CN104195619A - Composite electroplating solution and electroplating method through composite electroplating solution - Google Patents
Composite electroplating solution and electroplating method through composite electroplating solution Download PDFInfo
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- CN104195619A CN104195619A CN201410474945.7A CN201410474945A CN104195619A CN 104195619 A CN104195619 A CN 104195619A CN 201410474945 A CN201410474945 A CN 201410474945A CN 104195619 A CN104195619 A CN 104195619A
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Abstract
The invention relates to a composite electroplating solution and an electroplating method through the composite electroplating solution. The composite electroplating solution comprises a metal electroplating salt, at least one nitrate selected from aluminum, iron and copper, sulfamic acid and carbon nanofibers. The composite electroplating solution with the components has a synergistic effect. The uniform coating film can be formed on the surface of an electroplated component by the composite electroplating solution, and an effect which is better than that of the electroplating solution in the prior art can be realized through lower-concentration nitrate only.
Description
Technical field
The present invention relates to electroplating technology field, relate in particular to a kind of composite plating solution and use described composite plating solution to carry out electric plating method.
Background technology
Along with in the last few years to electronics such as miniaturization and the demand such as lightening, the trend of electronics being carried out to tight seal increases day by day, result, the installing space of the radiating element in electronics is more and more restricted.Therefore, strongly need the exploitation can be rapidly and the hot heat radiation part that more effectively radiation is produced by the electron device that is arranged on electronic equipment internal.
Prior art utilizes the metal to metal plate of high thermal conductivity to electroplate, thereby makes this heat radiation part.The so-called composite film coating that comprises carbon nanomaterial (for example carbon nanofiber) is used as described metal, and wherein said carbon nanomaterial is extremely excellent thermal-radiating material.There is document description, by adding carbon nanofiber etc. to increase heat-radiating properties and the thermal conductivity of composite film coating.From nearest demand angle, need to develop the more excellent heat radiation part of a kind of thermal radiation property.
The inventor has studied above-mentioned correlation technique and has found, the composite plating solution effects on surface that comprises carbon nanomaterial (for example carbon nanofiber) when utilization is formed with spill and convex while electroplating with the long-pending heat radiation part of optimizing surface, described recessed/the galvanic deposit homogeneity of convex surface is not enough.
Particularly, the electroplating thickness on concave bottom surfaces and/or side is not enough, and has larger unhomogeneity between these surfaces and convex end face.
CN102650072A discloses a kind of composite plating solution, and it comprises: the salt of plated metal; At least one is selected from the vitriol of the element in alkali and alkaline earth metal ions; Boric acid; Carbon nanotube; And dispersion agent.Although this patent application declares effectively to solve the problem of homogeneity, the inventor finds that its homogeneity need to improve after deliberation.
Based on above-mentioned cognition, the inventor has carried out research energetically, and has found a kind of specific composite plating solution that comprises carbon nanomaterial (for example carbon nanofiber), thereby has completed the present invention.When utilize above-mentioned composite plating solution on surface, have complicated recessed/during the enterprising electroplating of hardware of convex form, whole complexity recessed/formed the metal coating of thickness homogeneous on convex form, thereby the carbon nanomaterial that makes it contain q.s.
Summary of the invention
The object of the present invention is to provide a kind of composite plating solution and use described composite plating solution to carry out electric plating method.Described composite plating solution and method can solve the unhomogeneity problem between plating piece surface and convex end face better than prior art.
The present invention includes following technical scheme:
In first aspect, the invention provides a kind of composite plating solution, it is characterized in that, described composite plating solution comprises:
The salt of plated metal;
At least one is selected from the nitrate of aluminium, iron or copper;
Thionamic acid; With
Carbon nanofiber.
As the preferred technical solution of the present invention, described composite plating solution also comprises: dispersion agent.
As the preferred technical solution of the present invention, described dispersion agent is polyacrylic acid, Styrene-methyl Acrylic Acid Copolymer, alkyl acrylate-acrylic copolymer, vinylbenzene-methacrylic acid phenylester-Sipacril 2739OF, Lalgine or hyaluronic acid.
As the preferred technical solution of the present invention, described plated metal at least comprises nickel.
As the preferred technical solution of the present invention, the concentration of the salt of described plated metal is 25g/L to 75g/L, and the concentration of described nitrate is 100g/L to 500g/L.
In second aspect, the invention provides a kind of composite plating solution, described composite plating solution is composed of the following components:
The salt of plated metal;
At least one is selected from the nitrate of aluminium, iron or copper;
Thionamic acid;
Carbon nanofiber; With
Dispersion agent.
In the third aspect, the invention provides and a kind ofly adopt the composite plating solution described in first aspect or second aspect to carry out electric plating method to member.
In fourth aspect, the invention provides a kind of composite film coating forming by the electro-plating method described in the third aspect.
Aspect the 5th, the invention provides a kind of member through electroplating, described member comprises the composite film coating described in fourth aspect.
Aspect the 6th, the invention provides a kind of heat radiation part, described heat radiation part comprises:
The first surface on it with a plurality of grooves; With
Composite film coating described in fourth aspect, this composite film coating is formed on the whole surface of described first surface, and the thickness of described composite film coating is homogeneous on described first surface.
Beneficial effect of the present invention is: the salt that composite plating solution of the present invention comprises plated metal; At least one is selected from the nitrate of aluminium, iron or copper; Thionamic acid; And carbon nanofiber.Due to the synergy of said components, composite plating solution of the present invention can form the plated film of homogeneous on plating piece surface, only needs the nitrate of low concentration just can reach the effect more excellent than prior art.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.It will be understood to those of skill in the art that following examples are only the preferred embodiments of the present invention, so that understand better the present invention, thereby should not be considered as limiting scope of the present invention.For a person skilled in the art, the present invention can have various modifications and variations, within the spirit and principles in the present invention all, any modification of doing, is equal to and replaces or improvement etc., within all should being included in protection scope of the present invention.
Composite plating solution
Composite plating solution of the present invention is Water Soluble Compound electroplate liquid, the salt that it comprises plated metal; At least one is selected from the nitrate of aluminium, iron or copper; Thionamic acid; And carbon nanofiber.Optionally, also comprise dispersion agent.
The salt of plated metal is the salt that utilizes the metal that electroplate liquid of the present invention deposits.Kind to plated metal is not particularly limited, and according to the object of electroplating, can select suitable metal.Particularly, for the thermal radiation of electronics or electron device, can select the metal that thermal conductivity is high.Its concrete example is metals such as nickel, silver, gold, cobalt, copper and palladium, or the alloy of Ferrious material and phosphorus and/or boron.
Salt to plated metal is not particularly limited, and it can be any water-soluble salt of metal used.Concrete example is vitriol, sulfamate and halogenide.When metal is nickel, the preferred example of water-soluble metal salt is single nickel salt, nickelous bromide, nickelous chloride and nickel sulfamic acid.Halogenide is particularly preferred salt, and bromide is best.
Content to the salt of plated metal is not particularly limited.Available concentration range is identical with the salt of common used plated metal, and can be 10g/L to 400g/L.Preferred concentration range is 10g/L to 200g/L, more preferably 10g/L to 100g/L.When the concentration of the salt of plated metal is within the scope of this, can there is not so-called incipient scorch, and as mentioned below, can obtain high galvanic deposit homogeneity.
Composite plating solution of the present invention is for also comprising the electroplate liquid that at least one is selected from the nitrate of aluminium, iron or copper.Nitrate is as so-called conducting salt.Its concrete example is aluminum nitrate, iron nitrate and cupric nitrate.In the present invention, for the object that obtains high galvanic deposit homogeneity, preferably use aluminum nitrate, iron nitrate.
Content to conducting salt is not particularly limited.Available concentration range is identical with the conducting salt that conventional electroplate liquid is used.In the present invention, in order to obtain high galvanic deposit homogeneity, preferably, the content of conducting salt (concentration) is greater than the content in conventional electroplate liquid, and in the scope of 150g/L to 800g/L.In order to obtain higher galvanic deposit homogeneity, preferably, the content of conducting salt is in the scope of 200g/L to 500g/L.In order to obtain higher galvanic deposit homogeneity, preferably, the salt of plated metal and the weight ratio between conducting salt are in the scope of 1: 3 to 1: 10.
A key character of composite plating solution of the present invention is that, except mentioned component, it also comprises thionamic acid.Thionamic acid is as buffer reagent.Therefore, the content of thionamic acid is not particularly limited, but its content should make it effectively as buffer reagent.Available concentration range is 20g/L to 60g/L.In order to obtain higher galvanic deposit homogeneity, preferably, for example, weight ratio between plated metal (nickel ion) and thionamic acid is in the scope of 1: 1 to 1: 5.
Another important being characterized as of composite plating solution of the present invention, it comprises carbon nanofiber.Carbon nanofiber is included in by electroplating in the metal coating forming.Including carbon nanofiber is the reason of using term " compound ".
In the present invention, as mentioned below, term " carbon nanofiber " belongs to " carbon nano-particle ", and refers to that thickness is that 1nm to 5 μ m (being preferably 10nm to 500nm) and length are the fibrous carbon nano particle of 0.5 μ m to 1000 μ m (being preferably 1 μ m to 100 μ m).
Term " fibrous carbon nano particle " comprise narrow sense carbon nanofiber, comprise carbon nanofiber such as predetermined substances such as metals, carbon nanohorn (the horn shape body that thickness (diameter) increases continuously to the other end from one end), carbon nanocoil (coiled type bent bodies), folded cup-shaped carbon nanofiber (polylayer forest of cup-shaped graphite cake), carbon nanofiber, carbon nano wire (center at carbon nanofiber has carbochain) etc.
To how obtaining carbon nanofiber used in the present invention, be not particularly limited.Can utilize conventional method (for example arc discharge method, laser ablation method or CVD) synthesize nano carbon fiber.Can also in statu quo use commercially available carbon nanofiber.
Content to carbon nanofiber is not particularly limited.Can suitably consider that the content of carbon nanofiber required in composite film coating sets the content of the carbon nanofiber in composite plating solution.For example, can consider carbon nanofiber size and shape, they are the content that the kind of functional group on individual layer or multilayer, each particle surface and the kind of amount and other compositions and amount etc. are suitably set the carbon nanofiber in composite plating solution.
With respect to total mass, the content of aqueous dispersant can be 0.0001 quality % to 20 quality %, is preferably 0.01 quality % to 5 quality %.If content is less than 0.0001 quality %, aqueous liquid dispersion may show not enough character.If content is greater than 20 quality %, may there is the problem of carbon nanofiber aggegation or precipitation.When plated metal is nickel, in order to strengthen thermal radiation property, it is desirable to the carbon nanofiber that composite film coating comprises 0.1 % by weight to 10 % by weight.
Another important feature of composite plating solution of the present invention is to have used suitable dispersion agent.Due to carbon nanofiber used in the present invention, normally water is non-wettable, it is therefore preferable that and utilizes dispersion agent that it is scattered in water-soluble electroplate liquid.That is, due under many circumstances, carbon nanofiber as described above is difficult to be dispersed in fully in water-soluble electroplate liquid, therefore, preferably with dispersion agent, their is disperseed.
In the present invention, the kind of dispersion agent is not particularly limited.Suitable dispersion agent can be selected from the known dispersion agent for carbon nanomaterial.The example of dispersion agent is anion surfactant, cats product, nonionic surface active agent, non-ionic water-soluble organic polymer, amphoterics, amphoteric water-soluble organic polymer, multiple water-soluble organic polymer dispersion agent, organic polymer positively charged ion and cyclodextrin.
Particularly, preferably use water-soluble organic polymer dispersion agent.Its concrete example is polyacrylic acid, Styrene-methyl Acrylic Acid Copolymer, alkyl acrylate-acrylic copolymer, vinylbenzene-methacrylic acid phenylester-Sipacril 2739OF, Lalgine and hyaluronic acid.
Particularly, preferably use polyacrylic acid.The polyacrylic polymerization degree is not particularly limited.Can adopt the suitable polymerization degree according to the kind of used carbon nanofiber and consumption.The example of polyacrylic molecular weight ranges is 1,000 to 100,000.
When being necessary, composite plating solution of the present invention can also comprise any multiple additives.The example of additive is pH adjusting agent, for example nickelous carbonate; Prevent the tensio-active agent of pit; And brightener, for example soluble saccharin.
Production/preparation method to composite plating solution of the present invention is not particularly limited.Can prepare like this composite plating solution: make them there is required content by composition as described above is admixed together, and if necessary, utilize agitator or ultrasonic unit that carbon nanofiber is disperseed.Can before using, prepare composite plating solution, and by its storage.Can also prepare in use composite plating solution.When preparing composite plating solution and being stored before using, if necessary, can use (plating) before and/or between the usage period, adopt suitable method to stir electroplate liquid, thereby increase the degree of scatter of carbon nanofiber.
To for analyzing the composition of composite plating solution of the present invention and the method for content is not particularly limited.Preferably use conventional analytical procedure.For example, can in statu quo by the conventional qualitative/quantitative analytical procedure of water-soluble metal ion, analyze metal ingredient.Its concrete example is general metal ion way of qualitative analysis and quantitative analysis methods such as ion chromatography and atomic absorption analysis.Thereby can make carbon nanofiber from electroplate liquid, separate out the amount of measuring them, or use electron microscope to measure the shape of carbon nanofiber, thereby carbon nanofiber (their kind, amount etc.) is analyzed.
Can utilize the weighting agents such as conventional adsorptive type, ion-exchange type to carry out column chromatography, thereby for example, by dispersion agent (polyacrylic acid) separation, carry out afterwards any multiple instrumental analysis (NMR, IR, UV-VIS etc.), thus qualitative or quantitatively dispersion agent is analyzed.
Composite plating method
Composite plating method of the present invention is to utilize composite plating solution of the present invention mentioned above, in compound mode, to electroplating target member, carries out electric plating method.
To applying material, size or the shape of the plating target member of composite plating method of the present invention, be not particularly limited.For example, when composite plating method of the present invention is used nickel as plated metal, composite plating method of the present invention can be for the multiple plating target member using in conventional nickel plating.
Particularly, composite plating method of the present invention has such feature: even electroplate the surface of the electroplated of target member have complicated recessed/convex form (on micro-scale or in macro-scale), also can form and there is plated film homogeneous, desired thickness, thus consistent with shape.Below to utilizing the formed plated film of electro-plating method of the present invention to be described below in greater detail.
The concrete example of electroplating the material of target member is various metals, metal alloy, resin and the matrix material that formed by resin and non-resin.Particularly, electro-plating method of the present invention can be suitably for metal and metal alloy.To electroplating the size of target material, be not particularly limited, and by setting suitable plating condition (below will be described plating condition) according to the size of electroplating target member, thereby electro-plating method of the present invention can be used suitably.
Phraseology " surface of electroplating the electroplated of target member have complicated recessed/convex form " implication not only comprise such situation: for example, the surface of plating target member as a whole (in macroscopic view) is not equidistant with anode, but curved, or there is crooked part or the back side; But also comprise such situation: although electroplate target member, in macroscopic view, be equidistant with anode, its surface has the complicated shape such as concaveconvex shape on microcosmic.
Term " complicated shape such as concaveconvex shape " refers to, and between anode, has the shape of the range difference (between proximal part and distal portions, for example, between convex tip and concave bottom) of several microns to several millimeters.The length-to-diameter ratio of recessed/convex form refers to, the ratio between the degree of depth of recess and the size of its opening.The object lesson with the plating target member of such surface shape is, its surface of electronics or electron device has recessed/convex form (groove, grid etc.) to increase the heat radiation part (heat sink, scatterer etc.) of surface-area.
Even electro-plating method of the present invention length-to-diameter ratio large whole recessed/can both obtain high galvanic deposit homogeneity on convex form.
Plating condition to electro-plating method of the present invention is not particularly limited.Can by statu quo with or the suitable following condition of change easily set plating condition, wherein said condition be the condition of for example, in the plating bath that uses any multiple routine of water-soluble electroplate liquid (, Watts bathes) employing.
Particularly, the size of the plating bath for electro-plating method of the present invention or shape are not limited.Can be according to electroplating the size and shape of target member, the amount of the size and shape of anode, electroplate liquid and other because of the size and shape of definite plating bath suitably usually.Can use suitable atmosphere according to object, for example air or rare gas element.
The type of the anode for electro-plating method of the present invention, size or shape are not particularly limited.In common situation, can use suitable anode according to the type of plated metal, plating amount, electroplating time and other factors.In the situation that nickel is electroplated, can use suitably the anode of being made by electrolytic nickel etc.
The target member of respectively electroplating as described above can be in common mode as negative electrode.Preferably, in plating tank, make negative electrode and positive electrode keeping parallelism.
Temperature to electro-plating method of the present invention is not particularly limited.Electro-plating method of the present invention can for example, carry out in the temperature range (10 ℃ to 90 ℃) of conventional Metal plating method.If necessary, can be in electroplating process appropriate change electroplating temperature.
PH scope to electro-plating method of the present invention is not particularly limited.Electro-plating method of the present invention can for example, carry out in the pH scope (pH1 to pH13) of conventional Metal plating method.In electroplating process, it is constant that pH both can keep, also can appropriate change.Can be by selecting suitably to set pH for the dispersion agent of electro-plating method of the present invention.Or can add suitable pH adjusting agent to regulate pH.When dispersion agent is polyacrylic acid, can use its part an alkali metal salt (for example sodium polyacrylate).
The current density of electro-plating method of the present invention and electroplating time are not particularly limited.Can be according to for example electroplating the size and shape of target member,, the composition of electroplate liquid and required electroplating quality (, the thickness of plated film, flow leveling and galvanic deposit homogeneity) adopt suitable current density and electroplating time.Electro-plating method of the present invention can for example, at () 0.1A/dm
2to 10A/dm
2current density range in carry out.In order to obtain high galvanic deposit homogeneity, 1A/dm
2to 5A/dm
2scope be preferred.
Composite film coating
The composite film coating that utilizes composite plating method of the present invention to form is under these conditions that a kind of carbon nanofiber is embedded in the coating in required metal coating, and described composite film coating has following characteristics.
The thickness of plated film can be set in to submicron to the scope of several millimeters.The thickness of plated film demonstrates high homogeneity (galvanic deposit homogeneity) electroplating in the whole surface shape of target member (comprise complicated recessed/convex form).Can select suitably described thickness according to the desired thickness of the shape of carbon nanofiber to be sneaked into (particularly length) and/or plated metal.
For example, can determine it aspect heat transmission, is being the thickness of preferred nickel metal layer, determine suitably afterwards size and the amount of carbon nanofiber, thereby make it possible to realize sufficient heat, transmit and thermal radiation.In this way, can make thermal conduction and radiation efficiency optimizing.
Can change by the method for multiple routine the various size (particularly length) of (for example shortening) carbon nanofiber.
Use electron microscope can easily measure feature and the thickness of the formed composite film coating of the present invention, and galvanic deposit homogeneity.This method makes it possible to observe surface and the tangent plane of composite film coating.
The kind of the metal comprising in plated film and amount can utilize conventional micron order metal analysis method (for example x-ray fluorescence analysis) to measure.
The kind of the carbon nanofiber comprising in plated film and amount can for example, be measured by conventional micron order elemental microanalysis method (x-ray fluorescence analysis), or measure by the following method, the method utilizes acid by dissolution of partial fiber surface, thereby acquisition solution example, then utilizes ordinary method to carry out ultimate analysis to this solution example.
Member and heat radiation part through electroplating
In the present invention, term " member through electroplating " refers to the member that is formed with composite film coating of the present invention (mentioned above) on its at least part of surface.Term " heat radiation part " refers to the parts with thermal radiation or thermal conducting function, for example scatterer, heat sink, heat pipe, soaking plate or heat exchanger.The prepared heat radiation part of the present invention is characterised in that, on its at least part of surface, is formed with composite film coating of the present invention.Therefore, the prepared heat radiation part of the present invention is characterised in that, it is formed with plated film by galvanic deposit in surface at least partly, this make to have formed in macroscopic view and microcosmic on highly homogeneous coating all.
Utilize electro-plating method of the present invention, make its surface have complicated shape (on microcosmic recessed/convex form, or length-to-diameter ratio large recessed/convex form) with the plating target member that obtains large surface-area its whole complexity be all formed with in shape the metal plating of thickness homogeneous, and this metal plating comprises the carbon nanofiber of q.s equably.Due to these features, the prepared member through electroplating can be used as heat radiation part (for example heat sink), and when this heat radiation part is used for electronics or electron device, it shows extremely excellent thermal conductivity and high radiation efficiency.
Although below utilize embodiment, in concrete mode, present invention is described, and scope of the present invention is not limited to these embodiment.
Embodiment
(1) general condition of electroplating
Negative electrode: the plating target member being made of copper (in the following embodiments its shape being described)
Anode: sheet nickel (50mm * 50mm)
Electroplating temperature: 50 ℃
Current density: 2A/dm
2
Treatment time: 25 minutes
(2) the electron microscope measuring condition of plated film:
Utilize SEM to measure with 2,000 ratio of enlargement effects on surface.The cross section of coating is carried out to polishing and cutting, and utilize SEM to measure gained cut surface with 2,000 ratio of enlargement.
(3) measurement of thermal radiation property:
Ceramic heater is installed on the copper billet of appointment, and utilizes tackiness agent that copper coin (measure sample) is fixed on this copper billet.In described copper billet, formation temperature meter patchhole, inserts this hole by thermometer, when constant voltage being applied to well heater, measures temperature in the time of 60 minutes.
Embodiment 1
Electroplate the preparation of target member: by cutting, on a surface of square no-oxygen copper plate, form and there is the groove of recessed/convex form (concave bottom is wide: 1.0mm, wall is high: 0.8mm, convex tip is wide: 2.0mm), the length of side of described square no-oxygen copper plate is 16mm to 49mm, and thickness is 1.27mm to 3mm.By degreasing, clean this plate.Surface-area is 31.62cm
2.
The preparation of composite plating solution: stirring is 5 by three hydration nickelous bromides (50g/L), aluminum nitrate (10g/L), thionamic acid (40g/L) and molecular weight, 000 polyacrylic acid (dispersion agent: solution 0.1g/L) forming, add diameter is that 100nm to 150nm and length are the carbon nanofiber (2g/L) of 10 μ m to 15 μ m simultaneously, and makes its dispersion.
Gained electroplate liquid (250mL) is kept in coating bath.When stirring electroplate liquid, with positive plate as described above, to electroplate, the surface towards/convex form recessed with having of negative plate as described above of this positive plate is relative.The pH of electroplate liquid is 4.8.
Utilize electron microscope observation composite film coating (thickness: 10 μ m).
Electron microscope observation: deposit the metallic nickel of q.s in convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.Also knownly in concave bottom, deposit the approximately metallic nickel identical with the amount of convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.On side, deposit the approximately metallic nickel identical with the amount of concave bottom with the amount of convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.These results show, the electro-plating method of embodiment 1 can obtain very high galvanic deposit homogeneity.
The measurement of thermal radiation property: under measuring condition as described above, the thermal radiation property that the composite film coating of embodiment 1 shows is lower 2 ℃ than the thermal radiation property of the composite film coating of comparative example 1.
Comparative example 1
According to the mode identical with embodiment 1, electroplate and electron microscope observation, difference is to make prepared electroplate liquid to have following composition.
The preparation of composite plating solution: stir by six hydration nickel sulfate (240g/L), sodium sulfate (45g/L), boric acid (30g/L), soluble saccharin (brightener: 2g/L), 2-butyne-1,4-glycol (brightener: be 0.2g/L) 5 with molecular weight, 000 polyacrylic acid (dispersion agent: solution 0.1g/L) forming, add diameter is that 100nm to 150nm and length are the carbon nanofiber (2g/L) of 10 μ m to 15 μ m simultaneously, and makes its dispersion.
Electron microscope observation: deposit the metallic nickel of q.s in convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.Yet known almost do not have metallic nickel deposition in concave bottom, and almost there is no carbon nanofiber.On side, almost there is no metallic nickel deposition, and almost there is no carbon nanofiber.
Embodiment 2
Electroplate the preparation of target member: by cutting, on a surface of square no-oxygen copper plate, form and there is the groove of recessed/convex form (concave bottom is wide: 1.0mm, wall is high: 0.8mm, convex tip is wide: 2.0mm), the length of side of described square no-oxygen copper plate is 16mm to 49mm, and thickness is 1.27mm to 3mm.By degreasing, clean this plate.Surface-area is 31.62cm
2.
The preparation of composite plating solution: stirring is 5 by three hydration nickelous bromides (50g/L), iron nitrate (10g/L), thionamic acid (40g/L) and molecular weight, 000 polyacrylic acid (dispersion agent: solution 0.1g/L) forming, add diameter is that 100nm to 150nm and length are the carbon nanofiber (2g/L) of 10 μ m to 15 μ m simultaneously, and makes its dispersion.
Gained electroplate liquid (250mL) is kept in coating bath.When stirring electroplate liquid, with positive plate as described above, to electroplate, the surface towards/convex form recessed with having of negative plate as described above of this positive plate is relative.The pH of electroplate liquid is 4.8.
Utilize electron microscope observation composite film coating (thickness: 10 μ m).
Electron microscope observation: deposit the metallic nickel of q.s in convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.Also knownly in concave bottom, deposit the approximately metallic nickel identical with the amount of convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.On side, deposit the approximately metallic nickel identical with the amount of concave bottom with the amount of convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.These results show, the electro-plating method of embodiment 2 can obtain very high galvanic deposit homogeneity.
The measurement of thermal radiation property: under measuring condition as described above, the thermal radiation property that the composite film coating of embodiment 2 shows is lower 2 ℃ than the thermal radiation property of the composite film coating of comparative example 2.
Comparative example 2
According to the mode identical with embodiment 2, electroplate and electron microscope observation, difference is to make prepared electroplate liquid to have following composition.
The preparation of composite plating solution: stir by six hydration nickel sulfate (240g/L), potassium sulfate (45g/L), boric acid (30g/L), soluble saccharin (brightener: 2g/L), 2-butyne-1,4-glycol (brightener: be 0.2g/L) 5 with molecular weight, 000 polyacrylic acid (dispersion agent: solution 0.1g/L) forming, add diameter is that 100nm to 150nm and length are the carbon nanofiber (2g/L) of 10 μ m to 15 μ m simultaneously, and makes its dispersion.
Electron microscope observation: deposit the metallic nickel of q.s in convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.Yet known almost do not have metallic nickel deposition in concave bottom, and almost there is no carbon nanofiber.On side, almost there is no metallic nickel deposition, and almost there is no carbon nanofiber.
Embodiment 3
Electroplate the preparation of target member: by cutting, on a surface of square no-oxygen copper plate, form and there is the groove of recessed/convex form (concave bottom is wide: 1.0mm, wall is high: 0.8mm, convex tip is wide: 2.0mm), the length of side of described square no-oxygen copper plate is 16mm to 49mm, and thickness is 1.27mm to 3mm.By degreasing, clean this plate.Surface-area is 31.62cm
2.
The preparation of composite plating solution: stirring is 5 by three hydration nickelous bromides (50g/L), cupric nitrate (10g/L), thionamic acid (40g/L) and molecular weight, 000 polyacrylic acid (dispersion agent: solution 0.1g/L) forming, add diameter is that 100nm to 150nm and length are the carbon nanofiber (2g/L) of 10 μ m to 15 μ m simultaneously, and makes its dispersion.
Gained electroplate liquid (250mL) is kept in coating bath.When stirring electroplate liquid, with positive plate as described above, to electroplate, the surface towards/convex form recessed with having of negative plate as described above of this positive plate is relative.The pH of electroplate liquid is 4.8.
Utilize electron microscope observation composite film coating (thickness: 10 μ m).
Electron microscope observation: deposit the metallic nickel of q.s in convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.Also knownly in concave bottom, deposit the approximately metallic nickel identical with the amount of convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.On side, deposit the approximately metallic nickel identical with the amount of concave bottom with the amount of convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.These results show, the electro-plating method of embodiment 3 can obtain very high galvanic deposit homogeneity.
The measurement of thermal radiation property: under measuring condition as described above, the thermal radiation property that the composite film coating of embodiment 3 shows is lower 2 ℃ than the thermal radiation property of the composite film coating of comparative example 3.
Comparative example 3
According to the mode identical with embodiment 3, electroplate and electron microscope observation, difference is to make prepared electroplate liquid to have following composition.
The preparation of composite plating solution: stir by six hydration nickel sulfate (240g/L), magnesium sulfate (80g/L), boric acid (30g/L), soluble saccharin (brightener: 2g/L), 2-butyne-1,4-glycol (brightener: be 0.2g/L) 5 with molecular weight, 000 polyacrylic acid (dispersion agent: solution 0.1g/L) forming, add diameter is that 100nm to 150nm and length are the carbon nanofiber (2g/L) of 10 μ m to 15 μ m simultaneously, and makes its dispersion.
Electron microscope observation: deposit the metallic nickel of q.s in convex tip, and have the carbon nanofiber (thickness: 10 μ m) of q.s.Yet known almost do not have metallic nickel deposition in concave bottom, and almost there is no carbon nanofiber.On side, almost there is no metallic nickel deposition, and almost there is no carbon nanofiber.
Applicant's statement, the present invention illustrates detailed features of the present invention and detailed method by above-described embodiment, but the present invention is not limited to above-mentioned detailed features and detailed method, do not mean that the present invention must rely on above-mentioned detailed features and detailed method could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention is selected the selection of the equivalence replacement of component and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope to the present invention.
Claims (10)
1. a composite plating solution, is characterized in that, described composite plating solution comprises:
The salt of plated metal;
At least one is selected from the nitrate of aluminium, iron or copper;
Thionamic acid; With
Carbon nanofiber.
2. composite plating solution according to claim 1, is characterized in that, described composite plating solution also comprises: dispersion agent.
3. composite plating solution according to claim 2, it is characterized in that, described dispersion agent is polyacrylic acid, Styrene-methyl Acrylic Acid Copolymer, alkyl acrylate-acrylic copolymer, vinylbenzene-methacrylic acid phenylester-Sipacril 2739OF, Lalgine or hyaluronic acid.
4. according to the composite plating solution described in claim 1-3 any one, it is characterized in that, described plated metal at least comprises nickel.
5. according to the composite plating solution described in claim 1-4 any one, it is characterized in that, the concentration of the salt of described plated metal is 25g/L to 75g/L, and the concentration of described nitrate is 100g/L to 500g/L.
6. a composite plating solution, is characterized in that, described composite plating solution is composed of the following components:
The salt of plated metal;
At least one is selected from the nitrate of aluminium, iron or copper;
Thionamic acid;
Carbon nanofiber; With
Dispersion agent.
7. one kind adopts the composite plating solution described in claim 1-6 any one to carry out electric plating method to member.
8. the composite film coating forming by electro-plating method claimed in claim 7.
9. the member through electroplating, is characterized in that, described member comprises composite film coating claimed in claim 8.
10. a heat radiation part, is characterized in that, described heat radiation part comprises:
The first surface on it with a plurality of grooves; With
Composite film coating claimed in claim 8, this composite film coating is formed on the whole surface of described first surface, and the thickness of described composite film coating is homogeneous on described first surface.
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| CN112410829A (en) * | 2020-11-14 | 2021-02-26 | 南京柯普新材料科技有限公司 | Nickel-plated carbon fiber and preparation process thereof |
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| CN112522747A (en) * | 2020-11-19 | 2021-03-19 | 瑞声科技（南京）有限公司 | Preparation method of upper cover plate of vapor chamber and vapor chamber |
| CN112522747B (en) * | 2020-11-19 | 2022-01-07 | 瑞声科技（南京）有限公司 | Preparation method of upper cover plate of vapor chamber and vapor chamber |
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