CN101195924A - Plating product and method for producing the same - Google Patents
Plating product and method for producing the same Download PDFInfo
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- CN101195924A CN101195924A CNA2006101621137A CN200610162113A CN101195924A CN 101195924 A CN101195924 A CN 101195924A CN A2006101621137 A CNA2006101621137 A CN A2006101621137A CN 200610162113 A CN200610162113 A CN 200610162113A CN 101195924 A CN101195924 A CN 101195924A
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Abstract
The invention relates to an electric plating product, which comprises parent material and copper-tin alloy composite coatings on the surface of the parent material, therein, the copper-tin alloy composite coatings adopts multilayer, the copper content of at least one layer of the copper-tin alloy composite coatings is different from the copper content of the other copper-tin alloy composite coatings. The invention also provides the preparation method of the electric plating product. The electric plating product comprises the multilayer copper-tin alloy composite coatings, at least one layer of the copper-tin alloy composite coatings is different from the copper content of the other copper-tin alloy composite coatings, thereby, the electric plating product simultaneously has higher vibration abrasion resistance and corrosion resistance, and the good combination property is realized.
Description
Technical field
The invention relates to a kind of plated item and preparation method thereof.
Background technology
Metal after the plating or nonmetal workpiece, not only good looking appearance, and coating can also play effects such as decoration and protection to body material.Traditional electroplating technology all will be used metallic nickel, and therefore the plated item that obtains comprises nickel coating.Nickel coating is able to widespread use owing to having good ornamental, protective and wear resistance.People discovered afterwards, and metallic nickel and people's skin contact can cause the responsive symptom of nickel, and therefore, many countries as made laws nickel content in the restriction jewelry of EU member country, require the amount of the separating out per week of metallic nickel must not surpass 0.5 microgram for every square centimeter.Therefore, research is studied no nickel, for the nickel electroplating technology more further meaning has been arranged just.
Electroplating copper tin alloy is to use more a kind of alloy plating, this method generally comprises the galvanized base material of desire is immersed in the plating bath that contains cupric ion, stannous ion and complexing agent as negative electrode, metal sheet or graphite cake are as anode, after connecting direct supply, will deposit cu-sn alloy coating at substrate material surface, obtain plated item.Cu-sn alloy coating has the silvery white outward appearance of light, but wearing and tearing or corrosion in use appear in the existing plated item that contains cu-sn alloy coating easily.
Summary of the invention
The objective of the invention is to occur wearing and tearing or corrosive shortcoming easily, and a kind of the have good vibration wear resistance and the plated item of erosion resistance are provided in order to overcome existing plated item.
Another object of the present invention provides the preparation method of above-mentioned plated item.
The present inventor finds, the existing plating product exists the major cause of above-mentioned shortcoming to be to have only one deck at the cu-sn alloy coating that substrate surface forms, if the copper content in the cu-sn alloy coating higher (copper content is greater than 54 weight %), then the erosion resistance of plated item is relatively poor, occurs corrosion easily; If the copper content in the cu-sn alloy coating lower (copper content is smaller or equal to 54 weight %), then the vibration wear resistance of plated item is lower, occurs wearing and tearing easily.The inventor finds that also if form the combination of two-layer or the cu-sn alloy coating that multiple layer of copper content is different on base material, the plated item that then obtains can have higher vibration wear resistance and erosion resistance simultaneously, thereby realizes good comprehensive performances.
The invention provides a kind of plated item, this plated item comprises the cu-sn alloy coating on body material and this substrate material surface, wherein, described cu-sn alloy coating is a multilayer, and the copper content of the cu-sn alloy coating of one deck at least in the described multiple layer of copper tin alloy coat is different with the copper content of other layer cu-sn alloy coating.
The present invention also provides the preparation method of described plated item, this method comprises electroplates body material in the plating bath that contains cupric ion, stannous ion and complexing agent, surface at body material forms cu-sn alloy coating, wherein, described galvanized process comprises a plurality of plating stages, and to account for the molecular fraction of the total amount of cupric ion and stannous ion in this plating bath different with the molecular fraction of cupric ion in other employed plating bath of plating stage for cupric ion at least one employed plating bath of plating stage.
Plated item provided by the invention comprises the multiple layer of copper tin alloy coat, the copper content of the cu-sn alloy coating of one deck at least in the described multiple layer of copper tin alloy coat is different with the copper content of other layer, therefore described plated item has higher vibration wear resistance and erosion resistance simultaneously, thereby realizes good comprehensive performances.
Embodiment
Plated item provided by the invention comprises the cu-sn alloy coating on body material and this substrate material surface, wherein, described cu-sn alloy coating is a multilayer, and the copper content of the cu-sn alloy coating of one deck at least in the described multiple layer of copper tin alloy coat is different with the copper content of other layer cu-sn alloy coating.
Copper content described herein is meant that respectively the amount with each cu-sn alloy coating is a benchmark, the weight percentage of copper in this cu-sn alloy coating.Copper content in the cu-sn alloy coating can adopt known the whole bag of tricks to measure, unless stated otherwise, in the present invention, the copper content in the cu-sn alloy coating makes coating dissolving back measure with inductively coupled plasma atomic emission spectrometry (ICP-AES).
Described multiple layer of copper tin alloy coat can be divided into the different cu-sn alloy coating of multiple copper content, and the difference of the copper content of the cu-sn alloy coating that every kind of copper content is different can be 0.5-20 weight %, is preferably 1-10 weight %.
Under the preferable case, described multiple layer of copper tin alloy coat is divided into the cu-sn alloy coating of high copper content and the cu-sn alloy coating of low copper content, the ratio of the total thickness of the cu-sn alloy coating of the total thickness of the cu-sn alloy coating of high copper content and low copper content is 1: 0.1-10 is preferably 1: 0.2-5.
Wherein, the copper content of the cu-sn alloy coating of described high copper content can be preferably 55-65 weight % for greater than 54 weight % to 80 weight %; The copper content of the cu-sn alloy coating of low copper content can be 20-54 weight %, is preferably 35-54 weight %.
There is no particular limitation to the thickness of the cu-sn alloy coating of the cu-sn alloy coating of the number of plies of the cu-sn alloy coating of the cu-sn alloy coating of high copper content and low copper content and every floor height copper content or low copper content in the present invention, as long as the ratio of total thickness of cu-sn alloy coating that can make the total thickness of cu-sn alloy coating of high copper content and low copper content is in above-mentioned scope, and the total thickness of multiple layer of copper tin alloy coat can be the thickness of coating of routine.
For example, the number of plies of the cu-sn alloy coating of high copper content can be 1-5, is preferably 1-3; The number of plies of the cu-sn alloy coating of low copper content can be 1-5, is preferably 1-3.The thickness of the cu-sn alloy coating of every floor height copper content or the cu-sn alloy coating of low copper content can be the 1-20 micron.
The thickness of each layer cu-sn alloy coating can adopt existing the whole bag of tricks to measure, unless stated otherwise, in the present invention, thickness in the cu-sn alloy coating is to use section method to measure, the process of section method generally comprises with microsection equipment plated item is cut into section, under metaloscope, observe the cross section of section then, measure the thickness of each layer cu-sn alloy coating.
Described body material can for example can be electro-conductive material or non-conducting material for existing any galvanized body material that is suitable for carrying out.Described non-conducting material can be plastics, fiber or resin, and described electro-conductive material can be various metals, as stainless steel.Described plastics can be electroplated or the plastics of electroless plating for various, and for example acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), nylon and polypropylene (PP) are preferably ABS.
When described body material was non-conducting material, plated item of the present invention also comprised chemical plating, and chemical plating is between body material and described electroplated metal layer.Chemical plating can be the chemical plating of routine, is preferably chemical plating copper layer and/or chemical Ni-plating layer.There is no particular limitation for the thickness of chemical plating, is preferably the 0.1-0.5 micron, more preferably the 0.2-0.3 micron.
The preparation method of plated item provided by the invention comprises body material is electroplated in the plating bath that contains cupric ion, stannous ion and complexing agent, surface at body material forms cu-sn alloy coating, wherein, described galvanized process comprises a plurality of plating stages, and to account for the molecular fraction of the total amount of cupric ion and stannous ion in this plating bath different with the molecular fraction of cupric ion in other employed plating bath of plating stage for cupric ion at least one employed plating bath of plating stage.
The cupric ion in the plating bath described herein and the total amount of stannous ion are meant the cupric ion contained in employed each plating bath of each plating stage and the total amount of stannous ion, rather than contained cupric ion and the total amount sum of stannous ion in each plating bath.
The plating bath in described a plurality of plating stages can be divided into the different plating bath of molecular fraction of multiple cupric ion, and the difference of the molecular fraction of the cupric ion of every kind of plating bath is 1-30 mole %, is preferably 1.5-20 mole %.
Under the preferable case, described multiple plating bath is divided into high plating bath of cupric ion molecular fraction and the low plating bath of cupric ion molecular fraction, the total thickness of the cu-sn alloy coating that forms in the high plating bath of cupric ion molecular fraction can be 1 with the ratio of the total thickness of the cu-sn alloy coating that forms in the low plating bath of cupric ion molecular fraction: 0.1-10 is preferably 1: 0.2-5.
The present invention is in the high plating bath of cupric ion molecular fraction and there is no particular limitation the number in the plating stage of carrying out in the low plating bath of cupric ion molecular fraction and time, as long as the ratio of the total thickness that makes the cu-sn alloy coating that forms in the high plating bath of cupric ion molecular fraction and the total thickness of the cu-sn alloy coating that forms in the low plating bath of cupric ion molecular fraction is in above-mentioned scope.
For example, the plating stage of carrying out in the high plating bath of cupric ion molecular fraction can be 1-5, is preferably 1-3; The plating stage of carrying out in the low plating bath of cupric ion molecular fraction is 1-5, is preferably 1-3.
Cupric ion molecular fraction in the low plating bath of described cupric ion molecular fraction can be 1-10 mole %, is preferably 3-10 mole %; Cupric ion molecular fraction in the high plating bath of described cupric ion molecular fraction can be preferably 10.5-25 mole % for greater than 10 moles of % to 30 mole of %.
Can be the galvanized condition of gunmetal of carrying out of routine in each plating condition of electroplating the stage, for example, bath temperature can be 10-60 ℃, and current density can be pacified for 0.2-5/square decimeter, and the galvanized time can be 1-20 minute.The galvanized time described herein is meant the time in each plating stage, rather than total electroplating time.The electro-plating method that is adopted in each plating stage can be the electro-plating method of routine, for example electro-plating method comprises body material is immersed in the plating bath as negative electrode, metal sheet or graphite cake behind the connection direct supply, will deposit cu-sn alloy coating at substrate material surface as anode.Described metal sheet can be copper coin or sheet tin.
In each employed plating bath of plating stage, content of copper ion and stannous ion content are that existing gunmetal is electroplated with content of copper ion and stannous ion content in the plating bath, for example, content of copper ion can be the 0.0015-0.008 mol, is preferably the 0.004-0.05 mol; Stannous ion content can be the 0.08-0.55 mol, is preferably the 0.12-0.4 mol.
Described plating bath is generally the aqueous solution that contains water-soluble mantoquita and water-soluble tin salt.Water-soluble mantoquita provides described cupric ion, the example of water-soluble mantoquita includes but not limited to copper sulfate, cupric nitrate, copper carbonate, copper methane sulfonate, thionamic acid copper, 2-ethylenehydrinsulfonic acid copper, 2-hydroxy-propanesulfonic acid copper, cupric chloride and cupric pyrophosphate, above-mentioned various water-soluble mantoquita can use separately, also can two kinds or be used in combination.
Water-soluble tin salt provides described stannous ion, the example of water-soluble tin salt includes but not limited to stannous pyrophosphate, tin protochloride, stannous sulfate, stannous acetate, the inferior tin of thionamic acid, the inferior tin of gluconic acid, stannous tartrate, tin protoxide, the inferior tin of methylsulfonic acid, the inferior tin of 2-ethylenehydrinsulfonic acid, the inferior tin of 2-hydroxy-propanesulfonic acid and bromine tin protofluoride, above-mentioned various water-soluble tin salt can use separately, also can two kinds or be used in combination.
The kind of described complexing agent and content have been conventionally known to one of skill in the art, for example, described complexing agent can be alkali metal pyrophosphate, and alkali metal pyrophosphate can be preferably potassium pyrophosphate and/or trisodium phosphate for potassium pyrophosphate, trisodium phosphate and tetra-sodium lithium.The concentration of complexing agent in plating bath can be the 200-400 grams per liter, is preferably the 250-350 grams per liter.
The pH value of each employed plating bath of plating stage can be 3-9, is preferably 6-8.Can use known method that the pH value of plating bath is transferred to above-mentioned scope.For example, can add the acid or the alkali that do not participate in reacting, as sodium hydroxide solution or hydrochloric acid.
Each employed plating bath of plating stage can also optionally contain stablizer, and the kind of described stablizer and content have been conventionally known to one of skill in the art.For example, the content of described stablizer can be the 0-100 grams per liter, is preferably the 20-80 grams per liter, and stablizer is organic sulfonic acid and/or organic sulfonate.The example of the organic sulfonic acid that be fit to use includes but not limited to: alkansulfonic acid, as methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid and isomers thereof, fourth sulfonic acid and isomers thereof, penta sulfonic acid and isomers thereof, own sulfonic acid and isomers thereof, the last of the ten Heavenly stems sulfonic acid and isomers thereof, 12 carbon sulfonic acid and isomerss thereof; Aromatic sulfonic acid is as Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid and sulfocarbolic acid; Alkanol sulfonic acids is as hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid and isomers thereof, hydroxyl butyl sulfonic acid and isomers thereof, hydroxyl amyl group sulfonic acid.The example of organic sulfonate includes but not limited to an alkali metal salt and the alkaline earth salt of above-mentioned organic sulfonic acid.
Each employed plating bath of plating stage can also optionally contain brightening agent, and the kind of described brightening agent and content have been conventionally known to one of skill in the art.For example, the content of described brightening agent is the 0-10 grams per liter, is preferably the 0.005-8 grams per liter, and this brightening agent is one or more in sulfonamide derivatives, epihalohydrin and the glycidyl ether compound.The sulfonamide derivatives, epihalohydrin and the glycidyl ether compound that are fit to use have detailed explanation in CN1665965A, do not repeat them here.
After above-mentioned each plating stage, electro-plating method of the present invention can also comprise washing and exsiccant step, to remove the residual solution of substrate material surface; The used water of described water-washing step is various water of the prior art, as municipal tap water, deionized water, distilled water, pure water or their mixture, is preferably deionized water.Can adopt the method for well known to a person skilled in the art to carry out drying, for example forced air drying, natural air drying or oven dry under 40-100 ℃.
Described body material can be electro-conductive material or non-conducting material.Described non-conducting material can be plastics, fiber or resin, and described electro-conductive material can be various metals, as stainless steel.Described plastics can be electroplated or the plastics of electroless plating for various, and for example acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), nylon and polypropylene (PP) are preferably ABS.
When described body material was non-conducting material, before electroplating, described preparation method can also comprise made the metallized step of body material.Can make the body material metallization by carry out electroless copper or chemical nickel plating at substrate material surface.
The method of electroless copper or chemical nickel plating can adopt conventional chemical plating method.For example, the method for electroless plating comprises body material is contacted with the chemical plating fluid that contains metal-salt and reductive agent.Metal-salt is selected from the water-soluble hydrochloride salt of metal and in the vitriol one or more, is preferably in nickelous chloride, single nickel salt, cupric chloride and the copper sulfate one or more.Reductive agent is selected from one or more in hypophosphite, formaldehyde and the hydroborate, and described hypophosphite is preferably sodium hypophosphite and/or potassium hypophosphite.The reaction conditions of electroless plating comprises that the electroless plating temperature is 40 ℃-90 ℃, is preferably 40-80 ℃; Chemical plating fluid pH value is 4-12; The electroless plating time is 0.05-0.5 hour, is preferably 0.1-0.2 hour; The concentration of reductive agent described in the chemical plating fluid is the 0.2-1.0 mol, and the concentration of metal-salt is the 0.1-0.25 mol.
Below will the invention will be further described by embodiment.
Embodiment 1
This embodiment is used to illustrate plated item provided by the invention and preparation method thereof.
With stainless steel work-piece immerse temperature be in 55 ℃ the plating bath (described plating bath contains 0.007 mol cupric pyrophosphate, 0.14 mol stannous pyrophosphate and 300 grams per liter potassium pyrophosphates, and the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 2 microns, and copper content is 53 weight %.
Then, then the stainless steel work-piece that is coated with the layer of copper tin alloy coat of above-mentioned oven dry is immersed temperature and is that (described plating bath contains 0.033 mol cupric pyrophosphate, 0.14 mol stannous pyrophosphate, 300 grams per liter potassium pyrophosphates, 30 grams per liter methylsulfonic acids and 2 grams per liter trolamines in 40 ℃ the plating bath, the pH value is 7.5) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 4 microns, and copper content is 57 weight %.
Obtain plated item D1.
Comparative Examples 1
This Comparative Examples is used to illustrate existing plating product and preparation method thereof.
With stainless steel work-piece immerse temperature be in 55 ℃ the plating bath (described plating bath contains 0.007 mol cupric pyrophosphate, 0.14 mol stannous pyrophosphate and 300 grams per liter potassium pyrophosphates, and the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 20 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 4.1 microns, and copper content is 53 weight %.
Obtain plated item CD1.
Comparative Examples 2
This Comparative Examples is used for existing plating product and preparation method thereof.
It is that (described plating bath contains 0.033 mol cupric pyrophosphate, 0.14 mol stannous pyrophosphate, 300 grams per liter potassium pyrophosphates, 30 grams per liter methylsulfonic acids and 2 grams per liter trolamines in 40 ℃ the plating bath that stainless steel work-piece is immersed temperature, the pH value is 7.5) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 20 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 7.8 microns, and copper content is 57 weight %.
Obtain plated item D2.
Embodiment 2
This embodiment illustrates plated item provided by the invention and preparation method thereof.
It is that (described plating bath contains 0.007 mol cupric pyrophosphate, 0.14 mol stannous pyrophosphate, 300 grams per liter potassium pyrophosphates, 50 grams per liter methylsulfonic acids and 5 grams per liter quadrols in 55 ℃ the plating bath that stainless steel work-piece is immersed temperature, the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 2 microns, and copper content is 53 weight %.
Then, it is that (described plating bath contains 0.02 mol cupric pyrophosphate, 0.14 mol stannous pyrophosphate and 300 grams per liter potassium pyrophosphates in 55 ℃ the plating bath that the stainless steel work-piece that is coated with the layer of copper tin alloy coat that then will dry immerses temperature, the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 3 microns, and copper content is 55 weight %.
Then, then the stainless steel work-piece that is coated with two-layer cu-sn alloy coating of above-mentioned oven dry is immersed temperature and is that (described plating bath contains 0.033 mol cupric pyrophosphate, 0.14 mol stannous pyrophosphate and 300 grams per liter potassium pyrophosphates in 40 ℃ the plating bath, the pH value is 7.5) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 4 microns, and copper content is 57 weight %.
Obtain plated item D2.
Embodiment 3
This embodiment illustrates plated item provided by the invention and preparation method thereof.
With stainless steel work-piece immerse temperature be in 50 ℃ the plating bath (described plating bath contains 0.007 mol cupric pyrophosphate, 0.17 mol stannous pyrophosphate and 320 grams per liter potassium pyrophosphates, and the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 2.1 microns, and copper content is 52 weight %.
Then, it is that (described plating bath contains 0.02 mol cupric pyrophosphate, 0.17 mol stannous pyrophosphate and 320 grams per liter potassium pyrophosphates in 55 ℃ the plating bath that the stainless steel work-piece that is coated with the layer of copper tin alloy coat that then will dry immerses temperature, the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 3.1 microns, and copper content is 54.3 weight %.
Then, then the stainless steel work-piece that is coated with two-layer cu-sn alloy coating of above-mentioned oven dry is immersed temperature and is that (described plating bath contains 0.033 mol cupric pyrophosphate, 0.17 mol stannous pyrophosphate, 320 grams per liter potassium pyrophosphates, 50 grams per liter methylsulfonic acids and 5 grams per liter quadrols in 40 ℃ the plating bath, the pH value is 7.5) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 4 microns, and copper content is 57 weight %.
Obtain plated item D3.
Embodiment 4
This embodiment illustrates plated item provided by the invention and preparation method thereof.
It is that (described plating bath contains 0.016 mol cupric pyrophosphate, 0.22 mol stannous pyrophosphate, 300 grams per liter potassium pyrophosphates, 40 grams per liter methylsulfonic acids and 3 grams per liter quadrols in 50 ℃ the plating bath that stainless steel work-piece is immersed temperature, the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 2.2 microns, and copper content is 50 weight %.
Then, it is that (described plating bath contains 0.02 mol cupric pyrophosphate, 0.22 mol stannous pyrophosphate, 300 grams per liter potassium pyrophosphates, 40 grams per liter methylsulfonic acids and 3 grams per liter quadrols in 55 ℃ the plating bath that the stainless steel work-piece that is coated with the layer of copper tin alloy coat that then will dry immerses temperature, the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 3.2 microns, and copper content is 54 weight %.
Then, then the stainless steel work-piece that is coated with two-layer cu-sn alloy coating of above-mentioned oven dry is immersed temperature and is that (described plating bath contains 0.033 mol cupric pyrophosphate, 0.22 mol stannous pyrophosphate, 300 grams per liter potassium pyrophosphates, 40 grams per liter methylsulfonic acids and 3 grams per liter quadrols in 40 ℃ the plating bath, the pH value is 7.5) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 10 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 4 microns, and copper content is 56.8 weight %.
Obtain plated item D4.
Embodiment 5
This embodiment illustrates plated item provided by the invention and preparation method thereof.
With stainless steel work-piece immerse temperature be in 50 ℃ the plating bath (described plating bath contains 0.075 mol cupric pyrophosphate, 0.3 mol stannous pyrophosphate and 300 grams per liter potassium pyrophosphates, and the pH value is 7.4) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 3 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 1.5 microns, and copper content is 63 weight %.
Then, then the stainless steel work-piece that is coated with the layer of copper tin alloy coat of above-mentioned oven dry is immersed temperature and is that (described plating bath contains 0.002 mol cupric pyrophosphate, 0.1 mol stannous pyrophosphate and 300 grams per liter potassium pyrophosphates in 40 ℃ the plating bath, the pH value is 7.5) as negative electrode, with the tin metal plate as anode.Connect galvanic current, current density is 1 peace/square decimeter, electroplates after 20 minutes, stops to electroplate, and takes out stainless steel work-piece and be washed to no acid ion to be detected, then 80 ℃ of oven dry down.The thickness of this cu-sn alloy coating is 3.4 microns, and copper content is 42 weight %.
Obtain plated item D5.
Embodiment 6-10
Embodiment 6-10 is used to measure vibration wear resistance and the erosion resistance of the plated item D1-5 that embodiment 1-5 makes.
The vibration wear resistance is measured:
Vibrate in the groove of wear-resisting test machine and fill abrasive mixt.Begin vibration-testing then, added about 0.5 liter of water in per 30 minutes, every check in ten minutes once,, see if there is red copper and expose with the raw sample contrast.The red copper of record exposes the used time, and the vibration wear resistance of long more then product of time is good more.
Corrosion resistance measurement: plated item is placed in the salt fog cabinet, at 35 ℃ is that the sodium chloride brine of 5% (weight) sprayed plated item after 2 hours with concentration down, taking out and placing the another one temperature is that 40 ℃, relative humidity are 80% climatic chamber, observe plated item, the unusual used time appears in record plated item surface, and the erosion resistance of long more then product of time is good more.
Measurement result is as shown in table 1.
Comparative Examples 3 and 4
Comparative Examples 3 and 4 is used to measure plated item CD1 that Comparative Examples 1 and 2 makes and vibration wear resistance and the erosion resistance of CD2.
Measure plated item CD1 that Comparative Examples 1 and 2 makes and vibration wear resistance and the erosion resistance of CD2 according to the method identical with embodiment 5-10.
The result is as shown in table 1.
Table 1
| The embodiment numbering | The plated item numbering | Salt fog (hour) | Vibrate wear-resisting (minute) |
| Embodiment 1 | D1 | 185 | 290 |
| Comparative Examples 1 | CD1 | 184 | 150 |
| Comparative Examples 2 | CD2 | 138 | 290 |
| Embodiment 2 | D2 | 160 | 180 |
| Embodiment 3 | D3 | 200 | 290 |
| Embodiment 4 | D4 | 191 | 300 |
| Embodiment 5 | D5 | 168 | 290 |
Data from table 1 as can be seen, the vibration wear resistance of the plated item D1-D5 that obtains according to the method for embodiment 1-5 provided by the invention obviously is better than the plated item CD1 of Comparative Examples 1, erosion resistance obviously is better than the plated item CD2 of Comparative Examples 2, illustrate that plated item provided by the invention has good vibration wear resistance and erosion resistance simultaneously, realize good comprehensive performances.
Claims (16)
1. plated item, this plated item comprises the cu-sn alloy coating on body material and this substrate material surface, it is characterized in that, described cu-sn alloy coating is a multilayer, and the copper content of the cu-sn alloy coating of one deck at least in the described multiple layer of copper tin alloy coat is different with the copper content of other layer cu-sn alloy coating.
2. plated item according to claim 1, wherein, described multiple layer of copper tin alloy coat is divided into the different cu-sn alloy coating of multiple copper content, and the difference of the copper content of the cu-sn alloy coating that every kind of copper content is different is 0.5-20 weight %.
3. plated item according to claim 2, wherein, described multiple layer of copper tin alloy coat is divided into the cu-sn alloy coating of high copper content and the cu-sn alloy coating of low copper content, and the ratio of the total thickness of the cu-sn alloy coating of the total thickness of the cu-sn alloy coating of high copper content and low copper content is 1: 0.1-10.
4. plated item according to claim 3, wherein, the number of plies of the cu-sn alloy coating of high copper content is 1-5, the number of plies of the cu-sn alloy coating of low copper content is 1-5.
5. according to claim 3 or 4 described plated item, wherein, the thickness of the cu-sn alloy coating of every floor height copper content or the cu-sn alloy coating of low copper content is the 1-20 micron.
6. plated item according to claim 3, wherein, the copper content of the cu-sn alloy coating of high copper content is greater than 54 weight % to 80 weight %, the copper content of the cu-sn alloy coating of low copper content is 20-54 weight %.
7. the preparation method of the described plated item of claim 1, this method comprises electroplates body material in the plating bath that contains cupric ion, stannous ion and complexing agent, surface at body material forms cu-sn alloy coating, it is characterized in that, described galvanized process comprises a plurality of plating stages, and to account for the molecular fraction of the total amount of cupric ion and stannous ion in this plating bath different with the molecular fraction of cupric ion in other employed plating bath of plating stage for cupric ion at least one employed plating bath of plating stage.
8. method according to claim 7, wherein, a plurality of employed plating baths of plating stage are divided into the different plating bath of molecular fraction of multiple cupric ion, and the difference of the molecular fraction of the cupric ion of every kind of plating bath is 1-30 mole %.
9. method according to claim 8, wherein, described multiple plating bath is divided into high plating bath of cupric ion molecular fraction and the low plating bath of cupric ion molecular fraction, and the total thickness of the cu-sn alloy coating that forms in the high plating bath of cupric ion molecular fraction is 1 with the ratio of the total thickness of the cu-sn alloy coating that forms in the low plating bath of cupric ion molecular fraction: 0.1-10.
10. method according to claim 9, wherein, the plating stage of carrying out in the high plating bath of cupric ion molecular fraction is 1-5, the plating stage of carrying out in the low plating bath of cupric ion molecular fraction is 1-5.
11. according to Claim 8 or 9 described methods, wherein, cupric ion molecular fraction in the low plating bath of described cupric ion molecular fraction is 1-10 mole %, and the cupric ion molecular fraction in the high plating bath of described cupric ion molecular fraction is greater than 10 moles of % to 30 mole of %.
12. method according to claim 7, wherein, in each plating stage, the plating condition comprises that bath temperature is 10-60 ℃, and current density is a 0.2-5 peace/square decimeter, and the galvanized time is 1-20 minute.
13. method according to claim 7, wherein, in each employed plating bath of plating stage, content of copper ion is the 0.0015-0.008 mol, and stannous ion content is the 0.08-0.55 mol.
14. method according to claim 7, wherein, described complexing agent is an alkali metal pyrophosphate, and the concentration of complexing agent in plating bath is the 200-400 grams per liter.
15. method according to claim 7, wherein, each employed plating bath of plating stage also contains the stablizer of 20-80 grams per liter, and this stablizer is organic sulfonic acid and/or organic sulfonate.
16. method according to claim 7, wherein, each employed plating bath of plating stage also contains the brightening agent of 0.005-8 grams per liter, and this brightening agent is one or more in sulfonamide derivatives, epihalohydrin and the glycidyl ether compound.
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| CNA2006101621137A CN101195924A (en) | 2006-12-05 | 2006-12-05 | Plating product and method for producing the same |
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