CN111411350B - Nickel plating solution for aluminum alloy surface and preparation method thereof - Google Patents
Nickel plating solution for aluminum alloy surface and preparation method thereof Download PDFInfo
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- CN111411350B CN111411350B CN202010293289.6A CN202010293289A CN111411350B CN 111411350 B CN111411350 B CN 111411350B CN 202010293289 A CN202010293289 A CN 202010293289A CN 111411350 B CN111411350 B CN 111411350B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
Abstract
The invention relates to the technical field of chemical nickel plating, and particularly provides a nickel plating solution for an aluminum alloy surface and a preparation method thereof. The first aspect of the invention provides a nickel plating solution for the surface of an aluminum alloy, which comprises the following components in concentration: 18-42 g/L nickel salt, 33-146 g/L organic acid and salt thereof, 17-35 g/L hypophosphite and 5-17 mg/L stabilizer. The nickel plating solution with high phosphorus content provided by the invention effectively improves the hardness of a plating layer and reduces the magnetic conductivity through the combined action of hypophosphite, nickel salt with higher concentration, organic acid and salt thereof, specific stabilizing agent and penetrating agent, and simultaneously improves the forming time of the plating layer and can ensure better brightness and flatness.
Description
Technical Field
The invention relates to the technical field of chemical nickel plating, and particularly provides a nickel plating solution for an aluminum alloy surface and a preparation method thereof.
Background
The aluminum alloy has low density, good corrosion resistance, higher fatigue resistance, larger specific strength and specific stiffness, is equivalent to structural steel or even ultra-high strength steel, is widely applied to the preparation of mobile phone components to reduce the weight of the mobile phone structure, and the support material of the current mobile phone lens is also formed by compression molding of the aluminum alloy.
In the actual use process, the aluminum alloy has low hardness and poor wear resistance, and the surface hardness and the wear resistance can be greatly improved after chemical nickel plating. Chemical nickel plating is a new surface treatment technology, and is widely applied to the industries because of good plating quality, excellent corrosion resistance and wear resistance and convenient operation.
However, most of the existing chemical nickel plating has some defects, such as that the nickel deposition speed and the stability of the plating solution are not in high-efficiency balance, some of the chemical nickel plating has a fast plating speed 20 minutes before plating, the plating speed is rapidly reduced 20 minutes after plating, the average plating speed is slow, the bonding force of the plating layer is poor, the plating layer is easy to fall off, the plating solution is unstable, and autocatalytic decomposition is easy to occur during high-temperature chemical nickel plating; some nickel deposition rates are too slow, one plating period is too long, and the efficiency is not high; more importantly, the nickel-plated workpiece on the surface of the aluminum alloy prepared at present has high magnetic conductivity, and is easy to generate adverse effects on mobile phone signals and the like in the use process of the mobile phone lens support.
Disclosure of Invention
The problems to be solved by the invention are as follows: the invention provides a nickel plating solution for the surface of an aluminum alloy, which improves the corrosion resistance, high temperature resistance and humidity resistance of the surface of the obtained nickel layer, improves the hardness of a plating layer, reduces the magnetic conductivity, improves the forming time of the plating layer, and can ensure better brightness and flatness.
The above technical problems are illustrative, and the technical idea of the present invention is not limited thereto.
In order to solve the above technical problems, a first aspect of the present invention provides a nickel plating solution for an aluminum alloy surface, comprising the following components in concentration: 18-42 g/L nickel salt, 33-146 g/L organic acid and salt thereof, 17-35 g/L hypophosphite and 5-17 mg/L stabilizer.
In a preferred embodiment of the present invention, the organic acid or a salt thereof is a carboxylic acid or a derivative thereof and/or an α -hydroxy acid or a derivative thereof.
In a preferred embodiment of the present invention, the α -hydroxy acid and its derivatives are selected from any one or a combination of glycolic acid, lactic acid, citric acid, sodium citrate, mandelic acid, malic acid, and salicylic acid.
In a preferred embodiment of the present invention, the stabilizer is a metal-based stabilizer including at least one of a metal element, a metal salt of the metal element, and a metal oxide of the metal element.
In a preferred embodiment of the present invention, the metal element includes at least one of tin, zinc, magnesium, lead, cadmium, selenium, tellurium, molybdenum, arsenic, bismuth, and zirconium.
As a preferred technical scheme of the invention, the pH value of the nickel plating solution is 4.2-5.5.
As a preferable technical scheme, the biological agent also comprises 20-100 mg/L of penetrating agent.
The second aspect of the invention provides a use method of the nickel plating solution for the aluminum alloy surface, wherein the plating temperature is 76-93 ℃.
The third aspect of the invention provides an electroless nickel plating piece, which comprises a workpiece made of an aluminum alloy material and a plating layer positioned on the surface of the workpiece, wherein the plating layer is formed by the nickel plating solution.
The fourth aspect of the invention provides the application of the electroless nickel plating piece, which is applied to the frame of a mobile phone camera.
Compared with the prior art, the nickel plating solution with high phosphorus content provided by the invention has the advantages that the hardness of a plating layer is effectively improved, the magnetic conductivity is reduced, the forming time of the plating layer is prolonged, and the good brightness and flatness can be ensured through the combined action of hypophosphite, nickel salt with high concentration, organic acid and salt thereof, and specific stabilizing agent and penetrating agent.
Particularly, the nickel-plated layer formed by the method can not change under a salt spray experiment of 24H, and has good corrosion resistance; the magnetic permeability of the nickel-plated layer can reach 1.005, which is far less than that of the plating layer on the market by about 1.01, and the nickel-plated layer can be better applied to a mobile phone lens frame, thereby obviously improving the performance of a mobile phone component.
The effects of the present invention described above are illustrative, and the scope of the present invention is not limited to such effects.
Drawings
FIG. 1: and (3) a workpiece schematic diagram of the nickel plating solution obtained in the example 3 for forming a plating layer on the surface of the aluminum alloy.
Detailed Description
In order to further understand the structure, characteristics and other objects of the present invention, the following detailed description is given with reference to the accompanying preferred embodiments, which are only used for illustrating the technical solutions of the present invention and are not limited to the present invention. The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. 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 application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will also be understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "containing," and/or "containing," when used in this specification denotes a stated composition, step, method, article, or apparatus, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or apparatuses. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The invention mainly improves the hardness, deposition speed and magnetic conductivity of the nickel coating on the surface of the aluminum alloy bracket applied to the mobile phone lens, ensures that the surface of the obtained nickel coating has better flatness and brightness, and ensures that the obtained nickel plating solution has better stability and can not be decomposed in a short time.
The first aspect of the invention provides a nickel plating solution for an aluminum alloy surface, which comprises the following components: solvent, nickel salt, organic acid and salt thereof, hypophosphite and stabilizer.
The pH value of the nickel plating solution is 4.2-5.5, and the pH range and the components of the nickel plating solution act together, so that the stability of nickel plating, the forming speed of a plating layer, and the flatness, the brightness, the hardness and the magnetic conductivity of the obtained plating layer in a system are all better.
The solvent constitutes a large part of the nickel plating solution, and the solvent may be of a type well known to those skilled in the art, and is not particularly limited, such as water and the like.
The nickel salt may be dissolved in the solvent, and the nickel salt may supply nickel ions for plating to a plating object to form a nickel plating layer on a surface of the plating object. The nickel salt is well known to those skilled in the art, and is any one or combination of nickel salts for nickel plating, such as nickel sulfamate, nickel sulfate, nickel chloride, nickel nitrate, nickel oxide and nickel carbonate, and is preferably nickel sulfate.
The concentration of the nickel salt in the nickel plating solution is 18-42 g/L; preferably 27-36 g/L; the application adopts higher sulfate concentration, which is different from the prior art that the concentration is generally lower, and generally, when the concentration of nickel sulfate is higher than 15g/L, because the stability of nickel plating solution is reduced, self-decomposition can occur, the plating time is longer, a plating layer has defects, the hardness is poorer, and the flatness and the brightness are also poorer; the applicant also finds that, in the overall technical scheme of the application, when the content of nickel sulfate is 18-42 g/L, the magnetic permeability of the obtained plating layer is low, the hardness of the plating layer is high, the plating efficiency is high, when the content of nickel sulfate is low or nickel chloride is adopted, the performance of the plating layer is deteriorated, the self-decomposition of nickel plating solution at high concentration and the reduction of the content of impurities containing nickel are avoided probably due to the combined action of the nickel sulfate, specific organic acid and salt thereof, a stabilizing agent and a penetrating agent in the scheme of the application, the formation of a uniform plating layer on the surface of a plating object is promoted, when the concentration is low, the formation of a nickel layer on the surface of the plating object is influenced, and the increase of the tensile stress of the plating layer and the reduction of the corrosion resistance of the plating layer due to the accumulation of Cl-ions are avoided.
The organic acid and its salt can be dissolved in a solution, and the organic acid and its salt are carboxylic acid and its derivatives and/or alpha-hydroxy acid and its derivatives.
As the carboxylic acid and its derivative, for example, but not limited to: acetic acid, adipic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, oxalic acid, malonic acid, tartaric acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, adipic acid, and the like.
The alpha-hydroxy acid and its derivatives are selected from glycolic acid, lactic acid, citric acid, sodium citrate, mandelic acid, malic acid, salicylic acid.
Preferably, the organic acid and salts thereof are alpha-hydroxy acids; further preferably, the organic acid and its salt include sodium citrate, malic acid and lactic acid.
The organic acid and the salt thereof can be chemically combined with the nickel ions to form a nickel complex, and the type and the content of the organic acid and the salt thereof have a large relationship with the stability of the nickel plating solution, the hardness and the magnetic permeability of a plating layer or the plating efficiency and the like in the actual use process, so that the selection of the appropriate organic acid and the salt thereof according to the actual needs and the actually solved problems or purposes is very important in the use process; in the technical scheme of the application, the applicant has unexpectedly found that when sodium citrate, malic acid and lactic acid are adopted to act together with 18-42 g/L nickel sulfate, and simultaneously act together with a stabilizer and a penetrant, the magnetic conductivity of the plating layer is low, the hardness of the plating layer is high, and the plating efficiency is high; probably because the malic acid is a hydroxycarboxylic acid substance containing 4 carbon atoms and two carboxyl groups, the malic acid is ionized under neutral conditions and is not ionized under acidic conditions, and the malic acid and the citric acid and the lactic acid containing 3 carbon atoms and one carboxyl group have the combined action of two organic acids with better complexing action, so that the generation content and speed of hydrogen ions are reduced, and the pH of the nickel plating solution is prevented from changing sharply.
Preferably, the concentration of the organic acid and the salt thereof is 33-146 g/L; more preferably, the concentration of the organic acid and the salt thereof is 90-125 g/L; more preferably the concentration of the organic acid and salts thereof is 110 g/L.
Preferably, the weight ratio of the sodium citrate, the malic acid and the lactic acid is 1: (1.5-5): (4-20); further preferably, the weight ratio of the sodium citrate, the malic acid and the lactic acid is 1: (1.5-2.6): (6.2-9.2); more preferably, the weight ratio of the sodium citrate, the malic acid and the lactic acid is 1: 2: 8.
as described above, the contents of the organic acid and its salt have a large relationship with respect to the stability of the nickel plating solution, the hardness and permeability of the plating layer, the plating efficiency, and the like, and the applicant found that when the weight ratio of the sodium citrate, the malic acid, and the lactic acid is 1: (1.5-5): (4-20); particularly, when the weight ratio of the sodium citrate to the malic acid to the lactic acid is 1: (1.5-2.6): (6.2-9.2), the performance of the obtained coating is good, and probably because a stable network structure is formed between the organic acid and the salt thereof and the nickel ions under the condition that the pH of the system is controlled to be stable under the condition, the generation of a complexing agent, an impurity simple substance and the like in the plating process is avoided, and the deposition at the concave part of the aluminum alloy is promoted.
The concentration of the hypophosphite is 17-35 g/L; the nickel plating solution system is a nickel plating solution system with high phosphorus content, and the concentration is preferably 21-29 g/L; further preferably 23-26 g/L; more preferably 25 g/L. In the technical scheme of the application, when the concentration of hypophosphite is low, the uniformity of the plating layer is damaged, and the magnetic permeability of the plating layer is also reduced.
The stabilizer is a metal stabilizer and comprises at least one of a metal element, a metal salt of the metal element and a metal oxide of the metal element; preferably, the metal element comprises at least one of tin, zinc, magnesium, lead, cadmium, selenium, tellurium, molybdenum, arsenic, bismuth and zirconium; further preferably, the stabilizer comprises zinc sulfate and zirconium nitrate; further preferably, the weight ratio of zinc sulfate to zirconium nitrate is 1: (0.25 to 0.46); more preferably, the weight ratio of zinc sulfate to zirconium nitrate is 1: 0.33.
the concentration of the stabilizer is 5-17 mg/L; preferably 5-10 mg/L; more preferably 6.5 to 8.5 mg/L. The zinc sulfate and the zirconium nitrate are added into the system to inhibit the speed of reduction reaction, the rate of phosphate precipitation is controlled, and black precipitates in the system are prevented from being formed, so that the quality of a coating is influenced.
The nickel plating solution also comprises 20-100 mg/L of penetrating agent, wherein the penetrating agent comprises at least one of ruthenium, rhodium, palladium, osmium, iridium, platinum and metal salts or metal oxides thereof, such as palladium salt and palladium chloride; preferably, the concentration of the penetrating agent is 30-50 mg/L; more preferably 36 to 42 mg/L. The application adopts a specific metal substance as a penetrating agent, can act together with the stabilizer, nickel salt, organic acid and salt thereof, improves the stability of the plating solution and the stability of the deposition speed, avoids the instability of the system caused by high nickel sulfate concentration, and simultaneously, the applicant finds that the content of the components exists in a certain proportion, thereby being beneficial to rapidly seeping into tiny gaps on the surface of the aluminum alloy while depositing nickel, being beneficial to the smooth proceeding of the die casting process of the aluminum alloy in the process of a mobile phone lens frame and being beneficial to the reduction of the magnetic conductivity of the material.
The second aspect of the invention provides a use method of the nickel plating solution for the aluminum alloy surface, wherein the plating temperature is 76-93 ℃, namely the plating process is carried out within the temperature range.
The third aspect of the present invention provides an electroless nickel-plated article, which includes a workpiece made of an aluminum alloy and a plating layer on a surface of the workpiece, wherein the plating layer is formed by the above nickel-plating solution, and the kind of the aluminum alloy is not particularly limited, such as 1 series, 2 series, 3 series, 4 series, 5 series, 6 series, and the like, and more specifically, such as, but not limited to 1060, 2024, 5052, 6061, 6063, 7075, and the like.
The fourth aspect of the invention provides the application of the electroless nickel plating piece, which is applied to the frame of a mobile phone camera.
The fifth aspect of the invention provides a plating process of the nickel plating solution on the surface of the aluminum alloy, which sequentially comprises the following steps: removing oil, removing silicon, depositing zinc and nickel for the first time, depositing zinc and nickel for the second time, plating alkaline nickel, plating acidic nickel, sealing holes and drying.
Preferably, the plating process of the nickel plating solution on the surface of the aluminum alloy sequentially comprises the following steps:
(1) oil removal: placing the aluminum alloy workpiece in an oil removing tank containing an alkaline reagent, and treating for 5-10 min at 45-55 ℃; wherein the alkaline agent is at least one of sodium hydroxide aqueous solution, sodium carbonate aqueous solution or saponified alkali solution; the concentration of the sodium hydroxide is 50-75 wt%;
(2) silicon removal: then, continuously placing the aluminum alloy workpiece obtained in the step (1) in a silicon removal tank containing a strong oxidant and/or a fluorine-containing reagent, and treating for 30-90 s at 10-30 ℃; preferably 50-70 s;
the kind of the strong oxidizing agent is not particularly limited in the present invention, and is an oxide well known to those skilled in the art, such as an aqueous hydrogen peroxide solution; further preferably, the concentration of the hydrogen peroxide is 50-70 mL/L;
the kind of the fluorine-containing agent is not particularly limited in the present invention, and is a fluorine-containing compound for removing silicon, such as ammonium bifluoride;
(3) depositing zinc and nickel for the first time: soaking the aluminum alloy workpiece obtained in the step (2) in a mixed aqueous solution containing nickel ions and with the temperature of 20-40 ℃ for depositing zinc and nickel for the first time for 30-60 s; the mixed aqueous solution containing nickel ions comprises the following components in concentration: 30-50 g/L nickel sulfate, 50-130 g/L nickel chloride, 20-60 g/L sodium hydroxide and 20-30 g/L zinc sulfate;
(4) and (3) depositing zinc and nickel for the second time: soaking the aluminum alloy workpiece obtained in the step (3) in a mixed aqueous solution containing nickel ions and with the temperature of 20-40 ℃ for depositing zinc and nickel for the second time for 10-50 s; the nickel ion-containing mixed aqueous solution has the same components as the first nickel ion-containing mixed aqueous solution;
(5) alkaline nickel plating: soaking the aluminum alloy workpiece obtained in the step (4) in an alkaline nickel plating reagent at the temperature of 20-45 ℃ for 3-8 min; the mixed aqueous solution of the alkaline nickel plating reagent comprises the following components in concentration: 30-50 g/L nickel sulfamate, 10-40 g/L sodium hypophosphite and 10-30 g/L ammonia water;
(6) acid nickel plating: soaking the aluminum alloy workpiece obtained in the step (5) in an acidic nickel plating reagent at 76-93 ℃ for 25-100 min; the acidic nickel plating reagent is nickel plating solution for the surface of the aluminum alloy provided by the first aspect of the invention;
(7) hole sealing: placing the aluminum alloy workpiece obtained in the step (6) at 60-80 ℃ for 3-10 min, and sealing holes and processing;
(8) and (3) drying: and (4) placing the aluminum alloy workpiece obtained in the step (7) in a drying oven at the temperature of 150-260 ℃ for 1-3 h.
Preferably, the plating process of the nickel plating solution on the surface of the aluminum alloy sequentially comprises the following steps:
(1) oil removal: placing the aluminum alloy workpiece in an oil removing tank containing an alkaline reagent, and treating for 5-10 min at 48-52 ℃; wherein the alkaline agent is at least one of sodium hydroxide aqueous solution, sodium carbonate aqueous solution or saponified alkali solution; the concentration of the sodium hydroxide is 65-75 wt%;
(2) silicon removal: then, continuously placing the aluminum alloy workpiece obtained in the step (1) in a silicon removal tank containing a strong oxidant and/or a fluorine-containing reagent, and treating for 30-90 s at 10-30 ℃; preferably 50-70 s;
the kind of the strong oxidizing agent is not particularly limited in the present invention, and is an oxide well known to those skilled in the art, such as an aqueous hydrogen peroxide solution; further preferably, the concentration of the hydrogen peroxide is 60-65 mL/L;
the kind of the fluorine-containing agent is not particularly limited in the present invention, and is a fluorine-containing compound for removing silicon, such as ammonium bifluoride;
(3) depositing zinc and nickel for the first time: soaking the aluminum alloy workpiece obtained in the step (2) in a mixed aqueous solution containing nickel ions and used for depositing zinc and nickel for the first time at 26-33 ℃ for 44-52 s; the mixed aqueous solution containing nickel ions comprises the following components in concentration: 35-41 g/L nickel sulfate, 56-62 g/L nickel chloride, 38-45 g/L sodium hydroxide and 23-27 g/L zinc sulfate;
(4) and (3) depositing zinc and nickel for the second time: soaking the aluminum alloy workpiece obtained in the step (3) in a mixed aqueous solution containing nickel ions and with the temperature of 26-33 ℃ for depositing zinc and nickel for the second time for 20-45 s; the nickel ion-containing mixed aqueous solution has the same components as the first nickel ion-containing mixed aqueous solution;
(5) alkaline nickel plating: soaking the aluminum alloy workpiece obtained in the step (4) in an alkaline nickel plating reagent at the temperature of 36-41 ℃ for 3-8 min; the mixed aqueous solution of the alkaline nickel plating reagent comprises the following components in concentration: 35-46 g/L nickel sulfamate, 27-32 g/L sodium hypophosphite and 15-26 g/L ammonia water;
(6) acid nickel plating: soaking the aluminum alloy workpiece obtained in the step (5) in an acidic nickel plating reagent at 76-93 ℃ for 60-90 min; the acidic nickel plating reagent is nickel plating solution for the surface of the aluminum alloy provided by the first aspect of the invention;
(7) hole sealing: placing the aluminum alloy workpiece obtained in the step (6) at 68-75 ℃ for 3-10 min, and treating by using a hole sealing agent;
the sealant comprises water and the following components in concentration: 5-10 g/L of siloxane, 300-600 mL/L of polyethylene glycol and 25-30 g/L of octadecanethiol;
the siloxane comprises isobutyl triethoxysilane and gamma-aminopropyl triethoxysilane; further preferably, the weight ratio of the isobutyl triethoxysilane to the gamma-aminopropyltriethoxysilane is (0.2-0.4): 1;
polyethylene glycol includes polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 800; the weight ratio of polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 800 is 1: (2.5-3): (0.3 to 0.6);
(8) and (3) drying: and (5) placing the aluminum alloy workpiece obtained in the step (7) in a drying oven at the temperature of 200-240 ℃ for 1.5-2.5 h.
Example 1
Embodiment 1 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components: 18g/L of nickel salt, 33g/L of organic acid and salt thereof, 17g/L of hypophosphite, 5mg/L of stabilizer and 20mg/L of penetrating agent, wherein the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, malic acid and lactic acid, and the weight ratio of the sodium citrate to the malic acid to the lactic acid is 1: 1.5: 4;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.25;
the penetrant is palladium chloride.
Example 2
Embodiment 2 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 42g/L of nickel salt, 146g/L of organic acid and salt thereof, 35g/L of hypophosphite, 17mg/L of stabilizer and 50mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 5: 20;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.46 of;
the penetrant is palladium chloride.
Example 3
Embodiment 3 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is palladium chloride.
Example 4
Embodiment 4 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel chloride;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is palladium chloride.
Example 5
Embodiment 5 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components: 10g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is palladium chloride.
Example 6
Embodiment 6 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate and lactic acid, wherein the weight ratio of the sodium citrate to the lactic acid is 1: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is palladium chloride.
Example 7
Embodiment 7 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise lactic acid and malic acid, and the weight ratio of the lactic acid to the malic acid is 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is palladium chloride.
Example 8
Embodiment 8 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof are lactic acid;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is palladium chloride.
Example 9
Embodiment 9 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, malic acid and lactic acid, and the weight ratio of the sodium citrate to the malic acid to the lactic acid is 1: 2: 4;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is palladium chloride.
Example 10
Embodiment 10 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is sodium thiocyanate;
the penetrant is palladium chloride.
Example 11
Embodiment 11 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is lead nitrate;
the penetrant is palladium chloride.
Example 12
Embodiment 12 of the present invention provides a nickel plating solution for an aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite and 7.5mg/L of stabilizer; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33.
example 13
Embodiment 13 of the present invention provides a nickel plating solution for aluminum alloy surface, including a solvent and the following components in concentration: 33g/L of nickel salt, 110g/L of organic acid and salt thereof, 25g/L of hypophosphite, 7.5mg/L of stabilizer and 39mg/L of penetrant; the solvent is water;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof comprise sodium citrate, lactic acid and malic acid, and the weight ratio of the sodium citrate to the lactic acid to the malic acid is 1: 2: 8;
the hypophosphite is sodium hypophosphite;
the stabilizer is zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the penetrant is cerous sulfate.
Carrying out nickel plating treatment on the surface of the aluminum alloy by using the nickel plating solution of the embodiment 1-13, wherein the specific nickel plating process is as follows, wherein the aluminum alloy material is 6061;
the plating process of the nickel plating solution on the surface of the aluminum alloy sequentially comprises the following steps:
(1) oil removal: placing the aluminum alloy workpiece in an oil removing tank containing an alkaline reagent, and treating for 5-8 min at 50-52 ℃; wherein the alkaline reagent is sodium hydroxide aqueous solution, and the concentration of the sodium hydroxide is 70 wt%;
(2) silicon removal: then, continuously placing the aluminum alloy workpiece obtained in the step (1) in a silicon removal tank containing a strong oxidant, and treating for 60-66 seconds at 28-30 ℃;
the strong oxidant is hydrogen peroxide aqueous solution; the concentration of the hydrogen peroxide is 65 mL/L;
(3) depositing zinc and nickel for the first time: soaking the aluminum alloy workpiece obtained in the step (2) in a mixed aqueous solution containing nickel ions for depositing zinc and nickel for the first time at the temperature of 30-33 ℃ for 50 s; the mixed aqueous solution containing nickel ions comprises the following components in concentration: 38g/L nickel sulfate, 62g/L nickel chloride, 45g/L sodium hydroxide and 27g/L zinc sulfate;
(4) and (3) depositing zinc and nickel for the second time: soaking the aluminum alloy workpiece obtained in the step (3) in a mixed aqueous solution containing nickel ions and with the temperature of 30-33 ℃ for depositing zinc and nickel for the second time for 35 s; the nickel ion-containing mixed aqueous solution has the same components as the first nickel ion-containing mixed aqueous solution;
(5) alkaline nickel plating: soaking the aluminum alloy workpiece obtained in the step (4) in an alkaline nickel plating reagent at the temperature of 40-41 ℃ for 8 min; the alkaline nickel plating reagent comprises water and the following components in concentration: 42g/L of nickel sulfamate, 30g/L of sodium hypophosphite and 24g/L of ammonia water;
(6) acid nickel plating: soaking the aluminum alloy workpiece obtained in the step (5) in an acidic nickel plating reagent at 87-90 ℃ for 75 min; the acid nickel plating reagent is the nickel plating solution for the aluminum alloy surface provided by the corresponding embodiment;
(7) hole sealing: placing the aluminum alloy workpiece obtained in the step (6) at 70-73 ℃ for 8min, and treating by using a hole sealing agent;
the hole sealing agent comprises water, 8g/L siloxane, 450mL/L polyethylene glycol and 28g/L octadecanethiol with the following concentrations;
the siloxane comprises isobutyl triethoxysilane and gamma-aminopropyl triethoxysilane; the weight ratio of isobutyl triethoxysilane to gamma-aminopropyltriethoxysilane is 0.3: 1;
polyethylene glycol includes polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 800; the weight ratio of polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 800 is 1: 2.9: 0.5;
(8) and (3) drying: and (4) placing the aluminum alloy workpiece obtained in the step (7) in a drying oven at 220-230 ℃ for 2 h.
Performance evaluation
1. Film thickness: the thickness of the plating layer obtained in example 3 was measured by a film thickness meter to be 5 pm.
2. And (3) corrosion resistance testing: the coating obtained in the embodiments 1 to 4 is subjected to a smoke experiment by using a smoke machine, and the experiment shows that the smoke experiment treatment under 24H has no influence on the coatings obtained in the embodiments 1 to 3, and has no corrosion problem; the surface of the plating layer obtained in example 4 had corroded portions;
3. and (3) testing high temperature and high humidity resistance: carrying out high-temperature and high-humidity resistance test on the plating layers obtained in the embodiments 1 to 3 by using a high-temperature and high-humidity box, wherein the humidity is 85-90%, and the temperature is 90 ℃; after 120H treatment, the plating layers obtained in the embodiments 1-3 have no obvious change, and particularly have good high-temperature and high-humidity resistance;
4. testing the residual magnetic rate: nickel plating is carried out on the surface of the aluminum alloy by utilizing the embodiments 1-3, and a gauss meter is used for carrying out a remanence test, wherein the test result is that the embodiment 1 is 0.7Gs, the embodiment 2 is 0.7Gs, and the embodiment 3 is 0.5 Gs;
5. and (3) magnetic permeability test: carrying out nickel plating on the surface of the aluminum alloy by using the embodiments 1-3 and the embodiments 5-13, and carrying out a magnetic conductivity test by using a magnetic conductivity tester;
6. and (3) hardness testing: nickel plating the surface of the aluminum alloy by using the examples 1 to 3 and the examples 5 to 13, and performing a hardness test;
7. plating layer formation time test: measuring the deposition rate V of the nickel plating solutions of examples 1 to 3 and examples 5 to 13 when a plating layer is formed on the surface of the aluminum alloy; grade A: when the deposition rate is 16< V <22 μm/h; grade B: when the deposition rate is 12< V <16 μm/h; grade C: when the deposition rate is V <12 mu m/h;
8. and (3) testing the flatness and smoothness of the plating layer: observing the flatness and smoothness of the plating layer formed on the surface of the aluminum alloy by the nickel plating solution of the embodiments 1 to 3 and 5 to 13, namely observing whether the formed plating layer has depressions or projections or black spots, wherein the evaluation grade standard is as follows: each example corresponds to 45 samples, a: the number of the pits or projections or black spots is 0-3; b: the number of the pits or projections or black spots is 4-13; c: the number of the pits or projections or black spots is 14-28; d: the number of the concave or convex or black spots is 29-45.
TABLE 1
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (3)
1. The nickel plating solution for the aluminum alloy surface is characterized by comprising a solvent and the following components in concentration: 27-36 g/L of nickel salt, 33-146 g/L of organic acid and salt thereof, 17-35 g/L of hypophosphite and 5-17 mg/L of stabilizer;
the nickel salt is nickel sulfate;
the organic acid and the salt thereof are sodium citrate, malic acid and lactic acid;
the concentration of the organic acid and the salt thereof is 110 g/L;
the weight ratio of the sodium citrate to the malic acid to the lactic acid is 1: 2: 8;
the stabilizer comprises zinc sulfate and zirconium nitrate, and the weight ratio of the zinc sulfate to the zirconium nitrate is 1: 0.33;
the nickel plating solution also comprises 36-42 mg/L of penetrant;
the penetrating agent comprises at least one of ruthenium, rhodium, palladium, osmium, iridium, platinum and metal salts or metal oxides thereof;
the pH value of the nickel plating solution is 4.2-5.5;
the plating temperature of the nickel plating solution is 76-93 ℃.
2. An electroless nickel-plated article comprising a workpiece made of an aluminum alloy and a plating layer formed on a surface of the workpiece, wherein the plating layer is formed from the nickel plating solution according to claim 1.
3. An electroless nickel plating piece according to claim 2 applied to a frame of a camera of a mobile phone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1962938A (en) * | 2005-11-08 | 2007-05-16 | 佛山市顺德区汉达精密电子科技有限公司 | Process for chemical nickel plating on surface of aluminum alloy containing silicon, copper, and magnesium |
| CN101036201A (en) * | 2004-10-08 | 2007-09-12 | 东丽株式会社 | Conductive film |
| CN110318044A (en) * | 2019-06-20 | 2019-10-11 | 深圳市宏达秋科技有限公司 | A kind of chemical nickel-plating liquid and preparation method thereof |
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| CN101638778A (en) * | 2009-02-27 | 2010-02-03 | 郑建国 | Nickel-phosphorus chemical precipitation plating layer of aluminium alloy |
| CN101619448A (en) * | 2009-07-31 | 2010-01-06 | 辽宁石油化工大学 | Pretreatment solution used for electroless nickel-phosphorus alloy plating layer on surface of aluminum alloy |
| CN101736333B (en) * | 2010-01-18 | 2013-03-13 | 海洋王照明科技股份有限公司 | Aluminium alloy workpiece surface treatment method and aluminium alloy workpiece |
| CN103103508A (en) * | 2011-11-14 | 2013-05-15 | 深圳富泰宏精密工业有限公司 | Surface treatment method for aluminum or aluminum alloy and product prepared thereby |
| KR101487890B1 (en) * | 2013-07-16 | 2015-02-03 | 한국생산기술연구원 | Electroless plating solution, method of electroless nickel plating using the same, and flexible nickel plating layer using the same |
| CN107587123A (en) * | 2017-09-12 | 2018-01-16 | 高金荣 | A kind of phone housing process of surface treatment |
| CN111074250B (en) * | 2020-02-13 | 2021-05-28 | 西安交通大学 | High-corrosion-resistance stable chemical nickel plating solution for aluminum alloy surface, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101036201A (en) * | 2004-10-08 | 2007-09-12 | 东丽株式会社 | Conductive film |
| CN1962938A (en) * | 2005-11-08 | 2007-05-16 | 佛山市顺德区汉达精密电子科技有限公司 | Process for chemical nickel plating on surface of aluminum alloy containing silicon, copper, and magnesium |
| CN110318044A (en) * | 2019-06-20 | 2019-10-11 | 深圳市宏达秋科技有限公司 | A kind of chemical nickel-plating liquid and preparation method thereof |
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