CN110777405A - Compositions and methods for electrodepositing tin-bismuth alloys on metal substrates - Google Patents

Compositions and methods for electrodepositing tin-bismuth alloys on metal substrates Download PDF

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CN110777405A
CN110777405A CN201910661565.7A CN201910661565A CN110777405A CN 110777405 A CN110777405 A CN 110777405A CN 201910661565 A CN201910661565 A CN 201910661565A CN 110777405 A CN110777405 A CN 110777405A
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electrolyte
substrate
bismuth
activation solution
anode
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S·R·苏布拉马尼亚拉加
E·R·布龙多
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Boeing Co
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

The present invention relates to compositions and methods for electrodepositing tin-bismuth alloys on metal substrates. The method comprises the following steps: (1) immersing the substrate and an anode in an electrolyte comprising an acid of at least one of water, a stannous salt, a bismuth salt, sulfuric acid and sulfamic acid, the anode comprising tin and optionally bismuth, (2) passing an electric current between the substrate and the anode to form a deposit on the substrate.

Description

Compositions and methods for electrodepositing tin-bismuth alloys on metal substrates
Technical Field
The present application relates to the deposition of materials on substrates, and more particularly, to compositions and methods for activating metal substrates, and for electrodepositing tin-bismuth alloys on metal substrates.
Background
Mechanical fasteners are widely used to join two or more components of a structural assembly. For example, mechanical fasteners are widely used to connect structural components of aircraft frames.
Aircraft experience electromagnetic effects (EME) from various sources, such as lightning strikes and precipitation static electricity. Metal aircraft structures are readily conductive and therefore relatively immune to electromagnetic effects. However, composite (e.g., carbon fiber reinforced plastic) aircraft structures do not readily conduct away large currents and electromagnetic forces generated by electromagnetic effects. 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 may be provided to the mechanical fastener in the form of a conductive metal surface deposit (e.g., a metal plating). While various metal surface deposits can provide suitable electrical conductivity to impart electromagnetic effect protection, other factors (such as lubricity and electrical compatibility with carbon fiber reinforced plastics) are also considerations for mechanical fasteners used in the aerospace industry.
Tin is present in α and β phases α tin is gray, powdery and forms a nuisance, while β tin is white and has a body centered tetragonal crystal structure when tin is alloyed with bismuth at concentrations greater than 0.4 weight percent bismuth, it begins to be present in β phase tin-bismuth has shown promise as a suitable metal surface deposit for mechanical fasteners due to its electrical conductivity, lubricity and electrical compatibility with carbon fiber reinforced plastics.
Disclosure of Invention
Embodiments herein include:
an electrolyte includes water, a stannous salt, a bismuth salt, and an acid.
An electrolyte comprising water, at least one of stannous sulfate, stannous chloride, and stannous fluoride dissolved in water, at least one of bismuth sulfate, bismuth oxide, bismuth nitrate, bismuth chloride, and bismuth trifluoride dissolved in water, and at least one of sulfuric acid and sulfamic acid dissolved in water.
An electrolyte includes water, stannous sulfate, bismuth sulfate, and sulfuric acid.
An electrolyte comprising water, at least one of stannous sulfate, stannous chloride, and stannous fluoride dissolved in water in a concentration of about 15 g/l to about 200 g/l based on a total volume of the electrolyte, at least one of bismuth sulfate, bismuth oxide, bismuth nitrate, bismuth chloride, and bismuth trifluoride dissolved in water in a concentration of about 0.25 g/l to about 10 g/l based on a total volume of the electrolyte, and at least one of sulfuric acid and sulfamic acid dissolved in water in a concentration of about 50 ml/l to about 150 ml/l based on a total volume of the electrolyte.
A method of making an electrolyte comprising the steps of: (1) mixing at least one of sulfuric acid and sulfamic acid with water to produce an acidic solution, (2) dissolving a stannous salt in the acidic solution, and (3) dissolving a bismuth salt in the acidic solution.
An electrodeposition system, comprising: a current source having a first terminal and a second terminal; a bath containing an electrolyte comprising water, a stannous salt, a bismuth salt, and an acid; a substrate immersed in the electrolyte, the substrate being electrically connected to a first terminal of the current source; and an anode comprising tin, the anode being immersed in the electrolyte and electrically connected to the second terminal of the current source.
A method of depositing a tin-bismuth alloy on a substrate, the method comprising the steps of: (1) immersing the substrate and an anode in an electrolyte, the anode comprising tin, the electrolyte comprising water, a stannous salt, a bismuth salt, and an acid, and (2) passing an electric current between the substrate and the anode to form a deposit on the substrate.
A method of depositing a tin-bismuth alloy on a substrate, the method comprising the steps of: (1) activating the substrate, (2) impact plating the substrate, (3) immersing the substrate and an anode in an electrolyte, the anode comprising tin, the electrolyte comprising water, a stannous salt, a bismuth salt, and an acid, and (4) passing an electric current between the substrate and the anode to form a deposit on the substrate.
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.
Drawings
FIG. 1 is a flow chart depicting the disclosed method for depositing a material on a substrate;
FIG. 2 is a photomicrograph of a tin-bismuth alloy deposited on a titanium substrate according to the method of FIG. 1;
FIG. 3 is a flow chart depicting one disclosed method for activating a substrate, such as a titanium substrate, in accordance with the method of FIG. 1;
FIG. 4 is a schematic view of a system for activating a substrate according to the method of FIG. 3;
FIG. 5 is a flow chart depicting another disclosed method for activating a substrate, such as a titanium substrate, in accordance with the method of FIG. 1;
FIG. 6 is a schematic view of a system for activating a substrate according to the method of FIG. 5;
FIG. 7 is a flow chart depicting yet another disclosed method for activating a substrate, such as a titanium substrate, in accordance with the method of FIG. 1;
FIG. 8 is a schematic view of a system for activating a substrate according to the method of FIG. 7;
FIG. 9 is a schematic view of a system for impact plating a substrate according to the method of FIG. 1;
FIG. 10 is a flow chart depicting one disclosed method for electrodepositing a tin-bismuth alloy on a substrate in accordance with the method of FIG. 1;
FIG. 11 is a schematic view of an electrodeposition system for depositing a tin-bismuth alloy according to the method of FIG. 10;
FIG. 12 is a flow chart of an aircraft manufacturing and service method; and
fig. 13 is a block diagram of an aircraft.
Detailed Description
Disclosed herein are compositions, systems, and methods for activating metal substrates (e.g., metal fasteners or other parts/components). Also disclosed herein are compositions, systems, and methods for depositing materials on metal substrates (e.g., metal fasteners or other parts/components). The disclosed compositions, systems, and methods can be used alone or in various combinations to achieve desired deposition of materials on a substrate.
Referring to fig. 1, a method, generally designated 10, for depositing a material on a substrate is disclosed. While only three general steps are shown, those skilled in the art will appreciate that various additional steps may be performed before, after, or between the steps presented without departing from the scope of the disclosure.
The initial step (block 12) of the method 10 includes pretreating the substrate to render the substrate suitable for receiving material, such as metallic deposits or other metallic/non-metallic materials, thereon. Various pretreatments such as cleaning, degreasing, etching, and the like may be performed. In particular, the pre-treatment step (block 12) may include activating (block 14) the surface of the substrate. For example, in the case of a titanium substrate, the step of activating (block 14) the surface of the substrate may remove (or at least substantially reduce) a tough oxide layer known to form thereon.
An intermediate step (block 16) of the method 10 includes impact plating the pretreated substrate. The step of impact plating the pretreated substrate (block 16) may form a thin metal layer on the surface of the substrate, thereby providing the substrate with a surface more suitable for receiving and binding subsequent metal deposits. In certain embodiments, the impact plating step (block 16) may form a thin layer of nickel on the surface of the substrate.
The final step of the method 10 (block 18) includes electrodeposition on the impact plated substrate. The electrodeposition step (block 18) may form a metal deposit on the substrate surface. In particular embodiments, the electrodeposition step (block 18) may deposit a tin-bismuth alloy on the substrate surface.
Referring to FIG. 2, the disclosed method 10 is for depositing a thin layer of tin-bismuth alloy on a surface of a titanium alloy (Ti-6Al-4V) substrate. The result is an excellent bond between the tin-bismuth alloy deposit and the underlying titanium alloy substrate.
While the present disclosure focuses primarily on titanium substrates, i.e., substrates formed of titanium or titanium alloys (e.g., Ti-6Al-4V), it is believed that the disclosed method 10, as well as the various steps of the disclosed method 10 (e.g., the activation step (block 14), the impact plating step (block 16), and/or the electrodeposition step (block 18)) may be applied to non-titanium substrates. Examples of non-titanium substrates that may benefit from the present disclosure include, but are not limited to, iron alloys, copper alloys, and nickel alloys (e.g., Inconel).
Activation of
Disclosed herein are three methods of activation, including related compositions and systems. Only one of the disclosed activation methods may be used to activate a metal substrate, such as a titanium substrate. Alternatively, a variety of activation methods (e.g., a series of activation methods) including one or more of the disclosed activation methods can be used to activate a metal substrate, such as a titanium substrate.
Referring to fig. 3 and 4, a first activation method, generally designated 100, may begin at block 110 (fig. 3) with the step of preparing a bath 152 (shown in fig. 4) containing an activation solution 154. Bath 152 and activation solution 154 may constitute a first activation system 150.
Bath 152 may be any container suitable for receiving and containing an activation solution 154. Compositionally, the material forming bath 152 should be chemically compatible with activation solution 154. Of course, the bath 152 should be sized and shaped to receive the substrate 156 therein to be activated by the first activation system 150.
The activation solution 154 includes water (H) 2O), ammonium salt dissolved in water and sulfuric acid (H) dissolved in water 2SO 4). The activation solution 154 may be maintained at atmospheric pressure (e.g., 1atm) and a temperature of about 15 ℃ to about 50 ℃ (e.g., room temperature (-21 ℃)). However, the use of higher and lower pressures and higher and lower temperatures are contemplated and would not result in a departure from the scope of the present disclosure.
The ammonium salt in the activation solution 154 may have a fluorine-containing anion. In one formulation, the ammonium salt in the activation solution 154 is ammonium bifluoride (NH) 4HF 2). In another formulation, the ammonium salt in the activation solution 154 is ammonium tetrafluoroborate (NH) 4BF 4). In another formulation, the ammonium salt in the activation solution 154 includes ammonium hydrogen fluoride (NH) 4HF 2) And ammonium tetrafluoroborate (NH) 4BF 4)。
The ammonium salt in the activation solution 154 may be present at a concentration of about 10 grams/liter to about 150 grams/liter based on the total volume of the activation solution 154. In an alternative, the ammonium salt concentration ranges from about 20 grams/liter to about 120 grams/liter based on the total volume of the activation solution 154. In another alternative, the concentration of ammonium salt ranges from about 30 grams/liter to about 110 grams/liter based on the total volume of the activation solution 154. In another alternative, the concentration of ammonium salt ranges from about 40 grams/liter to about 100 grams/liter based on the total volume of the activation solution 154. In another alternative, the concentration of ammonium salt ranges from about 50 grams/liter to about 100 grams/liter based on the total volume of the activation solution 154. In another alternative, the concentration of ammonium salt ranges from about 60 grams/liter to about 100 grams/liter based on the total volume of the activation solution 154. In another alternative, the concentration of ammonium salt ranges from about 70 grams/liter to about 90 grams/liter based on the total volume of the activation solution 154. In another alternative, the concentration of ammonium salt is about 80 grams/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 of about 1% to about 70% by volume, based on the total volume of the activation solution 154. In an alternative, the concentration of sulfuric acid ranges from about 2% to about 50% by volume, based on the total volume of the activation solution 154. In another alternative, the concentration of sulfuric acid ranges from about 3% to about 40% by volume based on the total volume of the activation solution 154. In another alternative, the sulfuric acid concentration ranges from about 4% to about 30% by volume, based on the total volume of the activation solution 154. In another alternative, the concentration of sulfuric acid ranges from about 5% to about 25% by volume based on the total volume of the activation solution 154. In another alternative, the concentration of sulfuric acid ranges from about 5% to about 15% by volume based on the total volume of the activation solution 154. In another alternative, the concentration of sulfuric acid is about 10 volume percent based on the total volume of the activation solution 154.
As a specific, non-limiting example, the activation solution 154 includes water, 80 grams/liter of ammonium bifluoride (NH) 4HF 2) And 10% by volume of sulfuric acid (H) 2SO 4)。
The activation solution 154 may be manufactured in various ways without departing from the scope of the present disclosure. In one particular embodiment, the disclosed method for making the activation solution 154 includes the steps of: (1) mixing sulfuric acid (e.g., 66 baume sulfuric acid) with water (e.g., deionized water) to produce an acidic solution, (2) dissolving an ammonium salt (e.g., ammonium bifluoride and/or ammonium tetrafluoroborate) in the acidic solution; and (3) adding additional water as necessary to make up the total volume required for the activation solution 154.
At block 120 (fig. 3), the substrate 156 is immersed (e.g., fully immersed) in the activation solution 154. The substrate 156 may remain immersed in the activation solution 154 for a predetermined time before the substrate 156 is removed from the activation solution 154 as shown in block 130 (fig. 3). In the case of a titanium substrate (substrate 156), the predetermined time may be selected such that the activation solution 154 has sufficient time to reduce/eliminate the tough oxide layer on the substrate 156 without significantly disturbing the titanium/titanium alloy underlying the oxide layer. In one approach, the predetermined time is about 5 seconds to about 120 seconds. In another approach, the predetermined time is about 10 seconds to about 100 seconds. In another approach, the predetermined time is about 20 seconds to about 40 seconds. In another approach, the predetermined time is about 30 seconds.
At block 140 (fig. 3), the substrate 156 removed from the activation solution 154 may be rinsed with a rinse solution. As an example, the cleaning fluid may be water, such as deionized water.
Referring to fig. 5 and 6, a second activation method, generally designated 200, may begin at block 202 (fig. 5) with the step of preparing a bath 252 (shown in fig. 6) containing an activation solution 254. Bath 252 and activation solution 254 may constitute a second activation system 250.
Bath 252 may be any container suitable for receiving and containing an activation solution 254. Compositionally, the material forming bath 252 should be chemically compatible with activation solution 254. Of course, the bath 252 should be sized and shaped to receive the substrate 256 therein to be activated by the second activation system 250.
The activation solution 254 includes water (H) 2O), fluoride salt dissolved in water, hydrofluoric acid (HF) dissolved in water, and sulfuric acid (H) dissolved in water 2SO 4). The activation solution 254 may be maintained at atmospheric pressure (e.g., 1atm) and a temperature of about 15 ℃ to about 50 ℃ (e.g., room temperature (-21 ℃). However, the use of higher and lower pressures and higher and lower temperatures are contemplated and would not result in a departure from the scope of the present disclosure.
The fluoride salt in the activation solution 254 may haveThere are alkali metal cations and/or alkaline earth metal cations. In one formulation, the fluoride salt in the activation solution 254 is potassium fluoride (KF). In another formulation, the fluoride salt in the activation solution 254 is lithium fluoride (LiF). In another formulation, the fluoride salt in the activation solution 254 is sodium fluoride (NaF). In another formulation, the fluoride salt in the activation solution 254 is rubidium fluoride (RuF). In another formulation, the fluoride salt in the activation solution 254 is barium fluoride (BaF) 2). In another formulation, the fluoride salt in the activation solution 254 is strontium fluoride (SrF) 2). In another formulation, the fluoride salt in the activation solution 254 includes potassium fluoride (KF), lithium fluoride (LiF), sodium fluoride (NaF), rubidium fluoride (RuF), barium fluoride (BaF) 2) And strontium fluoride (SrF) 2) At least two of them.
The fluoride salt in the activation solution 254 may be present at a concentration of about 5 grams/liter to about 120 grams/liter based on the total volume of the activation solution 254. In an alternative approach, the concentration of the fluoride salt ranges from about 10 grams/liter to about 100 grams/liter based on the total volume of the activation solution 254. In another alternative, the concentration of the fluoride salt ranges from about 15 grams/liter to about 75 grams/liter based on the total volume of the activation solution 254. In another alternative, the concentration of the fluoride salt ranges from about 15 grams/liter to about 50 grams/liter based on the total volume of the activation solution 254. In another alternative, the concentration of the fluoride salt ranges from about 15 grams/liter to about 30 grams/liter based on the total volume of the activation solution 254. In another alternative, the concentration of the fluoride salt is about 20 grams/liter based on the total volume of the activation solution 254.
The hydrofluoric acid in the activation solution 254 may be present at a concentration of about 5 ml/l to about 250 ml/l based on the total volume of the activation solution 254. In an alternative approach, the concentration of hydrofluoric acid ranges from about 10 ml/l to about 200 ml/l based on the total volume of the activation solution 254. In another alternative, the concentration of hydrofluoric acid ranges from about 15 ml/l to about 150 ml/l based on the total volume of the activation solution 254. In another alternative, the concentration of hydrofluoric acid ranges from about 20 ml/l to about 150 ml/l based on the total volume of the activation solution 254. In another alternative, the concentration of hydrofluoric acid ranges from about 30 ml/l to about 100 ml/l based on the total volume of the activation solution 254. In another alternative, the concentration of hydrofluoric acid ranges from about 40 ml/l to about 80 ml/l based on the total volume of the activation solution 254. In another alternative, 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 of about 1% to about 45% by volume, based on the total volume of the activation solution 254. In an alternative, the concentration of sulfuric acid ranges from about 2% to about 35% by volume, based on the total volume of the activation solution 254. In another alternative, the concentration of sulfuric acid ranges from about 2% to about 20% by volume based on the total volume of the activation solution 254. In another alternative, the sulfuric acid concentration ranges from about 3% to about 15% by volume based on the total volume of the activation solution 254. In another alternative, the concentration of sulfuric acid ranges from about 3% to about 10% by volume based on the total volume of the activation solution 254. In another alternative, the concentration of sulfuric acid is about 5 volume percent based on the total volume of the activation solution 254.
As a specific, non-limiting example, the activation solution 254 includes water, 20 grams/liter potassium fluoride (KF), 60 milliliters/liter hydrofluoric acid (HF), and 5 volume percent sulfuric acid (H) 2SO 4)。
The activation solution 254 may be manufactured in various ways without departing from the scope of the present disclosure. In one particular embodiment, the disclosed method for making the activation solution 254 comprises the steps of: (1) mixing sulfuric acid (e.g., 66 baume sulfuric acid) with water (e.g., deionized water) to produce a first acidic solution, (2) mixing hydrofluoric acid (e.g., a 48 wt% aqueous solution) with the first acidic solution to produce a second acidic solution; (3) dissolving a fluoride salt (e.g., potassium fluoride) in a second acidic solution; and (4) adding additional water as necessary to make up the total volume required for the activation solution 254.
At block 204 (fig. 5), the substrate 256 is immersed (e.g., fully immersed) in the activation solution 254. The substrate 256 may remain immersed in the activation solution 154 for a predetermined time before the substrate 256 is removed from the activation solution 254 as shown in block 206 (fig. 5). In the case of a titanium substrate (substrate 256), the predetermined time may be selected such that the activation solution 254 has sufficient time to reduce/eliminate the tough oxide layer on the substrate 256 without significantly disturbing the titanium/titanium alloy underlying the oxide layer. In one approach, the predetermined time is about 5 seconds to about 120 seconds. In another approach, the predetermined time is about 10 seconds to about 100 seconds. In another approach, the predetermined time is about 20 seconds to about 40 seconds. In another approach, the predetermined time is about 30 seconds.
At block 208 (fig. 5), the substrate 256 removed from the activation solution 254 may be cleaned with a cleaning solution. As an example, the cleaning fluid may be water, such as deionized water.
Referring to fig. 7 and 8, a third activation method, generally designated 300, may begin at block 302 (fig. 7) with the step of preparing a bath 352 (shown in fig. 8) containing an activation solution 354. Bath 352 and activation solution 354, along with graphite electrode 358 and current source 360, may constitute a third activation system 350 that may be used to perform the anodic sulfuric acid process (third activation process 300) described herein.
Bath 352 may be any container suitable for receiving and containing activation solution 354. Compositionally, the material forming bath 352 should be chemically compatible with activation solution 354. Of course, bath 352 should be sized and shaped to receive graphite anode 358 therein and substrate 356 to be activated by third activation system 350.
The activation solution 354 includes water (H) 2O) and sulfuric acid (H) dissolved in water 2SO 4). The activation solution 354 may be maintained at atmospheric pressure (e.g., 1atm) and a temperature of about 15 ℃ to about 50 ℃ (e.g., room temperature (-21 ℃). However, the use of higher and lower pressures and higher and lower temperatures are contemplated and would not result in a departure from the scope of the present disclosure.
The sulfuric acid in the activation solution 354 may be present at a concentration of about 5 vol% to about 45 vol%, based on the total volume of the activation solution 354. In an alternative, the concentration of sulfuric acid ranges from about 5% to about 35% by volume based on the total volume of the activation solution 354. In another alternative, the concentration of sulfuric acid ranges from about 5% to about 30% by volume based on the total volume of the activation solution 354. In another alternative, the sulfuric acid concentration ranges from about 5% to about 25% by volume based on the total volume of the activation solution 354. In another alternative, the concentration of sulfuric acid ranges from about 10% to about 20% by volume based on the total volume of the activation solution 354. In another alternative, the concentration of sulfuric acid is about 15 volume percent based on the total volume of the activation solution 354.
As a specific non-limiting example, the activation solution 354 includes water and 15 volume percent sulfuric acid (H) 2SO 4)。
At block 304 (fig. 7), the substrate 356 is immersed (e.g., fully immersed) in the activation solution 354. A conductive wire 368 can electrically connect the immersed substrate 356 to the first terminal 364 of the current source 360.
At block 306 (fig. 7), the graphite electrode 358 is immersed (e.g., fully immersed) in the activation solution 354. A wire 366 may electrically connect the immersed graphite electrode 358 to the second terminal 362 of the current source 360.
At block 308 (fig. 7), the current source 360 is activated such that a current passes between the substrate 356 and the graphite electrode 358. The current source 360 may be configured to cause the substrate 356 to act as an anode, thereby etching the substrate 356. In the case of a titanium substrate (substrate 356), the anodic sulfuric acid process (third activation process 300) can reduce/eliminate the tough oxide layer on the substrate 356 without significantly disturbing the titanium/titanium alloy underlying the oxide layer.
The step of passing current (block 308) may be performed at various current densities without departing from the scope of the present disclosure. Those skilled in the art will appreciate that current density is a controllable parameter, and that selection of an appropriate current density may require consideration of various factors, such as the duration of the energizing step (block 308), and the like. In one approach, the current density of the current passed during the energizing step (block 308) may be about 10 amps per square foot to about 80 amps per square foot based on the surface area of the substrate 356. In another approach, the current density of the current passed during the energizing step (block 308) may be about 20 amps per square foot to about 60 amps per square foot based on the surface area of the substrate 356. In another approach, the current density of the current passed during the energizing step (block 308) may be about 20 amps per square foot to about 40 amps per square foot based on the surface area of the substrate 356. In another approach, the current density of the current passed during the energizing step (block 308) may be about 30 amps per square foot based on the surface area of the substrate 356.
The step of energizing (block 308) may be performed for various durations without departing from the scope of the present disclosure. Those skilled in the art will appreciate that current duration is a controllable parameter, and selection of an appropriate duration may require consideration of various factors, such as current density. In one approach, the step of energizing (block 308) may be performed for about 5 seconds to about 120 seconds. In another approach, the step of energizing (block 308) may be performed for about 10 seconds to about 100 seconds. In another approach, the step of energizing (block 308) may be performed for about 10 seconds to about 60 seconds. In another approach, the step of energizing (block 308) may be performed for about 15 seconds to about 45 seconds. In yet another approach, the step of energizing (block 308) may be performed 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 may be cleaned with a cleaning solution. As an example, the cleaning fluid may be water, such as deionized water.
Impact plating
Various impact plating methods are known in the art, including nickel impact plating methods (e.g., wood nickel impact), and may be used for the method 10 of fig. 1 without departing from the scope of the present disclosure. However, a specific nickel impact plating process is disclosed herein that can produce excellent substrate-to-subsequent plating bond, as shown in fig. 2.
Referring to fig. 9, an impact plating system, generally designated 450, includes a bath 452, an electrolyte 454 contained in the bath 452, a nickel anode 458 immersed in the electrolyte 454, and a current source 460. Current source 460 may include a first terminal 462 and a second terminal 464. The nickel anode 458 may be electrically connected to the second terminal 464 by a wire 468.
Bath 452 may be any container suitable for receiving and containing electrolyte 454. Compositionally, the material forming bath 452 should be chemically compatible with electrolyte 454. Of course, the bath 452 should be sized and shaped to receive the substrate 456 and nickel anode 458 therein.
Electrolyte 454 includes water (H) 2O), nickel chloride (NiCl) dissolved in water 2) And hydrochloric acid (HCl) dissolved in water. The electrolyte 454 may be maintained at atmospheric pressure (e.g., 1atm) and a temperature of about 15 ℃ to about 50 ℃ (e.g., room temperature (-21 ℃). However, the use of higher and lower pressures and higher and lower temperatures are contemplated and would not result in a departure from the scope of the present disclosure.
The nickel chloride in the electrolyte 454 may be present at a concentration of about 50 grams/liter to about 400 grams/liter based on the total volume of the electrolyte 454. In an alternative, the concentration of nickel chloride ranges from about 75 grams/liter to about 350 grams/liter based on the total volume of the electrolyte 454. In another alternative, the concentration of nickel chloride ranges from about 100 grams/liter to about 300 grams/liter based on the total volume of the electrolyte 454. In another alternative, the concentration of nickel chloride ranges from about 125 grams/liter to about 275 grams/liter based on the total volume of the electrolyte 454. In another alternative, the concentration of nickel chloride ranges from about 150 grams/liter to about 250 grams/liter based on the total volume of the electrolyte 454. In another alternative, the concentration of nickel chloride ranges from about 175 g/l to about 225 g/l based on the total volume of the electrolyte 454.
The hydrochloric acid in the electrolyte 454 may be present at a concentration of about 25 ml/l to about 300 ml/l based on the total volume of the electrolyte 454. In an alternative, the concentration of hydrochloric acid ranges from about 50 ml/l to about 250 ml/l based on the total volume of the electrolyte 454. In another alternative, the concentration of hydrochloric acid ranges from about 75 ml/l to about 225 ml/l based on the total volume of the electrolyte 454. In another alternative, the concentration of hydrochloric acid ranges from about 100 ml/l to about 200 ml/l based on the total volume of the electrolyte 454. In another alternative, the concentration of hydrochloric acid ranges from about 125 ml/l to about 175 ml/l based on the total volume of the electrolyte 454.
As a specific non-limiting example, the electrolyte 454 includes water, 200 grams/liter nickel chloride (NiCl) 2) And 150 ml/l hydrochloric acid (HCl).
As shown in fig. 9, a substrate 456 is immersed (e.g., fully immersed) in the electrolyte 454 of the bath 452. The substrate 456 is then electrically connected to a first terminal 462 of a current source 460 by a conductive line 466.
To initiate impact plating, the current source 460 is activated, causing current to pass between the substrate 456 and the nickel anode 458, and deposits form on the substrate 456. Alternatively, before starting the cathodic blasting, anodic blasting (the substrate 456 serves as an anode) may be performed to etch the substrate 456.
The anodic attack (etching) may be performed at various current densities and durations without departing from the scope of the present disclosure. In one approach, the anodic impact can be conducted at a current density of about 25 amps per square foot to about 75 amps per square foot for a duration of about 1 second to about 30 seconds, based on the surface area of the substrate 456. For example, the anodic impact can be performed at a current density of about 120 amps per square foot for about 10 seconds based on the surface area of the substrate 456.
The cathodic blasting (strike plating) may be performed at various current densities and durations without departing from the scope of the present disclosure. In one approach, the cathodic impingement may be performed at a current density of about 80 amps per square foot to about 160 amps per square foot for a duration of about 30 seconds to about 10 minutes, based on the surface area of the substrate 456. For example, the cathodic impingement may be performed at a current density of about 120 amps per square foot for about 5 minutes, based on the surface area of the substrate 456.
Once the current source 460 is turned off, the substrate 456 may be disconnected from the current source 460 and removed from the electrolyte 454. The substrate 456 may then be cleaned with a cleaning solution (e.g., deionized water).
Electrodeposition
Various impact electrodeposition methods may be used in the method 10 of fig. 1 without departing from the scope of the present disclosure. However, a specific tin-bismuth electrodeposition process is disclosed herein that, when used in sequence with one of the disclosed activation processes and the disclosed nickel strike plating process, can result in excellent substrate-subsequent plating bonding, as shown in fig. 2.
Referring to fig. 10 and 11, the disclosed electrodeposition method, generally designated 500, may begin at block 502 (fig. 10) with the step of preparing a bath 552 (shown in fig. 11) containing an electrolyte 554. The bath 552 and activation solution 554, along with the anode 558 and current source 560, can comprise the disclosed electrodeposition system 550, which can be used to deposit a tin-bismuth alloy on a substrate 556.
Substrate 556 can be a titanium substrate, such as a titanium mechanical fastener or the like. Other metal substrates 556, such as iron, copper, and nickel substrates (e.g., Inconel), may also be used with the disclosed electrodeposition method 500 and system 550 without departing from the scope of the present disclosure.
The anode 558 of the disclosed electrodeposition system 550 may be a tin anode (e.g., 99.99% pure tin) or a tin-bismuth anode. As a common example, anode 558 can include about 2 wt.% to about 5 wt.% bismuth, with the balance being substantially tin. As a specific example, anode 558 can include about 3 wt% bismuth, with the balance being substantially tin.
Bath 552 may be any container suitable for receiving and containing electrolyte 554. Compositionally, the material forming bath 552 should be chemically compatible with activation solution 554. Of course, the bath 552 should be sized and shaped to receive the anode 558 and the substrate 556 therein.
The electrolyte 554 includes water (H) 2O), stannous salts dissolved in water, bismuth salts dissolved in water and acids. The electrolyte 554 may be maintained at atmospheric pressure (e.g., 1atm) and a temperature of about 15 ℃ to about 50 ℃ (e.g., room temperature (-21 ℃). However, the use of higher and lower pressures and higher and lower temperatures are contemplated and would not result in a departure from the scope of the present disclosure.
The stannous salt in the electrolyte 554 provides stannous (tin (II) 2+) Ions. In one formulation, the stannous salt in the electrolyte 554 is stannous sulfate (SnSO) 4). In another formulation, in the electrolyte 554The stannous salt is stannous chloride (SnCl) 2). In another formulation, the stannous salt in the electrolyte 554 is stannous fluoride (SnF) 2). In another formulation, the stannous salt in the electrolyte 554 comprises stannous sulfate (SnSO) 4) Stannous chloride (SnCl) 2) And stannous fluoride (SnF) 2) At least two of them.
The stannous salt in the electrolyte 554 may be present at a concentration of about 15 grams/liter to about 200 grams/liter based on the total volume of the electrolyte 554. In an alternative approach, the concentration of the stannous salt ranges from about 15 grams/liter to about 150 grams/liter based on the total volume of the electrolyte 554. In another alternative, the concentration of the stannous salt ranges from about 15 grams/liter to about 100 grams/liter based on the total volume of the electrolyte 554. In another alternative, the concentration of the stannous salt ranges from about 20 grams/liter to about 100 grams/liter based on the total volume of the electrolyte 554. In another alternative, the concentration of the stannous salt ranges from about 20 grams/liter to about 50 grams/liter based on the total volume of the electrolyte 554. In another alternative, the concentration of the stannous salt ranges from about 25 grams/liter to about 35 grams/liter based on the total volume of the electrolyte 554.
Bismuth salt in electrolyte 554 provides bismuth (Bi) 3+) Ions. In one formulation, the bismuth salt in the electrolyte 554 is bismuth sulfate (Bi) 2(SO 4) 3). In another formulation, the bismuth salt in the electrolyte 554 is bismuth oxide (Bi) 2O 3). In another formulation, the bismuth salt in the electrolyte 554 is bismuth nitrate (Bi (NO) 3) 3). In another formulation, the bismuth salt in the electrolyte 554 is bismuth chloride (BiCl) 3). In another formulation, the bismuth salt in the electrolyte 554 is bismuth trifluoride (BiF) 3). In another formulation, the bismuth salt in the electrolyte 554 includes bismuth sulfate (Bi) 2(SO 4) 3) Bismuth oxide (Bi) 2O 3) Bismuth nitrate (Bi (NO) 3) 3) Bismuth chloride (BiCl) 3) And bismuth trifluoride (BiF) 3) At least two of them.
The bismuth salt in the electrolyte 554 may be present at a concentration of about 0.25 g/l to about 10 g/l based on the total volume of the electrolyte 554. In an alternative, the concentration of the bismuth salt ranges from about 0.25 g/l to about 5 g/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the bismuth salt ranges from about 0.25 g/l to about 2.5 g/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the bismuth salt ranges from about 0.25 g/l to about 1 g/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the bismuth salt ranges from about 0.3 g/l to about 0.8 g/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the bismuth salt ranges from about 0.4 g/l to about 4 g/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the bismuth salt ranges from about 0.4 g/l to about 0.7 g/l based on the total volume of the electrolyte 554.
The acid lowers the pH of the electrolyte 554. In one formulation, the acid in the electrolyte 554 is sulfuric acid (H) 2SO 4). In another formulation, the acid in the electrolyte 554 is sulfamic acid (H) 3NSO 3). In another formulation, the acid in the electrolyte 554 includes sulfuric acid (H) 2SO 4) And sulfamic acid (H) 3NSO 3) Both of which are described below.
The acid in the electrolyte 554 may be present at a concentration of about 50 ml/l to about 150 ml/l based on the total volume of the electrolyte 554. In an alternative, the concentration of the acid ranges from about 60 ml/l to about 140 ml/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the acid ranges from about 70 ml/l to about 130 ml/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the acid ranges from about 75 ml/l to about 125 ml/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the acid ranges from 80 ml/l to about 120 ml/l based on the total volume of the electrolyte 554. In another alternative, the concentration of the acid ranges from about 90 ml/l to about 110 ml/l based on the total volume of the electrolyte 554.
Other components may be included in the electrolyte 554 without departing from the scope of the present disclosure. Various carriers and/or additives may be included in the electrolyte 554. As a specific non-limiting example, electrolyte 554 may include TIN MACHT STARTER A, a proprietary surfactant available from MacDermid, Waterbury, Connecticut, USA. As another specific, non-limiting example, electrolyte 554 may include TIN MAC HT STARTER B, a proprietary source of methacrylic acid, which is commercially available from MacDermid, Waterbury, connecticut. As another specific, non-limiting example, electrolyte 554 may include TIN MAC HT REPLENISHER, which is a proprietary source of dipropylene glycol methyl ether and surfactants, commercially available from MacDermid, Waterbury, connecticut. In one embodiment, the electrolyte further includes at least one of a surfactant, methacrylic acid, and dipropylene glycol methyl ether.
As a specific non-limiting example, the electrolyte 554 includes water, 30 grams/liter stannous sulfate (SnSO) 4) 0.58 g/l bismuth sulfate (Bi) 2(SO 4) 3) 105 ml/l sulfuric acid (H) 2SO 4) 20 ml/l TIN MAC HTSTARTER A, 5 ml/l TIN MAC HT STARTER B and 3 ml/l TIN MAC HT REPLENISHER.
The electrolyte 554 may be manufactured in various ways without departing from the scope of the present disclosure. In a particular embodiment, the disclosed method for manufacturing the electrolyte 554 includes the steps of: (1) mixing an acid (e.g., 66 baume sulfuric acid) with at least a portion of the water (e.g., deionized water) to produce an acidic solution, (2) adding a stannous salt (e.g., stannous sulfate (SnSO) 4) Dissolving in acidic solution, and (3) dissolving bismuth salt (such as bismuth sulfate (Bi) 2(SO 4) 3) Dissolved in an acidic solution, (4) optionally adding one or more additives/carriers (e.g., TIN MAC HT STARTER A, TIN MAC HT STARTER B, and/or TIN MAC HT REPLENISHER), and (5) adding additional water as necessary to make up the total volume of electrolyte 554 desired.
At block 504 (fig. 10), the substrate 556 is immersed (e.g., fully immersed) in the electrolyte 554. A wire 566 may electrically connect the immersed substrate 556 to the first terminal 562 of the current source 560.
At block 506 (fig. 10), the anode 558 is immersed (e.g., fully immersed) in the electrolyte 554. A wire 568 may electrically connect the immersed anode 558 to the second terminal 564 of the current source 560.
At block 508 (fig. 10), the current source 560 is activated to pass current between the substrate 556 and the anode 558. The current will cause the tin-bismuth alloy to deposit on the substrate 556.
The step of passing current (block 508) may be performed at various current densities without departing from the scope of the present disclosure. Those skilled in the art will appreciate that current density is a controllable parameter, and selection of an appropriate current density may require consideration of various factors, such as the duration of the energizing step (block 508). In one approach, the current density of the current passed during the energizing step (block 508) can range from about 10 amps per square foot to about 80 amps per square foot based on the surface area of the substrate 556. In another approach, the current density of the current passed during the energizing step (block 508) may range from about 10 amps per square foot to about 50 amps per square foot based on the surface area of the substrate 556. In another approach, the current density of the current passed during the energizing step (block 508) can range from about 20 amps per square foot to about 40 amps per square foot based on the surface area of the substrate 556. In another approach, the current density of the current passed during the energizing step (block 508) can range from about 15 amps per square foot to about 30 amps per square foot based on the surface area of the substrate 556. In another approach, the current density of the current passed during the energizing step (block 508) may be about 30 amps per square foot based on the surface area of the substrate 556.
The step of energizing (block 508) may be performed for various durations without departing from the scope of the present disclosure. Those skilled in the art will appreciate that current duration is a controllable parameter, and selection of an appropriate duration may require consideration of various factors, such as current density. In one approach, the step of passing current (block 508) may be performed for about 5 minutes to about 120 minutes. In another approach, the step of passing current (block 508) may be performed for about 5 minutes to about 60 minutes. In another approach, the step of passing current (block 508) may be performed for about 10 minutes to about 30 minutes. In another approach, the step of passing current (block 508) may be performed for about 10 minutes to about 20 minutes. In another approach, the step of passing current (block 508) may be performed for about 15 minutes.
At block 510 (fig. 10), the substrate 556 is disconnected from the current source 560 and removed from the electrolyte 554.
At block 512 (fig. 10), the substrate 556 may be cleaned with a cleaning solution. As an example, the cleaning fluid may be water, such as deionized water.
Examples of the present disclosure may be illustrated in the context of aircraft manufacturing and service method 1000 shown in FIG. 12 and aircraft 1002 shown in FIG. 13. During pre-production, aircraft manufacturing and service method 1000 may include specification and design 1004 of aircraft 1002 and material procurement 1006. During production, component/subassembly manufacturing 1008 and system integration 1010 of aircraft 1002 occurs. Thereafter, the aircraft 1002 may undergo certification and delivery 1012 in order to be placed into service 1014. During customer service, aircraft 1002 may be scheduled for routine maintenance and service 1016, which may also include modification, reconfiguration, refurbishment, and so on.
The various processes of method 1000 may be performed or carried out by a system integrator, a third party, and/or an operator (e.g., a customer). For purposes of this description, a system integrator may include, but is not limited to, any number of aircraft manufacturers and major-system subcontractors; third parties may include, but are not limited to, any number of suppliers, subcontractors, and vendors; the operator may be an airline, leasing company, military entity, service organization, and so on.
As shown in fig. 13, an aircraft 1002 produced by example method 1000 may include a rack 1018 having a plurality of systems 1020 and an interior 1022. Examples of the plurality of systems 1020 may include one or more of a propulsion system 1024, an electrical system 1026, a hydraulic system 1028, and an environmental system 1030. Any number of other systems may be included.
The disclosed compositions and methods may be used during any one or more stages of aircraft manufacturing and service method 1000. As one example, components or sub-assemblies corresponding to component/sub-assembly manufacturing 1008, system integration 1010, and/or maintenance and service 1016 may be manufactured or fabricated using the disclosed compositions and methods. As another example, the frame 1018 may be constructed using the disclosed compositions and methods. Also, for example, one or more device instantiations, method instantiations, or combinations thereof may be utilized during component/subassembly manufacturing 1008 and/or system integration 1010 by substantially expediting assembly of aircraft 1002 (e.g., racks 1018 and/or interior 1022) or reducing costs of aircraft 1002. Similarly, one or more of a system instance, a method instance, or a combination thereof may be used while aircraft 1002 is in service, for example and without limitation, to maintenance and service 1016.
Although the disclosed compositions and methods are described in the context of an aircraft, one of ordinary skill in the art will readily recognize that the disclosed compositions and methods may be used in a variety of applications. For example, the disclosed compositions and methods can be implemented in various types of vehicles, including, for example, helicopters, passenger ships, automobiles, marine products (hulls and engines, etc.), and the like.
While various aspects of the disclosed compositions and methods for electrodepositing a tin-bismuth alloy on a metal substrate have been shown and described, modifications may occur to those skilled in the art upon reading the specification. This application includes such modifications and is limited only by the scope of the claims.

Claims (10)

1. An electrolyte (554), comprising:
water;
a stannous salt;
a bismuth salt; and
at least one of sulfuric acid and sulfamic acid.
2. The electrolyte (554) of claim 1, wherein the stannous salt comprises at least one of stannous sulfate, stannous chloride, and stannous fluoride.
3. The electrolyte (554) of claim 1, wherein the bismuth salt includes at least one of bismuth sulfate, bismuth oxide, bismuth nitrate, bismuth chloride, and bismuth trifluoride.
4. The electrolyte (554) of claim 1, comprising stannous sulfate, bismuth sulfate, and sulfuric acid.
5. The electrolyte (554) of claim 1, further comprising at least one of a surfactant, methacrylic acid, and dipropylene glycol methyl ether.
6. A method of making the electrolyte (554) of claim 1, the method comprising:
mixing at least one of sulfuric acid and sulfamic acid with at least a portion of the water to produce an acidic solution;
dissolving the stannous salt in the acidic solution; and
dissolving the bismuth salt in the acidic solution.
7. An electrodeposition system (550), comprising:
a current source (560) having a first terminal (562) and a second terminal (564);
a bath comprising the electrolyte (554) of claim 1;
a substrate (556) immersed in the electrolyte (554), the substrate (556) being electrically connected to the first terminal (562) of the current source (560); and
an anode (558) comprising tin, the anode (558) being immersed in the electrolyte (554) and electrically connected to a second terminal (564) of the current source (560).
8. The electrodeposition system (550) of claim 7, wherein the anode (558) further comprises bismuth.
9. The electrodeposition system (550) of claim 7, wherein the anode (558) further comprises about 2 wt.% to about 5 wt.% bismuth, wherein substantially the balance of the anode is tin.
10. A method (500) of depositing a tin-bismuth alloy on a substrate (556), the method (500) comprising:
a step (504) of immersing the substrate (556) and an anode (558) in the electrolyte (554) of claim 1, the anode (558) comprising tin; and
a step (508) of passing an electric current between the substrate (556) and the anode (558) to form a deposit on the substrate (556).
CN201910661565.7A 2018-07-25 2019-07-22 Compositions and methods for electrodepositing tin-bismuth alloys on metal substrates Pending CN110777405A (en)

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