JP2020037738A - Composition and method for electrodepositing tin-bismuth alloy on metal substrate - Google Patents

Abstract

To provide a composition and a method for electrodepositing a tin-bismuth alloy on a metal substrate.SOLUTION: A composition and a method include: (1) a process in which a substrate and an anode are immersed in an electrolytic solution containing at least one of water, tin salt, sulfuric acid, and sulfamic acid, and in which the anode includes tin and optional bismuth; and (2) a process in which a sediment is formed on the substrate by passing an electric current through between the substrate and the anode.SELECTED DRAWING: None

Description

  The present application relates to depositing materials on substrates, and more specifically, compositions and methods for activating metal substrates, and for depositing tin-bismuth alloys on metal substrates. Compositions and methods.

  Mechanical fasteners are widely used to join two or more components for a structural assembly. For example, mechanical fasteners are widely used to join structural components of an aircraft fuselage.

  Aircraft are subject to electro-magnetic effects (EME) due to various factors (eg, lightning strikes and precipitation statics). Metallic aircraft structures are relatively insensitive to electromagnetic effects because they are directly conductive. However, composite (eg, carbon fiber reinforced plastic) aircraft structures do not immediately dissipate large currents and electromagnetic forces due to the electromagnetic effect. Therefore, when mechanical fasteners are used in composite aircraft structures, measures must be taken to protect them from electromagnetic effects.

  Protection from the electromagnetic effect can be provided to the mechanical fastener in the form of a conductive metal surface deposit (eg, metal plating). To provide protection from the electromagnetic effect, various metal surface deposits can provide adequate conductivity, while other factors such as lubricity and galvanic compatibility with carbon fiber reinforced plastics Gender) are also considered for mechanical fasteners intended for the aerospace industry.

  Tin exists in the α and β phases. Alpha tin is gray in color and forms a plague in powder form, while beta tin is white and has a tetragonal crystal structure. When tin is alloyed with bismuth at concentrations greater than 0.4 weight percent bismuth, tin begins to exist as a beta phase. Tin-bismuth has proved promising as a metal surface deposit suitable for mechanical fasteners due to its electrical conductivity, lubricity, and galvanic compatibility with carbon fiber reinforced plastics.

  Embodiments include the following:

  An electrolyte solution containing water, a tin salt, a bismuth salt, and an acid.

  Water, at least one of tin sulfate, tin chloride and tin fluoride dissolved in water, and at least one of bismuth sulfate, bismuth oxide, bismuth nitrate, bismuth chloride and bismuth trifluoride dissolved in water And an at least one of sulfuric acid and sulfamic acid dissolved in water.

  An electrolyte solution containing water, tin sulfate, bismuth sulfate, and sulfuric acid.

  Water, at least one of tin sulfate, tin chloride, and tin fluoride dissolved in water at a concentration of about 15 grams per liter to about 200 grams per liter based on the total volume of the electrolyte solution; At least one of bismuth sulfate, bismuth oxide, bismuth nitrate, bismuth chloride and bismuth trifluoride dissolved in water at a concentration of about 0.25 grams per liter to about 10 grams per liter based on total volume; An electrolyte solution comprising at least one of sulfuric acid and sulfamic acid dissolved in water at a concentration of about 50 ml per liter to about 150 ml per liter based on the total volume of the electrolyte solution.

A method for producing an electrolyte solution, comprising:
(1) a step of mixing at least one of sulfuric acid and sulfamic acid with water to obtain an acidic solution;
(2) A method comprising the steps of: dissolving a tin salt in an acidic solution; and (3) dissolving a bismuth salt in an acidic solution.

An electrodeposition system,
A current source having a first terminal and a second terminal;
A bath containing an electrolyte solution, wherein the electrolyte solution contains water, a tin salt, a bismuth salt, and an acid;
A substrate immersed in the electrolyte solution, the substrate being electrically connected to the first terminal of the current source; and an anode including tin, immersed in the electrolyte solution, and An anode electrically connected to the second terminal,
An electrodeposition system comprising:

A method for depositing a tin-bismuth alloy on a substrate, comprising:
(1) a step of immersing a substrate and an anode containing tin in an electrolyte solution containing water, a tin salt, a bismuth salt and an acid; and (2) passing an electric current between the substrate and the anode, A method, comprising forming a deposit.

A method for depositing a tin-bismuth alloy on a substrate, comprising:
(1) a step of activating the substrate,
(2) a step of strike plating the substrate;
(3) a step of immersing the substrate and the anode containing tin in an electrolyte solution containing water, a tin salt, a bismuth salt and an acid; and (4) passing an electric current between the substrate and the anode, A method, comprising forming a deposit.

  Other aspects of the disclosed compositions and methods for electrodepositing a tin-bismuth alloy on a metal substrate will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

1 is a flow diagram illustrating a method according to the present disclosure for depositing a material on a substrate. 2 is a photomicrograph of a tin-bismuth alloy deposited on a titanium substrate according to the method of FIG. 2 is a flow diagram illustrating one method according to the present disclosure for activating a substrate (eg, a titanium substrate) according to the method of FIG. 4 schematically illustrates a system for activating a substrate according to the method of FIG. 2 is a flow diagram illustrating another method according to the present disclosure for activating a substrate (eg, a titanium substrate) according to the method of FIG. 6 schematically illustrates a system for activating a substrate according to the method of FIG. 5 is a flow diagram illustrating yet another method in accordance with the present disclosure for activating a substrate (eg, a titanium substrate) according to the method of FIG. 8 schematically illustrates a system for activating a substrate according to the method of FIG. 2 schematically illustrates a system for strike plating a substrate according to the method of FIG. 1. 2 is a flow diagram illustrating one method according to the present disclosure for electrodepositing a tin-bismuth alloy on a substrate according to the method of FIG. 1. 11 schematically illustrates an electrodeposition system for depositing a tin-bismuth alloy according to the method of FIG. 2 is a flow diagram of an aircraft manufacturing and operation technique. 1 is a block diagram of an aircraft.

  Disclosed herein are compositions, systems and methods for activating metal substrates (eg, metal fasteners or other components / components). Also disclosed are compositions, systems and methods for depositing materials on metal substrates (eg, metal fasteners or other components / components). The compositions, systems and methods disclosed herein can be used separately or in various combinations to achieve a desired material deposition on a substrate.

  Referring to FIG. 1, a method for depositing a material on a substrate (generally designated 10) is disclosed. Although only three general steps are shown, it will be appreciated by those skilled in the art that various additional steps can be performed before, after, or during the steps presented herein without departing from the scope of the present disclosure. Will be understood.

  The first step (block 12) of method 10 is to form the substrate into a substrate suitable for receiving a material (eg, a metal deposit or other metallic / non-metallic material) on the substrate. Including preprocessing. Various pretreatments (eg, cleaning, degreasing, etching, etc.) can be performed. In particular, the pretreatment step (block 12) may include activation of the substrate surface (block 14). For example, in the case of a titanium substrate, the step of activating the substrate surface (block 14) removes (or at least substantially reduces) a strong oxide layer known to form on the substrate. )be able to.

  The intermediate step of method 10 (block 16) involves strike plating the pretreated substrate. The step of strike plating the substrate surface (block 16) allows a thin metal layer to be formed on the substrate surface, whereby the substrate receives and deposits subsequent metal deposits. With a more suitable surface for bonding. In certain implementations, a thin nickel layer can be formed on the substrate surface in the strike plating step (block 16).

  The final step of method 10 (block 18) involves electrodeposition on a strike plated substrate. In the electrodeposition step (block 18), a metal deposit can be formed on the substrate surface. In certain implementations, in the electrodeposition step (block 18), a tin-bismuth alloy can be deposited on the substrate surface.

  Referring to FIG. 2, the disclosed method 10 was used to deposit a thin layer of a tin-bismuth alloy on the surface of a titanium alloy (Ti-6Al-4V) substrate. The result was an excellent bond between the tin-bismuth alloy deposit and the underlying titanium alloy substrate.

  Although the present disclosure focuses primarily on titanium substrates (substrates formed from titanium or titanium alloys, such as Ti-6Al-4V), the disclosed method 10 and each of the disclosed methods 10 The steps (eg, activation step (block 14), strike plating step (block 16), and / or electrodeposition step (block 18)) may be suitable for non-titanium substrates. Examples of non-titanium substrates that benefit from the present disclosure include, but are not limited to, iron alloys, copper alloys, and nickel alloys (eg, Inconel).

Activation Three activation methods are disclosed, including related compositions and systems. Metal substrates, such as titanium substrates, can be activated using only one of the disclosed activation methods. Alternatively, a metal substrate, eg, a titanium substrate, can be activated using a plurality of activation methods (eg, a series of activation methods), wherein one or more of the disclosed activation methods are used. included.

  Referring to FIGS. 3 and 4, a first activation method (generally designated as 100) may begin at block 110 (FIG. 3), where a bath containing an activation solution 154, as shown in FIG. 152. The bath 152 and the activation solution 154 can include a first activation system 150.

  Bath 152 can be any suitable container for receiving and containing activating solution 154. Compositionally, the material forming the bath 152 must be chemically compatible with the activation solution 154. Of course, the bath 152 must be sized and shaped to accept the substrate 156 to be activated by the first activation system 150 into the bath.

The activation solution 154 contains water (H ₂ O), an ammonium salt dissolved in water, and sulfuric acid (H ₂ SO ₄ ) dissolved in water. The activation solution 154 can be maintained at atmospheric pressure (eg, 1 atm) and at about 15 ° C. to about 50 ° C. (eg, room temperature (about 21 ° C.)). However, it is contemplated that higher and lower pressures may be used, as well as higher and lower temperatures, without departing from the scope of the present disclosure.

The ammonium salt in the activation solution 154 can have a fluorine-containing anion. In one preparation, ammonium salts in the activation solution 154 is ammonium bifluoride _(NH 4 HF _2). In another preparation, the ammonium salt in the activation solution 154 is ammonium tetrafluoroborate (NH ₄ BF ₄ ). In yet another preparation, the ammonium salt in the activation solution 154 includes both ammonium bifluoride (NH ₄ HF ₂ ) and ammonium tetrafluoroborate (NH ₄ BF ₄ ).

  The ammonium salt in the activation solution 154 may be present at a concentration ranging from about 10 grams per liter to about 150 grams per liter based on the total volume of the activation solution 154. In one alternative expression, the concentration of the ammonium salt ranges from about 20 grams per liter to about 120 grams per liter based on the total volume of the activation solution 154. In another alternative expression, the concentration of the ammonium salt ranges from about 30 grams per liter to about 110 grams per liter based on the total volume of the activation solution 154. In another alternative expression, the concentration of the ammonium salt ranges from about 40 grams per liter to about 100 grams per liter based on the total volume of the activation solution 154. In another alternative expression, the concentration of the ammonium salt ranges from about 50 grams per liter to about 100 grams per liter based on the total volume of the activation solution 154. In another alternative expression, the concentration of the ammonium salt ranges from about 60 grams per liter to about 100 grams per liter based on the total volume of the activation solution 154. In another alternative, the concentration of the ammonium salt ranges from about 70 grams per liter to about 90 grams per liter based on the total volume of the activation solution 154. In a further alternative expression, the concentration of the ammonium salt is about 80 grams per liter, based on the total volume of the activation solution 154.

  The sulfuric acid in the activation solution 154 may be present at a concentration ranging from about 1 volume percent to about 70 volume percent, based on the total volume of the activation solution 154. In one alternative expression, the concentration of the sulfuric acid ranges from about 2 volume percent to about 50 volume percent, based on the total volume of the activation solution 154. In another alternative expression, the concentration of the sulfuric acid ranges from about 3 volume percent to about 40 volume percent, based on the total volume of the activation solution 154. In another alternative expression, the concentration of the sulfuric acid ranges from about 4 percent to about 30 percent by volume, based on the total volume of the activation solution 154. In another alternative expression, the concentration of the sulfuric acid ranges from about 5 volume percent to about 25 volume percent, based on the total volume of the activation solution 154. In another alternative expression, the concentration of the sulfuric acid ranges from about 5 volume percent to about 15 volume percent, based on the total volume of the activation solution 154. In a further alternative expression, the concentration of sulfuric acid is about 10 volume percent, based on the total volume of the activation solution 154.

In one specific, non-limiting example, the activation solution 154 comprises water, 80 grams per liter of ammonium bifluoride (NH ₄ HF ₂ ), and 10 volume percent sulfuric acid (H ₂ SO ₄ ). including.

Activation solution 154 can be manufactured in various ways without departing from the scope of the present disclosure. In one specific implementation, the disclosed method for producing activation solution 154 includes the following steps:
(1) mixing sulfuric acid (for example, sulfuric acid at 66 degrees with Baume) and water (for example, deionized water) to obtain an acidic solution;
(2) dissolving the ammonium salt (eg, ammonium bifluoride and / or ammonium tetrafluoroborate) in the acidic solution; and (3) necessary to bring the activation solution 154 to the required total volume. Step of adding more water, if any.

  In block 120 (FIG. 3), the substrate 156 is immersed (eg, completely immersed) in the activation solution 154. The substrate 156 may remain immersed in the activation solution 154 for a predetermined period of time before removing the substrate 156 from the activation solution 154, as shown in block 130 (FIG. 3). In the case of a titanium substrate (substrate 156), the activation solution 154 removes the strong oxide layer on the substrate 156 for a predetermined period of time without significantly damaging the underlying oxide layer of the titanium / titanium alloy. It can be chosen to have sufficient time to reduce / eliminate. In one expression, the predetermined time is between about 5 seconds and about 120 seconds. In another expression, the predetermined time is between about 10 seconds and about 100 seconds. In another expression, the predetermined time is between about 20 seconds and about 40 seconds. In yet another expression, the predetermined time is about 30 seconds.

  At block 140 (FIG. 3), the substrate 156 removed from the activation solution 154 can be rinsed with a rinsing fluid. As one example, the rinsing fluid may be water, for example, deionized water.

  Referring to FIGS. 5 and 6, a second activation method (generally designated 200) may begin at block 202 (FIG. 5), where a bath containing an activation solution 254 is provided, as shown in FIG. 252. Bath 252 and activation solution 254 may include a second activation system 250.

  Bath 252 can be any suitable container for receiving and containing activating solution 254. Compositionally, the material forming the bath 252 must be chemically compatible with the activation solution 254. Of course, the bath 252 must be sized and shaped to accept the substrate 256 to be activated by the second activation system 250 into the bath.

The activation solution 254 contains water (H ₂ O), a fluoride salt dissolved in water, hydrofluoric acid (HF) dissolved in water, and sulfuric acid (H ₂ SO ₄ ) dissolved in water. I do. Activation solution 254 can be maintained at atmospheric pressure (eg, 1 atm) and at about 15 ° C. to about 50 ° C. (eg, room temperature (about 21 ° C.)). However, it is contemplated that higher and lower pressures may be used, as well as higher and lower temperatures, without departing from the scope of the present disclosure.

The fluoride salt in the activation solution 254 can have an alkali metal cation and / or an alkaline earth metal cation. In one preparation, the fluoride salt in the activation solution 254 is potassium fluoride (KF). In another preparation, the fluoride salt in the activation solution 254 is lithium fluoride (LiF). In another preparation, the fluoride salt in the activation solution 254 is sodium fluoride (NaF). In another preparation, the fluoride salt in the activation solution 254 is rubidium fluoride (RuF). In another preparation, fluoride salts in the activation solution 254, a barium fluoride (BaF _2). In another preparation, fluoride salts in the activation solution 254, a strontium fluoride (SrF _2). In yet another preparation, the ammonium salt in the activation solution 254 is potassium fluoride (KF), lithium fluoride (LiF), sodium fluoride (NaF), rubidium fluoride (RuF), barium fluoride (BaF). ₂ ) and strontium fluoride (SrF ₂ ).

  The fluoride salt in the activation solution 254 can be present at a concentration ranging from about 5 grams per liter to about 120 grams per liter based on the total volume of the activation solution 254. In one alternative expression, the concentration of the fluoride salt ranges from about 10 grams per liter to about 100 grams per liter based on the total volume of the activation solution 254. In another alternative expression, the fluoride salt concentration ranges from about 15 grams per liter to about 75 grams per liter based on the total volume of the activation solution 254. In another alternative expression, the fluoride salt concentration ranges from about 15 grams per liter to about 50 grams per liter based on the total volume of the activation solution 254. In another alternative expression, the fluoride salt concentration ranges from about 15 grams per liter to about 30 grams per liter based on the total volume of the activation solution 254. In a further alternative expression, the concentration of the fluoride salt is about 20 grams per liter, based on the total volume of the activation solution 254.

  Hydrofluoric acid in the activation solution 254 may be present at a concentration ranging from about 5 milliliters per liter to about 250 milliliters per liter based on the total volume of the activation solution 254. In one alternative expression, the concentration of hydrofluoric acid ranges from about 10 milliliters per liter to about 200 milliliters per liter based on the total volume of the activation solution 254. In another alternative expression, the concentration of hydrofluoric acid ranges from about 15 milliliters per liter to about 150 milliliters per liter based on the total volume of the activation solution 254. In another alternative expression, the concentration of hydrofluoric acid ranges from about 20 milliliters per liter to about 150 milliliters per liter, based on the total volume of the activation solution 254. In another alternative expression, the concentration of hydrofluoric acid ranges from about 30 milliliters per liter to about 100 milliliters per liter based on the total volume of the activation solution 254. In another alternative expression, the concentration of hydrofluoric acid ranges from about 40 milliliters per liter to about 80 milliliters per liter based on the total volume of the activation solution 254. In a further alternative expression, the concentration of hydrofluoric acid is about 60 milliliters per liter, based on the total volume of the activation solution 254.

  The sulfuric acid in the activation solution 254 may be present at a concentration ranging from about 1 volume percent to about 45 volume percent, based on the total volume of the activation solution 254. In one alternative expression, the concentration of sulfuric acid ranges from about 2 volume percent to about 35 volume percent, based on the total volume of the activation solution 254. In another alternative expression, the concentration of the sulfuric acid ranges from about 2 volume percent to about 20 volume percent, based on the total volume of the activation solution 254. In another alternative expression, the concentration of the sulfuric acid ranges from about 3 volume percent to about 15 volume percent, based on the total volume of the activation solution 254. In another alternative expression, the concentration of sulfuric acid ranges from about 3 volume percent to about 10 volume percent, based on the total volume of the activation solution 254. In a further alternative expression, the concentration of sulfuric acid is about 5 volume percent, based on the total volume of the activation solution 254.

In one specific, non-limiting example, the activation solution 254 comprises water, 20 grams of potassium fluoride (KF) per liter, 60 milliliters of hydrofluoric acid (HF) per liter, and 5 Contains volume percent sulfuric acid (H ₂ SO ₄ ).

Activation solution 254 can be manufactured in various ways without departing from the scope of the present disclosure. In one specific implementation, the disclosed method for producing activation solution 254 includes the following steps:
(1) mixing sulfuric acid (eg, sulfuric acid at 66 ° in Baume) and water (eg, deionized water) to obtain a first acidic solution;
(2) mixing hydrofluoric acid (for example, 48% by weight in water) with the first acidic solution to obtain a second acidic solution;
(3) dissolving the fluoride salt (eg, potassium fluoride) in the second acidic solution; and (4) if necessary, to bring the activation solution 254 to the required total volume. Adding more water.

  In block 204 (FIG. 5), the substrate 256 is immersed (eg, completely immersed) in the activation solution 254. The substrate 256 may remain immersed in the activation solution 254 for a predetermined period of time, as shown in block 206 (FIG. 5), before removing the substrate 256 from the activation solution 254. In the case of a titanium substrate (substrate 256), the activation solution 254 removes the strong oxide layer on the substrate 256 without significantly damaging the underlying oxide layer of the titanium / titanium alloy. It can be chosen to have sufficient time to reduce / eliminate. In one expression, the predetermined time is between about 5 seconds and about 120 seconds. In another expression, the predetermined time is between about 10 seconds and about 100 seconds. In another expression, the predetermined time is between about 20 seconds and about 40 seconds. In yet another expression, the predetermined time is about 30 seconds.

  At block 208 (FIG. 5), the substrate 256 removed from the activation solution 254 can be rinsed with a rinsing fluid. As one example, the rinsing fluid may be water, for example, deionized water.

  Referring to FIGS. 7 and 8, a third activation method (generally indicated at 300) may begin at block 302 (FIG. 7), where a bath containing an activation solution 354, as shown in FIG. 352. The bath 352 and the activation solution 354, along with the graphite electrode 358 and the current source 360, can include a third activation system 350, which, as described herein, includes an anodic sulfuric acid method (third To activate the method 300).

  Bath 352 can be any suitable container for receiving and containing activating solution 354. Compositionally, the material forming the bath 352 must be chemically compatible with the activation solution 354. Of course, bath 352 must be sized and shaped to accept graphite electrode 358 and substrate 356 to be activated by third activation system 350 in the bath.

The activation solution 354 contains water (H ₂ O) and sulfuric acid (H ₂ SO ₄ ) dissolved in water. Activation solution 354 can be maintained at atmospheric pressure (eg, 1 atm) and at about 15 ° C. to about 50 ° C. (eg, room temperature (about 21 ° C.)). However, it is contemplated that higher and lower pressures may be used, as well as higher and lower temperatures, without departing from the scope of the present disclosure.

  The sulfuric acid in the activation solution 354 may be present at a concentration ranging from about 5 volume percent to about 45 volume percent, based on the total volume of the activation solution 354. In one alternative expression, the concentration of the sulfuric acid ranges from about 5 volume percent to about 35 volume percent, based on the total volume of the activation solution 354. In another alternative expression, the concentration of sulfuric acid ranges from about 5 volume percent to about 30 volume percent, based on the total volume of the activation solution 354. In another alternative expression, the concentration of the sulfuric acid ranges from about 5 volume percent to about 25 volume percent, based on the total volume of the activation solution 354. In another alternative expression, the concentration of the sulfuric acid ranges from about 10 volume percent to about 20 volume percent, based on the total volume of the activation solution 254. In a further alternative expression, the concentration of sulfuric acid is about 15 volume percent, based on the total volume of the activation solution 354.

One specific, non-limiting examples, including the activation solution 354, water, and 15% by volume of sulfuric acid _(H 2 SO _4).

  In block 304 (FIG. 7), the substrate 356 is immersed (eg, completely immersed) in the activation solution 354. The conducting wire 368 can electrically connect the dipped base material 356 to the first terminal 364 of the current source 360.

  In block 306 (FIG. 7), the graphite electrode 358 is immersed (eg, completely immersed) in the activation solution 354. The conducting wire 366 can electrically connect the dipped graphite electrode 358 and the second terminal 362 of the current source 360.

  At block 308 (FIG. 7), the current source 360 is activated so that current passes between the substrate 356 and the graphite electrode 358. The current source 360 may be configured such that the substrate 356 is etched by the substrate 356 acting as an anode. In the case of a titanium substrate (substrate 356), the anodic sulfuric acid method (third activation method 300) provides a strong oxidation on substrate 356 without significantly damaging the underlying oxide layer of the titanium / titanium alloy. Layers can be reduced / eliminated.

  The step of passing current (block 308) can be performed at various current densities without departing from the scope of the present disclosure. Those skilled in the art will appreciate that the current density is a controllable parameter, and that various factors (such as, for example, the duration of the step of passing current (block 308), among other factors) may be necessary to select an appropriate current density. Will need to be considered positively. In one representation, the current passed during the current passing step (block 308) is a current density ranging from about 10 amps per square foot to about 80 amps per square foot, based on the surface area of the substrate 356. Can have. In another expression, the current passed during the current passing step (block 308) is a current density ranging from about 20 amps per square foot to about 60 amps per square foot, based on the surface area of the substrate 356. Can have. In another expression, the current passed during the current passing step (block 308) is a current density ranging from about 20 amps per square foot to about 40 amps per square foot, based on the surface area of the substrate 356. Can have. In yet another expression, the current passed during the current passing step (block 308) can have a current density of about 30 amps per square foot based on the surface area of the substrate 356.

  The step of passing current (block 308) can be performed for various durations without departing from the scope of the present disclosure. One skilled in the art will appreciate that current density is a controllable parameter and that various factors (eg, current density, among other factors) need to be considered in order to select an appropriate duration. Will be evaluated. In one expression, passing the current (block 308) can occur for about 5 seconds to about 120 seconds. In another expression, passing the current (block 308) can occur for about 10 seconds to about 100 seconds. In other words, passing the current (block 308) can occur for about 10 seconds to about 60 seconds. In other words, passing the current (block 308) can occur for about 15 seconds to about 45 seconds. In yet another expression, passing the current (block 308) can occur for about 20 seconds to about 30 seconds.

  At block 310 (FIG. 7), the substrate 356 is disconnected from the current source 360 and removed from the activation solution 354.

  At block 312 (FIG. 7), the substrate 356 can be rinsed with a rinsing fluid. As one example, the rinsing fluid may be water, for example, deionized water.

Strike Plating Various strike plating processes (including nickel strike plating processes: e.g., wood bath nickel strike) are known in the art and can be used in method 10 of FIG. 1 without departing from the scope of the present disclosure. However, a specific nickel strike plating method was disclosed, which provided excellent bonding with the substrate by subsequent plating (see FIG. 2).

  Referring to FIG. 9, a strike plating system (generally designated 450) includes a bath 452, an electrolyte solution 454 received in the bath 452, a nickel anode 458 immersed in the electrolyte solution 454, and a current source 460. Including. The current source 460 can include a first terminal 462 and a second terminal 464. Nickel anode 458 may be electrically connected to second terminal 464 by conductor 468.

  Bath 452 can be any suitable container for receiving and containing electrolyte solution 454. Compositionally, the material forming the bath 452 must be chemically compatible with the electrolyte solution 454. Of course, bath 452 must be sized and shaped to accommodate substrate 456 and nickel anode 458 in the bath.

Electrolyte solution 454 contains water (H ₂ O), nickel chloride (NiCl ₂ ) dissolved in water, and hydrochloric acid (HCl) dissolved in water. Electrolyte solution 454 can be maintained at atmospheric pressure (e.g., 1 atm) and at about 15C to about 50C (e.g., room temperature (about 21C)). However, it is contemplated that higher and lower pressures may be used, as well as higher and lower temperatures, without departing from the scope of the present disclosure.

  Nickel chloride in the electrolyte solution 454 may be present at a concentration ranging from about 50 grams per liter to about 400 grams per liter based on the total volume of the activation solution 354. In one alternative expression, the concentration of nickel chloride ranges from about 75 grams per liter to about 350 grams per liter based on the total volume of the activation solution 354. In another alternative expression, the concentration of nickel chloride ranges from about 100 grams per liter to about 300 grams per liter based on the total volume of the activation solution 354. In another alternative expression, the concentration of nickel chloride ranges from about 125 grams per liter to about 275 grams per liter based on the total volume of the activation solution 354. In another alternative expression, the concentration of nickel chloride ranges from about 150 grams per liter to about 250 grams per liter based on the total volume of the activation solution 354. In another alternative expression, the concentration of nickel chloride ranges from about 175 grams per liter to about 225 grams per liter based on the total volume of the activation solution 354.

  Hydrochloric acid in the electrolyte solution 454 can be present at a concentration ranging from about 25 milliliters per liter to about 300 milliliters per liter, based on the total volume of the electrolyte solution 454. In one alternative expression, the concentration of hydrochloric acid ranges from about 50 milliliters per liter to about 250 milliliters per liter, based on the total volume of the electrolyte solution 454. In another alternative expression, the concentration of hydrochloric acid ranges from about 75 milliliters per liter to about 225 milliliters per liter, based on the total volume of the electrolyte solution 454. In another alternative expression, the concentration of hydrochloric acid ranges from about 100 milliliters per liter to about 200 milliliters per liter based on the total volume of the electrolyte solution 454. In another alternative expression, the concentration of hydrochloric acid ranges from about 125 milliliters per liter to about 175 milliliters per liter based on the total volume of the electrolyte solution 454.

In one specific, non-limiting example, the electrolyte solution 454 includes water, 200 grams per liter of nickel chloride (NiCl ₂ ), and 150 milliliters per liter of hydrochloric acid (HCl).

  As shown in FIG. 9, substrate 456 is immersed (eg, completely immersed) in electrolyte solution 454 in bath 452. The base material 456 is electrically connected to the first terminal 462 of the current source 460 by the conducting wire 466.

  To begin strike plating, the current source 460 is activated so that current passes between the substrate 456 and the nickel anode 458 and deposits form on the substrate 456. Optionally, an anodic strike (substrate 456 acts as an anode) can be performed to etch substrate 456 before initiating a cathode strike.

  The anodic strike (etch) can be performed at various current densities and durations without departing from the scope of the present disclosure. In one expression, the anodic strike is at a current density ranging from about 25 amps per square foot to about 75 amps per square foot, based on the surface area of the substrate 456, for a duration of about 1 second to about 30 seconds. Over and can be done. For example, the anodic strike can be performed at a current density of about 120 amps per square foot, based on the surface area of the substrate 456, for about 10 seconds.

  Cathode strike (strike plating) can be performed at various current densities and durations without departing from the scope of the present disclosure. In one representation, the cathode strike is at a current density ranging from about 80 amps per square foot to about 160 amps per square foot, based on the surface area of the substrate 456, for a duration of about 30 seconds to about 10 minutes. Over and can be done. For example, the cathodic strike can be performed at a current density of about 120 amps per square foot, based on the surface area of the substrate 456, for about 5 minutes.

  When the current source 460 stops operating, the substrate 456 can be disconnected from the current source 460 and removed from the electrolyte solution 454. The substrate 356 can then be rinsed with a rinsing fluid (eg, deionized water).

Electrodeposition Various electrodeposition processes can be used in the method 10 of FIG. 1 without departing from the scope of the present disclosure. However, certain tin-bismuth electrodeposition methods are disclosed, which, when used following any of the activation methods according to the present disclosure and the disclosed nickel strike plating method, provide superior plating to the substrate due to subsequent plating. (See FIG. 2).

  Referring to FIGS. 10 and 11, the disclosed electrodeposition method (generally designated 500) may begin at block 502 (FIG. 10), where a bath 552 containing an electrolyte solution 554, as shown in FIG. The step of preparing The bath 552 and the activation solution 554, together with the anode 558 and the current source 560, can comprise the disclosed electrodeposition system 550 for depositing a tin-bismuth alloy on a substrate 556. Can be used.

  Substrate 556 may be a titanium substrate, such as a titanium mechanical fastener. Other metallic substrates 556 (eg, iron-based, copper-based, and nickel-based (eg, Inconel)) can also be used by the disclosed electrodeposition method 500 and system 550 without departing from the scope of the present disclosure. can do.

  The anode 558 of the disclosed electrodeposition system 550 can be a tin anode (eg, 99.99 percent pure tin), or a tin-bismuth anode. As one general example, anode 558 can include from about 2 weight percent to about 5 weight percent bismuth, with the balance being substantially tin. As one specific example, anode 558 can include about 3 weight percent bismuth, with the balance being substantially tin.

  Bath 552 can be any suitable container for receiving and containing electrolyte solution 554. Compositionally, the material forming the bath 552 must be chemically compatible with the activation solution 554. Of course, bath 552 must be sized and shaped to accept anode 558 and substrate 556 in the bath.

The electrolyte solution 554 contains water (H ₂ O), a tin salt dissolved in water, a bismuth salt dissolved in water, and an acid. The electrolyte solution 554 can be maintained at atmospheric pressure (eg, 1 atm) and at about 15 ° C. to about 50 ° C. (eg, room temperature (about 21 ° C.)). However, it is contemplated that higher and lower pressures may be used, as well as higher and lower temperatures, without departing from the scope of the present disclosure.

The tin salt in the electrolyte solution 554 provides tin (tin (II) ²⁺ ) ions. In one preparation, tin salt in the electrolyte solution 554, tin sulfate (SnSO _4). In another preparation, a tin salt in the electrolyte solution 554, tin chloride (SnCl _2). In another preparation, a tin salt in the electrolyte solution 554, a tin fluoride (SnF _2). In yet another preparation, the tin salt in the electrolyte solution 554 comprises at least two of tin sulfate (SnSO ₄ ), tin chloride (SnCl ₂ ), and tin fluoride (SnF ₂ ).

  The tin salt in the electrolyte solution 554 may be present at a concentration of about 15 grams per liter to about 200 grams per liter based on the total volume of the activation solution 554. In one alternative expression, the concentration of the tin salt ranges from about 15 grams per liter to about 150 grams per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the tin salt ranges from about 15 grams per liter to about 100 grams per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the tin salt ranges from about 20 grams per liter to about 100 grams per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the tin salt ranges from about 20 grams per liter to about 50 grams per liter based on the total volume of the electrolyte solution 554. In yet another alternative expression, the concentration of the tin salt ranges from about 25 grams per liter to about 35 grams per liter based on the total volume of the electrolyte solution 554.

The bismuth salt in the electrolyte solution 554 supplies bismuth (Bi ³⁺ ) ions. In one preparation, the bismuth salt in the electrolyte solution 554 is bismuth sulfate (Bi ₂ (SO ₄ ) _{3. In} another preparation, the bismuth salt in the electrolyte solution 554 is bismuth oxide (Bi ₂ O ₃ ) it is. in another preparation, bismuth salts in the electrolyte solution 554, a bismuth nitrate (Bi (NO _{3) 3).} in another preparation, bismuth salt in the electrolyte solution 554, bismuth chloride ( BiCl ₃₎ is. in another preparation, bismuth salts in the electrolyte solution 554, a three-a bismuth fluoride (BiF _3). in yet another preparation, bismuth salt in the electrolyte solution 554, bismuth sulfate _{(Bi 2 (SO 4) 3} ), bismuth oxide _{(Bi 2 O} 3), bismuth nitrate _{(Bi (NO 3) 3)} , bismuth chloride (BiCl _3), and trifluoride bismuth (Bi ₃₎ Of the at least two.

  The bismuth salt in the electrolyte solution 554 may be present at a concentration of about 0.25 grams per liter to about 10 grams per liter based on the total volume of the activation solution 554. In one alternative expression, the concentration of the bismuth salt ranges from about 0.25 grams per liter to about 5 grams per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the bismuth salt ranges from about 0.25 grams per liter to about 2.5 grams per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the bismuth salt ranges from about 0.25 grams per liter to about 1 gram per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the bismuth salt ranges from about 0.3 grams per liter to about 0.8 grams per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the bismuth salt ranges from about 0.4 grams per liter to about 4 grams per liter based on the total volume of the electrolyte solution 554. In a further alternative expression, the concentration of the bismuth salt ranges from about 0.4 grams per liter to about 0.7 grams per liter based on the total volume of the electrolyte solution 554.

The acid lowers the pH of the electrolyte solution 554. In one preparation, the acid in the electrolyte solution 554, a sulfuric acid _(H 2 SO _4). In another preparation, the acid in the electrolyte solution 554 is sulfamic acid (H ₃ NSO ₃ ). In yet another preparation, the acid in the activation solution 554 includes both sulfuric acid (H ₂ SO ₄ ) and sulfamic acid (H ₃ NSO ₃ ).

  The acid in the electrolyte solution 554 may be present at a concentration ranging from about 50 milliliters per liter to about 150 milliliters per liter based on the total volume of the electrolyte solution 554. In one alternative expression, the acid concentration ranges from about 60 milliliters per liter to about 140 milliliters per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the acid concentration ranges from about 70 milliliters per liter to about 130 milliliters per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the concentration of the acid ranges from about 75 milliliters per liter to about 125 milliliters per liter based on the total volume of the electrolyte solution 554. In another alternative expression, the acid concentration ranges from about 80 milliliters per liter to about 120 milliliters per liter based on the total volume of the electrolyte solution 554. In yet another alternative expression, the acid concentration ranges from about 90 milliliters per liter to about 110 milliliters per liter based on the total volume of the electrolyte solution 554.

  Additional components may be included in the electrolyte solution 554 without departing from the scope of the present disclosure. Various carriers and / or additives may be included in the electrolyte solution 554. As one specific, non-limiting example, the electrolyte solution 554 may include TIN MAC HT STARTER A (a surfactant protected by intellectual property, commercially available from MacDermid of Waterbury, Connecticut). it can. As another specific, non-limiting example, the electrolyte solution 554 includes TIN MAC HT STARTER B (a methacrylic acid source protected by intellectual property, commercially available from MacDermid of Waterbury, Connecticut). Can be. As yet another specific, non-limiting example, the electrolyte solution 554 can be obtained from TIN MAC HT REPLENISHER (a source and surfactant of dipropylene glycol methyl ether protected by intellectual property, MacDermid of Waterbury, Connecticut). Commercially available). In one embodiment, the electrolyte solution further contains at least one of a surfactant, methacrylic acid, and dipropylene glycol methyl ether.

As one specific, non-limiting example, the electrolyte solution 554 may be water, 30 grams per liter of tin sulfate (SnSO ₄ ), 0.58 grams per liter of bismuth sulfate (Bi ₂ (SO ₄ ) ₃ ), 1105 per milliliter liter of sulfuric acid _(H 2 _SO 4), 1 liter per 20 ml TIN MAC HT STARTER a, 1 5 per milliliter liter TIN MAC HT STARTER B, and 1 liter 3 per ml of TIN MAC HT Including REPLENISHER.

The electrolyte solution 554 can be manufactured in various ways without departing from the scope of the present disclosure. In one particular implementation, a method according to the present disclosure for producing an electrolyte solution 554 includes the following steps:
(1) mixing an acid (eg, sulfuric acid at 66 ° in Baume) and at least a portion of water (eg, deionized water) to obtain an acidic solution;
(2) dissolving a tin salt (for example, tin sulfate (SnSO ₄ )) in an acid solution;
(3) a step of dissolving a bismuth salt (e.g. bismuth sulfate _{(Bi 2 (SO 4)} 3)) in an acidic solution,
(4) optionally adding one or more additives / carriers (eg, TIN MAC HT STARTER A, TIN MAC HT STARTER B, and / or TIN MAC HT REPLENISHER); and (5) adding the electrolyte solution 554 Include the step of adding more water, if necessary, to bring the total volume required.

  In block 504 (FIG. 10), the substrate 556 is immersed (eg, completely immersed) in the electrolyte solution 554. The conducting wire 566 can electrically connect the soaked base material 556 and the first terminal 562 of the current source 560.

  At block 506 (FIG. 10), the anode 558 is immersed (eg, completely immersed) in the electrolyte solution 554. Conductor 568 can electrically connect immersed anode 558 to second terminal 564 of current source 560.

  At block 508 (FIG. 10), the current source 560 is activated so that current passes between the substrate 556 and the anode 558. The current causes a tin-bismuth alloy to be deposited on the substrate 556.

  The step of passing current (block 508) can be performed at various current densities without departing from the scope of the present disclosure. One skilled in the art will understand that the current density is a controllable parameter, and that selecting the appropriate current density depends on a variety of factors, including, among other factors, the duration of the step of passing current (block 508). Will need to be considered positively. In one representation, the current passed during the current passing step (block 508) is a current density ranging from about 10 amps per square foot to about 80 amps per square foot, based on the surface area of the substrate 556. Can have. In another expression, the current passed during the current passing step (block 508) is a current density ranging from about 10 amps per square foot to about 50 amps per square foot, based on the surface area of the substrate 556. Can have. In another expression, the current passed during the current passing step (block 508) is a current density ranging from about 20 amps per square foot to about 40 amps per square foot, based on the surface area of the substrate 556. Can have. In another expression, the current passed during the current passing step (block 508) is a current density ranging from about 15 amps per square foot to about 30 amps per square foot, based on the surface area of the substrate 556. Can have. In yet another expression, the current passed during the current passing step (block 508) may have a current density of about 30 amps per square foot based on the surface area of the substrate 556.

  The step of passing current (block 508) can be performed for various durations without departing from the scope of the present disclosure. One skilled in the art will appreciate that current density is a controllable parameter and that various factors (eg, current density, among other factors) need to be considered in order to select an appropriate duration. Will be evaluated. In one expression, the step of passing a current (block 508) can be performed for about 5 minutes to about 120 minutes. In other words, passing the current (block 508) can occur over a period of about 5 minutes to about 60 minutes. In another expression, the step of passing a current (block 508) can be performed for about 10 minutes to about 30 minutes. In another expression, the step of passing a current (block 508) can be performed for about 10 minutes to about 20 minutes. In yet another expression, the step of passing a current (block 508) can be performed over about 15 minutes.

  At block 510 (FIG. 10), the substrate 556 is disconnected from the current source 560 and removed from the electrolyte solution 554.

  At block 512 (FIG. 10), the substrate 556 can be rinsed with a rinsing fluid. As one example, the rinsing fluid may be water, for example, deionized water.

  Examples of the present disclosure may be described in the context of an aircraft manufacturing and operating method 1000 shown in FIG. 12, and an aircraft 1002 shown in FIG. During pre-production, aircraft construction and operation method 1000 may include specifications and design 1004 for aircraft 1002, and material procurement 1006. During production, component / subassembly production 1008 and aircraft 1002 system integration 1010 are performed. Thereafter, aircraft 1002 may be inspected, transported 1012, and moved to operation 1014. While in service by a customer, aircraft 1002 is scheduled for regular maintenance and operation 1016 (which may include transformation, rebuilding, refurbishment, etc.).

  Each step of the operating method 1000 may be performed or performed by a system integrator, a third party, and / or an operator (eg, a customer). For the purposes of this specification, a system integrator may include, but is not limited to, any number of aircraft manufacturers and subcontractors of key systems, and third parties may include, but are not limited to, any number of vendors. , Subcontractors, and suppliers, and workers can be airlines, leasing companies, military organizations, service agencies, and the like.

  As shown in FIG. 13, an aircraft 1002 manufactured by the example method 1000 may include an airframe 1018 having a plurality of systems 1020 and an interior 1022. Examples of multiple systems 1020 can include one or more of one or more propulsion systems 1024, electrical systems 1026, hydraulic systems 1028, and environmental systems 1030. One or more other systems may be included.

  The compositions and methods disclosed herein can be used during one or more steps in the aircraft construction and operation method 1000. As one example, a component or subassembly 1008, system integration 1010, and / or maintenance and operation 1016 corresponding to component / subassembly manufacturing may be made or manufactured using the compositions and methods disclosed herein. Can be done. As another example, airframe 1018 may be configured using the compositions and methods disclosed herein. Also, one or more examples of devices, examples of methods, or combinations thereof, may also be used during component / subassembly fabrication 1008 and / or system integration 1010, for example, by significantly accelerating the assembly of aircraft. Or, for example, by reducing the cost of aircraft 1002 (eg, airframe 1018 and / or interior 1022). Similarly, one or more example systems, example methods, or combinations thereof, may be utilized while aircraft 1002 is in operation, for example, for maintenance and operation 1016, but are not limited to such.

  The present disclosure further includes the following illustrative, non-limiting examples, which may or may not be included in the claims.

Example 1: A method for producing an electrolyte solution,
Mixing at least one of sulfuric acid and sulfamic acid with at least a portion of water to obtain an acidic solution;
A method comprising: dissolving a tin salt in an acidic solution; and dissolving a bismuth salt in the acidic solution.

Example 2: An electrodeposition system,
A current source having a first terminal and a second terminal;
A bath comprising the electrolyte solution of Example 1;
A substrate immersed in the electrolyte solution, the substrate being electrically connected to the first terminal of the current source; and an anode including tin, immersed in the electrolyte solution, and An anode electrically connected to the second terminal,
An electrodeposition system comprising:

  Example 3 The electrodeposition system according to example 1 or 2, wherein the anode further comprises bismuth.

  Example 4: The electrodeposition system of any of Examples 1 to 3, wherein the anode further comprises from about 2 weight percent to about 5 weight percent bismuth and the substantial balance of the anode is tin.

Example 5: A method for depositing a tin-bismuth alloy on a substrate, comprising:
A method comprising immersing a substrate and an anode comprising tin in the electrolyte solution of Example 1, and passing a current between the substrate and the anode to form a deposit on the substrate.

  Example 6: The method of Example 5, wherein the anode further comprises from about 2 weight percent to about 5 weight percent bismuth, and a substantial balance of the anode is tin.

  Example 7: The method of Examples 5 or 6, wherein the current has a current density of about 10 amps per square foot to about 50 amps per square foot based on the surface area of the substrate.

  Example 8: The method of Example 7, wherein the current has a current density of about 15 amps per square foot to about 30 amps per square foot based on the surface area of the substrate.

  Example 9: The method of Example 8, wherein the current has a current density of about 15 amps per square foot to about 30 amps per square foot based on the surface area of the substrate.

  Example 10: The method of any of Examples 5-9, wherein the current is passed for a duration, wherein the duration is from about 5 minutes to about 120 minutes.

  Example 11: The method of Example 10, wherein the current is passed for a duration, wherein the duration is from about 10 minutes to about 20 minutes.

  Example 12: The method of any of Examples 5 to 11, further comprising activating the substrate prior to soaking and passing an electrical current.

  Example 13: Examples 5 to 12, wherein the activating comprises immersing the substrate in the activating solution for a predetermined time, wherein the activating solution comprises water, an ammonium salt containing a fluorine-containing anion, and sulfuric acid. The method according to any of the above.

  Example 14: From Example 5, wherein activating comprises immersing the substrate in the activating solution for a predetermined time, wherein the activating solution comprises water, a fluoride salt, hydrofluoric acid, and sulfuric acid. 14. The method according to any of 13.

  Example 15: The method of any of Examples 5 to 14, wherein activating comprises subjecting the substrate to an anodic sulfuric acid process.

  Example 16: The method of any of Examples 5 to 15, further comprising strike plating the substrate prior to dipping and passing current.

  Example 17: The method according to any of Examples 5 to 16, wherein the strike plating comprises nickel strike plating.

Example 18: strike plating
18. The method of any of Examples 5 to 17, comprising immersing the substrate and the nickel anode in a strike plating electrolyte solution containing nickel chloride, hydrochloric acid and water, and passing an electric current between the substrate and the nickel anode. the method of.

Example 19: The strike plating electrolyte solution is
About 100 grams per liter to about 300 grams of nickel chloride per liter based on the total volume of strike plating electrolyte solution, and about 50 milliliters per liter to 1 liter based on total volume of strike plating electrolyte solution 19. The method according to any of Examples 5 to 18, comprising about 250 milliliters of hydrochloric acid.

Example 20: An electrolyte solution,
An electrolyte solution containing water, a tin salt, a bismuth salt, and at least one of sulfuric acid and sulfamic acid.

  Example 21: The electrolyte solution of example 20, wherein the tin salt comprises tin sulfate.

  Example 22: The electrolyte solution of examples 20 or 21, wherein the tin salt is present at a concentration ranging from 20 grams per liter to 100 grams per liter based on the total volume of the electrolyte solution.

  Example 23: The electrolyte solution according to any of Examples 20 to 22, wherein the bismuth salt comprises bismuth sulfate.

  Example 24. The electrolyte solution of any of Examples 20 to 23, wherein the bismuth salt is present at a concentration ranging from 0.4 grams per liter to 4 grams per liter based on the total volume of the electrolyte solution.

  Example 25: Any of Examples 20 to 24, wherein at least one of sulfuric acid and sulfamic acid is present at a concentration ranging from 75 milliliters per liter to 125 milliliters per liter based on the total volume of the electrolyte solution. Electrolyte solution.

Example 26: an electrodeposition system,
A current source having a first terminal and a second terminal;
A bath comprising the electrolyte solution of Example 20;
A substrate immersed in the electrolyte solution, the substrate being electrically connected to the first terminal of the current source; and an anode including tin, immersed in the electrolyte solution, and An anode electrically connected to the second terminal,
An electrodeposition system comprising:

  Example 27: The electrodeposition system of example 26, wherein the anode further comprises bismuth.

  While the compositions and methods disclosed herein have been described in the context of an aircraft, those skilled in the art will readily appreciate that the disclosed compositions and methods can be used for a variety of applications. There will be. For example, the disclosed compositions and methods can be practiced on various types of vehicles, including, for example, helicopters, passenger ships, automobiles, marine products (ships, motors, etc.), and the like.

  While various embodiments of the disclosed compositions and methods for electrodepositing a tin-bismuth alloy on a metal substrate have been shown and described, those skilled in the art, having read this specification, may make appropriate changes. It is possible. The present application includes such modifications and the present application is limited only by the claims.

Claims (10)

An electrolyte solution,
water and,
Tin salt,
Bismuth salt,
At least one of sulfuric acid and sulfamic acid;
An electrolyte solution containing   The electrolyte solution according to claim 1, wherein the tin salt contains at least one of tin sulfate, tin chloride, and tin fluoride.   3. The electrolyte solution according to claim 1 or 2, wherein the tin salt is present at a concentration ranging from 15 grams per liter to 200 grams per liter based on the total volume of the electrolyte solution.   The electrolyte solution according to claim 1, wherein the bismuth salt contains at least one of bismuth sulfate, bismuth oxide, bismuth nitrate, bismuth chloride, and bismuth trifluoride.   The electrolyte solution according to any one of claims 1 to 4, wherein the bismuth salt is present at a concentration ranging from 0.25 grams per liter to 10 grams per liter based on the total volume of the electrolyte solution. .   The electrolyte solution of claim 1, wherein at least one of sulfuric acid and sulfamic acid is present at a concentration ranging from 50 milliliters per liter to 150 milliliters per liter, based on the total volume of the electrolyte solution.   2. The electrolyte solution according to claim 1, comprising tin sulfate, bismuth sulfate, and sulfuric acid.   The electrolyte solution according to any one of claims 1 to 7, further comprising at least one of a surfactant, methacrylic acid, and dipropylene glycol methyl ether. An electrodeposition system,
A current source having a first terminal and a second terminal;
A bath containing the electrolyte solution according to claim 1,
A substrate immersed in the electrolyte solution, a substrate electrically connected to the first terminal of the current source, and an anode including tin, immersed in the electrolyte solution; An electrodeposition system comprising an anode electrically connected to the second terminal of the current source. The electrodeposition system of claim 9, wherein the anode further comprises from about 2 weight percent to about 5 weight percent bismuth, and a substantial balance of the anode is tin.