CN102002747B - Method for preparing metal surface fullerene film by electrophoresis - Google Patents
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Abstract
The invention provides a method for preparing metal surface fullerene film by electrophoresis, including the following steps: (1) pre-treatment is carried out on metal material surface, including oil removing cleaning, acid cleaning and activation on metal material; (2) electrophoresis solution is prepared, fullerene is dispersed in organic solution, ultrasonic oscillation, filtering and reducing are carried out, pH value is regulated to be 8-12; (3) film forming is carried out by adopting fullerene electrophoresis method; (4) heating is carried out. The method of the invention can be used for metal surface modification treatment, especially novel surface coated metal material can be derived by utilizing excellent characteristic of fullerene material, thus obtaining brand new metal product.
Description
Technical field
The present invention relates to field of nanometer technology, specifically, the present invention relates to that a kind of electrophoresis prepares the method for fullerene thin film in the metallic surface.
Background technology
Human discovery and understanding to carbon is of long duration, along with the discovery of soccerballene carbon bunch, C
60Get in people's the research visual field with the new allotropic substance as carbon such as carbon nanotube.1985; Britain scientist Kroto and U.S. scientist Curl, Smalley have found the allotropic substance of the carbon of similar football structure jointly; And with its called after soccerballene; Because the cage structure of soccerballene and the excellent properties that is had, the research of soccerballene has been become a new scientific research branch field.
In soccerballene carbon bunch, C
60Having the symmetry of height, all round the p electronic cloud, is the cage type molecule that 60 atoms are arranged inside and outside its cage, and each carbon atom and three atoms on every side are with sp
2.28Hybridized orbital overlaps to form the s key, about 108 ° or 120 ° of bond angle.C
60Each carbon atom all is of equal value in the molecule, and the static charge of each atom all is zero, and whole molecule presents electroneutral.C
60After modifying, because additive group has destroyed C
60Original symmetry, the C after therefore modifying
60Polarity is comparatively obvious.Whole C
60Molecule presents the character of electron deficiency alkene.Employed material mainly is C in the Experiment Preparation at present
60With C
70Mixture, wherein, C
60Occupy than large portion.
At present to C
60Research and utilize and mainly to concentrate on superconductor technology field, light transfer characteristic, C
60The restricted and medical field of storage, new catalyst, light of development, hydrogen and oxygen of modification and characteristic aspect, molecular device.
The patent documentation of in iron and steel, using about soccerballene seldom, mostly the research object of existing patent documentation is carbon nanotube and carbon dust etc.The contriver finds through retrieval; 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; Because the stability of carbon nanotube is high; Its fusing point is the highest in the present known materials, therefore can at high temperature prepare, but then inapplicable for soccerballene.In american documentation literature 6783745 disclosed methods through carbon dust (is contained C
60Or SWCN) adopt high-temperature high-pressure craft to prepare the 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, is used as the magnetic device that disk is used.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, referring to Chinese patent document 200480011554.6.
In sum, up to the present, soccerballene is not seen report as yet at the film coating technique of metallic surface.Therefore, the object of the present invention is to provide a kind of technology that is coated with that adopts electrophoresis method fullerene-based material to be prepared in the metallic surface.
Summary of the invention
The present invention provides the preparation method of a kind of metallic surface fullerene thin film, it is characterized in that, may further comprise the steps:
(1) metal material surface pre-treatment comprises metallic substance is carried out oil removing cleaning, pickling and activation;
(2) preparation of electrophoresis liquid: with soccerballene dispersion in organic solution, sonic oscillation, filtration, reduction, adjusting pH value is 8～12;
(3) soccerballene electrophoretic method film forming;
(4) heating.
According to the preparation method of metallic surface of the present invention fullerene thin film, preferably, in said step (1), said oil removing is cleaned to carry out ultrasonic cleaning with ethanol or acetone.
According to the preparation method of metallic surface of the present invention fullerene thin film, preferably, in said step (1), the said ultrasonic cleaning time is 5～60 minutes.
According to the preparation method of metallic surface of the present invention fullerene thin film, preferably, in said step (1), the pickle solution of said pickling is the sulphuric acid soln of 3～8mol/L.
According to the preparation method of metallic surface of the present invention fullerene thin film, preferably, in said step (2), said organic solution is THF.
According to the preparation method of metallic surface of the present invention fullerene 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 fullerene 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 fullerene 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 fullerene thin film, preferably, in said step (4), said Heating temperature is 80～280 ℃, and the time is 15 minutes.
Be implemented in the metallic surface and prepare fullerene coatedly, roughly be divided into following step: metallic surface pre-treatment, preparation electrophoresis liquid, metallic surface film forming and surperficial aftertreatment.Specify as follows:
1, metallic surface pre-treatment
Pre-treating technology mainly is oil removing, pickling and the activation treatment of metallic surface, can metal be immersed in to carry out ultrasonic cleaning in the acetone solvent to remove the greasy dirt of metallic surface; Pickling and activation adopt dilute sulphuric acid that metal substrate is handled, and improve the bonding force of rete and matrix when being beneficial to electrophoretic method and preparing fullerene thin film.
2, preparation electrophoresis liquid
The organic solution dispersion liquid that at first prepares soccerballene, sonic oscillation obtains dark-brown C after scattered soccerballene/organic solution filtered with nylon
60Dispersion liquid, 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, metallic surface soccerballene film forming
Adopt the electrophoretic method deposition method, soccerballene is prepared on the metal base surface.By the phenomenon that the charged colloidal particle particle moves in DC electric field, carry out the separation and the coating of material, wherein, electrophoretic separation be coated with technological different based on particle migration speed, do not relate to electrode reaction.Though process such as galvanic deposit and plating also has electrophoresis, it mainly acts on is electrode reaction, so be not the electrophoretic technique that the present invention adopted.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, and fullerene thin film thickness is even.Can also regulate the thickness of fullerene thin film according to the electrophoresis parameter.
4, surperficial aftertreatment
Suitably heating (Heating temperature is between 80～280 ℃) utilizes soccerballene active strong, is easy to the phenomenon in the metal inside diffusion, strengthens interface binding power.
Beneficial effect of the present invention is:
The present invention has successfully realized soccerballene being coated with of metallic surface, and controllable thickness, and coating is even, has verified that electrophoresis method is feasible in preparation fullerene thin film technology.Adopt electrophoresis process mainly to be because soccerballene is electronegative in dispersion liquid; Thereby can not as electroplating technology (negative electrode precipitating metal positively charged ion), separate out at electrode cathode; And the positive good utilisation of electrophoretic technique the flow phenomenon of electronegative soccerballene ion in electric field, thereby success on anodically deposit fullerene molecule group bunch.
Description of drawings
Fig. 1 is a soccerballene electrocoating film synoptic diagram;
Fig. 2 is the fullerene thin film that electrophoresis method prepares at surface of low-carbon steel among the embodiment 2;
Fig. 3 is the IR Characterization figure of prepared soccerballene electrocoating film among the embodiment 2;
Fig. 4 is the frictional coefficient curve of soccerballene among the embodiment 2-soft steel composite package;
Fig. 5 be among the embodiment 3 electrophoresis method at the fullerene thin film of IF steel surface preparation;
Fig. 6 is the Raman phenogram of prepared soccerballene electrocoating film among the embodiment 3.
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
Fullerene coated in the copper surface preparation, step is following:
(1) the copper surface is cleaned
The copper coin surface is immersed in carries out ultrasonic cleaning 15 minutes in the acetone solvent removing surface and oil contaminant, and adopt the sulphuric acid soln of 6mol/L to soak copper base is handled 1min;
(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
The electrophoresis parameter is electrophoretic voltage 30V, electric current 0.15A, electrophoresis time 2 minutes.
Electrophoretic method is better in the effect of copper surface deposition soccerballene, the color and luster bright and clean, and adhesion property is good.
Embodiment 2
Prepare fullerene coatedly at surface of low-carbon steel, step is following:
(1) surface of low-carbon steel is carried out surperficial pre-treatment
Surface of low-carbon steel is immersed in carries out ultrasonic cleaning 30 minutes in the acetone solvent removing surface and oil contaminant, and adopt the sulphuric acid soln of 5mol/L to soak copper base is handled 2min;
(2) preparation electrophoresis liquid
The 0.9g soccerballene is added in 300ml 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 15 minutes, added the aqueous solution (120ml zero(ppm) water) that contains 0.6g NaOH composition; And sonic oscillation to 15 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
The electrophoresis parameter is electrophoretic voltage 25V, electric current 0.13A, electrophoresis time 1 minute and 30 seconds.
At last prepared is fullerene coated as shown in Figure 2; Figure is as shown in Figure 3 for its IR Characterization, and the infrared signature peak has explained that the molecular material that electrophoretic method is deposited on surface of low-carbon steel is a soccerballene; The frictional coefficient curve of its soccerballene-soft steel composite package (pressure 400g, revolution 300r/min) as shown in Figure 4, as can be seen from Figure 4, the frictional coefficient of low carbon steel substrate has been lowered in enforcement of the present invention, has strengthened the wear resistance of low carbon steel substrate.
Embodiment 3
Fullerene coated in IF steel surface preparation, step is following:
(1) IF steel surface is cleaned
The IF surface of steel plate is immersed in carries out ultrasonic cleaning 20 minutes in the acetone solvent removing surface and oil contaminant, and adopt the sulphuric acid soln of 5mol/L to soak copper base is handled 1.5min;
(2) preparation electrophoresis liquid
The 1.5g 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 15 minutes, added the aqueous solution (120ml zero(ppm) water) that contains 1g 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
The electrophoresis parameter is electrophoretic voltage 20V, electric current 0.1A, electrophoresis time 3 minutes.
At last prepared is fullerene coated as shown in Figure 5, and its Raman phenogram is as shown in Figure 6, and the Raman characteristic peak has explained that it is soccerballene that electrophoretic method is deposited on the surperficial molecular material of IF steel.
Can observe film thickness increases along with the increase of electrophoresis time, and this also is one of method of control film thickness, thereby can realize the controllable growth of fullerene thin film.Embodiment and drawings clear have explained that the present invention has successfully realized soccerballene being coated with of metallic surface, and controllable thickness, and coating is even, has verified that electrophoresis method is feasible in preparation fullerene thin film technology.
Claims (7)
1. the preparation method of a metallic surface fullerene thin film is characterized in that, may further comprise the steps:
(1) metal material surface pre-treatment comprises metallic substance is carried out oil removing cleaning, pickling and activation;
(2) preparation of electrophoresis liquid: with soccerballene dispersion in organic solution, sonic oscillation, filtration, reduction, adjusting pH value is 8～12, and said organic solution is THF, and said reduction is a reductive agent with the Zn powder, and strength of solution is reached capacity;
(3) soccerballene electrophoretic method film forming;
(4) heating.
2. the preparation method of metallic surface as claimed in claim 1 fullerene thin film is characterized in that, in said step (1), said oil removing is cleaned to carry out ultrasonic cleaning with ethanol or acetone.
3. the preparation method of metallic surface as claimed in claim 2 fullerene 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 1 fullerene thin film is characterized in that, in said step (1), the pickle solution of said pickling is the sulphuric acid soln of 3～8mol/L.
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 pH value of solution value.
6. the preparation method of metallic surface as claimed in claim 1 fullerene thin film is characterized in that, 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.
7. the preparation method of metallic surface as claimed in claim 1 fullerene thin film is characterized in that, in said step (4), said Heating temperature is 80～280 ℃, and the time is 15 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225269B (en) * | 2011-04-08 | 2013-07-03 | 王东伟 | Vacuum treating and deep cleaning method for stainless steel metal mesh |
| RU2495965C1 (en) * | 2012-05-11 | 2013-10-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Челябинская государственная агроинженерная академия" | Electrophoretic method of making coating from graphene |
| RU2510675C1 (en) * | 2012-10-18 | 2014-04-10 | Александр Алексеевич Козеев | Electrochemical precipitation of fullerene film on current-conducting materials |
| RU2519438C1 (en) * | 2012-12-07 | 2014-06-10 | Александр Алексеевич Козеев | Electrochemical precipitation of nanostructured carbon film on current-conducting materials |
| 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 |
| RU2694683C2 (en) * | 2017-01-27 | 2019-07-16 | Федеральное государственное казенное военное образовательное учреждение высшего образования "ВОЕННАЯ АКАДЕМИЯ МАТЕРИАЛЬНО-ТЕХНИЧЕСКОГО ОБЕСПЕЧЕНИЯ имени генерала армии А.В. Хрулева" Министерства обороны Российской Федерации | Electrolyte for electrochemical mechanical hardening of steel |
| CN107419246A (en) * | 2017-06-30 | 2017-12-01 | 浙江省平湖铰链有限公司 | One kind improves environment-friendly type hinge basic unit composite film coating technique |
| CN107448083A (en) * | 2017-06-30 | 2017-12-08 | 浙江省平湖铰链有限公司 | A kind of environment-friendly type hinge and its processing technology |
| RU2676549C1 (en) * | 2018-07-25 | 2019-01-09 | федеральное государственное автономное образовательное учреждение высшего образования "Южный федеральный университет" (Южный федеральный университет) | Method of conducting material electrochemical deposition of silicon-carbon films |
| RU2711072C1 (en) * | 2019-04-24 | 2020-01-15 | федеральное государственное автономное образовательное учреждение высшего образования "Южный федеральный университет" (Южный федеральный университет) | Method of electrochemical deposition of silicon-carbon films on dielectric substrates |
| CN111394772A (en) * | 2020-04-17 | 2020-07-10 | 安徽澳新工具有限公司 | Hammer surface electrophoresis treatment method |
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