CN102041543B - Preparation method of fullerene/metal composite film on metal surface - Google Patents
Preparation method of fullerene/metal composite film on metal surface Download PDFInfo
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- CN102041543B CN102041543B CN200910197386A CN200910197386A CN102041543B CN 102041543 B CN102041543 B CN 102041543B CN 200910197386 A CN200910197386 A CN 200910197386A CN 200910197386 A CN200910197386 A CN 200910197386A CN 102041543 B CN102041543 B CN 102041543B
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Abstract
The invention provides a preparation method of a fullerene/metal composite film on a metal surface. The preparation method is characterized by comprising the following steps of: (1) surface pretreatment of a substrate material: cleaning, acid-cleaning and activating a metal surface; (2) preparation of an electrophoresis solution, dispersing fullerene in tetrahydrofuran, ultrasonically oscillating, filtering, reducing and regulating pH value to be 8-12; (3) preparation of a fullerene film on the metal surface with an electrophoresis method; (4) preparation of electroplating liquid: preparing the electroplating liquid containing Ni, Sn, Zn, Cu, Cr, and the like; (5) preparation of a fullerene/metal composite coating on a metal plate, which is provided with the fullerene film and obtained from the step (3), by adopting an electroplating method; and (6) heating. The method provided by the invention can be used for modifying the metal surface; and particularly a novel surface coating film metal material can be derived and a brand-new nano composite plating metal product can be developed by utilizing the thermal diffusion characteristic of the fullerene material.
Description
Technical field
The present invention relates to field of nanometer technology, specifically, the present invention relates to the plating method of a kind of soccerballene/metallic substance at the composite package of metal base surface.
Background technology
Composite deposite (composite coating) is exactly with one or more insoluble solid particulates, is mingled with formed special coating in the metal plating equably.The technology of preparation composite deposite roughly comprises methods such as galvanic deposit, built-up welding, thermospray and cold spraying, and wherein, with electrodip process, just composite plating (composite plating) is comparatively commonly used.This technology obtains fast development in recent years, and obtains widespread use in field of engineering technology.Nano material joined just developed into nano combined coating technology in the metal plating; Because nano material has particular performances such as scale effect, surface effects, quantum size effect and quantum tunneling effect; Nano material is joined in the coating, will help improving the performances such as intensity, toughness and wear resistance of such coating.And fullerene-based material itself has perfect symplex structure, can produce novel characteristic at aspects such as ir absorption, superconduction, electromagnetic propertys.About the nano composite plating Study on Technology, at the early-stage both at home and abroad, especially the material doped research in the metal plating of fullerene molecule is still belonged to blank both at home and abroad.
Mostly the research object of existing patent is carbon nanotube and carbon dust etc.; For example except physical vapor deposition and chemical vapour deposition etc. the method; Chinese patent document 02115095.8 discloses a kind of method that acetylene gas prepares carbon nano-tube film that directly on the stainless steel surface that process is cleaned, feeds, but because the stability height of carbon nanotube, its fusing point is the highest in the present known materials; Can at high temperature prepare, this is then inapplicable for soccerballene.American documentation literature 6783745 discloses a kind of through carbon dust (is contained C
60Or SWCN) adopt the method for the high-temperature high-pressure craft preparation new carbon similar with ferrous materials hardness, and can form random shapes such as cylinder, bar, pipe through PM technique, novel material is easy to mix and be converted into diamond.Chinese patent document 200420052200.3 discloses a kind of electrostatic coating method, and nanometer powder is sprayed on the iron skill assembly, makes its corrosion resisting property improve 5 times.Chinese patent document 01812239.6,01812313.9 discloses a kind of preparation method of super thin protective coatings, and it is fullerene coated to form individual layer through the particle flux producer at magnetic disk surface, with the magnetic device of using as disk.Soccerballene has also obtained Preliminary Applications on semiconducter device; As Chinese patent document 01822518.7 disclose a kind of outside semi-conductor processing unit parts surface deposition soccerballene form the method for anti-corrosion layer, sedimentary soccerballene thickness is 0.001～0.050 inch.In addition, contain fullerene coated can also be as luminescent device, of Chinese patent document 200480011554.6.
In sum, up to the present, soccerballene/metallic substance is not seen report as yet in the composite film coating technology of preparing of metal base surface.Therefore, the object of the present invention is to provide a kind of technology that is coated with that adopts electrophoresis/composite electroplated film coating method fullerene-based material and metal plating to be prepared in the metallic surface.
Summary of the invention
The present invention provides the preparation method of a kind of metallic surface soccerballene/metal composite thin film, may further comprise the steps:
(1) metal material surface pre-treatment comprises decontamination, pickling and the activation treatment of metallic surface;
(2) preparation of electrophoresis liquid: with soccerballene dispersion in THF, sonic oscillation, filtration, reduction, adjusting pH value is 8～12;
(3) electrophoretic method prepares fullerene thin film in the metallic surface;
(4) preparation of electroplate liquid: the electroplate liquid of configuration Ni, Sn, Zn, Cu, Cr etc.;
(5) plating method have at step (3) gained on the metal sheet of fullerene thin film and prepare soccerballene/metal composite cladding;
(6) heating.
According to the preparation method of metallic surface of the present invention soccerballene/metal composite thin film, preferably, in said step (1), said decontamination is for to carry out ultrasonic cleaning with ethanol or acetone; More excellent is, the said ultrasonic cleaning time is 5～60 minutes, and said pickling and activation adopt 10～30% Hydrogen chloride to handle.
According to the preparation method of metallic surface of the present invention soccerballene/metal composite thin film, preferably, in said step (2), said reduction is a reductive agent with the Zn powder, and strength of solution is reached capacity.
According to the preparation method of metallic surface of the present invention soccerballene/metal composite thin film, preferably, in said step (2), said adjusting pH value is 8～12 for adding NaOH adjustment solution pH value.
According to the preparation method of metallic surface of the present invention soccerballene/metal composite thin film, preferably, in said step (3), said electrophoretic voltage is 5～50V, and electric current is 0.1～0.5A, and the time is 1 minute～1 hour.
According to the preparation method of metallic surface of the present invention soccerballene/metal composite thin film, preferably, in said step (5), said galvanized electric current is 0.2～1.5A, and density is 0.1～5A/dm
2, the time is 5 minutes～5 hours.
According to the preparation method of metallic surface of the present invention soccerballene/metal composite thin film, preferably, in said step (6), said Heating temperature is 50～300 ℃.
Prepare soccerballene/metal composite cladding in order to be implemented in the metallic surface, roughly be divided into following step and carry out: matrix surface pre-treatment, C
60Dispersion, the preparation of electrophoresis liquid, electrophoretic method prepare fullerene thin film in the metallic surface, configuration electroplate liquid, plating method prepare soccerballene/metal composite cladding, surperficial aftertreatment.
1, matrix surface pre-treatment
Pre-treating technology mainly is decontamination, pickling and the activation treatment of metallic surface; In the experiment metal is immersed in and carries out ultrasonic cleaning in ethanol or the acetone solvent to remove the greasy dirt of metallic surface; Pickling is used to remove the sull of metallic surface, and activation is used for the bonding force of enhanced surface film and matrix.
2, the preparation of electrophoresis liquid
The THF dispersion liquid that at first prepares soccerballene; Sonic oscillation; Obtain dark-brown fullerene dispersion liquid after scattered soccerballene/THF filtered with nylon, and adopt the reductive agent of Zn powder as soccerballene, using sodium hydroxide to regulate the electrophoresis liquid pH value at last is between 8～12.
3, electrophoretic method prepares fullerene thin film in the metallic surface
Adopt the electrophoretic method deposition method, soccerballene is prepared on the metal base surface.Electrophoresis carries out under 5～50V voltage, and control current is at 0.1～0.5A, and electrophoresis time is 1 minute～1 hour.Finally obtain being coated with the film of soccerballene.
4, configuration electroplate liquid
Plated metal is selected from Ni, Sn, Zn, Cu, Cr etc.
5, plating method prepare soccerballene/metal composite cladding
The metal sheet with fullerene thin film that the 3rd step was prepared places electroplate liquid; Between constant current 0.2～1.5A; Electroplate, can with Metal platings such as metal Ni, Sn, Zn, Cu, Cr on fullerene thin film, form the soccerballene/metal composite cladding of metallic surface.
6, surperficial aftertreatment
Suitably heating (Heating temperature is between 50～300 ℃) utilizes soccerballene active strong, is easy to the phenomenon in the metal inside diffusion, strengthens interface binding power.In the process of heat tracing, the diffusion decisive role, the diffusion of atom is generally carried out through modes such as lattice diffusion (or bulk diffusion), crystal boundary diffusion and free surface diffusions.Along with the rising of temperature and the increase of soaking time, greatly promoted the dispersion process of fullerene molecule in metal.The motivating force of diffusion is the reduction of metal inside free energy; Under certain conditions; Fullerene molecule combines with metal level to produce more stable dispersed texture, has minimum free energy, and therefore the net result of diffusion is that fullerene molecule permeates into metal level inside and outside surface.
The interfacial diffusion mass transfer is a kind of basic interface process, comprises the diffusion along surface and interface, the diffusion and the multiple mass transfer relevant with the interface atomic motion such as interface movement of passing through the interface.Fullerene molecule and metal generation solid state reaction come down to the process of interfacial diffusion and interfacial migration.The locomotory movement at interface is the important foundation of all kinds of transformations, and growing up of cenotype comes down to the result of interfacial migration in the transformation.
Beneficial effect of the present invention is:
The present invention has successfully realized being coated with of soccerballene/metal composite layer of metallic surface, and controllable thickness, and coating is even, and metal-modified new direction is provided.
Description of drawings
Fig. 1 prepares the synoptic diagram of composite package in the metallic surface for soccerballene/metal among the present invention;
Fig. 2 representes the diffusion phenomena of soccerballene coating in the metal Sn coating of Cu matrix surface in the embodiment of the invention 1;
Fig. 3 representes the soccerballene/Ni composite deposite of electrophoresis in the embodiment of the invention 2/plating two-step approach in the surface of low-carbon steel preparation;
Fig. 4 representes the soccerballene/Zn composite deposite of electrophoresis in the embodiment of the invention 3/plating two-step approach in the surface of low-carbon steel preparation.
Embodiment
Below combine accompanying drawing that the present invention is made more detailed description with embodiment.These embodiment only are the descriptions to best mode for carrying out the invention, scope of the present invention are not had any restriction.
Embodiment 1:
In copper surface preparation soccerballene/metallic tin coating, step is following:
(1) the copper surface is cleaned
At first the copper coin matrix was placed the acetone soln ultra-sonic dispersion 15 minutes, preparing mixing solutions then is the vitriol oil: concentrated nitric acid: water=8: 25: 17, the copper coin matrix is immersed in about 1min in the mixing solutions, and washing then, dry down at 50 ℃;
(2) preparation electrophoresis liquid
The 1g soccerballene is added in 300ml THF (THF) solution; Stir and also to add 1.6g Zn powder, logical argon gas was removed behind the oxygen in the THF sonic oscillation 15 minutes, added the aqueous solution (120ml zero(ppm) water) that contains 0.8g NaOH composition; And sonic oscillation to 20 is minute to avoid the coagulation again of soccerballene; Filter the impurity of removing in the mixing solutions, logical argon gas is removed the THF in the solution, obtains the electrophoresis liquid for preparing at last;
(3) electrophoretic method prepares fullerene coated
In preprepared electrophoresis chamber, carry out electrophoresis, the electrophoresis parameter is voltage 30V, electric current 0.15A, electrophoresis time 2 minutes;
(4) preparation electrodeposit liquid
Electroplate liquid disposes as follows: SnSO
4(50g/L), phenol sulfonic acid PSA (60g/L), the naphthyl alcohol sulfonic acid ENSA (5.0g/L) of ethoxylation, the pH value of solution value is 1.0;
(5) electroplate
In preprepared plating tank, electroplate, electroplating parameter is current density (1.5A/dm
2), constant current 0.9A, electroplating time 50 minutes;
(6) heating
Sample is put into tube furnace be heated to 200 ℃, insulation is more than 10 hours.
Deposited the fullerene-based material of 1 micron of thickness on the copper surface through electrophoretic technique, be characterized by soccerballene coating, 8 microns metallic tin on the soccerballene electroplating surface again through the Raman spectrum; About 11 hours of insulation heating is after the Raman spectrum is characterized by the coating of Sn; The characteristic peak of no soccerballene, along with the increase of soaking time, it is obvious that the characteristic peak of soccerballene becomes; This explanation fullerene molecule passes the Sn coating, has arrived new sample surfaces (as shown in Figure 2).
Embodiment 2:
Prepare soccerballene/metallic nickel coating at surface of low-carbon steel, step is following:
(1) surface of low-carbon steel is cleaned
At first the soft steel steel matrix was placed the acetone soln ultra-sonic dispersion 30 minutes, prepare sulphuric acid soln (5mol/L) then, steel matrix is immersed in about 1min in the sulphuric acid soln, washing then, dry down at 60 ℃;
(2) preparation electrophoresis liquid
The 1g soccerballene is added in 280ml THF (THF) solution; Stir and also to add 2.5g Zn powder, logical argon gas was removed behind the oxygen in the THF sonic oscillation 20 minutes, added the aqueous solution (120ml zero(ppm) water) that contains 0.8g NaOH composition; And sonic oscillation to 30 is minute to avoid the coagulation again of soccerballene; Filter the impurity of removing in the mixing solutions, logical argon gas is removed the THF in the solution, obtains the electrophoresis liquid for preparing at last;
(3) electrophoretic method prepares fullerene coated
In preprepared electrophoresis chamber, carry out electrophoresis, the electrophoresis parameter is electrophoretic voltage 25V, electric current 0.15A, electrophoresis time 4 minutes;
(4) preparation electrodeposit liquid
Electroplate liquid disposes as follows: NiSO
47H
2O (150g/L), boric acid H
3BO
3(45g/L), NaCl 12g/L, the pH value of solution value is 5.0;
(5) electroplate
In preprepared plating tank, electroplate, electroplating parameter is 50～60 ℃ of constant current 0.467A, aqueous temperatures, electroplating time 43 minutes;
(6) heating.
Sample is put into tube furnace be heated to 200 ℃, be incubated 3 hours.
The steel plate of gained soccerballene/Ni composite deposite is as shown in Figure 3.
Embodiment 3:
Prepare soccerballene/metallic zinc coating at surface of low-carbon steel, step is following:
(1) surface of low-carbon steel is cleaned
At first the soft steel steel matrix was placed the acetone soln ultra-sonic dispersion 25 minutes, prepare sulphuric acid soln (5mol/L) then, steel matrix is immersed in about 1min in the sulphuric acid soln, washing then, dry down at 80 ℃;
(2) preparation electrophoresis liquid
The 1g soccerballene is added in 300ml THF (THF) solution; Stir and also to add 3g Zn powder, logical argon gas was removed behind the oxygen in the THF sonic oscillation 25 minutes, added the aqueous solution (120ml zero(ppm) water) that contains 0.8g NaOH composition; And sonic oscillation to 25 is minute to avoid the coagulation again of soccerballene; Filter the impurity of removing in the mixing solutions, logical argon gas is removed the THF in the solution, obtains the electrophoresis liquid for preparing at last;
(3) electrophoretic method prepares fullerene coated
In preprepared electrophoresis chamber, carry out electrophoresis, the electrophoresis parameter is electrophoretic voltage 30V, electric current 0.196A, electrophoresis time 3 minutes;
(4) preparation electrodeposit liquid
Electroplate liquid disposes as follows: ZnSO
47H
2O (300g/L), boric acid H
3BO
3(25g/L), using sulfuric acid regulation solution pH value is 5.0;
(5) electroplate;
In preprepared plating tank, electroplate, electroplating parameter is constant current 0.987A, current density 2A/dm
2, electroplating time 40 minutes;
(6) heating.
Sample is put into tube furnace be heated to 300 ℃, be incubated 2 hours.
The steel plate of gained soccerballene/Zn composite deposite is as shown in Figure 4, from figure, can see, coating comparatively evenly and thicknesses of layers influenced by current density and current time controlled.
The present invention has successfully realized being coated with of soccerballene/metal composite layer of metallic surface, and controllable thickness, and coating is even, and metal-modified new direction is provided.
Claims (6)
1. the preparation method of a metallic surface soccerballene/metal composite thin film is characterized in that, may further comprise the steps:
(1) metal material surface pre-treatment comprises decontamination, pickling and the activation treatment of metallic surface;
(2) preparation of electrophoresis liquid: with soccerballene dispersion in THF, sonic oscillation, filtration, reduction, adjusting pH value is 8～12, and said reduction is a reductive agent with the Zn powder, and strength of solution is reached capacity;
(3) electrophoretic method prepares fullerene thin film in the metallic surface, and said electrophoretic voltage is 5～50V, and electric current is 0.1～0.5A, and the time is 1 minute～1 hour;
(4) preparation of electroplate liquid: the electroplate liquid of configuration Ni, Sn, Zn, Cu, Cr;
(5) plating method have at step (3) gained on the metal sheet of fullerene thin film and prepare soccerballene/metal composite cladding, and said galvanized electric current is 0.2～1.5A, and density is 0.1～5A/dm
2, the time is 5 minutes～5 hours;
(6) heating.
2. the preparation method of metallic surface as claimed in claim 1 soccerballene/metal composite thin film is characterized in that, in said step (1), said decontamination is for to carry out ultrasonic cleaning with ethanol or acetone.
3. the preparation method of metallic surface as claimed in claim 2 soccerballene/metal composite thin film is characterized in that, in said step (1), the said ultrasonic cleaning time is 5～60 minutes.
4. the preparation method of metallic surface as claimed in claim 2 soccerballene/metal composite thin film is characterized in that, in said step (1), the Hydrogen chloride of said pickling and activation employing 10～30% is handled.
5. the preparation method of metallic surface as claimed in claim 1 fullerene thin film is characterized in that, in said step (2), said adjusting pH value is 8～12 for adding NaOH adjustment solution pH value.
6. the preparation method of metallic surface as claimed in claim 1 soccerballene/metal composite thin film is characterized in that, in said step (6), said Heating temperature is 50～300 ℃.
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| EP2571072A1 (en) * | 2011-09-13 | 2013-03-20 | LANXESS Deutschland GmbH | Semiconducting thin [60]fullerene films and their use |
| CN105728038B (en) * | 2016-03-14 | 2018-08-24 | 黄山学院 | The nanometer particle film and its preparation method and application of fullerene derivate/palladium |
| CN105728039B (en) * | 2016-03-15 | 2018-08-14 | 黄山学院 | Fullerene derivative/palladium nanoparticle film and preparation method and application thereof |
| CN113394017B (en) * | 2021-06-10 | 2023-11-03 | 北京工业大学 | Method for diffusion sintering of neodymium iron boron through electroplating and electrophoresis collaborative deposition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003909A (en) * | 2006-12-21 | 2007-07-25 | 上海交通大学 | Electrochemical combined deposition method for preparing structure of composite membrane of Nano carbon tube - metal |
| CN101258269A (en) * | 2005-09-07 | 2008-09-03 | 日产自动车株式会社 | Nanocarbon/aluminum composite material, process for producing the same, and plating liquid for use in said process |
| CN101358369A (en) * | 2007-08-02 | 2009-02-04 | 香港中文大学 | Functionalized carbon nanotube coating and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258269A (en) * | 2005-09-07 | 2008-09-03 | 日产自动车株式会社 | Nanocarbon/aluminum composite material, process for producing the same, and plating liquid for use in said process |
| CN101003909A (en) * | 2006-12-21 | 2007-07-25 | 上海交通大学 | Electrochemical combined deposition method for preparing structure of composite membrane of Nano carbon tube - metal |
| CN101358369A (en) * | 2007-08-02 | 2009-02-04 | 香港中文大学 | Functionalized carbon nanotube coating and use thereof |
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