CROSS-REFERENCE TO RELATED APPLICATOINS

[0001] This applications claims priority to U.S. provisional application No. 63/375,087, the entire content of which is incorporated herein by reference.

FIELD OF THE INVENTION

[0002] The present disclosure relates to the creation of a textured nano-scale surface on conductive material.

BACKGROUND OF THE INVENTION

[0003] The purpose of the invention is to passivate metal surfaces to prevent corrosion, clean metal surfaces with minimal material loss, or create nanotextured surfaces on metals that may be used in the biomedical industry and other commercial industries. These fabrication processes are related to the passivation of metals such as piping used in industrial applications where corrosion is a problem, passivation of weld joints, selective dissolution of metallic species from surfaces to prevent contamination of fluids or gasses or allergic reactions in patient contacting materials, increasing the surface area for catalysts to more efficiently run reactions.

[0004] Currently does not exist a commercially viable way to produce a nano-texture on stainless steel 316L and cobalt chrome surfaces. The disclosed process can also generate nano surfaces on titanium, titanium alloys, aluminum, and possibly other metals and ceramics. The purpose has been to develop a process that is cost-effective, safe-to-manufacture parts, produces biocompatible surfaces for implants, and can improve corrosion resistance. The process in this disclosure allows for the creation of nanoscale textures on surfaces previously unachievable across an array of different metals. The process can also be used to clean the surface of unwanted material or contaminants, reduce the presence of specific material on the metal surface, or improve corrosion resistance. The process can also be done using less hazardous electrolytes in comparison to conventional anodization techniques, replacing strong acids and bases with less hazardous salts or acids with very low concentration. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the inventions and together with the detailed description herein, serve to explain the principles of the inventions. It is emphasized that, in accordance with the standard practice in the industry, various features may or may not be drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion. The drawings are only for purposes of illustrating embodiments of inventions of the disclosure and are not to be construed as limiting the inventions.

[0006] Figures 1(a) and (b) show SEM images of an aged Ti pulsed nano surface, in accordance with an aspect of the present disclosure.

[0007] Figures 2(a), (b), (c) and (d) show SEM images of stainless steel anodized and pulsed created nano surface, in accordance with an aspect of the present disclosure.

[0008] Figures 3(a), (b), (c) and (d) show SEM images of stainless steel anodized and pulsed created nano surface, in accordance with an aspect of the present disclosure.

[0009] Figures 4(a), (b), (c) and (d) show SEM images of stainless steel anodized and pulsed created nano surface, in accordance with an aspect of the present disclosure.

[0010] Figures 5(a), (b), (c), (d), (e) and (f) show SEM images of stainless steel surfaces that have been sequentially processed with two different chemistries to produce a more ideal nano surface for protein, cell and tissue interactions on the nanoscale. Surface chemistry can be altered after the nano surface is created if the surface needs to be further optimized for a specific need, in accordance with an aspect of the present disclosure.

[0011] Figures 6(a), (b), (c) and (d) show SEM images of anodized stainless steel both passivated and non-passivated nano surfaces, in accordance with an aspect of the present disclosure.

[0012] Figures 7 (a), (b), (c) and (d) show SEM images of Aluminum nano surfaces (a) and (b) and Cobalt Chrome nano surfaces (c) and (d) post-pulsing, in accordance with an aspect of the present disclosure.

[0013] Figures 8-13 show SEM images of stainless steel nano surfaces created using various pulsing durations, acid concentrations and voltage magnitudes, in accordance with an aspect of the present disclosure. [0014] Figure 14 shows as SEM image of Cobalt Chrome nano surface post-pulsing, in accordance with an aspect of the present disclosure.

[0015] Figure 15 and 16 shows SEM images of ELI Ti nano surfaces post-pulsing, in accordance with an aspect of the present disclosure.

[0016] Figure 17 is a schematic of the circuit used in the method, in accordance with an aspect of the present disclosure.

[0017] Figure 18 shows the system to create the nano surface on a metal, in accordance with an aspect of the present disclosure.

DETAILED DESCRIPTION FOR CARRYING OUT THE INVENTION

[0018] In this detailed description and the following claims, a method, process and system to fabricate a nano scale surface on stainless steel, other metals and conductive materials is described. The creation of the nano surface features on the various metals, including for example, stainless steel is accomplished by applying high voltage pulsing to the metal substrate immersed in an electrolyte solution thereby creating desired nano-texture surface. The texture may be a result of the electric pulses in the electrolyte selectively removing specific elements, ions, oxides, material, molecules, contaminants or combinations thereof from the surface. The disclosed methods, systems and products may improve corrosion resistance of the metal. The disclosed methods may be done with low concentration acids and bases that are currently used in other anodization processes, making the process safer for the manufacturer and less harmful to the environment. Alternatively, the process may utilize electrolytes such as salts that non- aggressively etch or do not etch the surface between pulses, making it a safer process compared to some processes requiring higher concentration acids. The electrolyte may contain halogens, halogen ions, halogen salts or combinations thereof.

[0019] The short duration of the voltage pulses allows for a tunability to the degree to which the metal surface is modified by controlling the number of pulses or the total energy applied to the surface. The fine control in pulse duration and voltage that is allowed by the pulse generator electronics provides the means to precisely control the amount of energy applied to the surface. Pulse trains can be varied in frequency of application and total number of pulses through programmable electronic controls. This gives the operator more control over the outcome and surface characteristics.

[0020] The use of specific chemistries in the electrolyte solution combined with the short duration application of energy to the metal surface through high voltage pulses gives control over the resulting surface chemistry. Chemistries can be chosen to selectively remove iron, chromium, and nickel from stainless steel, beta phase crystals from titanium alloy or cobalt from CoCr Mo alloys. Removing nickel helps reduce the possibility of allergic reactions to stainless steel by some individuals. Reducing the presence of nickel also reduces the ability of some bacteria that use nickel in enzyme chemistry to utilize the stainless surface to establish an infection. Aluminum has been successfully nano surfaced as well. Other chemistry for other metals, alloys and ceramics along with their industrial applications continue to be evaluated.

[0021] Methods of manufacturing medical devices such as milling, grinding, EDM, 3D printing, etc. leave surfaces largely devoid of nanotexture. In the case of stainless steel, the smooth surface is more corrosion resistant than a rough surface. For titanium, the roughness is inconsequential. The process described herein can produce surfaces that are present as polished by uniformly removing material from the surface or can be more nano-textured by selectively removing material. The combination of chemistry and pulsed energy delivery can attack/etch the crystal structure of the metal revealing the structure of the crystals and fractures within the crystals achieved through previous manufacturing steps, such as cold rolling, forging, quenching, shot peening, and laser etching, etc. In an example, the disclosed methods and systems may increase the polish on a conductive surface. Polished surfaces may have more corrosion resistance, less ability for microbe attachment, decreased abrasiveness, altered optical properties such as altered light absorbance and reflectance and reduced friction. The tunability of the disclosed system and methods may allow control of these and other properties of textured or etched surfaces.

[0022] In the case of increasing the nanostructure present on the resulting metal surface, the outcome can be to increase surface area for further chemical modification or binding material to the surface. This could be through surface adsorption, chemical linking to the metal-oxide (or other functional groups: -OH, -NO3, -SO4, -N, -PO4, etc.), or attachment of various inorganic, organic, or hybrid nanoparticles, biological molecules (DNA, RNA, proteins, antibodies, antibody drug conjugates, growth factors, cytokines, antibiotics) and microorganisms such as bacteria, virus etc.). The resulting nano surface can also alter the proteins, biological molecules and microorganism and their topographical presentation that would adsorb from body fluids to alter the biological interaction of the body with the resulting surface. Possible surfaces could improve cell attachment, inhibit bacterial attachment, improve/accelerate differentiation of stem cells, remove bacteria and virus particles, improve vascularization of an implant surface, and reduce the immune profile of the surface. Surfaces generated on titanium and stainless steel have shown biocompatibility through increased cell adhesion. Chromium oxidation states that are potentially carcinogenic (Cr VI) can be avoided with this process on stainless steel and CoCr Mo alloys.

[0023] The disclosed method and systems function by using ultra-short duration pulses of electricity in a setup like conventional DC anodization (See FIG. 18) to create a nano textured surface on conductive materials. In an example, high voltage electric pulses deposits energy at the interface between the metal surface and the electrolyte solution. The electrochemical combination of the solute chemistry, the energy deposited and the directional chemistry from the DC pulse act to modify the surface of the metal.

[0024] The disclosed methods and systems may be used to create textures on conductive surfaces. Conductive surfaces include devices, regions of devices, less than an entire surface, the complete surface, specific regions of one or more surfaces. A device may have at least one conductive surface. A device may have moving components. A device may be solid, hollow, jointed, electronic controlled, metal, polymer, or any combination thereof. A device may include fasteners. Fasteners include screws, nails, anchors, plates, rods, wires, washers, pins, bolts and nuts.

[0025] Textures may be added to any conductive surface of a device. Textured surfaces may be created by the removal of the surface material, atoms, metal ions, metal oxides, electrons, ions of metals complexed with salts or metals or any combination thereof. The mechanism by which a specific example works may vary according to any one or more of the electric charge of the surface, the voltage, duration and frequency a of the electric pulse, the total number of pulses, the chemical makeup and concentration of the electrolyte. Textures may be of various sizes depending on the pulse voltage, pulse frequency, electrolyte concentration, electrolyte composition, total pulse number or any combination thereof. Textures may be isolated to a specific surface of a device or on a specific metal or conductive surface used in a device. One or more textures may be created on at least one surface of a device. A texture may be on at least one internal surface of a device. A texture may be on at least one external surface of a device. A texture may be on at least one external surface of a device and on at least one internal surface of a device. A device may have one or more textures. A fastener may have a specific texture while another surface of a device may have another texture. One or more textures may be created using one or more electrolyte solutions, one or more electric pulse voltages, pulse frequencies, pulse durations, total pulse number or any combination thereof. Textures include nano textures and nanostructures.

[0026] Nano textures include textures or structures where at least one dimension is about 1 to about 1000 nanometers. A nano texture may include nanofibers, nanoparticles, nanospheres, nanopores, nano micelles, or other nano- scale structures on a surface. Nano structures may be of any shape including polymorphous, cylindrical, hexagonal, rectangular, spherical or any combination thereof. Nano structures may result from removal of nano sized material from the surface of a device. The nano scale of the nano texture or nano structure may be determined by electric pulse voltage, pulse duration, pulse frequency or total pulse number. In an example, the depth of a nanopore may be enlarged by increasing the total number of electric pulses. The texture may be described as roughness. A rougher texture may have larger nano textures or nanostructures structures than a smoother texture. A polished texture may have very fine, small nano textures and nano structures. Nanosurfacing includes creating nano textures and nano structures and etching a surface of a device. A method of modifying the surface of a device includes nanosurfacing, etching, creating nano textures and nano structures.

[0027] The electrolyte solution can be selectively chosen or engineered to accomplish a specific outcome. Many electrolyte solutions may be used to achieve the desired effect (polishing, contamination removal, nano texturing, and corrosion resistance, modification of surface chemistry, etc.). [0028] In an example, stainless steel was tested in an electrolyte solution containing 0.1M sodium fluoride (NaF) solution. The electric pulse duration parameters may be from 10 ns to 10,000 ns, with a preferred range of 50 ns to 1000 ns, and tested range from 100 ns to 300 ns. The pulse intensity range, for example, could be from 1 V to 300,000 V. To remove material from the surface using electric pulses to create nano surface characteristics, a range from 1000 to 10,000 V was used with a functionally tested range from 1000 to 8000 V.

[0029] Electric pulses may be applied after other processes have been undertaken to clean a surface, pretreat a surface, passivate a surface, create a nanotextured surface or any combination thereof. Pretreatments may consist of acid etching, anodization, heat treatment, plasma treatment, and laser treatment or deposition of another source material onto the metal surface. Selective or protective coating or masking of the conductive surface to restrict the treatment area can be done to create distinct regions that have differing surface properties for an intended application or functionality. Masking the surface may allow for selective etching or removal of material. Masking also allows etching or material removal in specific patterns, shapes or regions of a surface. In an example, a pattern is etched in an alloy. Geometries or patterning of the surface on a micron or macro scale can alter the location of cell attachment, proliferation vs. differentiation, and vascularization pathways or electrical circuitry.

[0030] Pretreatments to create microscale roughness, like low voltage anodization, shot peening, abrasion or acid etching, combined with high voltage pulsing have been demonstrated to achieve greater micron and nano structures on the metal surfaces that would be beneficial for increasing surface area and improving cell attachment and response. There can also be post-treatments to mitigate corrosion, like citric or nitric acid passivation. Surface decoration with a variety of chemistries, biologic molecules, antimicrobial (molecules, metals, particles), dyes or indicators can be applied to further functionalize the metal surface. Further exploration is underway on the pulse parameter ranges to identify target surface properties and applications. Nano structures or nanotextures may impart catalytic activity for promoting certain chemical or biological reactions. [0031] In some embodiments that utilize high voltage electric pulses, the electrolyte chemistry can be modified. Higher energy generally correlates with a faster reaction rate for an etching process. Chemicals that would etch the surface without the application of the pulsed voltage or pulsed current would easily remove the nano surface. Thus, the chemicals can be reduced in concentration to limit the etching potential and retain newly created nano surfaces. The etching chemical may also be replaced with a safer chemical that would not etch on its own, but when combined with the ultra-short duration voltage pulses the safe chemistry becomes reactive with the surface metal or metal ions. The concentration can also be lowered to reduce the reaction rate, making the manufacturing process safer and cheaper.

[0032] The ionization of surface metal may also contribute to the reactivity of the surface in the modification process. Anodization in part works by generating metal ions that can migrate to the surface under the influence of the applied voltage and current. The ultra-short duration of the pulse allows for ionization of the surface metal by pulling some electrons away from the surface of the metal. The ionized metal at the surface can then react with the ions in solution. The resulting chemistry can be soluble and thus remove material from the surface or it can be insoluble and thus adding material to the surface. That ion in solution can be as simple as a chloride or a complex molecule such as for example, an antiseptic, antibiotic, drug, hormone, steroid, DNA, RNA, protein, enzyme, dye, monomer, linker, catalyst, and many others.

[0033] The disclosed systems have some similarities to a conventional anodization system. An electrolyte solution is created with the metal surface of the conductive device being submerged into the solution. An electric potential is then applied to the conductive device. In the disclosed methods, instead of a voltage being applied for long periods of time to the conductive device, like in a conventional anodization processes, nanosecond electric pulses are applied which substantially lower the overall energy in the process. The disclosed process has been shown to create nanoscale surface characteristics on 316L Stainless Steel, CoCr Mo, Titanium, and Aluminum. It has been observed that varying one or more parameters (concentrations and compositions of the electrolyte, pulse duration, pulse magnitude, pulse frequency and total pulse number) can result in the creation of nanoscale surface characteristics for other metals. The disclosed methods includes the following steps with the understanding that the parameters as listed may be changed and are for example purposes only:

1. Clean the surface of the conductive device by using for example, ultrasonic IPA cleaning or other commercially available techniques including but not limited to plasma cleaning, light acid etching, electropolishing or ultraviolet light.

2. Pre-treat the target surface of the conductive device with micro- scale texture or macroporous structures via one or more of the following techniques: a. Acid etching 3min 2%HF + 3%HNO3; b. Mechanical grinding; c. Shot peening; d. Conventional DC anodization; e. High polish passivation; or f. 3D printing

3. Place conductive device into the electrolyte set up with light stirring one or more of the following electrolytes: a. O.lM to lM NaF (FIGS. 8 and 9) b. 0.2% to 2% HC1 (FIGS. 10 and 11) c. 0.1% HF (FIG. 12) d. 0.1M NaCl (FIG. 13)

*The above listed electrolyte solutions can be used in combination or in a series of surface modification steps.

4. Ultrashort duration electric pulsing of the conductive device with the anode comprising the conductive device with the following example parameters a. 4kv to 8kv 300ns pulses 1000 to 20000 pulse count. Pulse frequency of 4hrz or higher ranging from for example lOOhrz up to 10s of khertz.

5. Passivate the conductive device a. 10% Citric Acid at 65C for lOmin

[0034] The disclosed methods may act to etch, remove or texture a surface of a metals and alloys. The amount of etching or material removal may be controlled by adjusting parameters of the disclosed method. The concentration of the electrolyte may be increased or decreased. In an example, the concentration of the fluoride in solution may be adjusted. In an embodiment, a higher concentration of fluoride in the electrolyte solution results in more etching. The pulse voltage may be adjusted. In an example, higher pulse voltage results in more etching or removal of material from a surface of a device. Duration of the pulse may be adjusted. In an example, a longer nanosecond duration of the pulse may result in more etching or removal of material. The total number of pulses applied may be adjusted or varied. In an example, increasing the total electrical pulses results in more etching or removal of material. Etching and removal of the material may both be used to describe the removal of ions, metals, molecules, oxides from a surface of a device through the application of nanosecond pulses in the disclosed methods. In some examples etching is used to describe a chemical process where one or more acid, base, salt or halogen may remove material from the surface of a device. In an example etching may be removal of material with electrical pulses, etching a surface with a chemical process or combination thereof. In an embodiment, etching is the modification of a surface through removal of material and the creation of nano structure, nano textures and combinations thereof.

[0035] The disclosed systems and methods may be used to etch metals, alloys or combinations thereof. In one embodiment, electric pulses may generate an oxide layer in a conductive surface that may be removed using a halogen in the electrolyte. In another example at least one halogen is added to the electrolyte for nanosurfacing a material. In an embodiment, at least one halogen is added to the electrolyte to etch a surface of a device. In another example, at least one halogen is added to the electrolyte. The halogen may include Cl, F, Br, I or combinations thereof.

[0036] The disclosed systems and methods operate in a variety of conditions and ranges. The following are non-limiting examples of conditions and ranges of the disclosed systems and methods.

[0037] One or more electric pulse may be about 1 volt, or about 5 volts, or about 10 volts, or about 20 volts, or about 50 volts, or 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 1000 volts, or about 2000 volts, or about 3000 volts, or about 4000 volts, or about 5000 volts, or about 6000 volts, or about 7000 volts, or about 8000 volts, or about 9000 volts, or about 10000 volts, or about 20000 volts, or about 30000 volts, or about 40000 volts, or about 50000 volts, or about 60000 volts, or about 70000 volts, or about 80000 volts, or about 90000 volts, or about 100000 volts, or about 200000 volts, or about 300000 volts.

[0038] One or more electric pulse frequency may be 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 1.5 hertz, or about 2 hertz, or about 2.5 hertz, or about 3 hertz, or about 3.5 hertz, or about 4 hertz, or about 4.5 hertz, or about 5 hertz, or about 5.5 hertz, or about 6 hertz, or about 6.5 hertz, or about 7 hertz, or about 7.5 hertz, or about 8 hertz, or about 8.5 hertz, or about 9 hertz, or about 9.5 hertz, or about 10 hertz, or about 20 hertz, or about 30 hertz, or about 40 hertz, or about 50 hertz, or about 60 hertz, or about 70 hertz, or about 80 hertz, or about 90 hertz, or about 100 hertz, or about 200 hertz, or about 300 hertz, or about 400 hertz, or about 500 hertz, or about 600 hertz, or about 700 hertz, or about 800 hertz, or about 900 hertz, or about 1000 hertz.

[0039] A total number of electric pulses may be about 1 pulse, or about 10 pulses, or about 100 pulses, or about 200 pulses, or about 300 pulses, or about 400 pulses, or about 500 pulses, or about 600 pulses, or about 700 pulses, or about 800 pulses, or about 900 pulses, or about 1000 pulses, or about 2000 pulses, or about 3000 pulses, or about 4000 pulses, or about 5000 pulses, or about 6000 pulses, or about 7000 pulses, or about 8000 pulses, or about 9000 pulses, or about 10000 pulses, or about 20000 pulses, or about 30000 pulses, or about 40000 pulses, or about 50000 pulses, or about 60000 pulses, or about 70000 pulses, or about 80000 pulses, or about 90000 pulses, or about 100000 pulses, or about 200000 pulses, or about 300000 pulses, or about 400000 pulses, or about 500000 pulses, or about 600000 pulses, or about 700000 pulses, or about 800000 pulses, or about 900000 pulses, or about 1000000 pulses

[0040] An electric pulse may be about 1 amp, or about 5 amps, or about 10 amps, or about 20 amps, or about 30 amps, or about 40 amps, or about 50 amps, or about 60 amps, or about 70 amps, or about 80 amps, or about 90 amps, or about 100 amps, or about 200 amps, or about 300 amps, or about 400 amps, or about 500 amps, or about 600 amps, or about 700 amps, or about 800 amps, or about 900 amps, or about 1000 amps, or about 2000 amps, or about 3000 amps, or about 4000 amps, or about 5000 amps, or about 6000 amps, or about 7000 amps, or about 8000 amps, or about 9000 amps, or about 10000 amps.

[0041] An electric pulse current density may be about 1 amps/ square centimeter (amps/cm2), or about 5 amps/cm2, or about 10 amps/cm2, or about 20 amps/cm2, or about 30 amps/cm2, or about 40 amps/cm2, or about 50 amps/cm2, or about 60 amps/cm2, or about 70 amps/cm2, or about 80 amps/cm2, or about 90 amps/cm2, or about 100 amps/cm2, or about 200 amps/cm2, or about 300 amps/cm2, or about 400 amps/cm2, or about 500 amps/cm2, or about 600 amps/cm2, or about 700 amps/cm2, or about 800 amps/cm2, or about 900 amps/cm2, or about 1000 amps/cm2, or about 2000 amps/cm2, or about 3000 amps/cm2, or about 4000 amps/cm2, or about 5000 amps/cm2, or about 6000 amps/cm2, or about 7000 amps/cm2, or about 8000 amps/cm2, or about 9000 amps/cm2, or about 10000 amps/cm2.

[0042] An electric pulse electric field may be about 1 volt/cm, or about 5 volts/cm, or about 10 volts/cm, or about 20 volts/cm, or about 30 volts/cm, or about 40 volts/cm, or about 50 volts/cm, or about 60 volts/cm, or about 70 volts/cm, or about 80 volts/cm, or about 90 volts/cm, or about 100 volts/cm, or about 200 volts/cm, or about 300 volts/cm, or about 400 volts/cm, or about 500 volts/cm, or about 600 volts/cm, or about 700 volts/cm, or about 800 volts/cm, or about 900 volts/cm, or about 1000 volts/cm, or about 2000 volts/cm, or about 3000 volts/cm, or about 4000 volts/cm, or about 5000 volts/cm, or about 6000 volts/cm, or about 7000 volts/cm, or about 8000 volts/cm, or about 9000 volts/cm, or about 10000 volts/cm, or about 20000 volts/cm, or about 30000 volts/cm, or about 40000 volts/cm, or about 50000 volts/cm, or about 60000 volts/cm, or about 70000 volts/cm, or about 80000 volts/cm, or about 90000 volts/cm, or about 100000 volts/cm

[0043] One or more nanosurfacing, etching, nano texture, nano structure and combinations thereof may be cover a surface of a device about 0.01 percent, or about 0.015 percent, or about 0.02 percent, or about 0.025 percent, or about 0.03 percent, or about 0.035 percent, or about 0.04 percent, or about 0.045 percent, or about 0.05 percent, or about 0.055 percent, or about 0.06 percent, or about 0.065 percent, or about 0.07 percent, or about 0.075 percent, or about 0.08 percent, or about 0.085 percent, or about 0.09 percent, or about 0.095 percent, or about 0.1 percent, or about 0.5 percent, or about 1 percent, or about 1.5 percent, or about 2 percent, or about 2.5 percent, or about 3 percent, or about 3.5 percent, or about 4 percent, or about 4.5 percent, or about 5 percent, or about 5.5 percent, or about 6 percent, or about 6.5 percent, or about 7 percent, or about 7.5 percent, or about 8 percent, or about 8.5 percent, or about 9 percent, or about 9.5 percent, or about 10 percent, or about 20 percent, or about 30 percent, or about 40 percent, or about 50 percent, or about 60 percent, or about 70 percent, or about 80 percent, or about 90 percent, or about 100 percent

[0044] A modification of a surface including nanosurfacing, etching, nano textures and nano structures may occur through the removal of material where about 1 nanometers of material is removed, or about 2 nanometers of material is removed, or about 5 nanometers of material is removed, or about 10 nanometers of material is removed, or about 15 nanometers of material is removed, or about 20 nanometers of material is removed, or about 25 nanometers of material is removed, or about 30 nanometers of material is removed, or about 35 nanometers of material is removed, or about 40 nanometers of material is removed, or about 45 nanometers of material is removed, or about 50 nanometers of material is removed, or about 55 nanometers of material is removed, or about 60 nanometers of material is removed, or about 65 nanometers of material is removed, or about 70 nanometers of material is removed, or about 75 nanometers of material is removed, or about 80 nanometers of material is removed, or about 85 nanometers of material is removed, or about 90 nanometers of material is removed, or about 95 nanometers of material is removed, or about 100 nanometers of material is removed, or about 200 nanometers of material is removed, or about 300 nanometers of material is removed, or about 400 nanometers of material is removed, or about 500 nanometers of material is removed, or about 600 nanometers of material is removed, or about 700 nanometers of material is removed, or about 800 nanometers of material is removed, or about 900 nanometers of material is removed, or about 1000 nanometers of material is removed, or about 2000 nanometers of material is removed, or about 3000 nanometers of material is removed, or about 4000 nanometers of material is removed, or about 5000 nanometers of material is removed, or about 6000 nanometers of material is removed, or about 7000 nanometers of material is removed, or about 8000 nanometers of material is removed, or about 9000 nanometers of material is removed, or about 10000 nanometers of material is removed, or about 20000 nanometers of material is removed, or about 30000 nanometers of material is removed, or about 40000 nanometers of material is removed, or about 50000 nanometers of material is removed, or about 60000 nanometers of material is removed, or about 70000 nanometers of material is removed, or about 80000 nanometers of material is removed, or about 90000 nanometers of material is removed, or about 100000 nanometers of material is removed.

[0045] A nanosurface, surface etch, nano texture and nano structure may have at least one dimension about 1 nanometer, or about 2 nanometers, or about 3 nanometers, or about 4 nanometers, or about 5 nanometers, or about 6 nanometers, or about 7 nanometers, or about 8 nanometers, or about 9 nanometers, or about 10 nanometers, or about 20 nanometers, or about 30 nanometers, or about 40 nanometers, or about 50 nanometers, or about 60 nanometers, or about 70 nanometers, or about 80 nanometers, or about 90 nanometers, or about 100 nanometers, or about 200 nanometers, or about 300 nanometers, or about 400 nanometers, or about 500 nanometers, or about 600 nanometers, or about 700 nanometers, or about 800 nanometers, or about 900 nanometers, or about 1000 nanometers.

[0046] EXAMPLES

[0047] The following examples are intended to illustrate particular embodiments of the present disclosure but are by no means intended to limit the scope thereof.

[0048] 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.

[0049] 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 are contemplated as being part of the inventive subject matter disclosed herein and may be used to achieve the benefits and advantages described herein. [0050] Figure 1 shows a non-limiting example of titanium nanosurface created by first adding the titanium to age in pure water for a month to create an irregular oxide surface. In this example, the titanium acted as the anode in an electrolyte containing 0.1M NaCl where 1000 total electric pulses at 8 kV for 300 ns duration with a pulse frequency of 2 Hz acted to remove material to create the nano texture. The nano features are cylinders on the size of roughly 50 nm with an aspect ratio of 2. The crystalline phase of the titanium had an effect on the surface where the beta phase only has nanoscale roughness not the cylindrical features.

[0051] Figure 2 shows a non-limiting example of stainless steel nano-surface. In this example, the stainless steel was first prepared with direct current anodization to achieve microscale roughness and remove any irregular oxides (a) and (b): anodization only in 0.5M HNO3 + 0.5M H2SO4 at 3 V for 5 minutes, (c) and (d): anodization followed by electric pulsing. Pulsing parameters: anodic configuration, stainless steel acted as the anode, in aqueous 0.1M NaF, with 6 kV 5000 total pulses of 300 ns applied at 4 Hz. All samples were passivated in 5wt.% citric acid at 60°C for 10 minutes.

[0052] Figure 3 shows a non-limiting example of stainless steel nano-surface demonstrating how preconditioning steps can affect not only the microscale roughness but also the pulsed nano step. Compared to figure 2 the nanotexture is different in depth and size with the same pulsed removal step, (a) and (b): anodization only in 0.1M HNO3 + 0.05M HF at 3.5 V for 5 minutes, (c) and (d): anodization followed by pulsing. Pulsing parameters: anodic configuration in aqueous 0.1M NaF, 6 kV 5000 total pulses with a duration of 300 ns applied at 4 Hz. All samples were passivated in 5wt.% citric acid at 60°C for 10 minutes.

[0053] Figure 4 shows a non-limiting example of stainless steel nano-surface. This example demonstrates how preconditioning steps can affect not only the microscale roughness but also texture created by the nanosecond pulses. Compared to figure 2 and 3 the nanotexture is different in depth and size with the same pulsed removal step, (a) and (b): anodization only in 0.5M HN03 + 0.05M HF at 3 V for 5 minutes, (c) and (d): anodization followed by pulsing. Pulsing parameters: 0.1M NaF, 6 kV, 5000 total pulses of a 300 ns duration applied at 4 Hz. All samples were passivated in 5wt.% citric acid at 60°C for 10 minutes.

[0054] Figure 5 shows a non-limiting example of sequentially nanosurfacing stainless steel with two separate conditions. Stainless steel was acid etched in 2% HF and 3% HNO3 for 30 seconds and then nanosurfaced with 2% HC1 in water, anodically applying, stainless steel as anode, 6 kV, 5000 total pulses, 300 ns duration applied at 4 Hz (a, b); Nanosurfacing stainless steel with 0.1M NaF, 8 kV, 5000 total pulses, 300 ns pulse duration (c, d); Sequential nanosurfacing with process from (a, b) and then the less aggressive etching potential chemistry process from (c, d) to produce the surface in (e, f) that has greater nanosurface roughness than either process alone. Figure 5 demonstrates the sequential processing of a stainless steel surface with two different chemistries to produce a more ideal nanosurface for protein, cell and tissue interactions on the nanoscale due to size and depth of the nanofeatures at around 30-50 nm in diameter and 10 nm in depth. Surface chemistry can be altered after the nanosurface is created if the surface needs to be further optimized for a specific need.

[0055] Figure 6 shows a non-limiting example of SEM images of Stainless steel anodized in a mixed acid solution of 0.5M HN03 and 0.5M H2SO4 at 2.5V for 5 minutes without passivation (a-b) and with passivation (c-d). Passivation condition: 5wt.% citric acid at 60°C for 10 minutes. [0056] Figure 7 shows non-limiting examples of SEM images of aluminum and cobalt chrome. Aluminum nanosurfacing conditions were 0.1M NaCl in water 6 kV with anodic application of 5000 total pulses at a frequency of 4 Hz (a, b) and cobalt chrome nanosurfacing conditions 2% HC1 in water with anodic application of 6 kV, 5000 total pulses at 4 Hz (c, d). This example also demonstrates how the materials and chemistries have an affect on the nanoscale features produced by the process. Figure 7D have the same process as 5A with the difference being stainless steel vs cobalt chrome being processed. The use of a specific metal may allow for the creation of a specific texture. The use of a specific metal or alloy may allow for the creation of a specific texture.

[0057] Figure 8 shows a non-limiting example of stainless steel nanosurfacing in 0.1M NaF with 5000 total pulses at 8 kV where the pulse duration was 300 ns applied anodically at 1Hz with mechanical grinding with 800 grit sandpaper to prepare the surface. This example is similar to figure 8, except the electrolyte concentration is lower in figure 7, leading to smaller nano structures and nanotextures.

[0058] Figure 9 shows a non-limiting example of stainless steel nanosurfacing in IM NaF with 5000 total pulses at 8 kV where the pulses duration is 300 ns applied anodically at 1Hz with mechanical grinding with 800 grit sandpaper to prepare the surface. This example is similar to figure 7, though the higher NaF concentration results in larger texture sizes demonstrating how changing one parameter allows the ability to adjust the texture.

[0059] Figure 10 shows a non-limiting example of a stainless steel nanosurfacing in 2% HC1 with 5000 total pulses at 8 kV for a duration of 300 ns applied anodically at 1Hz with mechanical grinding with 800 grit sandpaper to prepare the surface. The example in figure 9 is similar to the example in figure 10 except the concentration of HC1 in figure 9 is tenfold higher resulting in a more aggressive etch or removal of material creating more defined nano texture and nano structures.

[0060] Figure 11 shows a non-limiting example of stainless steel nanosurfacing in 0.2% HC1 with 5000 total pulses at 8 kV for a duration of 300 ns applied anodically at 1Hz with mechanical grinding with 800 grit sandpaper to prepare the surface.

[0061] Figure 12 shows a non-limiting example of stainless steel nanosurfacing in 0.1% HF with 1000 total pulses applied at 8 kV applied at 1 Hz anodically to a surface mechanical grinded with 800 grit sandpaper to prepare the surface.

[0062] Figure 13 shows a non-limiting example of stainless steel nanosurfacing in 0.1M NaCl with 5000 total pulses at 8 kV for a duration of 300 ns applied anodically at 1Hz with mechanical grinding with 800 grit sandpaper to prepare the surface.

[0063] Figure 14 shows a non-limiting example of CrCoMo nanosurfacing in 2% HCL with 1000 total pulses at 6 kV for a duration of 300 ns applied anodically at 4 Hz polished.

[0064] Figure 15 shows a non-limiting example of ELI Ti nanosurfacing in 0. IM NaF using 5000 total pulses at 8 kV for pulse duration of 300 ns applied anodically at 1 Hz acid etched in 2% HF and 3% HNO3 for 3 mins.

[0065] Figure 16 shows a non-limiting example of ELI Ti 0.1M NaCl lOOOp 8kv 300ns H2O long pre-soak for 1 month to build up a non-uniform oxide layer.

[0066] Figure 17 shows a non-limiting example of a circuit used in the disclosed methods, products and systems. Providing an example of how a blumlein configuration transmission line based pulse forming network can provide the necessary high voltage high power short duration pulses when charged with a capable high voltage direct current power supply (HV DC Power). [0067] Figure 18 shows a non-limiting example of a system used in the disclosed systems, products and methods. In an example the device is the anode. In another example the device is the cathode. In an embodiment one or more device may be one or more anode. In another embodiment one or more device may be one or more anode. In an embodiment, at least one device is the cathode and at least one device is the anode.