CN113930814A - Silver alloy plating solution, electric brush plating process, silver alloy plating layer and application - Google Patents
Silver alloy plating solution, electric brush plating process, silver alloy plating layer and application Download PDFInfo
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- CN113930814A CN113930814A CN202111337055.8A CN202111337055A CN113930814A CN 113930814 A CN113930814 A CN 113930814A CN 202111337055 A CN202111337055 A CN 202111337055A CN 113930814 A CN113930814 A CN 113930814A
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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
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
Abstract
The invention provides a silver alloy plating solution which comprises the following components in parts by weight: 20-70 g/L of silver nitrate, 2-60 g/L of sodium methanesulfonate, 180-240 g/L of sodium thiosulfate, 30-60 g/L of potassium metabisulfite, 5-80 g/L of sodium potassium tartrate, 0.1-30 g/L of bismuth nitrate, 5-40 g/L of ammonium acetate, 5-20 g/L of dodecylbenzene sulfonic acid isopropanolamine salt, 0.1-2 g/L of bipyridyl and 0.2-5 g/L of a brightening additive. The invention also provides a preparation method and a brush plating process of the electroplating solution, and a silver alloy plating layer obtained by the brush plating process and application thereof. The invention adopts multi-element coordination, increases the cathode polarization effect in the process of brush plating, regulates and controls the reduction discharge speed of silver ions, and obtains a high-performance plating layer. Bismuth salt is added into the acid plating solution to form Ag-Bi alloy codeposition, Bi atoms are preferentially gathered at the grain boundary of the Ag crystal with the face-centered cubic structure through the grain boundary segregation effect, the grain boundary energy is reduced, thus a polycrystalline structure refined to the nanometer level is obtained, and the prepared plating layer has good comprehensive performance.
Description
Technical Field
The invention relates to the technical field of precision machining, in particular to a silver alloy plating solution, an electric brush plating process, a silver alloy plating layer and application.
Background
In equipment such as a transformer, a circuit breaker, an isolating switch and the like in a power system, a current guide part such as a current guide plate, a contact and the like often causes surface damage due to oxidation, corrosion, abrasion and the like in the service process, so that the contact area is overheated and even has an arcing phenomenon, and great hidden danger is brought to the safe operation of the equipment.
For this problem, the conventional treatment is to apply conductive paste and perform part replacement. The prior operation experience shows that the performance of the part coated with the conductive adhesive is reduced again after the part is in service for a short time, so that the contact resistance is increased, and the risk of failure is generated. And carrying out the part and changing and need have a power failure to overhaul, increased electric wire netting dispatch work load and construction cost by a wide margin, some equipment even are difficult to carry out the change of single conductive part, need break down the maintenance to equipment, cause great economic loss.
The brush plating technique does not adopt the bath plating, but uses the plating pen dipped with the special plating solution to make relative motion with the plating piece to obtain the plating layer. The technology has the characteristics of simple equipment, flexible process, high deposition efficiency and suitability for field operation, and is an effective means for repairing the conductive coating.
The silver metal has good heat conduction and electric conduction performance and stable chemical property, so the silver metal is a metal which can improve the electrical performance of the surface of a component. In addition, the wear resistance and corrosion resistance of the electroplated layer can be further improved through alloying, and the conductive plating metal is prepared. Because the conventional silver plating solution is cyanide plating solution, the cyanide plating solution has severe toxicity and is difficult to meet the requirements of field application. Cyanide is extremely toxic and has environmental protection problems, and various links such as production, transportation, storage, use, waste discharge and the like have great safety threats to the environment and people.
Disclosure of Invention
The invention provides a silver alloy plating solution, an electric brush plating process, a silver alloy coating and application, and has the advantages of field use, high coating compactness, high bonding strength, suitability for preparation of various coatings and the like.
The technical scheme of the invention is realized as follows:
according to a first aspect of embodiments of the present invention, there is provided a silver alloy plating solution.
In some embodiments, the silver alloy plating solution comprises the following components in parts by weight:
20-70 g/L of silver nitrate, 2-60 g/L of sodium methanesulfonate, 180-240 g/L of sodium thiosulfate, 30-60 g/L of potassium metabisulfite, 5-80 g/L of sodium potassium tartrate, 0.1-30 g/L of bismuth nitrate, 5-40 g/L of ammonium acetate, 5-20 g/L of dodecylbenzene sulfonic acid isopropanolamine salt, 0.1-2 g/L of bipyridyl and 0.2-5 g/L of a brightening additive.
Optionally, the composition comprises the following components in parts by weight:
30-45 g/L of silver nitrate, 5-15 g/L of sodium methanesulfonate, 200-220 g/L of sodium thiosulfate, 30-50 g/L of potassium metabisulfite, 10-20 g/L of sodium potassium tartrate, 0.1-10 g/L of bismuth nitrate, 10-20 g/L of ammonium acetate, 10-20 g/L of dodecylbenzene sulfonic acid isopropanolamine salt, 0.5-1 g/L of bipyridyl and 0.5-1 g/L of a brightening additive.
Optionally, the pH value of the silver alloy plating solution is 4-5. The pH value has an important influence on the quality of the coating.
Optionally, the pH adjustment is performed with potassium hydroxide, ammonia, nitric acid, sulfuric acid.
According to a second aspect of embodiments of the present invention, there is provided a method of preparing the silver alloy plating solution described above.
In some embodiments, the silver alloy plating solution is prepared by the following steps:
mixing potassium metabisulfite and silver nitrate according to the weight part to form a solution with white precipitates;
adding the solution with the white precipitate into a sodium thiosulfate solution;
step three, sequentially adding sodium methanesulfonate, ammonium acetate, sodium potassium tartrate, dodecylbenzene sulfonic acid isopropylamine salt, bipyridine and a brightening additive into the solution obtained in the step two;
and step four, adding bismuth nitrate into the solution obtained in the step three.
The adding sequence of the steps provided by the invention has important influence on the preparation of the silver alloy plating solution. Mixing potassium metabisulfite with silver nitrate, adding into sodium thiosulfate solution, and preparing silver thiosulfate plating solution by reversing the order to form black Ag2S insoluble matter is precipitated. Sodium methanesulfonate, ammonium acetate and potassium sodium tartrate are sequentially added to form a multi-element complex plating solution so as to enhance the polarization capability in the electroplating process. The dodecyl benzene sulfonic acid isopropyl alcohol amine salt is used for enhancing the surface wettability of the coating and is beneficial to the desorption of bubbles. The bipyridine and the brightening additive are organic additives, play a chemical inhibition role and enhance the compactness and the brightness of the plating layer.
According to a third aspect of the embodiments of the present invention, there is provided a brush plating process of the silver alloy plating solution described above.
In some embodiments, in the brush plating process of the silver alloy plating solution, the target workpiece is connected with the negative electrode of a direct current power supply, the brush plating pen is connected with the positive electrode of the direct current power supply, the voltage is 0.5-4V, and the relative moving speed of the brush plating pen and the target workpiece is 0.08-0.2 m/s. The time and thickness of the brush plating are determined according to the thickness requirement of the plating layer.
Optionally, the above-mentioned brush plating process further comprises a pretreatment step, wherein the pretreatment step sequentially comprises the following steps:
(1) polishing the surface of a target workpiece until the roughness of the surface of the workpiece is not lower than Ra2.5 mu m;
(2) performing electric cleaning treatment on the surface of a target workpiece, wherein the workpiece is connected with a positive electrode, and the voltage is 5-15V;
(3) and (3) carrying out activation treatment on the surface of a target workpiece, wherein the workpiece is connected with a positive electrode, and the voltage is 9-14V.
Optionally, in the step (2), the electric cleaning liquid adopted by the electric cleaning treatment is composed of the following components in parts by weight: 20-70 g/L trisodium phosphate, 10-30 g/L sodium carbonate, 5-20 g/L sodium silicate and 5-30 g/L sodium hydroxide.
Optionally, in the step (3), the activating treatment adopts an activating solution,
the activating solution adopted by the copper matrix target workpiece comprises the following components in parts by weight: 20-80 g/L of sodium sulfite, 10-40 g/L of sodium bicarbonate, 5-20 g/L of sodium dihydrogen phosphate and 5-30 g/L of trisodium citrate; the copper matrix target workpiece comprises a copper and copper alloy workpiece surface;
the activating solution adopted by the aluminum matrix target workpiece comprises the following components in parts by weight: 20-40 mL/L of hydrochloric acid, 60-100 g/L of sodium chloride, 0.5-2 g/L of cobalt chloride and 10-30 g/L of citric acid; the aluminum substrate target workpieces include aluminum and aluminum alloy workpieces.
Optionally, the brush plating pen comprises a pen body and a sheath, wherein the pen body is made of graphite or titanium alloy with a platinum coating, and the sheath is made of polyester or absorbent cotton.
According to a fourth aspect of embodiments of the present invention, there is provided a silver alloy plating layer prepared by the above brush plating process.
According to a fifth aspect of embodiments of the present invention, there is provided a use of the silver alloy plating described above.
In some embodiments, the silver alloy plating is electroplated onto the surface of the copper-based workpiece.
According to a sixth aspect of embodiments of the present invention, there is provided a use of the silver alloy plating described above.
In some embodiments, the surface of the copper substrate workpiece is plated with a transition layer, the silver alloy plating layer is plated on the transition layer, and the purpose of the transition layer is to enhance the bonding strength and reduce the stress of the plating layer.
Optionally, the transition layer is a nickel transition layer.
Optionally, the thickness of the transition layer is 0.5-50 μm.
According to a seventh aspect of embodiments of the present invention, there is provided a use of the silver alloy plating layer described above.
In some embodiments, the aluminum-based workpiece is plated with a copper plating on the surface, and the silver alloy plating is electroplated on the copper plating, the copper plating being provided to reduce plating stress and improve bond strength.
According to an eighth aspect of embodiments of the present invention, there is provided a use of the silver alloy plating described above.
In some embodiments, the aluminum-based workpiece is coated with a copper coating, the copper coating is coated with a transition layer, and the transition layer is coated with the silver alloy coating, wherein the transition layer is used for enhancing the bonding strength and reducing the coating stress.
Optionally, the transition layer is a nickel transition layer.
Optionally, the thickness of the transition layer is 0.5-50 μm.
The invention has the beneficial effects that:
the invention adopts the multi-element complex silver electroplating solution, increases the cathode polarization effect in the brush plating process through multi-element coordination, regulates the reduction discharge speed of silver ions, and obtains a high-performance plating layer. After a plurality of complexing agents are added, the plating solution can form a mixed ligand besides a single silver ion complex, so that the coordination capability to silver ions is enhanced on the whole, and a more compact and fine silver alloy plating layer is obtained. More importantly, bismuth salt is added into the acidic plating solution to form Ag-Bi alloy codeposition, Bi atoms are preferentially gathered at the grain boundary of the Ag crystal with the face-centered cubic structure through the grain boundary segregation effect, the grain boundary energy is reduced, so that a polycrystalline structure refined to a nanometer level is obtained, the hardness and the atmospheric corrosion resistance of the prepared plating layer are improved, the comprehensive performance is good, and the problem of performance reduction caused again after the contact is coated with conductive adhesive for short-term service can be avoided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of a copper substrate coated with a silver alloy coating according to the present invention;
FIG. 2 is a schematic structural view of a copper substrate plated with a nickel transition layer and then plated with a silver alloy plating layer of the present invention;
FIG. 3 is a schematic structural view of a copper plating layer on an aluminum substrate followed by plating with a silver alloy plating layer of the present invention;
FIG. 4 is a schematic structural view of a copper plating layer on an aluminum substrate, a nickel transition layer and a silver alloy plating layer of the present invention;
FIG. 5 is a scanning electron microscope image of the electroplated silver alloy layer according to example 4 of the present invention, wherein FIG. 5(a) is a scanning electron microscope 500 times, and FIG. 5(b) is a scanning electron microscope 5000 times;
FIG. 6 is an XRD pattern of an electroplated silver alloy layer of example 4 of the present invention;
FIG. 7 is a scanning electron microscope image of the electroplated silver alloy layer according to example 5 of the present invention, wherein FIG. 7(a) is a scanning electron microscope 500 times, and FIG. 7(b) is a scanning electron microscope 5000 times;
FIG. 8 is an XRD pattern of an electroplated silver alloy layer of example 5 of the present invention;
FIG. 9 is a scanning electron microscope image of the electroplated silver alloy layer according to example 6 of the present invention, wherein FIG. 9(a) is a scanning electron microscope 500 times, and FIG. 9(b) is a scanning electron microscope 5000 times;
fig. 10 is an XRD spectrum of the electroplated silver alloy layer of example 6 of the present invention.
Reference numerals:
1. copper base work piece, 2, silver alloy coating, 3, nickel transition layer, 4, aluminum base work piece, 5, copper coating.
Detailed Description
To make the features and effects of the present invention comprehensible to those having ordinary knowledge in the art, general description and definitions are made with respect to terms and phrases mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the precision of the number of significant digits of the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49. In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that a sub-group of all elements or any individual element within a Markush group or list of options may also be used to describe the invention. For example, if X is described as "selected from the group consisting of1、X2And X3The group "also indicates that X has been fully described as X1Is claimed with X1And/or X2Claim (5). Furthermore, where Markush group or option terms are used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all elements or individual elements within the Markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of1、X2And X3Group consisting of "and Y is described as" selected from Y1、Y2And Y3The group "formed indicates that X has been fully described as X1Or X2Or X3And Y is Y1Or Y2Or Y3Claim (5).
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.
Example 1
The silver alloy plating solution comprises the following components in parts by weight:
30g/L of silver nitrate, 5g/L of sodium methanesulfonate, 200g/L of sodium thiosulfate, 30g/L of potassium metabisulfite, 10g/L of sodium potassium tartrate, 0.1g/L of bismuth nitrate, 10g/L of ammonium acetate, 10g/L of dodecylbenzene sulfonic acid isopropylamine salt, 0.5g/L of bipyridyl and 0.5g/L of a brightening additive.
The preparation method of the silver alloy plating solution comprises the following steps:
mixing potassium metabisulfite and silver nitrate according to the weight part to form a solution with white precipitates;
adding the solution with the white precipitate into a sodium thiosulfate solution;
step three, sequentially adding sodium methanesulfonate, ammonium acetate, sodium potassium tartrate, dodecylbenzene sulfonic acid isopropylamine salt, bipyridine and a brightening additive into the solution obtained in the step two;
and step four, adding bismuth nitrate into the solution obtained in the step three.
Example 2
The silver alloy plating solution comprises the following components in parts by weight:
40g/L of silver nitrate, 10g/L of sodium methanesulfonate, 210g/L of sodium thiosulfate, 40g/L of potassium metabisulfite, 15g/L of sodium potassium tartrate, 2g/L of bismuth nitrate, 15g/L of ammonium acetate, 15g/L of dodecylbenzene sulfonic acid isopropylamine salt, 0.7g/L of bipyridyl and 0.7g/L of brightening additive.
The preparation method of the silver alloy plating solution is the same as that of example 1.
Example 3
The silver alloy plating solution comprises the following components in parts by weight:
45g/L of silver nitrate, 15g/L of sodium methanesulfonate, 220g/L of sodium thiosulfate, 50g/L of potassium metabisulfite, 20g/L of sodium potassium tartrate, 10g/L of bismuth nitrate, 20g/L of ammonium acetate, 20g/L of dodecylbenzene sulfonic acid isopropylamine salt, 1g/L of bipyridyl and 1g/L of brightening additive.
The preparation method of the silver alloy plating solution is the same as that of example 1.
Example 4
In the present embodiment, the target workpiece is a T2 copper workpiece.
The embodiment also provides an electric brush plating process of the silver alloy plating solution, which comprises the following steps of firstly pretreating a workpiece T2 copper workpiece:
(1) polishing the surface of a T2 copper workpiece until the roughness of the surface of the workpiece is not lower than Ra2.5 mu m;
(2) performing electric cleaning treatment on the surface of a T2 copper workpiece, wherein the electric cleaning solution adopted by the electric cleaning treatment comprises the following components in parts by weight: 20-70 g/L trisodium phosphate, 10-30 g/L sodium carbonate, 5-20 g/L sodium silicate and 5-30 g/L sodium hydroxide; the workpiece is connected with the anode, and the voltage is 5-15V;
(3) the method comprises the following steps of carrying out activation treatment on the surface of a T2 copper workpiece, wherein the activation treatment adopts an activation solution which comprises the following components in parts by weight: 20-80 g/L of sodium sulfite, 10-40 g/L of sodium bicarbonate, 5-20 g/L of sodium dihydrogen phosphate and 5-30 g/L of trisodium citrate; the workpiece is connected with the anode, and the voltage is 9-14V.
After pretreatment, the T2 copper workpiece is connected with the negative pole of a direct current power supply, the brush plating pen is connected with the positive pole of the direct current power supply, the voltage is 1.6-2V, the silver alloy plating solution of the embodiment 1 is adopted as the electric brush plating solution, and the relative moving speed of the brush plating pen and the T2 copper workpiece is 0.12-0.15/s, so that a silver alloy plating layer is obtained.
Optionally, the brush plating pen comprises a pen body and a sheath, wherein the pen body is made of graphite, and the sheath is made of polyester.
The brush plating time was about 350s, the thickness of the silver alloy plating layer was 15.8 μm, the surface roughness Ra was 0.36 μm, the Bi content in the plating layer was 0.83 wt.%, and the plating hardness was HV 129. The prepared silver alloy plating layer has smooth and bright appearance.
The scanning electron microscope picture of the silver alloy plating layer is shown in fig. 5, and it can be seen that the structure of the plating layer is compact and the crystal grains are fine. The XRD spectrum of the silver alloy plating is shown in fig. 6, and it can be seen that the phase formed is a single-phase solid solution, the diffraction peak exhibits a broadening characteristic, and the diffraction peak of the plating is slightly shifted to the left as compared with pure silver.
Example 5
In the present embodiment, the target workpiece is a T2 copper workpiece. The workpiece T2 was first pretreated with copper, the pretreatment procedure being the same as in example 4.
And after pretreatment, carrying out brush nickel plating on the surface of the T2 copper workpiece to obtain a nickel transition layer. Wherein, the components of the brush nickel plating solution are as follows: 360g/L nickel sulfate, 30mL/L acetic acid, 20g/L sodium acetate, 0.1g/L sodium sulfanilate and 0.01g/L sodium dodecyl sulfate, and the pH value is 3.5. In the process of plating nickel on the electric brush, the working voltage is 8-14V, and the workpiece is connected with a negative electrode.
Optionally, the thickness of the transition layer is 0.5-50 μm.
The silver alloy plating layer was brush-plated on the nickel transition layer, and the silver alloy plating solution of example 2 was used as the brush-plating solution. The T2 workpiece is connected with the negative pole of the DC power supply, the brush plating pen is connected with the positive pole of the DC power supply, the voltage is 1.6-2V, and the relative moving speed of the brush plating pen and the T2 copper workpiece is 0.12-0.15/s, so as to obtain the silver alloy plating layer.
The brush plating time was about 350s, the thickness of the silver alloy plating layer was 17.64 μm, the surface roughness Ra was 0.18 μm, and the Bi content was 2.49%. The prepared silver alloy plating layer has smooth and bright appearance.
The scanning electron microscope picture of the silver alloy plating layer is shown in fig. 7, and it can be seen that the structure of the plating layer is compact and becomes smoother, and the crystal grains are very fine. The XRD spectrum of the silver alloy plating layer is shown in fig. 8, and it can be seen that the phase formed is a single-phase solid solution Ag, the diffraction peak exhibits a broadening characteristic, and as the content of Bi in the plating layer increases, the diffraction peak of the plating layer shifts to the left side, and the diffraction peak widens.
Example 6
In this example, the target workpiece is a 5083 aluminum alloy base. Firstly, pretreating a 5083 aluminum alloy substrate, wherein the pretreatment sequentially comprises the following steps:
(1) polishing the surface of a 5083 aluminum alloy substrate workpiece until the roughness of the surface of the workpiece is not lower than Ra2.5 mu m;
(2) the surface of a 5083 aluminum alloy substrate workpiece is subjected to electric cleaning treatment, and electric cleaning liquid adopted by the electric cleaning treatment comprises the following components in parts by weight: 20-40 mL/L of hydrochloric acid, 60-100 g/L of sodium chloride, 0.5-2 g/L of cobalt chloride and 10-30 g/L of citric acid, wherein the workpiece is connected with a positive electrode, and the voltage is 5-15V;
(3) the surface of a 5083 aluminum alloy substrate workpiece is subjected to activation treatment, the activation treatment adopts an activation solution, and the activation solution comprises the following components in parts by weight: 20-40 mL/L of hydrochloric acid, 60-100 g/L of sodium chloride, 0.5-2 g/L of cobalt chloride and 10-30 g/L of citric acid; the workpiece is connected with the anode, and the voltage is 9-14V.
And after pretreatment, plating copper on the surface of a 5083 aluminum alloy substrate workpiece by using an electric brush to obtain a copper plating layer. Wherein, the copper plating solution comprises the following components: 325g/L of methanesulfonic acid, 175g/L of ethylenediamine, 1g/L of sodium chloride and 160g/L of basic copper carbonate, wherein the pH value is 8.5-9.5. The working voltage is 8-14V, the relative movement speed is 0.12-2 m/s, and the workpiece is connected with a cathode.
The silver alloy plating solution of example 3 was used for brush plating of the silver alloy plating layer on the copper plating layer. And connecting the 5083 aluminum alloy substrate workpiece with the negative electrode of a direct current power supply, connecting the brushing and plating pen with the positive electrode of the direct current power supply, wherein the voltage is 1.6-2V, and the relative movement speed of the brushing and plating pen and the 5083 aluminum alloy substrate workpiece is 0.12-0.15/s to obtain the silver alloy coating.
The brush plating time was about 350s, the thickness of the silver alloy plating layer was 20.6 μm, the surface roughness Ra was 0.144 μm, the Bi content in the plating layer was 10.26 wt.%, and the plating layer hardness was HV 175. The prepared silver alloy plating layer has smooth and bright appearance.
The scanning electron microscope picture of the silver alloy coating is shown in fig. 9, and it can be seen that the structure of the coating is compact, the coating is flat, and the crystal grains are very fine and reach the nanometer level. The XRD pattern of the silver alloy plating layer is shown in fig. 10, which shows that the phase formed is two-phase composition, which is Ag and Bi, and the diffraction peak presents a broadening feature more obvious, corresponding to the decrease of the grain size.
The invention adopts the brush silver-plating alloy plating layer to be applied to plating layer repair of copper-based and aluminum-based substrates, provides the cyanide-free silver alloy plating solution formula and the preparation method thereof, can be used on site, has the outstanding characteristics of high plating layer compactness and high bonding strength, is suitable for preparation of various plating layers, is not limited by the shape and the size of a workpiece, and can be used in workpieces with plane and revolution surface characteristics, such as lead connecting plates, isolating switch leads, contact fingers, current transformer lead connecting plates and repair of other areas easy to generate heat. The invention has important significance for eliminating the defects of heating and arcing of the conductive component of the equipment and improving the power supply reliability, and can generate obvious economic benefit and social benefit.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (16)
1. The silver alloy plating solution is characterized by comprising the following components in parts by weight:
20-70 g/L of silver nitrate, 2-60 g/L of sodium methanesulfonate, 180-240 g/L of sodium thiosulfate, 30-60 g/L of potassium metabisulfite, 5-80 g/L of sodium potassium tartrate, 0.1-30 g/L of bismuth nitrate, 5-40 g/L of ammonium acetate, 5-20 g/L of dodecylbenzene sulfonic acid isopropanolamine salt, 0.1-2 g/L of bipyridyl and 0.2-5 g/L of a brightening additive.
2. The silver alloy plating solution according to claim 1, which comprises the following components in parts by weight:
30-45 g/L of silver nitrate, 5-15 g/L of sodium methanesulfonate, 200-220 g/L of sodium thiosulfate, 30-50 g/L of potassium metabisulfite, 10-20 g/L of sodium potassium tartrate, 0.1-10 g/L of bismuth nitrate, 10-20 g/L of ammonium acetate, 10-20 g/L of dodecylbenzene sulfonic acid isopropanolamine salt, 0.5-1 g/L of bipyridyl and 0.5-1 g/L of a brightening additive.
3. A silver alloy plating solution according to claim 2, prepared by the steps of:
mixing potassium metabisulfite and silver nitrate according to the weight part to form a solution with white precipitates;
adding the solution with the white precipitate into a sodium thiosulfate solution;
step three, sequentially adding sodium methanesulfonate, ammonium acetate, sodium potassium tartrate, dodecylbenzene sulfonic acid isopropylamine salt, bipyridine and a brightening additive into the solution obtained in the step two;
and step four, adding bismuth nitrate into the solution obtained in the step three.
4. A process for brush plating a silver alloy plating solution according to any one of claims 1 to 3,
the target workpiece is connected with the negative electrode of the direct current power supply, the brush plating pen is connected with the positive electrode of the direct current power supply, the voltage is 0.5-4V, and the relative moving speed of the brush plating pen and the target workpiece is 0.08-0.2 m/s.
5. The process according to claim 4, wherein the plating solution is a silver alloy plating solution,
the method also comprises a pretreatment step, wherein the pretreatment step sequentially comprises the following steps:
polishing the surface of a target workpiece until the roughness of the surface of the workpiece is not lower than Ra2.5 mu m;
performing electric cleaning treatment on the surface of a target workpiece, wherein the workpiece is connected with a positive electrode, and the voltage is 5-15V;
and (3) carrying out activation treatment on the surface of a target workpiece, wherein the workpiece is connected with a positive electrode, and the voltage is 9-14V.
6. The process according to claim 5, wherein the plating solution is a silver alloy plating solution,
in the step of performing electric cleaning treatment on the surface of the target workpiece, electric cleaning liquid adopted by the electric cleaning treatment is composed of the following components in parts by weight: 20-70 g/L trisodium phosphate, 10-30 g/L sodium carbonate, 5-20 g/L sodium silicate and 5-30 g/L sodium hydroxide.
7. The process according to claim 5, wherein the plating solution is a silver alloy plating solution,
in the step of performing the activation treatment on the surface of the target workpiece, the activation treatment adopts an activation solution,
the activating solution adopted by the copper matrix target workpiece comprises the following components in parts by weight: 20-80 g/L of sodium sulfite, 10-40 g/L of sodium bicarbonate, 5-20 g/L of sodium dihydrogen phosphate and 5-30 g/L of trisodium citrate;
the activating solution adopted by the aluminum matrix target workpiece comprises the following components in parts by weight: 20-40 mL/L of hydrochloric acid, 60-100 g/L of sodium chloride, 0.5-2 g/L of cobalt chloride and 10-30 g/L of citric acid.
8. The process according to claim 4, wherein the plating solution is a silver alloy plating solution,
the brush plating pen comprises a pen body and a sheath, wherein the pen body is made of graphite or titanium alloy with a platinum coating, and the sheath is made of polyester or absorbent cotton.
9. A silver alloy plating layer produced by a brush plating process of a silver alloy plating solution as set forth in any one of claims 4 to 8.
10. Use of a silver alloy coating according to claim 9,
the silver alloy plating layer is electroplated on the surface of the copper substrate workpiece.
11. Use of a silver alloy coating according to claim 9,
and plating a transition layer on the surface of the copper-based workpiece, and plating the silver alloy plating layer on the transition layer.
12. Use of a silver alloy coating according to claim 11,
the transition layer is a nickel transition layer.
13. Use of a silver alloy coating according to claim 9,
the surface of the aluminum substrate workpiece is plated with a copper plating layer, and the silver alloy plating layer is electroplated on the copper plating layer.
14. Use of a silver alloy coating according to claim 9,
the surface of the aluminum-based workpiece is plated with a copper plating layer, the copper plating layer is plated with a transition layer, and the transition layer is plated with the silver alloy plating layer.
15. Use of a silver alloy coating according to claim 14,
the transition layer is a nickel transition layer.
16. Use of a silver alloy coating according to claim 12 or 15,
the thickness of the transition layer is 0.5-50 μm.
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