn, Hg) and Group VIA (O, S, Se, Te, Po). In an example, CdTe is an electrodeposition material. In another example, HgTe is an electrodeposition material.

[0071] In another example, one or more of tin-oxide, cadmium-tin-oxide, zinc-tin-oxide, indium-tin-oxide, zinc-oxide and combinations thereof are electrodeposited onto a substrate to increase the conductivity of the substrate. In an example multiple layers of electrodeposition materials, alloys or mixtures are used as electrodeposition materials. In an example, n- or p-type dopant which is electrodeposited simultaneously with the nanocrystal layer in proportions to form a desired n- or p-type layer.

[0072] As used herein, the term “about” means that the numerical value is approximate and small variations would not significantly affect the practice of the disclosed embodiments. Where a numerical limitation is used, unless indicated otherwise by the context, “about” means the numerical value may vary by ±1 or ±10%, or any point therein, and remain within the scope of the disclosed embodiments.

[0073] The voltage used for electrodeposition as disclosed herein may be about 1 volt, about 5 volts, about 10 volts, about 15 volts, about 20 volts, about 30 volts, about 40 volts, about 50 volts, about 60 volts, about 70 volts, about 80 volts, about 90 volts, about 100 volts, or about 200 volts, or about 300 volts, or about 400 volts, or about 500 volts, or about 600 volts, or about 700 volts, or about 800 volts, or about 900 volts, or about 1,000 volts, or about 2,000 volts, or about 3,000 volts, or about 4,000 volts, or about 5,000 volts, or about 6,000 volts, or about 7,000 volts, or about 8,000 volts, or about 9,000 volts, or about 10,000 volts, or about 20,000 volts or greater than 20,000 volts.

[0074] The frequency of the electric pulses as disclosed herein may be measured in cycles per second referred to as hertz. The frequency of the electric pulses may be or about 0.001 hertz, or about 0.005 hertz, or about 0.01 hertz, or about 0.015 hertz, or about 0.02 hertz, or about 0.025 hertz, or about 0.03 hertz, or about 0.035 hertz, or about 0.04 hertz, or about 0.045 hertz, or about 0.05 hertz, or about 0.055 hertz, or about 0.06 hertz, or about 0.065 hertz, or about 0.07 hertz, or about 0.075 hertz, or about 0.08 hertz, or about 0.085 hertz, or about 0.09 hertz, or about 0.095 hertz, or about 0.1 hertz, or about 0.5 hertz, or about 1 hertz, or about 5 hertz, or about 10 hertz, or about 20 hertz, or about 50 hertz, or about 75 hertz, or about 100 hertz, or about 250 hertz, or about 500 hertz, or about 750 hertz, or about 1000 hertz.

[0075] The electric pulses as disclosed herein may have a duration of about 1 nanosecond, or about 5 nanoseconds, or about 10 nanoseconds, or about 15 nanoseconds, or about 20 nanoseconds, or about 25 nanoseconds, or about 30 nanoseconds, or about 35 nanoseconds, or about 40 nanoseconds, or about 45 nanoseconds, or about 50 nanoseconds, or about 55 nanoseconds, or about 60 nanoseconds, or about 65 nanoseconds, or about 70 nanoseconds, or about 75 nanoseconds, or about 80 nanoseconds, or about 85 nanoseconds, or about 90 nanoseconds, or about 95 nanoseconds, or about 100 nanoseconds, or about 105 nanoseconds, or about 110 nanoseconds, or about 115 nanoseconds, or about 120 nanoseconds, or about 125 nanoseconds, or about 130 nanoseconds, or about 135 nanoseconds, or about 140 nanoseconds, or about 145 nanoseconds, or about 150 nanoseconds, or about 200 nanoseconds, or about 250 nanoseconds, or about 300 nanoseconds, or about 350 nanoseconds, or about 400 nanoseconds, or about 450 nanoseconds, or about 500 nanoseconds, or about 550 nanoseconds, or about 600 nanoseconds, or about 650 nanoseconds, or about 700 nanoseconds, or about 750 nanoseconds, or about 800 nanoseconds, or about 850 nanoseconds, or about 900 nanoseconds, or about 950 nanoseconds, or about 1000 nanoseconds.

[0076] The thickness of the nanoparticle coating on the substrate may be about 1 nm, or about 5 nanometers, or about 10 nanometers, or about 15 nanometers, or about 20 nanometers, or about 25 nanometers, or about 30 nanometers, or about 35 nanometers, or about 40 nanometers, or about 45 nanometers, or about 50 nanometers, or about 55 nanometers, or about 60 nanometers, or about 65 nanometers, or about 70 nanometers, or about 75 nanometers, or about 80 nanometers, or about 85 nanometers, or about 90 nanometers, or about 95 nanometers, or about 100 nanometers, or about 105 nanometers, or about 110 nanometers, or about 115 nanometers, or about 120 nanometers, or about 125 nanometers, or about 130 nanometers, or about 135 nanometers, or about 140 nanometers, or about 145 nanometers, or about 150 nanometers, or about 200 nanometers, or about 250 nanometers, or about 300 nanometers, or about 350 nanometers, or about 400 nanometers, or about 450 nanometers, or about 500 nanometers, or about 550 nanometers, or about 600 nanometers, or about 650 nanometers, or about 700 nanometers, or about 750 nanometers, or about 800 nanometers, or about 850 nanometers, or about 900 nanometers, or about 950 nanometers, or about 1000 nanometers.

[0077] The size of the nanoparticles of the electrodeposited material on the substrate may be about 0.1 nm, or about 0.25 nm, or about 0.5 nm, or about 0.75 nm, or about 1 nm, or about 5 nanometers, or about 10 nanometers, or about 15 nanometers, or about 20 nanometers, or about 25 nanometers, or about 30 nanometers, or about 35 nanometers, or about 40 nanometers, or about 45 nanometers, or about 50 nanometers, or about 55 nanometers, or about 60 nanometers, or about 65 nanometers, or about 70 nanometers, or about 75 nanometers, or about 80 nanometers, or about 85 nanometers, or about 90 nanometers, or about 95 nanometers, or about 100 nanometers, or about 105 nanometers, or about 110 nanometers, or about 115 nanometers, or about 120 nanometers, or about 125 nanometers, or about 130 nanometers, or about 135 nanometers, or about 140 nanometers, or about 145 nanometers, or about 150 nanometers, or about 200 nanometers, or about 250 nanometers, or about 300 nanometers, or about 350 nanometers, or about 400 nanometers, or about 450 nanometers, or about 500 nanometers, or about 550 nanometers, or about 600 nanometers, or about 650 nanometers, or about 700 nanometers, or about 750 nanometers, or about 800 nanometers, or about 850 nanometers, or about 900 nanometers, or about 950 nanometers, or about 1000 nanometers.

[0078] The percent coverage of the substrate may be about or about 0.1 percent, or about 0.2 percent, or about 0.25 percent, or about 0.3 percent, or about 0.5 percent, or about 0.6 percent, or about 0.75 percent, or about 1 percent, or about 2 percent, or about 3 percent, or about 4 percent, or about 5 percent, or about 10 percent, or about 15 percent, or about 20 percent, or about 25 percent, or about 30 percent, or about 35 percent, or about 40 percent, or about 45 percent, or about 50 percent, or about 55 percent, or about 60 percent, or about 65 percent, or about 70 percent, or about 75 percent, or about 80 percent, or about 85 percent, or about 90 percent, or about 95 percent, or about 100 percent.

[0079] The degree of crystallization may be the percentage of crystal nanoparticles in a particular coating. The degree of crystallization may be about 1 percent, or about 5 percent, or about 10 percent, or about 15 percent, or about 20 percent, or about 25 percent, or about 30 percent, or about 35 percent, or about 40 percent, or about 45 percent, or about 50 percent, or about 55 percent, or about 60 percent, or about 65 percent, or about 70 percent, or about 75 percent, or about 80 percent, or about 85 percent, or about 90 percent, or about 95 percent, or about 100 percent.

[0080] Materials and ions that are of low solubility in water or aqueous liquids include but are not limited to the chlorides, bromides, and iodides of lead, silver and mercury; the sulfates of lead, mercury, barium, and calcium; hydroxides of alkaline earth metals (Group II) OH— with Ca2+, Sr2+, etc., hydroxides of most metals; carbonates, oxalates, chromates, and phosphates CO32-, C2O42-, CrO42-, and PO43-.

[0081] The ionic concentration of the liquid, the material concentration in the solution or any combination thereof may be about 0 millimolar, or about 1 millimolar, or about 10 millimolar, or about 20 millimolar, or about 30 millimolar, or about 40 millimolar, or about 50 millimolar, or about 60 millimolar, or about 70 millimolar, or about 80 millimolar, or about 90 millimolar, or about 100 millimolar, or about 200 millimolar, or about 300 millimolar, or about 400 millimolar, or about 500 millimolar, or about 600 millimolar, or about 700 millimolar, or about 800 millimolar, or about 900 millimolar, or about 1000 millimolar, or about 1 molar, or about 2 molar, or about 3 molar, or about 4 molar, or about 5 molar, or about 6 molar, or about 7 molar, or about 8 molar, or about 9 molar, or about 10 molar.EXAMPLES

[0082] The following examples are intended to illustrate particular embodiments of the present disclosure but are by no means intended to limit the scope thereof.

[0083] Although some non-limiting examples have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions, and the like may be made without departing from the spirit of the present disclosure and these are therefore considered to be within the scope of the present disclosure as defined in the claims that follow.

[0084] It should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail herein (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein. In particular, all combinations of claimed subject matter appearing at the end of this disclosure are contemplated as being part of the inventive subject matter disclosed herein and may be used to achieve the benefits and advantages described herein.

[0085] FIG. 1 shows a non-limiting example of a substrate 120 in a deposition liquid 125 in a container 130 holding the deposition liquid 125 where a power supply 105 provides pules of electricity between a cathode 110 and anode 115 and a material in the deposition liquid 125 is electrodeposited onto the surface of the substrate 120. In another example the substrate 120 is attached to the anode 110 and the cathode 115 provides the counter electrode. In an example the container 130 is plastic. In another example, the container 130 is any non-conductive substance or material. In an example, the container is made of a conductive material acting as the cathode or anode in the system.

[0086] FIG. 2 shows a non-limiting example of an SEM image of a stainless-steel substrate. No material has been electrodeposited onto the substrate and the image is an example of a stainless-steel substrate without any electrodeposition material.

[0087] FIG. 3 shows a non-limiting example of cathodic deposition of calcium phosphate onto a stainless-steel substrate. Stainless-steel was electrically connected to the cathode and thereby negatively charged during the electrical pulses. The electric pulse voltage was 4,000 volts, the electric pulse duration was 300 nanoseconds, the electric pulse period was 5 hertz, and the total number of electric pulses was 2,000. The concentration of the electrodeposition liquid was 25 mM CaCl2, 3 mM NH4H2PO4, and 50 mM NaCl. The NaCl acts as a bystander ion to adjust the solution conductivity. The amorphous calcium phosphate layer has an approximate 200 nm thickness with a texture less than 200 nm.TotalSubstratedepositionpulsePulsePulseSamplechargeliquidnumberVoltsnanosecondsfrequencyStainlessCathodeCaCl2 5 mM2,0004,0003005 hertzsteelNegativeNH4H2PO4 3 mMchargeNaCl 50 mM

[0088] FIG. 4 shows a non-limiting example of calcium phosphate deposited onto a silica wafter substrate. The silica wafer was electrically connected to the cathode and thereby negatively charged during the electrical pulses. The electric pulse voltage was 8,000 volts, the electric pulse duration was 300 nanoseconds, the electric pulse period was 2 hertz and the total number of electric pulses was 10,000. The concentration of the electrodeposition liquid was 5 mM CaCl2, 3 mM NH4H2PO4, and 50 mM NaCl. The uniform color of the silica wafer indicates a uniform thickness of the electrodeposition material based on light refraction through the deposited layer. The uniform optical property of the substrate demonstrates uniform electrodeposition of calcium phosphate. As seen in the top of the image of FIG. 4, there is a line where the silica wafter exited the electrodeposition liquid and was not coated above the line showing a clear distinction between the coated and non-coated substrate in terms of optical characteristics. The optical characteristics of the silica wafer were modified with the electrodeposition of material onto the substrate. The color is attributed to the thin film interference associated with uniform films in the nanometer thickness range.TotalSubstratedepositionpulsePulsePulseSamplechargeliquidnumberVoltsnanosecondsfrequencySilicaCathodeCaCl2 5 mM10,0008,0003002 hertzwaferNegativeNH4H2PO4 3 mMchargeNaCl 50 mM

[0089] FIG. 5 shows a non-limiting example of silica deposited on a stainless-steel washer (0.5 inch). A solution of 3M NaOH with 1 M SiO2 dissolved to saturation is further diluted to a 0.01M solution of deposition liquid. The material being electrodeposited is silica and the stainless-steel substrate is electrically connected to the cathode and thereby negatively charged. The electric pulse is 8,000 volts, the pulse duration is 300 nanoseconds, the pulse frequency is 2 hertz with a total of 5,000 pulses. The silica can be seen on the surface of the stainless-steel substrate. In the SEM image the distance between each line of the scale represents 500 nanometers. The deposited silica is uniform in coverage and uniform in thickness and size. The nanoscale morphology of the deposited silica is consistent. This example represents nanometer scale electrodeposition of silica onto a substrate in an aqueous liquid. The percentage of coverage is consistent as is the nanomorphology and size of the electrodeposited nanoparticles.TotalPulseSubstratedepositionpulsedurationPulseSamplechargeliquidnumberVoltsnanosecondsfrequencyStainlessCathode3M NaOH with5,0008,0003002 hertzsteelNegative1M SiO2Chargedissolved tosaturation.Dilute to 0.01Msolution.

[0090] FIG. 6 shows a non-limiting example of silver deposition on a stainless-steel substrate. The deposition liquid was 10 mM AgNO3, the electric pulse voltage was 4,000 volts, the pulse duration was 300 nanoseconds, and the pulse period was 5 hertz. The total number of electric pulses was 1,000. The substrate was electrically connected to the cathode and thereby negatively charged. This is an example of nanoscale electrodeposition of silver where crystals form at dispersed nucleation sites instead of a uniform thickness at the nanometer scale.TotalPulseSubstratedepositionpulsedurationPulseSamplechargeliquidnumberVoltsnanosecondsfrequencyStainlessCathode10 mM1,0004,0003005 hertzsteelNegativeAgNO3charge

[0091] FIG. 7 shows a non-limiting example of silver doped calcium phosphate electrodeposition. The deposition liquid consisted of 3 mM NH4H2PO4, 4.5 mM Ca(NO3)2·4H2O and 0.5M AgNO3. The electric pulse voltage was 4,000 volts. The pulse duration was 300 nanoseconds. The pulse period was 5 hertz. The total number of pulses was 500. The stainless-steel substrate was electrically connected to the cathode and thereby negatively charged. The nanoscale semi-crystalline morphology is very consistent. A uniform coating of similar sized nanoparticles of silver doped calcium phosphate can be observed.TotalPulseSubstratedepositionpulsedurationPulseSamplechargeliquidnumberVoltsnanosecondsfrequencyStainlessCathode3 mM5004,0003005 hertzsteelNegativeNH4H2PO4charge4.5 mMCa(NO3)2•4H2O0.5M AgNO3

[0092] FIG. 8 shows a non-limiting example of the electrodeposition of zinc oxide (ZnO) on a stainless-steel substrate. The electrodeposition liquid was 0.17 g / L ZnNO3+0.5 g / L NaCl. The electric pulse voltage was 5,000 volts. The pulse duration was 300 nanoseconds. The pulse period was 5 hertz. The total number of electric pulses was 1,000. The substrate was electrically connected to the anode and thereby positively charged. The conditions in this example are the same as FIG. 9, except the concentration of the material in the electrodeposition liquid. The lower concentration of material in the liquid resulted in electrodeposited material being less thick, smaller and of a different nanoscale morphology in FIG.I 8 as compared to FIG. 9. The dilute concentration of material in the electrodeposition liquid resulted in smaller nanocrystals of electrodeposited material. The smaller nucleation sites and smaller deposited nanoparticles resulted in different optical properties of the coated substrate. The substrate in FIG. 8 absorbs light and appears black. The substrate in FIG. 9 reflects light and appears bright. SEM image of zinc oxide (ZnO) electrodeposition onto stainless-steel washer (0.5 inch).TotalPulseSubstratedepositionpulsedurationPulseSamplechargeliquidnumberVoltsnanosecondsfrequencyStainlessAnode0.17 g / L1,0005,0003005 hertzsteelPositiveZnNO3 +charge0.5 g / L NaCl

[0093] FIG. 9 shows a non-limiting example of zinc oxide (ZnO) electrodeposited on a stainless-steel substrate. The electrodeposition liquid was 1.7 g / L ZnNO3. The electric pulse voltage was 5,000 volts. The pulse duration was 300 nanoseconds. The pulse period was 5 hertz. The total number of pulses was 1,000. The substrate was electrically connected to the anode and thereby positively charged. The nanoscale size and morphology of the electrodeposition of zinc changes the optical properties of the substrate. The larger zinc electrodeposition material in FIG. 9 reflects light and the substrate appears bright as compared to FIG. 8 where the smaller zinc electrodeposition particles absorbs light and appears dark. The concentration of the material in the electrodeposition liquid of FIG. 9 was 10 times higher than FIG. 8. The modification of the electrodeposition liquid modified the size of the electrodeposition material, the morphology and the thickness (compare FIG. 8 and FIG. 9). SEM image of zinc oxide (ZnO) electrodeposition onto stainless-steel washer (0.5 inch).TotalPulseSubstratedepositionpulsedurationPulseSamplechargeliquidnumberVoltsnanosecondsfrequencyStainlessAnode1.7 g / L1,0005,0003005 hertzsteelPositiveZnNO3charge

[0094] FIG. 10 shows a non-limiting example of amorphous calcium phosphate electrodeposition on 316L stainless-steel washer. The colorful appearance on the washer is from the uniform nanometer thick film which causes light interference. This is an example of modification of the optical properties on the surface of a substrate.

[0095] FIG. 11 shows a non-limiting example of an SEM image of amorphous base calcium phosphate electrodeposition on stainless-steel washer from FIG. 10 then post processed to a crystalline state. The electrodeposition liquid was CaCl2 5 mM, NH4H2PO4 3 mM and NaCl 50 mM. The electric pulse voltage was 4,000 volts. The electric pulse duration was 300 nanoseconds. The total number of pulses was 1,500. The washer was electrically connected to the cathode and thereby negatively charged. After electrodeposition the substrate was treated in a bath of NaOH 0.5M for 2 hours at 65° C. This sodium hydroxide treatment converts amorphous deposition to crystalline deposition. The nanoscale morphology of the electrodeposition material is small as compared to FIG. 13, which has similar conditions except the pulse number is higher and the concentration of the NaOH is ten-fold less concentrated in FIG. 13.Conditions:TotalPulseSubstrateDepositionpulsedurationPulseSamplechargeliquidnumberVoltsnanosecondsfrequency316CathodeCaCl2 5 mM1,5004,0003005 hertzWasherNegativeNH4H2PO4Smallcharge3 mMTextureNaCl 50 mMPost Electrodeposition Substrate Treatment:NaOHConversion Time0.5M2 hr @65 C.FIG. 12 shows a non-limiting example of amorphous calcium phosphate electrodeposition on stainless-steel washer. The thicker nanometer film of the electrodeposition material in FIG. 12 has different optical characteristics as compared to FIG. 10 due to the wavelength of light interference corresponding to the film thickness. Amorphous calcium phosphate electrodeposition onto 316L stainless-steels washer. Amorphous stage morphology of crystalline calcium phosphate. Medium thickness film corresponding to the pre-NaOH soak surface of FIG. 13.

[0097] FIG. 13 shows a non-limiting example of crystalline calcium phosphate electrodeposition on stainless-steel. The electrodeposition liquid was CaCl2) 5 mM, NH4H2PO4 3 mM and NaCl 50 mM. The electric pulse voltage was 4,000 volts. The electric pulse duration was 300 nanoseconds. The total number of pulses was 2,500. The substrate was electrically connected to the cathode and thereby negatively charged. After electrodeposition the substrate was treated in a bath of NaOH 0.05M for 2 hours at 65° C. This sodium hydroxide treatments converts the amorphous deposition nanoscale morphology to a crystalline nanoscale morphology The nanoscale morphology of the electrodeposition material is larger than FIG. 11 which has similar conditions except for the total count of electric pulses was 1,500 in FIG. 11 and the concentration of the post processing NaOH was ten-fold higher in FIG. 11. The larger topology of the surface having altered biological properties compared to FIG. 11. SEM image of crystalline calcium phosphate electrodeposition onto 316L stainless-steels washer. Crystalline calcium phosphate. Medium texture, medium size nanomaterial deposited on surface.Conditions:TotalPulseSubstrateDepositionpulsedurationPulseSamplechargeliquidnumberVoltsnanosecondsfrequency316CathodeCaCl2 5 mM2,5004,0003005 hertzWasherNegativeNH4H2PO4Mediumcharge3 mMTextureNaCl 50 mMPost Electrodeposition Substrate Treatment:NaOHConversion Time0.05M2 hr @65 C.Prophetic example 1. The electrodeposition of one or more silica, semiconductor or combinations thereof onto a silica substrate is contemplated by this disclosure. The electrodeposition of silica onto a silica substrate, such as a silica wafer, in an aqueous liquid is contemplated. An electrodeposition liquid will be made from a solution of 3M NaOH with 1 M SiO2 dissolved to saturation will be further diluted to a 0.01M solution. The diluted SiO2 solution will be electrodeposited onto a silica substrate that is electrically connected to the cathode and thereby negatively charged. The electric pulse will be 8,000 volts, pulsed at 2 hertz for a total of 5,000 pulses. The silica is expected to form a uniform thickness. The size of the deposited silica nanoparticles will be controlled by a combination of the pulse duration, the voltage and the concentration of the electrodeposition liquid. The silica substrate may be partially manufactured. The silica substrate may be electrodeposited with silica one or more times. The silica substrate may be doped or combined with other elements, metals, semiconductors, alloys or combinations thereof. The silica substrate may be processed or treated prior to electrodeposition or after electrodeposition one or more times. The silica substrate may have one or more metal, alloy, silica, semiconductor or combinations thereof electrodeposited one or more times with treatment or processing steps before or after any one or more electrodeposition.

[0099] Prophetic example 2. The electrodeposition of one or more metals and alloys onto a silica substrate is contemplated by this disclosure. The electrodeposition of metals and alloys onto a silica substrate, such as a silica wafer, in an aqueous liquid is contemplated. An electrodeposition liquid will be made from an appropriate solution with metal or alloy ions of opposite charge to the silica substrate. The electric pulse will be 8,000 volts, pulsed at 2 hertz for a total of 5,000 pulses. The metal or alloy is expected to form a uniform thickness on the silica substrate. The size of the deposited nanoparticles will be controlled by a combination of the pulse duration, the voltage and the concentration of the electrodeposition liquid. One or more metal or alloy may be electrodeposited on to the silica substrate one or more times. The silica substrate may be masked one or more times. The silica substrate may be processed before electrodeposition or after electrodeposition and may then have one or more material electrodeposited and may have one or more cycles of processing and electrodeposition of one or more materials. The silica substrate, metal, alloys or combinations thereof may be doped or combined with other elements, metals, semiconductors, alloys or combinations thereof.

Claims

1. A method comprising:providing an apparatus comprising an anode and a cathode, coupled to each other through a power supply;providing, in contact with the anode and the cathode, a liquid comprising a substrate and a material; andproviding a series of electric pulses between the cathode and the anode with pulse durations in the range of 10 to 1000 nanoseconds, wherein the material is electrodeposited onto a surface of the substrate, wherein the substrate acts as either a cathode or an anode in the liquid.

2. The method of claim 1, wherein the electric pulse has a period of about 0.001 Hz to 10,000 Hz.

3. The method of claim 1, wherein the electric pulse has a period of about 1 to 10 Hz.

4. The method of claim 1, wherein the electric pulse has a period of about 10 to 100 Hz.

5. The method of claim 1, wherein the electric pulse has a period of about 100 to 1000 Hz.

6. The method of claim 1, wherein the electric pulse has a period of about 100 to 10000 Hz.

7. The method of claim 1, wherein the electric pulse is from about 10 to 1000 volts.

8. The method of claim 1, wherein the electric pulse is from about 1000 to 50000 volts.

9. The method of claim 1, where int the electric pulse is from about 4000 to 8000 volts.

10. The method of claim 1, wherein a total electric pulse count is about 10 to 100,000,000.

11. The method of claim 1, wherein a total electric pulse count is about 1000 to 20000.

12. The method of claim 1, wherein a total electric pulse count is about 100000 to 1000000.

13. The method of claim 1, wherein the electric pulse is from about 10 to 10,000 amps.

14. The method of claim 1, wherein the electric pulse is from about 100 to 1000 amps.

15. The method of claim 1, wherein the electric pulse creates a current density in the substrate from about 1 to 2,000 amps / cm2.

16. The method of claim 1, wherein the electrodeposited material covers about 90 to 100% of the surface of the substrate that is electrically conductive, and / or the electrodeposited material thickness variation is less than about 1%.

17. The method of claim 1, wherein the electrodeposited material thickness is about 10 to 500 nanometers.

18. The method of claim 1, further comprising adding one or more additional material to the liquid, wherein the one or more additional material is electrodeposited onto the surface of the substrate.

19. The method of claim 1, wherein one or more of:(i) the electrodeposited material is silica;(ii) the substrate is stainless steel; and(iii) the liquid is an aqueous solution.

20. A device comprising:an apparatus comprising an anode and a cathode, coupled to each other through a power supply; wherein the anode and the cathode contact a liquid comprising a substrate and a material; and wherein the power supply is configured to provide a series of electric pulses between the cathode and the anode with a pulse duration in the range of 10 to 1000 nanoseconds, such that the material is electrodeposited onto a surface of the substrate wherein the substrate contacts either a cathode or an anode in the liquid.

Images