PORTABLE ELECTROLYTIC DEPOSITION SYSTEM INCLUDING HYDROGELS AND METHODS OF USING SAME

Description

BACKGROUND OF CERTAIN ASPECTS OF THE DISCLOSURE

Electroplating, electrochemical conversion coatings, and anodizing are widely used to treat metal surfaces to improve corrosion resistance, increase adhesion of subsequent coatings such as paint, form a decorative finish, or retain electrical conductivity. While each of these processes involve different chemistries, each of these processes include the use of an electric current that initiates a reaction that forms a layer on a substrate. For example, anodizing is an electrolytic passivation process used to increase a thickness of a natural oxide layer on a surface of a substrate such as a metal. Similarly, electrochemical conversion coatings convert the surface of the substrate to an oxide of the metal. Electroplating includes plating a metal onto the surface of the substrate. Each of these processes are formed by applying a solution to the substrate and applying an electric current across the substrate and the solution. The solution and the substrate react to convert or modify the substrate surface with the desired functional characteristics.

Metal surfaces may be subject to corrosion or other types of degradation as the metal surfaces are exposed to the elements or other operational conditions. For example, metal pipes in industrial facilities may be exposed to the elements or may be exposed to harsh operating environments that may degrade or corrode the metal surface. Replacing the degraded or corroded metals pipes is costly and often requires the industrial facility to shut down during repairs. Furthermore, applying solutions during operations typically involves manually brushing on the solutions with brushes or sprayers that may cause workers to be exposed to chemicals within the solutions. Additionally, the brushes and sprayers typically apply excess solution that may spread to other areas of the industrial facility that were not intended to be coated, requiring extensive clean up.

Furthermore, at least some of the processes described above typically require large, expensive equipment to treat the substrate. For example, at least some of the processed described above require large tanks of solution and require that the entire substrate to be dipped into the solution in order to coat or treat the substrate. The large equipment required to contain the solution and the equipment to be treated may require a large capital expenditure to acquire and to operate. As such, these processes can be costly to operate and may require the equipment to be treated to be taken apart, increasing down time and operating costs.

At least some known processes enable localized treatment of a substrate. For example, brush anodizing and brush electroplating enable an operator to locally anodize or electroplate a substrate. Specifically, in brush electroplating, the brush is typically a stainless-steel wand wrapped in a cloth that includes a plating solution and prevents the substrate and the brush from making direct contact. The brush is dipped in plating solution and allows for localized plating by an operator. Skilled operators can use such a selective electroplating system to apply an even distribution of plated material across the substrate's localized area. Unlike full electroplating techniques described above, which require an immersion in an electrolyte bath, selective plating allows the operator to target a specific area using a plating solution of electrolyte and anode connected to a wire. Brush anodizing involves a similar process.

However, both brush electroplating and brush anodizing typically require expensive, complex equipment to enable an operator to locally treat a substrate. For example, brush anodizers typically include pumps, vacuum system, rectifier, heaters, and controls for the solution. Brush electroplaters require similar equipment. These systems can also require a large capital expenditure to acquire and to operate. Furthermore, these systems commonly require a skilled operator to properly treat the substrate. Moreover, both brush electroplating and brush anodizing are typically performed in a controlled environment where the expensive, complex equipment is kept. Thus, the localized treatment methods are difficult to carry out in the field where repairs are typically needed. As such, these processes can be costly to acquire and operate and may also be difficult to carry out in the field.

Accordingly, the applicants have discovered that there is a need for a handheld or at least highly portable system that electrolytically and locally treats substrates that minimizes exposure to the chemicals within the solutions, minimizes the cleanup required after the electrolytic coating has been applied, and reduces costs to apply the coatings.

BRIEF SUMMARY OF SOME ASPECTS OF THE DISCLOSURE

The applicants also believe they have discovered a number of the problems and issues identified in the Background above. Accordingly, they have invented a number of embodiments of a handheld, light weight, and/or portable reactive electrochemical application system configured to apply a reactive chemical solution or a reactive chemistry to a surface. In some embodiments, the reactive electrochemical application systems include a device capable of selectively applying a hydrogel infused with a reactive chemical solution to a particular, localized portion of a substrate surface, applying a current across the hydrogel and the localized substrate surface, and anodizing, electroplating, or forming a conversion coating on the localized substrate surface.

In some embodiments, the reactive electrochemical application systems are small and/or portable such that an operator (which could be a person, robot, or machine) can ergonomically transport the handheld reactive electrochemical application systems to a repair location, manipulate such systems to apply the hydrogel to the substrate, and maintain the hydrogel on the substrate until the substrate has been locally treated. Thus, some instances of the reactive electrochemical application systems describe herein enable an operator to repair localized regions of a facility or equipment and, in some embodiments, without deconstructing the facility or equipment and without significant downtime of the facility or equipment.

In some embodiments, the handheld reactive electrochemical application systems may include a removable and, in some embodiments, disposable applicator that enables quick and easy repairs of a facility, equipment, or substrate. In some applications, the manipulatable reactive electrochemical application systems include a head configured to quickly and easily receive the applicator such that an unskilled operator can simply snap or otherwise place the applicator on the head prior to use. The head also includes an electrode that can be manipulated to contact an infused hydrogel when the applicator is snapped or otherwise mounted or secured onto the head. Such reactive electrochemical application systems also include an electrical conductor that attaches to, or otherwise contacts or can electrically communicate with, the substrate. In some embodiments, during operations, the operator: snaps or otherwise mounts or secures the applicator onto the head; attaches a conductor or otherwise provides electrical communication to the substrate; applies the hydrogel to the substrate by pressing the infused hydrogel within the applicator onto the treatment area of the substrate; in cooperation with the electrical communication to the substrate, passes current through the substrate and the infused hydrogel; and in some embodiments optionally maintains the infused hydrogel on the substrate until the substrate has been locally treated, and removes the disposable applicator from the handheld reactive electrochemical application system by pulling the disposable applicator off of the head of the handheld reactive electrochemical application system. As such, in some applications, the reactive electrochemical application systems enable an unskilled operator to make quick and easy repairs to a facility or equipment without significant and costly downtime.

The reactive electrochemical application system can optionally include a hydrogel that contains the reactive chemical solution until the hydrogel and the reactive chemical solution contact the surface to be treated. The handheld reactive electrochemical application system also includes a power supply configured to pass a current through the hydrogel and the treatment surface. The hydrogel enables the reactive chemical solution to contact the treatment surface such that the reactive chemical solution reacts with the treatment surface to complete a desired chemical, physical, and/or mechanical transformation when the current is passed through the hydrogel and the treatment surface. The hydrogel may be configured to contain any reactive chemistry, including, in some embodiments, hazardous chemistries, provided the hydrogel does not unfavorably react with the reactive chemistry prior to application on the treatment surface and enables the reactive chemistry to contact and react with the treatment surface. The reactive electrochemical application systems contain the reactive chemical solution in the hydrogel, apply the reactive chemical solution to the treatment surface such that the reactive chemical solution reacts when the current is passed through the hydrogel and the treatment surface, and/or applied the reactive chemical solution in a manner that reduces waste, reduces mess, and reduces exposure to the reactive chemical solution.

In some embodiments, the reactive chemical solution typically includes a conversion coating solution, an anodizing solution, and/or an electroplating solution that can be used to form coatings. The reactive chemical solution is used to form a protective coating on a metal substrate and the handheld reactive electrochemical application system is used to apply the reactive chemical solution to the metal substrate. In some embodiments, the coating generally passivates the metal surface or, in other words, makes it less susceptible to corrosion and/or other undesirable reactions in the future.

Conversion coatings may be formed on the treatment surface of metals through the use of hydrogels that have been infused with a conversion coating solution and with a current passed through the hydrogel, the treatment surface of metals may be anodized through the use of hydrogels that have been infused with an anodizing solution and with a current passed through the hydrogel, and the treatment surface of metals may be electroplated through the use of hydrogels that have been infused with an electroplating solution and with a current passed through the hydrogel. The reactive chemical solution is infused into the hydrogel. The protective coating may then be formed on the metal substrate by placing the hydrogel on the treatment surface of the metal substrate for a period of time, passing a current through the hydrogel and the metal substrate, allowing the reactive chemical solution to diffuse out of the hydrogel, onto the treatment surface, react, and form the protective coating.

In some applications, the reactive electrochemical application system is easy to use and minimizes cleanup. Some hydrogels infused with an active substance are easy to handle and use. Hydrogels can often eliminate the need for liquid containers of the reactive chemical solution and/or reduce or eliminate chemicals running off (e.g., dripping off) the treatment surface. Some embodiments of the system can be applicable to preparatory chemistries as well—cleaners, activators, etc., so that, in some applications, the application and ultimate formation of the resulting coating does not waste chemicals and/or improves the safety of forming the coating because, in some instances, the materials are relatively contained and minimize the chance that the chemistry will spill on the user or on equipment and/or areas of the substrate that the chemistry may detrimental or otherwise unwanted.

There are other novel aspects and features of this disclosure. They will become apparent as this specification proceeds. Accordingly, this Brief Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This Summary and the Background sections are not intended to identify key concepts or essential aspects of the disclosed subject matter, nor should they be used to constrict or limit the scope of the claims. For example, the scope of the claims should not be limited based on whether the claimed subject matter includes any or all aspects noted in the Summary and/or addresses any of the issues noted in the Background sections.

DRAWINGS

The preferred and other embodiments are disclosed in association with the accompanying drawings in which:

FIG. 1 illustrates an exemplary block flow diagram of a handheld reactive electrochemical application system in accordance with aspects of the present disclosure;

FIG. 2 illustrates an exemplary schematic diagram of the handheld reactive electrochemical application system illustrated in FIG. 1 in accordance with aspects of the present disclosure;

FIG. 3 illustrates another exemplary schematic diagram of the handheld reactive electrochemical application system illustrated in FIG. 1 in accordance with aspects of the present disclosure;

FIG. 4 illustrates an exemplary schematic diagram of a disposable applicator without a hydrogel for use with the handheld reactive electrochemical application system illustrated in FIG. 1 in use in accordance with aspects of the present disclosure;

FIG. 5 illustrates an exemplary schematic diagram of the disposable applicator illustrated in FIG. 4 attached to the handheld reactive electrochemical application system illustrated in FIG. 1 in accordance with aspects of the present disclosure;

FIG. 6 illustrates an exemplary schematic diagram of the disposable applicator illustrated in FIG. 4 including a hydrogel and attached to the handheld reactive electrochemical application system illustrated in FIG. 1 in accordance with aspects of the present disclosure;

FIG. 7 illustrates an exemplary schematic diagram of the handheld reactive electrochemical application system illustrated in FIG. 1 treating a substrate in accordance with aspects of the present disclosure;

FIG. 8 illustrates a side schematic view of a removable and disposable applicator in accordance with aspects of the present disclosure;

FIG. 9 illustrates the handheld reactive electrochemical application system illustrated in FIG. 1 in an anodizing configuration in accordance with aspects of the present disclosure;

FIG. 10 illustrates the handheld reactive electrochemical application system illustrated in FIG. 1 in an electroplating configuration in accordance with aspects of the present disclosure;

FIG. 11 illustrates the handheld reactive electrochemical application system illustrated in FIG. 1 in an electrolytic conversion coating configuration in accordance with aspects of the present disclosure;

FIG. 12 illustrates a hydrogel illustrated in FIG. 1 in accordance with aspects of the present disclosure;

FIG. 13 is a schematic showing a 6061 aluminum alloy with a coating applied by a KM50K® hydrogel applicator from Katecho® including an anodizing solution in accordance with aspects of the present disclosure;

FIG. 14 is a schematic showing titanium with a coating applied by the KM50K® hydrogel applicator from Katecho® including the sodium bicarbonate solution in accordance with aspects of the present disclosure;

FIG. 15 is a schematic showing steel with a coating applied by the KM50K® hydrogel applicator from Katecho® including the nickel (II) sulfate solution in accordance with aspects of the present disclosure; and

FIG. 16 is a schematic showing a 6061 aluminum alloy with a coating applied by the KM50K® hydrogel applicator from Katecho® including the conversion coating solution in accordance with aspects of the present disclosure.

DETAILED DESCRIPTION

Reactive Electrochemical Application System

With reference to FIGS. 1-7, in the some embodiments, the reactive electrochemical application system 100 is hand-holdable, portable, small, and lightweight and includes a body 102 including a handle 104, a power supply 106 attached to the body 102, a head 108 attached to the body 102, an electrode 110 attached to the head 108, a removable and disposable applicator 112 attached to the head 108 and including a hydrogel 114, and a wire/electrode 116 attached to the head 108. The reactive electrochemical application system 100 may further include other components as described herein or as otherwise desired. For example, the power supply 106 may further include a controller 118 (shown in FIG. 4) configured to control one or more electrical variables of the system. The reactive electrochemical application system 100 is configured to apply a coating to a substrate 120. Specifically, the reactive electrochemical application system 100 is configured to electroplate the substrate 120, form an electrochemical conversion coating on the substrate 120, and/or anodize the substrate 120. The type of coating formed on the substrate 120 is dependent on the solution within the hydrogel and the arrangement of the reactive electrochemical application system 100.

The body 102 of the reactive electrochemical application system 100 is configured to connect each piece of the reactive electrochemical application system 100 together with an overall shape configured to achieve a specific goal. Specifically in the illustrated embodiment, the body 102 is compact such that the reactive electrochemical application system 100 is easily and manually operated by an operator in a handled or otherwise manipulated manner to, in some systems, make repairs close to the operator and in tight spaces. For example, the reactive electrochemical application system 100 illustrated in FIGS. 1-7 may be used to repair aircraft or industrial facilities where the repair has to take place in tight spaces. In some instances, the body 102 can be relatively small and maneuverable such that it can fit in these tight spaces to make the repair without having to disassemble the aircraft or the facility. In alternative embodiment, the body 102 may have a different shape to, in some instances, accomplish a different task. For example, in an alternative embodiment, the body 102 may have an elongated shape that enables it to make repairs in high, hard to reach places. In another alterative embodiment, the body 102 may be ring shaped such that the body 102 can be wrapped around pipes to repair pipes in chemical facilities. As such, the shape of the body 102 may be changed to accommodate different equipment or other environmental factors.

As shown in the illustrated embodiments, the handle 104 has a generally ergonomic shape configured to conform to the shape of an operator's hand or other grasping structure. In the illustrated embodiment, the handle 104 is shaped to accommodate a single hand or grasping structure of the operator. In an alternative embodiment, the handle 104 may be shaped to accommodate both hands of the operator. In some implementations, the handle 104 may include padding to increase the comfort of the operator. In alternative embodiments, the handle 104 may have any shape that enables the reactive electrochemical application system 100 to operate as described herein or as otherwise desired.

In some implementations, the power supply 106 may be any power supply that enables the reactive electrochemical application system 100 to operate as described herein or as otherwise desired. In some embodiments, the power supply 106 may be a direct current power supply. In alternative embodiments, the power supply 106 may be an alternating current power supply. In most embodiments, the power supply 106 is a direct current power supply. In some embodiments, the body 102 defines a battery cavity 122 and the power supply 106 includes a battery sized and shaped to be received in the battery cavity 122. In some instances, the battery 106 is inserted into the battery cavity 122 such that the battery 106 is electrically coupled to the reactive electrochemical application system 100 and capable of passing current though the hydrogel 114 and the substrate 120.

Additionally, it has surprisingly been found that at least some embodiments of the hydrogels 104 described herein are capable of withstanding the typical voltages applied for each of the processes described herein. As such, the power supply 106 is configured to apply a voltage of approximately 0.1 Volts (V) to approximately 150 V, depending on the process, the substrate, the thickness of the layer to be deposited on the substrate, and, for example, the metal to be deposited on the substrate. In alternative embodiments, the power supply 106 may be configured to apply any voltage to the substrate and the hydrogel that enables the reactive electrochemical application system 100 to operate as described herein or as otherwise desired.

In some instances, the controller 118 may control the power supply 106 depending on the process, the substrate, the thickness of the layer to be deposited on the substrate, and, for example, metal to be deposited on the substrate. Specifically, in some systems, the controller 118 may be configured to control the voltage of the power supply 106. In some implementations, the controller 118 includes a buck-boost converter configured to change the voltage of the power supply 106 to a voltage that is required for the selected process. For example, the battery 106 may be a standard voltage battery but the selected process may require a different voltage. In some embodiments, the buck-boost converter converts the voltage from the battery 106 to the voltage required by the process by either increasing or decreasing the voltage. As such, the reactive electrochemical application system 100 can have a single battery 106 that is capable of powering each of the processed described herein. In alternative embodiments, the power supply 106 may receive power from a plug in a typical wall and may convert the alternating current to direct current before delivering power to the remainder of the reactive electrochemical application system 100.

In some systems, the controller 118 may further include a polarity switch 124, at least one indicator 126, at least one switch 128, and at least one other control. The polarity switch 124 is configured to change the polarity of the hydrogel 114 and the substrate 120. The anodizing configuration and the electroplating configuration each require a different polarity configuration for the hydrogel 114 and the substrate 120. In some application, the polarity switch 124 enables the polarity to be switched such that the reactive electrochemical application system 100 is capable of performing both anodizing and electroplating. In some embodiments, the switch 128 is configured to turn on the reactive electrochemical application system 100 and may be further configured to control the reactive electrochemical application system 100. For example, in some embodiments, the reactive electrochemical application system 100 may include other switches or controls that electrically control the reactive electrochemical application system 100 such as voltage controls. In some implementations, the reactive electrochemical application system 100 may further include at least one indicator 126 configured to indicate the status of the reactive electrochemical application system 100. In some application, the indicator 126 may be a digital indicator that displays the voltage of the reactive electrochemical application system 100. In some systems, the reactive electrochemical application system 100 may further include other indicators 126 that indicate other electrical properties of the reactive electrochemical application system 100.

In some instances, the head 108 is attached to the body 102 and is configured to be rotatable relative to the body 102. In some embodiments, the rotatability of the head 108 enables the head 108 and the body 102 to be ergonomically positioned such that the reactive electrochemical application system 100 is capable of performing the processes described herein. In some embodiments, the head 108 includes electrical connections between the electrode 110 and the wire/electrode 116 and the power supply 106. In some implementations, the head 108 is sized and shaped to facilitate repairing a localized area of the substrate 120. In some application, the head 108 may be smaller or larger than illustrated in FIGS. 1-7 to repair areas of different sizes on the substrate 120. In some systems, the head 108 has a rectangular or square shape. In alternative embodiments, the head 108 may have a different shape, such as a circular shape, to repair localized areas of different shapes. In some embodiments, the area of the electrode 110 is approximately 1-5 square inches. In alternative embodiments, the area of the electrode 110 may be approximately 0.5 square feet up to approximately 1 square foot. The area of the electrode 110 is limited by the ability of the battery 106 to supply current. The area described herein is based on a current density of 20 amperes per square foot and dwell times of 30 to 60 minutes. A more powerful battery would enable the area described herein to increase. For the handheld unit described herein, the areas of the electrode 110 would probably not exceed approximately 1 square foot. However, industrial applications may include larger electrodes connected to a more powerful power source. As such, this disclosure is not limited to electrodes of the sizes described herein.

In some embodiments, the head 108 has been additively manufactured (3D printed) into a square shape to repair localized areas of the substrate 120. In some instances, the reactive electrochemical application system 100 may be designed and constructed such that the head 108 may be additively manufactured by the user in different shapes such that the shape of the head 108 may be specially designed for a specific use. Furthermore, in some embodiments, the electrode 110 may be detachable from the head 108 and may also be shaped according to the specific use. Additionally, in some implementations, the head 108 may be configured with ridges (not shown) that enable the removable and disposable applicator 112 to be removably attached to the head 108 and maintained on the head 108. In alternative embodiment, the removable and disposable applicator 112 may be attached to and maintained on the head 108 by any device that enables the reactive electrochemical application system 100 to operate as described herein or as otherwise desired.

As described above, in some application, the electrode 110 may be removably attached to the head 108 such that the electrode 110 may be changed based on the process to be carried out using the reactive electrochemical application system 100. An electrode is typically an electrical conductor used to make contact with a nonmetallic part of a circuit. In some embodiments, the electrode 110 is formed of an inert material, such as graphite, titanium, platinized steel, and aluminum that will not react with the hydrogel or interfere with the processes described herein. In other embodiments, such as the electroplating embodiment, the electrode 110 is formed of the metal that is to be plated on the substrate 120. As such, the electrode 110 may be selected and configured based on the selected process. In some systems, the electrode 110 is sized and shaped as described above with respect to the size and shape of the head 108 to interface with the hydrogel 114 within the removable and disposable applicator 112.

In some embodiments, the processes described herein may release gasses that are byproducts of the reactions at the treatment surface of the substrate. In some embodiments, the gases may interfere with the deposition process, reducing the overall efficiency of the process. In some instances, the electrode 110 and the hydrogel 114 are small enough such that the gasses escape from the sides of the hydrogel 114. However, if the electrode 110 and the hydrogel 114 are too large to adequately transport the gases to the sides, another mechanism of releasing the gases is required to maintain the efficiency of the deposition process. As shown in FIGS. 1-7, the electrode 110 includes at least one hole 130 for releasing gasses from the electrode 110 and the hydrogel 114. In some application, the electrode 110 includes a plurality of holes 130 for releasing gases from the electrode 110 and the hydrogel 114. In some implementations, the holes 130 are large enough to release gases from the electrode 110 and the hydrogel 114 but small enough that the reactive chemical solution can flow into the hole 130 and treat the substrate within the hole 130. In alternative embodiments, the electrode 110 may include any number of holes of any size that enable the electrode 110 to operate as described herein or as otherwise desired.

In some embodiments, the wire/electrode 116 include a wire attached to the power supply 106 and the substrate 120 as described herein or as otherwise desired. In some embodiments, the wire/electrode 116 may include a connector configured to connect the wire/electrode 116 to the substrate 120. For example, in some application, the wire/electrode 116 may include a conductive clip, a conductive glue, a magnet, a hydrogel, and/or any connector configured to electrically couple the wire/electrode 116 to the substrate 120.

In some embodiments, the removable and disposable applicator 112 includes a frame 132 and the hydrogel 114 positioned within the frame 132. In some instances, the frame 132 has a generally rectangular or square shape that corresponds to the size and shape of the head 108. In alternative embodiments, the frame 132 may be sized and shaped to correspond to the size and shape of the head 108 and the electrode 110. In some implementations, the frame 132 also defines an opening 134 that enables the hydrogel 114 to extend through the opening 134 when the electrode 110 presses against the hydrogel 114. More specifically, when the frame 132 is attached to the head 108, the electrode 110 is positioned on the head 108 such that the electrode 110 presses against the hydrogel 114 and extends the hydrogel 114 through the opening 134 towards the substrate 120.

FIG. 8 illustrates a side schematic view of an embodiment of a removable and disposable applicator 112 in accordance with aspects of the present disclosure. In some systems, the removable and disposable applicator 112 includes the frame 132 and the hydrogel 114. In some embodiments, the removable and disposable applicator 112 may optionally also include a first liner or cover 802 and a second liner or cover 804. In addition, the removable and disposable applicator 112 may include additional layers not illustrated in FIG. 8. For example, in some application, the hydrogel 114 may include a plurality of hydrogel layers to absorb and deposit a plurality of solutions. Additionally, in some embodiments, the first liner or cover 802 and the second liner or cover 804 may also include plurality of layers configured for strength, moisture retention, and adhesion such as, but not limited to, a scrim and/or a non-woven scrim. In some embodiments, the scrim and/or the non-woven scrim may be part of the first liner or cover 802, the hydrogel 114, and/or the second liner or cover 804 to provide additional support for the removable and disposable applicator 112.

In some implementations, the first liner or cover 802 is configured to hold, maintain, and protect the hydrogel 114 in place in the frame 132 and to be removed from the hydrogel 114 prior to application of the hydrogel 114 to the metal substrate. In some instances, the first liner or cover 802 includes an inert plastic or polymer that does not absorb the hydrogel or the solution. In some systems, the first liner or cover 802 is flexible but strong enough to hold the hydrogel and withstand the elements for short durations. As such, the first liner or cover 802 may include any material that is strong enough to hold the hydrogel 114, flexible enough to apply the hydrogel 114 over a metal substrate, and resistant to absorption of the solution. In some application, the first liner or cover 802 may include polyethylene, polyester, polypropylene, polyethylene terephthalate, medium-density polyethylene, and/or polytetrafluoroethylene. Additionally, in some embodiments, the first liner or cover 802 may include a carbon fiber cloth that is conductive but capable of providing structure to the hydrogel 114.

Similarly, in some embodiments, the second liner or cover 804 is also configured to hold and maintain the hydrogel 114 in place. However, in some embodiments, the second liner or cover 804 is configured to be removed from the hydrogel 114 prior to application of the hydrogel 114 to the metal substrate. In some implementations, the second liner or cover 804 also includes an inert plastic or polymer that does not absorb the hydrogel or the reactive chemical solution. In some embodiments, the second liner or cover 804 is also flexible but strong enough to hold the hydrogel and withstand the elements for short durations. As such, in some application, the second liner or cover 804 may include any material that is strong enough to hold the hydrogel 114 and resistant to absorption of the reactive chemical solution. In some systems, the second liner or cover 804 may include the same material as the first liner or cover 802. In some instances, the second liner or cover 804 may include polyethylene, polyester, polypropylene, polyethylene terephthalate, medium-density polyethylene, carbon fiber cloth, and/or polytetrafluoroethylene.

As described herein, in some embodiments, the removable and disposable applicator 112 is configured to hold the hydrogel 114 including the conversion coating solution until the first and second liner or cover 802 and 804 have been removed and the hydrogel 114 contacts a metal substrate. In some implementations, the reactive chemical solution then reacts with the metal substrate, diffuses toward the metal substrate as the reaction consumes the reactive chemical solution, and desorbs from the hydrogel 114 onto the metal substrate to react with the metal substrate. In some embodiments, the hydrogel 114 of the removable and disposable applicator 112 is then removed from the substrate and disconnected from the power supply 106. In some application, the removable and disposable applicator 112 may be disposable and sold as a unit. As such, when the removable and disposable applicator 112 has been used, it is simply properly disposed of and a new removable and disposable applicator 112 is used for a new treatment.

In some systems, the reactive electrochemical application system 100 may further include a computing device (not shown) configured to control any and all aspects of the processes described herein. For example, in some embodiments, the computing device may be configured to control the voltage such that the reactive electrochemical application system 100 applies a variable voltage to optimize the processes described herein. Additionally, in some instances, the reactive electrochemical application system 100 may be equipped with at least one camera for documenting the repair, inspecting the equipment or facility to identify where repairs need to take place, monitoring the repair process, and/or any other use. In some implementations, the camera may be any device configured to detect electromagnetic radiation including visual cameras, IR cameras, and/or any other type of camera.

Furthermore, in some embodiments, the camera may be used to automate portions of the repair process. For example, in some application, the camera may be positioned to view the repair area, may include software that recognizes what steps have been completed, and may provide instructions to the operator on which steps need to be completed next. In some embodiments, the computing device may include GIS functionality that identifies where the reactive electrochemical application system 100 is located in a facility and directs the operator where to go to complete the next repair. In some systems, the operator may then take a picture of the location and the computing device will confirm that the operator is in the correct location. Alternatively, in some embodiments, the operator may use the camera to scan the equipment to be repaired to confirm they are in the correct location. In some implementations, the removable and disposable applicator 112 may include a QR code that the camera scans to identify which process the removable and disposable applicator 112 is to be used for and that it matches the needs of the repair process. In some instances, the computing device may then use the camera to monitor and direct the operator during the repair process. Once the repair has been completed, the camera and the computing device may then be used to document the repair (take pictures of the repair) and upload the documentation to a database.

FIG. 9 illustrates an embodiment of the reactive electrochemical application system 100 in an anodizing configuration. Specifically, in some application, the hydrogel 114 is infused with an anodizing solution, the electrode 110 is attached to the hydrogel 114 such that the hydrogel 114 is electrically negative, or the cathode, and the wire/electrode 116 is attached to the substrate 120 such that the substrate 120 is electrically positive, or the anode. In some embodiments, the power supply 106 passes a current, usually direct current, through the hydrogel 114 and the substrate 120. In some embodiments, the current causes hydrogen to be released within the anodizing solution (cathode) and oxygen to be released at the treatment surface of the substrate 120 which creates a build-up of an anodic oxide (anodic aluminum oxide) to be formed on the treatment surface of the substrate 120. In some systems, the anodic oxide is formed from the substrate 120 and the reactions and chemistries are significantly different than the reactions and chemistries of electroplating and electrolytic conversion coating described below. In some embodiments, the aluminum oxide on the treatment surface of the substrate 120 provides resistance to corrosion and increases the adhesion of paints, primers, and glues to the substrate 120.

In some implementations, the reactive electrochemical application system 100 in the anodizing configuration illustrated in FIG. 9 may be configured to perform any anodizing process such that the anodized substrate satisfies any anodizing specification. For example, in some application, the reactive electrochemical application system 100 in the anodizing configuration may produce anodized substrates that satisfy U.S. Military Specifications MIL-A-8625 and MIL-A-63576 and industry specifications such as AMS 2469, AMS 2470, AMS 2471, AMS 2472, AMS 2482, ASTM B580, ASTM D3933, ISO 10074, and BS 5599. In some embodiments, the reactive electrochemical application system 100 in the anodizing configuration may be configured to perform any anodizing process including, but not limited to, chromic acid anodizing, sulfuric acid anodizing, organic acid anodizing, phosphoric acid anodizing, boric and tartaric acid anodizing, plasma electrolytic oxidation anodizing, and/or any other anodizing process. The substrate 120 in the anodizing configuration is typically aluminum. However, in alternative configurations, the substrate 120 in the anodizing configuration may also be magnesium, titanium, niobium, tantalum, zinc, and/or any other metal capable of being anodized.

FIG. 10 illustrates an embodiment of the reactive electrochemical application system 100 in an electroplating configuration. Specifically, in some applications, the hydrogel 114 is infused with an electroplating solution including dissolved salts of the metal that is to be plated onto the substrate 120, the electrode 110 is attached to the hydrogel 114 such that the hydrogel 114 is electrically positive, or the anode, and the wire/electrode 116 is attached to the substrate 120 such that the substrate 120 is electrically negative, or the cathode. In some instances, the power supply 106 passes a current, usually direct current, through the hydrogel 114 and the substrate 120. In some embodiments, the electroplating solution includes dissolved metallic cations and the current causes the dissolved metallic cations to be reduced at the treatment surface of the substrate 120 (the cathode) into the metal in the zero-valence state, forming a metal coating on the substrate 120. In some systems, the anode (the electrode in contact with the hydrogel 114) may be made of the same metal that is to be plated onto the substrate 120 and the current causes metal ions within the anode to be oxidized into dissolved cations. In some implementations, the dissolved metallic cations are then reduced at the treatment surface of the substrate 120 (the cathode) into the metal in the zero-valence state, forming a metal coating on the substrate 120. In some embodiments, the metallic plating is formed on the substrate 120 and the reactions and chemistries are significantly different than the reactions and chemistries of anodizing and electrolytic conversion coating described below. In some applications, the metal plating on the treatment surface of the substrate 120 provides resistance to corrosion to the substrate 120. In some embodiments, the anode (the electrode in contact with the hydrogel 114) may be made of the same metal that is to be plated onto the substrate 120 and may contribute cations to the electroplating solution during the plating process. In other embodiments, the anode (the electrode in contact with the hydrogel 114) may be made of an inert conductive material such as graphite.

In some instances, the reactive electrochemical application system 100 in the electroplating configuration illustrated in FIG. 10 may be configured to perform any electroplating process such that the electroplated substrate satisfies any electroplating specification. For example, in some embodiments, the reactive electrochemical application system 100 in the electroplating configuration may produce electroplated substrates that satisfy U.S. Military Specifications such as MIL-G-45204C, MIL-C-14550B, MIL-T-10727C, FED QQ-S-365D, QQ-C-320, and MIL-STD-171 and industry specifications such as ISO 2081:2008, ASTM B633, AMS-QQ-P-416. The reactive electrochemical application system 100 in the electroplating configuration may be configured to perform any electroplating process including, but not limited to, strike electroplating, pulse electroplating, brush electroplating, barrel electroplating, and/or any other electroplating process. The substrate 120 in the electroplating configuration is typically any metal. However, in alternative configurations, the substrate 120 in the electroplating configuration may also include other materials such as plastics, organic materials, fabrics, and/or any other metal capable of being electroplated.

Large electroplating facilities typically heat the electroplating solution in order to increase the efficiency of the electroplating process. However, it has surprisingly been found that the reactive electrochemical application system 100 in the electroplating configuration illustrated in FIG. 10 does not require heating of the hydrogel 114 or the electroplating solution within the hydrogel 114 in order to achieve similar or the same efficiencies. Without being bound by theory, it is believed that the increased contact between the substrate and the electroplating solution caused by the hydrogel 114 increases the efficiency of the electroplating process without heating the electroplating solution. That is, heating the solution in large electroplating facilities increases the reactivity of the solution towards the substrate and, in the reactive electrochemical application system 100 in the electroplating configuration illustrated in FIG. 10, the increased contact caused by the hydrogel 114 increases the contact between the solution and the substrate without heating. Heating the solution in large electroplating facilities typically considerably increases costs and the reactive electrochemical application system 100 in the electroplating configuration illustrated in FIG. 10 decreases operating costs by eliminating or reducing the requirement to heat the electroplating solution.

FIG. 11 illustrates an embodiment of the reactive electrochemical application system 100 in an electrolytic conversion coating configuration. Specifically, in some systems, the hydrogel 114 is infused with a conversion coating solution, the electrode 110 is attached to the hydrogel 114 such that the hydrogel 114 can be electrically positive or negative (anode or cathode) depending on the chemistry of the conversion coating solution, and the wire/electrode 116 is attached to the substrate 120 such that the substrate 120 also can be electrically positive or negative (anode or cathode) depending on the chemistry of the conversion coating solution. In some systems, the power supply 106 passes a current, usually direct current, through the hydrogel 114 and the substrate 120. In some applications, the current causes a redox reaction between chromium and the metal hydroxide ions to create a buildup of precipitates on the treatment surface of the substrate 120. In some implementations, the precipitates are formed from the substrate 120 and the reactions and chemistries are significantly different than the reactions and chemistries of electroplating and anodizing described herein. In some embodiments, the precipitates on the treatment surface of the substrate 120 provides resistance to corrosion and increases the adhesion of paints, primers, and glues to the substrate 120.

In some embodiments, the reactive electrochemical application system 100 in the electrolytic conversion coating configuration illustrated in FIG. 11 may be configured to perform any electrolytic conversion coating process such that the substrate satisfies any conversion coating specification. For example, in some embodiments, the reactive electrochemical application system 100 in the electrolytic conversion coating configuration may produce substrates that satisfy U.S. Military Specifications MIL-DTL-81706B Class 1A and Class 3 or the less stringent requirements of MIL-DTL-5541F Class 1A and Class 3. The reactive electrochemical application system 100 in the electrolytic conversion coating configuration may be configured to perform any electrolytic conversion coating process. The substrate 120 in the electrolytic conversion coating configuration is typically aluminum. However, in alternative configurations, the substrate 120 in the electrolytic conversion coating configuration may also be magnesium, titanium, niobium, tantalum, zinc, and/or any other metal capable of being treated.

Hydrogels

In some instances, the hydrogel 114 typically includes three-dimensional networks of hydrophilic polymers that swell in a fluid and contain a large amount of the fluid relative to their volume while maintaining the structure due to chemical or physical cross-linking of individual polymer chains. Hydrogels typically include at least 10% the fluid of the total weight (or volume), are hydrophilic, and are flexible such that hydrogels can conform to the shape of a treatment surface they are positioned on. The hydrophilicity of the network is due to the presence of hydrophilic groups such as —NH2, —COOH, —OH, —CONH2, —CONH—, and —SO3H.

In some applications, hydrogels may undergo a volume phase transition or gel-sol phase transition in response to certain physical and chemical stimuli. The physical stimuli may include temperature, electric and magnetic fields, solvent composition, light intensity, and pressure, and the chemical stimuli may include chemical reactions, pH, ions, and specific chemical compositions. Most conformational transitions are reversible, and the hydrogels are capable of returning to their initial state after a reaction as soon as the trigger is removed. The response of hydrogels to external stimuli is typically determined by the nature of the monomer, charge density, pendant chains, and the degree of cross-linkage. The magnitude of response is also typically directly proportional to the applied external stimulus.

In some systems, the hydrogel 114 includes a polymer hydrogel that is configured to: (1) absorb the solution, (2) desorb the solution when the hydrogel 114 contacts the substrate 120, and (3) is inert with respect to the solution. As such, in some implementations, the hydrogel 114 may include any network of hydrophilic polymers that can swell and hold the solution.

For example, in some embodiments, the hydrogel 114 may include any of the following hydrogel types: homopolymeric hydrogels, cationic hydrogels, natural hydrogels, physically cross linked hydrogels, amorphous hydrogels, copolymeric hydrogels, anionic hydrogels, synthetic hydrogels, chemically cross linked hydrogels, semicrystalline hydrogels, interpenetrating hydrogels, nonionic hydrogels, hybrid hydrogels, crystalline hydrogels, hydrocolloid aggregate hydrogels, and/or any other type of hydrogel. If the hydrogel is a synthetic hydrogel, the hydrogel 114 may include poly(vinyl alcohol), polyethylene oxide, poly(acrylic acid), poly(hydroxyethyl methacrylate), poly(glyceryl methacrylate), poly(hydroxypropyl methacrylate), polyacrylamide, poly(ethylene glycol), poly(vinylpyrrolidone), poly(ethyleneimine), polyhydric alcohol, polyacrylamide, polysaccharide, and/or any other type of polymer. If the hydrogel 114 includes a natural hydrogel, the hydrogel 114 may include chitosan, alginate, collagen, silk fibroin, hyaluronic acid, fibrin, gelatin, agarose, and/or any other type of natural hydrogel. The hydrogel 114 may include some commercially available hydrogels including Actiformcool®, Aquaflo®, Clearsite®, Geliperm®, Hydrosorb®, Novogel®, Primskin®, Suprasorb G®, AquaDerm®, Tegraderm®, and/or any other commercially available hydrogel.

In some embodiments, the processes described herein may release gasses that are byproducts of the reactions at the treatment surface of the substrate. In some embodiments, the gases may interfere with the deposition process, reducing the overall efficiency of the process. In some applications, the hydrogel 114 is small enough such that the gasses escape from the sides of the hydrogel 114. However, if the hydrogel 114 is too large to adequately transport the gases to the sides, another mechanism of releasing the gases is required to maintain the efficiency of the deposition process. FIG. 12 illustrates a hydrogel 1200 with at least one hole 1202 formed in the hydrogel 1200 for releasing gasses from the hydrogel 1200. In some systems, the hydrogel 1200 includes a plurality of holes 1202 for releasing gases from the hydrogel 1200. In some instances, the holes 1202 are large enough to release gases from the hydrogel 1200 but small enough that the reactive chemical solution can flow into the hole 1202 and treat the substrate within the hole 1202. In alternative embodiments, the hydrogel 1200 may include any number of holes of any size that enable the hydrogel 1200 to operate as described herein or as otherwise desired.

Solutions—Anodizing Solutions

In the anodizing configuration, the embodiments of the reactive chemical solution include an anodizing solution. The anodizing solution depends on the substrate to be anodized, the thickness of the layer to be formed on the substrate, and the dye to be formed on the substrate (if any). The most common type of anodizing solution is an acidic solution, and the most common type of acidic anodizing solution is a sulfuric acid anodizing solution. Specifically, if the substrate is aluminum, the most common type of anodizing solution is the sulfuric acid anodizing solution. The concentration of sulfuric acid in the sulfuric acid anodizing solution is typically approximately 10% to approximately 30 % depending on the desired thickness of the layer on the substrate. In alternative embodiments, the acidic anodizing solution may be any type of acidic anodizing solution including chromic acid, organic/weak acids (malic acid, oxalic acid, sulfosalicylic acid, and sulfonated aromatic compounds), phosphoric acid, and/or any other type of acid configured to anodize a substrate. If the substrate is titanium, the most common type of anodizing solution is sodium bicarbonate and the concentration of sodium bicarbonate in the anodizing solution may be approximately 1% to approximately 50%. However, a sulfuric acid anodizing solution may also be used for titanium anodizing. In other embodiments, the anodizing solution may include a boric or tartaric acid bath.

Solutions—Electroplating Solutions

In the electroplating configuration, the embodiments of the reactive chemical solution include an electroplating solution. The electroplating solution depends on the substrate to be electroplated and the thickness of the layer to be formed on the substrate. The most common type of electroplating solution is an electrolytic solution including positive ions (cations) of the metal to be plated on the substrate. Specifically, if the substrate is steel and the metal plating is nickel, the most common type of electroplating solution is a nickel salt. More specifically, if the substrate is steel and the metal plating is nickel, the most common type of electroplating solution is nickel(II) sulfate. The concentration of nickel(II) sulfate in the electroplating solution is typically approximately 10% to approximately 50 % depending on the desired thickness of the layer on the substrate. In alternative embodiments, the electroplating solution may be any type of electrolytic solution configured to electroplate a substrate.

Solutions—Conversion Coating Solutions

In some implementations, the reactive chemical solution includes a chromium compound for forming a conversion coating on the metal substrate. The chromium compound may be any type of chromium compound including, but not limited to, a trivalent chromium compound, a hexavalent chromium compound, and a non-hexavalent chromium compound. In alternative embodiments, the reactive chemical solution may include a non-chromium compound that is capable of forming a conversion coating on the metal substrate. More specifically, in some embodiments and in the Examples described herein, the reactive chemical solution includes a trivalent chromium compound.

In some embodiments, the trivalent chromium compound can be any suitable trivalent chromium compound capable of forming a conversion coating on the metal substrate. Examples of suitable trivalent chromium compounds can be found in the patents incorporated by reference at the end of the description.

In some applications, the trivalent chromium compound can be a water-soluble trivalent chromium compound such as a trivalent chromium salt. It is generally desirable to use chromium salts that provide anions that are not as corrosive as chlorides. Examples of such anions include nitrates, sulfates, phosphates, and acetates. In a preferred embodiment, the trivalent chromium compound is a trivalent chromium sulfate. Examples of such compounds include Cr₂(SO₄)₃, (NH₄)Cr(SO₄)₂, or KCr(SO₄)₂.

It should be appreciated that the conversion coating solution can include one or multiple trivalent chromium compounds. For example, in one embodiment, the conversion coating solution includes a single trivalent chromium compound. In another embodiment, the conversion coating solution includes two, three, four, or more trivalent chromium compounds.

The conversion coating solution can include any suitable quantity of the trivalent chromium compound. Examples of suitable quantities can be found in the patents incorporated by reference at the end of the description. In some embodiments, the conversion coating solution includes approximately 0.1 g/liter (0.01 wt %) to approximately 20 g/liter (2 wt %) of the trivalent chromium compound, approximately 0.2 g/liter (0.02 wt %) to approximately 10 g/liter (1 wt %) of the trivalent chromium compound, or approximately 0.5 g/liter (0.05 wt %) to approximately 8 g/liter (0.8 wt %) of the trivalent chromium compound.

In other embodiments, the conversion coating solution includes at least approximately 0.1 g/liter (0.01 wt %) of the trivalent chromium compound, at least approximately 0.2 g/liter (0.02 wt %) of the trivalent chromium compound, or at least approximately 0.5 g/liter (0.05 wt %) of the trivalent chromium compound. In still other embodiments, the conversion coating solution includes no more than 20 g/liter (2 wt %) of the trivalent chromium compound, no more than 10 g/liter (1 wt %) of the trivalent chromium compound, or no more than 8 g/liter (0.8 wt %) of the trivalent chromium compound.

The conversion coating solution can include a zirconate compound that can be any suitable zirconate compound that is capable of facilitating the formation of a protective coating on a substrate. Examples of suitable zirconate compounds include alkali metal hexafluorozirconate compounds such as potassium hexafluorozirconate, sodium hexafluorozirconate, and fluorozirconic acid.

In some systems, the conversion coating solution comprises approximately 0.2 g/liter (0.02 wt %) to approximately 20 g/liter (2 wt %) of the zirconate compound, approximately 0.5 g/liter (0.05 wt %) to approximately 18 g/liter (1.8 wt %) of the zirconate compound, or approximately 1 g/liter (0.1 wt %) to approximately 15 g/liter (1.5 wt %) of the zirconate compound.

In some other embodiments, the conversion coating solution comprises at least approximately 0.2 g/liter (0.02 wt %) of the zirconate compound, at least approximately 0.5 g/liter (0.05 wt %) of the zirconate compound, or at least approximately 1 g/liter (0.1 wt %) of the zirconate compound. In yet other embodiments, the conversion coating solution comprises no more than approximately 20 g/liter (2 wt %) of the zirconate compound, no more than approximately 18.0 g/liter (1.8 wt %) of the zirconate compound, or no more than approximately 15 g/liter (1.5 wt %) of the zirconate compound.

Solutions-Dye Compounds

In some instances, the reactive chemical solutions described herein may include dye compounds to colorize the substrate. The dye compound (alternatively referred to as a pigment compound or colorant compound) can be any material that is compatible with the reactive chemical solution and the hydrogel chemistry and is capable of imparting a color to the metal substrate. In some implementations, the dye compound includes one or more metal atoms and in other embodiments it does not. In those embodiments where the dye compound includes one or more metal atoms, the metal atom can be present as part of a metal complex.

In some embodiments, the dye compound can include an azo dye, a chromium complex dye, an anthraquinoid dye, and/or a methine dye. In a preferred embodiment, the dye compound includes a metal complex azo dye, a chromium complex dye, and/or metal free azo dye. It should be appreciated that azo dyes include monoazo dyes, disazo dyes, and/or trisazos dyes.

Numerous other dye compounds can be used as long as they are compatible with the other constituents in the reactive chemical solution and the hydrogel. Examples of such dyes include those used to anodize aluminum and colorize textiles. Other examples include acid dyes, mordant dyes, metal-complex dyes, triphenylmethane dyes, xanthene dyes, wool dyes, silk dyes, direct dyes, reactive dyes, vat dyes, and the like. It is understood that these dyes may be classified in more than one way such as by structure or by typical use—e.g., a dye may be referred to as a chrome dye, a mordant dye, a wool dye, etc.

It should be appreciated that the reactive chemical solution can include one or multiple dye compounds including any quantity and/or combination of the dyes described above. For example, in some applications, a trivalent chromium conversion coating solution comprises approximately 0.1 g/liter (0.01 wt %) to approximately 20 g/liter (2 wt %) of the dye compound, approximately 0.2 g/liter (0.02 wt %) to approximately 10 g/liter (1 wt %) of the dye compound, or approximately 0.5 g/liter (0.05 wt %) to approximately 5 g/liter (0.5 wt %).

In some other embodiments, the reactive chemical solution comprises at least approximately 0.1 g/liter (0.01 wt %) of the dye compound, at least approximately 0.2 g/liter (0.02 wt %) of the dye compound, or at least approximately 0.5 g/liter (0.05 wt %) of the dye compound. In yet other embodiments, the reactive chemical solution comprises no more than 20 g/liter (2 wt %) of the dye compound, no more than 10 g/liter (1 wt %) of the dye compound, or no more than 5 g/liter (0.5 wt %) of the dye compound.

Solutions—Other Compounds

In some implementations, the reactive chemical solutions can include a variety of additional compounds. Examples of additional compounds can be found in the patents incorporated by reference at the end of the description. Any individual compound or combination of compounds disclosed in the patents can be included in the reactive chemical solutions in any of the disclosed quantities.

In some systems, the reactive chemical solutions includes a phosphorous compound that further enhances corrosion protection of the metal substrate. In some instances, the improved corrosion protection is provided by adsorption of phosphonate groups from an organic amino-phosphonic acid compound on a treatment surface of the metal substrate to form a M-O-P covalent bond and subsequent formation of a network hydrophobic layer over any active corrosion site on the metal substrate.

Examples of suitable phosphorous compounds include derivatives of amino-phosphonic acids such as the salts and esters of nitrilotris(methylene)triphosphonic acid (NTMP), hydroxy-, amino-alkylphosphonic acids, ethylimido(methylene)phosphonic acids, diethylaminomethylphosphonic acid, and the like. Preferably, the derivative is soluble in water. A particularly suitable phosphorous compound for use as a corrosion inhibitor and solution stabilizer is nitrilotris(methylene)triphosphonic acid (NTMP).

In some implementations, the phosphorous compound can be present in the reactive chemical solution in any suitable amount. In some embodiments, the reactive chemical solution comprises approximately 5 ppm to approximately 100 ppm of the phosphorous compound or approximately 10 ppm to approximately 30 ppm of the phosphorous compound. In other embodiments, the reactive chemical solution comprises at least approximately 5 ppm of the phosphorous compound or at least approximately 10 ppm of the phosphorous compound. In still other embodiments, the reactive chemical solution comprises no more than approximately 100 ppm of the phosphorous compound or no more than 30 ppm of the phosphorous compound.

In some applications, the reactive chemical solutions can also comprise a fluoride compound. Examples of suitable fluoride compounds include alkali metal tetrafluoroborates (e.g., potassium tetrafluoroborate), alkali metal hexafluorosilicates (e.g., potassium hexafluorosilicate), and the like. In some implementations, the fluoride compound is preferably water soluble.

In some embodiments, the fluoride compound can be present in the reactive chemical solutions in any suitable amount. In some systems, the reactive chemical solutions comprises approximately 0.2 g/liter (0.02 wt %) to approximately 20 g/liter (2 wt %) of the fluoride compound or approximately 0.5 g/liter (0.05 wt %) to approximately 18 g/liter (1.8 wt %) of the fluoride compound. In other embodiments, the reactive chemical solutions comprises at least approximately 0.2 g/liter (0.02 wt %) of the fluoride compound or at least approximately 0.5 g/liter (0.05 wt %) of the fluoride compound. In still other embodiments, the reactive chemical solutions comprises no more than 20 g/liter (2 wt %) of the fluoride compound or no more than 18 g/liter (1.8 wt %) of the fluoride compound.

In some instances, the reactive chemical solutions includes a corrosion inhibitor additive that increases the corrosion resistance provided by the coating. Examples of suitable corrosion inhibitor compounds include any of those disclosed in CN 102888138. Other examples include 2-mercaptobenzothiazole (MBT), 2-mercaptobenzimidazole (MBI), 2-mercaptobenzoxazole (MBO) and/or benzotriazole (BTA). The addition of the corrosion inhibitor compound can increase the corrosion resistance of the coating.

In some embodiments, the reactive chemical solutions can also include other materials such as thickeners, surfactants, and the like. Examples of these materials can be found in the patents incorporated by reference at the end of the description. These materials can be included in the reactive chemical solutions in any of the quantities disclosed in the patents.

Solutions—Impurities

In some applications, certain impurities can reduce the corrosion resistance/color vibrance of the reactive chemical solutions. One example of such an impurity is iron (Fe). Iron impurities present in the dye may reduce the effectiveness so the coating. For example, dye containing 0 ppm of iron can produce test plates (aluminum) that show no corrosion for 800+ hours. However, dye containing 10 ppm of iron can produce plates (aluminum) that show no corrosion for 216 hours. In some embodiments, the corrosion resistance of the latter can be increased by adjusting other parameters of the solution such as the chromium content and/or corrosion inhibitor content, but the result is still not as good as those situations where the dye contains 0 ppm of iron.

In some embodiments, the dye and/or the reactive chemical solutions have no more than 100 ppm iron, no more than 50 ppm iron, no more than 25 ppm iron, no more than 10 ppm iron, no more than 5 ppm iron, no more than 2 ppm iron, no more than 1 ppm iron, or, preferably, no iron. In some embodiments, the dye and/or the reactive chemical solutions can have 0 -100 ppm iron.

In some systems, the reactive chemical solutions have no more than 750 ppb iron, no more than 500 ppb iron, no more than 300 ppb iron, no more than 100 ppb iron, no more than 50 ppb iron, or, preferably no iron.

Reactive Chemical Solution Formation

In some instances, the reactive chemical solutions can take a variety of forms. In some applications, the reactive chemical solutions are the final mixed solution having the concentrations of the various compounds described above. In some embodiments, the final mixed solution is then absorbed into the hydrogel 114 and the removable and disposable applicator 112 can be sold as an already mixed ready to use product.

In some embodiments, the reactive chemical solutions can be used to treat any suitable metal substrate. In some embodiments, the reactive chemical solutions can be used to treat substrates comprising aluminum, magnesium, and/or zinc. In some systems, the substrates can be pure or commercially pure aluminum, magnesium, or zinc. In some embodiments, the substrates can also be an alloy of these metals or an alloy that includes these metals.

In other embodiments, the reactive chemical solutions can be used to treat substrates comprising valve metals such as vanadium, tantalum, hafnium, niobium, and/or titanium. In some applications, the substrates can be a pure or commercially pure elemental valve metal. In some instances, the substrates can also be an alloy of a valve metal or an alloy that includes a valve metal.

In some embodiments, the metal substrate can be subjected to another treatment prior to being treated with the reactive chemical solutions. For example, in some embodiments, the metal substrate can be anodized before being treated with the conversion coating solution.

In some embodiments, the metal substrate can take a variety of forms. In some applications, the metal substrate is one or more treatment surfaces of a larger metal part or assembly. For example, in some systems, the metal substrate may be an exposed metal surface of an aircraft. In other embodiments, the metal substrate is a single part that can be made from a monolithic block of metal or from coupling multiple metal components together.

Preparatory Chemicals in the Conversion Coating Applicator

In some embodiments, the hydrogel 114 may include preparatory chemicals rather than the reactive chemical solutions. That is, in some instances, a reactive electrochemical application system 100 may include a plurality of electrolytic applicators with different chemicals infused in the hydrogels for different stages of the selected process. For example, in some embodiments, the selected process may include the steps of: (a) cleaning the metal substrate prior to application of the coating on the metal substrate, (b) activating the metal substrate prior to application of the coating on the metal substrate, (c) cleaning the metal substrate after application of the coating on the metal substrate, and (d) sealing the metal substrate after application of the coating on the metal substrate. In some embodiments, the hydrogel 114 may include cleaners, activators, desmutters, and/or deoxidizers that may prepare a metal substrate prior to the conversion coating process. Specifically, in some applications, the cleaners, activators, desmutters, and/or deoxidizers maybe absorbed into the hydrogel 114 and desorbed from the hydrogel 114 onto the metal substrate prior to the selected process.

Generally, in some embodiments, to form a conversion coating on the treatment surface of a substrate, to anodize the substrate, and/or to electroplate the substrate, the treatment surface is prepared either mechanically or chemically to remove soils and oxides that might inhibit the process chemistry. In some systems, mechanical preparation typically includes solvent wipe followed by mechanical abrasion with an abrasive pad. In some embodiments, chemical preparation typically includes cleaning and activation. Some cleaners are capable of both cleaning and activation in a single step. The treatment surface to be treated should/must exhibit a “water break free” condition prior to conversion coating. In some embodiments, this is affected by cleaning the treatment surface and removal of any loose or adherent oxides from the treatment surface.

Various classes of cleaner may be used including alkaline or acidic cleaners. The cleaners are generally non-etching for aluminum applications, though in some cases an etching cleaner is desired. In some instances, in manufacturing processes, these cleaners are generally heated up to make them effective. Cold cleaners do not clean well in immersion, spray, or brush processes. However, surprisingly it has been found that a hydrogel containing a cold cleaner or etching cleaner cleans very well. Without being bound by theory, it is believed that the intimate contact between the hydrogel and the substrate increases the ability of the cold cleaner to clean the substrate. Various classes of activators may be used including acidic activators including nitric acid. Additionally, the cleaner and/or activator may include desmutters or deoxidizers. The term “deoxidizer” refers to the solutions ability to remove oxides from the treatment surface. The deoxidizer contains strong oxidizing compounds such as persulfate or peroxide and is usually acidic. The acidic component can may include acids such as sulfuric acid, nitric acid, chromic acid, and hydrofluoric acid. These acids may be used individually or in combination. Fluoride is often added to enhance the removal of silicon and magnesium compounds. Iron in the ferric form is used in some deoxidizers as an oxidizing agent. Other chemical pretreatments include alkaline etching.

Method of Forming the Removable and Disposable Applicator

A variety of methods can be used to form the removable and disposable applicator. In general, the method can comprise one or more of the steps of: (a) forming the frame, (b) forming the first liner and attaching the first liner to the frame, (c) forming the reactive chemical solution, (d) forming the hydrogel on the first liner, (e) infusing the reactive chemical solution into the hydrogel, (f) attaching the second liner to the hydrogel, and/or (g) sealing the electrolytic applicator in packaging for storage. In some applications, (e) infusing the reactive chemical solution into the hydrogel may include dipping the hydrogel and first liner into the reactive chemical solution and diffusing the reactive chemical solution into the hydrogel. In another embodiment, (e) infusing the reactive chemical solution into the hydrogel may include spraying the reactive chemical solution onto the hydrogel and first liner and diffusing the reactive chemical solution into the hydrogel. In yet another embodiment, (e) infusing the reactive chemical solution into the hydrogel may include mixing the reactive chemical solution into a polymer prior to (d) forming the hydrogel on the first liner and the electrode and simultaneously (d) forming the hydrogel on the first liner and the electrode with the reactive chemical solution. In some embodiments, (a) forming the frame may include forming the frame using additive manufacturing.

Additionally, in some systems, the hydrogel may be formed on the first liner in a specific, predetermined geometry. For example, in some embodiments, the metal substrate the electrolytic applicator is to be used on may have a specific shape. In order to reduce waste, the hydrogel may be formed on the first liner such that the hydrogel has a shape that corresponds to the specific shape of the metal substate. In some embodiments, the electrolytic applicator is applied to the metal substrate and the corresponding shapes of the metal substrate and the hydrogel enable the electrolytic applicator to target a specific region of the metal substate and reduce waste. More specifically, as shown herein, the hydrogel is capable of forming a sharp edge or line of demarcation on the metal substrate. That is, the reactive chemical solution does not bleed onto the metal substrate beyond the hydrogel and shaping the hydrogel to correspond to a shape of a specific region of the metal substrate enables the electrolytic applicator to reduce the amount of reactive chemical solution used to form the coatings described herein. Additionally, the hydrogel may be shaped after it has been formed on the first liner. For example, the hydrogel may be cut after formation using a cutting device or method (such as laser trimming, X-Y moving blade cutter, die cut, etc.) to form the hydrogel into the shape that corresponds to the specific shape of a portion of the metal substate.

Method of Forming the Preparatory Electrolytic Applicator

A variety of methods can be used to form the preparatory electrolytic applicator. In general, the method can comprise one or more of the steps of: (a) forming the frame, (b) forming the first liner and attaching the first liner to the frame, (c) forming the preparatory solution, (d) forming the hydrogel on the first liner, (e) infusing the preparatory solution into the hydrogel, (f) attaching the second liner to the hydrogel, and/or (g) sealing the preparatory electrolytic applicator in packaging for storage. In some instances, (d) infusing the preparatory solution into the hydrogel may include dipping the hydrogel and first liner into the preparatory solution and diffusing the preparatory solution into the hydrogel. In another embodiment, (d) infusing the preparatory solution into the hydrogel may include spraying the preparatory solution onto the hydrogel and first liner and diffusing the preparatory solution into the hydrogel. In yet another embodiment, (d) infusing the preparatory solution into the hydrogel may include mixing the preparatory solution into a polymer prior to (c) forming the hydrogel on the first liner and simultaneously (c) forming the hydrogel on the first liner with the preparatory solution. In some applications, (a) forming the frame may include forming the frame using additive manufacturing.

Method of Forming a Conversion Coating on a Metal Substrate

A variety of methods can be used to treat the metal substrate with the handheld reactive electrochemical application system. In general, the method can comprise one or more of the steps of: (a) cleaning the metal substrate, (b) activating the metal substrates, (c) applying the removable and disposable applicator to the head of the handheld reactive electrochemical application system, (d) applying the trivalent chromium conversion coating solution to the metal substrate by placing the hydrogel on the metal substrate, (e) passing a current through the metal substrate and the hydrogel, (f) rinsing the conversion coating solution off the metal substrate, and (g) drying the metal substrate (either actively or passively). In some embodiments, (a) cleaning the metal substrate may include applying a cleaning applicator having a cleaning solution in the hydrogel to the metal substrate. In some systems, (b) activating the metal substrates may include applying an activator applicator having an activation solution in the hydrogel to the metal substrate. In some embodiments, (e) rinsing the conversion coating solution off the metal substrate may include applying a cleaning applicator having a cleaning solution in the hydrogel to the metal substrate.

Method of Anodizing a Metal Substrate

A variety of methods can be used to treat the metal substrate with the handheld reactive electrochemical application system. In general, the method can comprise one or more of the steps of: (a) cleaning the metal substrate, (b) activating the metal substrates, (c) applying the removable and disposable applicator to the head of the handheld reactive electrochemical application system, (d) applying the anodizing solution to the metal substrate by placing the hydrogel on the metal substrate, (e) passing a current through the metal substrate and the hydrogel, (f) rinsing the anodizing solution off the metal substrate, (g) drying the metal substrate (either actively or passively), and (h) sealing the metal substrate. In some embodiments, (a) cleaning the metal substrate may include applying a cleaning applicator having a cleaning solution in the hydrogel to the metal substrate. In some instances, (b) activating the metal substrates may include applying an activator applicator having an activation solution in the hydrogel to the metal substrate. In some applications, (e) rinsing the conversion coating solution off the metal substrate may include applying a cleaning applicator having a cleaning solution in the hydrogel to the metal substrate.

Method of Electroplating a Metal Substrate

A variety of methods can be used to treat the metal substrate with the handheld reactive electrochemical application system. In general, the method can comprise one or more of the steps of: (a) cleaning the metal substrate, (b) activating the metal substrates, (c) applying the removable and disposable applicator to the head of the handheld reactive electrochemical application system, (d) applying the electroplating solution to the metal substrate by placing the hydrogel on the metal substrate, (e) passing a current through the metal substrate and the hydrogel, (f) rinsing the anodizing solution off the metal substrate, and (g) drying the metal substrate (either actively or passively). In some embodiments, (a) cleaning the metal substrate may include applying a cleaning applicator having a cleaning solution in the hydrogel to the metal substrate. In some systems, (b) activating the metal substrates may include applying an activator applicator having an activation solution in the hydrogel to the metal substrate. In some embodiments, (e) rinsing the conversion coating solution off the metal substrate may include applying a cleaning applicator having a cleaning solution in the hydrogel to the metal substrate.

EXAMPLES

The following examples are provided to further illustrate the disclosed subject matter. They should not be used to constrict or limit the scope of the claims in any way.

Example 1

A first sample of a metal substrate (aluminum) was anodized with an anodizing solution (sulfuric acid) using the reactive electrochemical application system 100 described herein. The electrolytic applicator was formed by dipping a KM50K® hydrogel applicator from Katecho® into a sulfuric acid solution of 180-200 g/L. The KM50K® hydrogel applicator from Katecho® including the sulfuric acid solution was placed on the 6061 aluminum alloy and a current was passed through the KM50K® hydrogel applicator from Katecho® and the 6061 aluminum alloy.

FIG. 13 is a schematic showing a 6061 aluminum alloy with a coating applied by the KM50K® hydrogel applicator from Katecho® including the sulfuric acid solution. As shown in FIG. 13, a protective coating, illustrated as a shaded region on a substrate, is clearly and visibly formed on the 6061 aluminum alloy. After anodizing, the substrate was dyed with hydrogel patches including a black dye (CHEMEON Black Thincoat) and sealed with hydrogel patches including a nickel seal (CHEMEON Seal 6100). Accordingly, the handheld reactive electrochemical application systems 100 described herein are capable of anodizing 6061 aluminum.

Example 2

A second sample of a metal substrate (titanium) was anodized with an anodizing solution (sodium bicarbonate) using the reactive electrochemical application system 100 described herein. The electrolytic applicator was formed by dipping a KM50K® hydrogel applicator from Katecho® into a sodium bicarbonate solution of 30 g/L. The KM50K® hydrogel applicator from Katecho® including the sodium bicarbonate solution was placed on the titanium and a current was passed through the KM50K ® hydrogel applicator from Katecho® and the titanium.

FIG. 14 is a schematic showing titanium with a coating applied by the KM50K® hydrogel applicator from Katecho® including the sodium bicarbonate solution. As shown in FIG. 14, a protective coating, illustrated as a shaded region on a substrate, is clearly and visibly formed on the titanium. Accordingly, the handheld reactive electrochemical application systems 100 described herein are capable of anodizing titanium.

Example 3

A third sample of a metal substrate (steel) was electroplated with an electroplating solution (nickel(II) sulfate) using the reactive electrochemical application system 100 described herein. The electrolytic applicator was formed by dipping a KM50K® hydrogel applicator from Katecho® into a nickel(II) sulfate solution. The KM50K® hydrogel applicator from Katecho® including the nickel(II) sulfate solution was placed on the steel and a current was passed through the KM50K® hydrogel applicator from Katecho® and the steel.

FIG. 15 is a schematic showing steel with a coating applied by the KM50K® hydrogel applicator from Katecho® including the nickel(II) sulfate solution. As shown in FIG. 15, a protective coating, illustrated as a shaded region on a substrate, is clearly and visibly formed on the steel. Accordingly, the handheld reactive electrochemical application systems 100 described herein are capable of electroplating steel.

Example 4

A fourth sample of a metal substrate (aluminum) was coated with a conversion coating solution (CHEMEON TCP-HF) using the reactive electrochemical application system 100 described herein. The electrolytic applicator was formed by dipping a KM50K® hydrogel applicator from Katecho® into a 25% CHEMEON TCP-HF conversion coating solution including a trivalent chromium compound. The KM50K® hydrogel applicator from Katecho® including the conversion coating solution is placed on 6061 aluminum alloy.

FIG. 16 is a schematic showing a 6061 aluminum alloy with a coating applied by the KM50K® hydrogel applicator from Katecho® including the conversion coating solution. As shown in FIG. 16, a conversion coating, illustrated as a shaded region on a substrate, is clearly and visibly formed on the 6061 aluminum alloy. Accordingly, the reactive electrochemical application system 100 described herein are capable of forming conversion coatings that are capable of protecting the 6061 aluminum alloy from degradation.

Terminology and Interpretative Conventions

Any methods described in the claims or specification should not be interpreted to require the steps to be performed in a specific order unless stated otherwise. Also, the methods should be interpreted to provide support to perform the recited steps in any order unless stated otherwise.

Spatial or directional terms, such as “left,” “right,” “front,” “back,” and the like, relate to the subject matter as it is shown in the drawings. However, it is to be understood that the described subject matter may assume various alternative orientations and, accordingly, such terms are not to be considered as limiting.

Articles such as “the,” “a,” and “an” can connote the singular or plural. Also, the word “or” when used without a preceding “either” (or other similar language indicating that “or” is unequivocally meant to be exclusive—e.g., only one of x or y, etc.) shall be interpreted to be inclusive (e.g., “x or y” means one or both x or y).

The term “and/or” shall also be interpreted to be inclusive (e.g., “x and/or y” means one or both x or y). In situations where “and/or” or “or” are used as a conjunction for a group of three or more items, the group should be interpreted to include one item alone, all the items together, or any combination or number of the items.

The terms have, having, include, and including should be interpreted to be synonymous with the terms comprise and comprising. The use of these terms should also be understood as disclosing and providing support for narrower alternative embodiments where these terms are replaced by “consisting” or “consisting essentially of.”

Unless otherwise indicated, all numbers or expressions, such as those expressing dimensions, physical characteristics, and the like, used in the specification (other than the claims) are understood to be modified in all instances by the term “approximately.” At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical parameter recited in the specification or claims which is modified by the term “approximately” should be construed in light of the number of recited significant digits and by applying ordinary rounding techniques.

All disclosed ranges are to be understood to encompass and provide support for claims that recite any and all subranges or any and all individual values subsumed by each range. For example, a stated range of 1 to 10 should be considered to include and provide support for claims that recite any and all subranges or individual values that are between and/or inclusive of the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less (e.g., 5.5 to 10, 2.34 to 3.56, and so forth) or any values from 1 to 10 (e.g., 3, 5.8, 9.9994, and so forth).

All disclosed numerical values are to be understood as being variable from 0-100% in either direction and thus provide support for claims that recite such values or any and all ranges or subranges that can be formed by such values. For example, a stated numerical value of 8 should be understood to vary from 0 to 16(100 % in either direction) and provide support for claims that recite the range itself (e.g., 0 to 16), any subrange within the range (e.g., 2 to 12.5) or any individual value within that range (e.g., 15.2).

The terms recited in the claims should be given their ordinary and customary meaning as determined by reference to relevant entries in widely used general dictionaries and/or relevant technical dictionaries, commonly understood meanings by those in the art, etc., with the understanding that the broadest meaning imparted by any one or combination of these sources should be given to the claim terms (e.g., two or more relevant dictionary entries should be combined to provide the broadest meaning of the combination of entries, etc.) subject only to the following exceptions: (a) if a term is used in a manner that is more expansive than its ordinary and customary meaning, the term should be given its ordinary and customary meaning plus the additional expansive meaning, or (b) if a term has been explicitly defined to have a different meaning by reciting the term followed by the phrase “as used in this document shall mean” or similar language (e.g., “this term means,” “this term is defined as,” “for the purposes of this disclosure this term shall mean,” etc.). References to specific examples, use of “i.e.,” use of the word “invention,” etc., are not meant to invoke exception (b) or otherwise restrict the scope of the recited claim terms. Other than situations where exception (b) applies, nothing contained in this document should be considered a disclaimer or disavowal of claim scope.

The subject matter recited in the claims is not coextensive with and should not be interpreted to be coextensive with any embodiment, feature, or combination of features described or illustrated in this document. This is true even if only a single embodiment of the feature or combination of features is illustrated and described in this document.

Incorporation by Reference

The entire content of each of the documents listed below are incorporated by reference into this document. If the same term is used in both this document and one or more of the incorporated documents, then it should be interpreted to have the broadest meaning imparted by any one or combination of these sources unless the term has been explicitly defined to have a different meaning in this document. If there is an inconsistency between any of the following documents and this document, then this document shall govern. The incorporated subject matter should not be used to limit or narrow the scope of the explicitly recited or depicted subject matter.

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