CN108486619A - The preparation method of graphene oxide-cobalt nanocrystal-DLC film - Google Patents
The preparation method of graphene oxide-cobalt nanocrystal-DLC film Download PDFInfo
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- CN108486619A CN108486619A CN201810429106.1A CN201810429106A CN108486619A CN 108486619 A CN108486619 A CN 108486619A CN 201810429106 A CN201810429106 A CN 201810429106A CN 108486619 A CN108486619 A CN 108486619A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C—CHEMISTRY; METALLURGY
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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Abstract
The invention discloses a kind of preparation methods of graphene oxide cobalt nanocrystal DLC film, using the film for being electrochemically-deposited in silicon substrate surface and constructing multi-grade nano composite structure, to obtain the super hydrophobic surface with excellent properties, by 30~40 microns of polynary nanometer laminated films of thickness, which is the compound GO Co/a C of polynary nanometer that graphene oxide cooperates with metallic cobalt particle implantation on film surface layer:H films, micro-structure have typical nanocrystalline/amorphous characteristic.
Description
Technical field
The invention belongs to field of surface engineering technique, are related to a kind of super-hydrophobic/anticorrosive graphene oxide-cobalt nanocrystal-
The preparation method of DLC film.
Background technology
DLC film (DLC) is used as New Rigid lubricating function protective materials, has high rigidity, wear-resistant, low rubs
The characteristics such as factor, high resistivity, high transparency and high chemical stability are wiped, in necks such as mechanical processing, microelectronics, optics, magnetics
Domain has huge application potential, receives people's concern.In recent years, DLC film is in cutting tool, automated machine parts etc.
As hard lubricant coating, achievement unit divides industrial applications.However, DLC film internal stress is excessive, cause film substrate bond strength
Even coating shedding is reduced, the practicalization of DLC film is seriously constrained.By functional nano metallic particles (nickel, cobalt) point
It is scattered in amorphous carbon matrix, not only alleviates the internal stress of film, but also the size of effective stable metal nano particle, effectively prevent
Reunite and aoxidized, is conducive to the characteristic for giving full play to metal nanoparticle；On the other hand, the addition of metal nanoparticle is led to
Cross regulation and control DLC film internal structure, keeping outside DLC film intrinsic property, assign the new electronics of DLC film, magnetics, etc. side
The function in face, and the roughness of super hydrophobic surface can be met in the micro-nano granules of DLC film surface construction stratiform.
Currently, in terms of being concentrated mainly on mechanics and tribological property to the research of diamond-film-like, diamond-film-like surface energy is ground
Study carefully less.Come in the past few decades, people are inspired by animals and plants superficial phenomenon in nature, more next to the research of surface topography
More, super hydrophobic surface increasingly has been favored by people.The diversity of surface topography and structure can not only assign surface and dredge
Aqueous energy, while also otherwise property.Therefore coarse structure is constructed then with low-surface-energy point in material surface
The super hydrophobic surface that son modification obtains has certain practical significance for the anticorrosion and mechanical property that improve material.
Wetability is a key property of solid material, is spreading ability of the liquid in the surface of solids, and Static Contact
Angle is an important physical amount for defining surface wettability, and contact angle is the tangent line of liquid-vapor interface and the angle of the surface of solids
θ.In general, working as θ<At 90 °, surface is hydrophilic interface；Work as θ>At 90 °, surface is hydrophobic interfaces.Super hydrophobic surface refers to table
The contact angle of face and water is more than 150 °, and droplet is in spherical on surface, is a kind of extreme wetting phenomena.It is generally acknowledged that DLC film tool
There is intermediate hydrophobic, the water contact angle of non-hydrogen DLC film is at 60 ° or so, and the water contact angle of hydrogeneous DLC film is between 70 ° to 80 °.
Due to as it can be seen that prepare carbon-base film and substrate hydrophobic performance it is poor, can greatly limit their application.Although using nanometer
Metallic particles is incorporated into DLC film can be to a certain extent so that the surface of material obtains special surface structure and surpasses
Hydrophobic performance.But with the fast development that modern marine is equipped, developing the film of more excellent surface property becomes particularly to weigh
It wants.So how further to promote the surface property of layer of Nano composite diamond film also becomes the emphasis made great efforts.Graphite oxide
Alkene (GO) is a kind of typical oxygen-containing Graphene derivative of two dimension, have a large amount of oxygen-containing functional group, such as hydroxyl, epoxy group with
And carbonyl.Compared with graphene, the oxygen-containing functional group reactivity bigger of surface of graphene oxide imparts it with graphene not
With characteristic (as being easily surface modified, hydrophobicity is stronger etc.), and be easier to prepare that (laboratory is multi-purpose greatly at present
Hummers methods prepare graphene oxide).Graphene oxide have it is amphipathic, in water have superior dispersibility, such as boundary
Generally there are interfaces for face activating agent, and reduce the energy between interface.So when preparing nano combined DLC film into electrolyte
Incorporation graphene oxide can reduce the surface energy of film surface, while improve the asperity of film surface, and due to oxidation
Graphene surface oxygen-containing functional group is more, is conducive to the formation of super hydrophobic surface, improves the comprehensive performance of film.
Invention content
To achieve the above object, the present invention provides a kind of preparation side of graphene oxide-cobalt nanocrystal-DLC film
Method solves the problems, such as that the hydrophobicity of DLC film in the prior art and substrate is poor, asperity is bad.
The technical solution adopted in the present invention is the preparation method of graphene oxide-cobalt nanocrystal-DLC film,
Specifically follow the steps below：
Step S1, silicon chip pre-processes：Silicon chip is cleaned by ultrasonic 5 minutes in analyzing pure methanol, then puts silicon chip extracting
It is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxide layer of silicon chip surface to enter mass fraction, is finally again put into silicon chip point
It analyses in pure methanol and is cleaned by ultrasonic 5 minutes, finally use N2Drying；
Step S2, electrolyte is configured：Configure electrolyte：Electrolyte solvent is to analyze pure methanol, and acetylacetone cobalt (II) exists
A concentration of 0.06mg/mL-0.14mg/mL in electrolyte, a concentration of 0.003mg/mL- of graphene oxide in the electrolytic solution
0.011mg/mL；
Step S3, Preparatory work of experiment：The silicon chip handled well is fixed on cathode graphite electrode, platinized platinum is fixed on anode graphite
On electrode, two interelectrode distances of adjusting be 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, correctly connect
Connect the positive and negative anodes of electrolytic cell and the positive and negative anodes of DC high-voltage power supply；
Step S4, film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control, and temperature control is 55 DEG C；It is passed through nitrogen
Gas 8h；Additional power source uses high-voltage DC power supply, and voltage 1200V, under electric field action, sedimentation time control is 8h, Co2+、
CH3 +To movable cathode, although the graphene oxide in electrolyte is not involved in electrode reaction, but graphene oxide is in two high electricity
Under field action, by CH3 +And Co2+Drive is deposited on silicon chip, and it is thin that graphene oxide-cobalt nanocrystal-diamond-like is prepared
Film.
Further, the long 30mm of silicon chip, width 15mm, thickness 0.7mm in the step S1.
Further, the preparation method of graphene oxide in the electrolytic solution is in the step S2, and graphene oxide is added
Ultrasonic disperse is for 24 hours in ultrasonic wave in electrolyte.
Further, the distance between the step S3 Anodics and cathode are 8mm.
Further, platinized platinum is identical as die size in the step S3.
Further, the graphene oxide-cobalt nanocrystal-DLC film being prepared in the step S4 is thickness
30~40 microns of polynary nanometer laminated film, the polynary nanometer laminated film are that graphene oxide cooperates with metallic cobalt particle implantation
The compound GO-Co/a-C of polynary nanometer:H films, wherein GO are graphene oxide, a-C:H is noncrystal carbon, a amorphous
(amorphous).
The invention has the advantages that compared with prior art, the present invention uses the technique of electrochemical deposition in the liquid phase
Synthesize the diamond-like carbon composite film containing cobalt granule and graphene oxide, can uniform deposition on variously-shaped base material, one
As be to be carried out in the environment of room temperature or room temperature are high a bit, pass through and change structure, thickness that voltage, sedimentation time etc. control coating
Degree.The preparation method of the present invention has the characteristics that equipment is simple, of low cost, depositing temperature is low, film forming is uniform, reproducible,
It is suitable for industrialization production.Super-hydrophobic diamond-like carbon composite film prepared by this method has good superhydrophobic characteristic, is heavy
Product diamond-like-carbon nano compound film provides a kind of new thinking, and to expand the research of DLC film and applying model
It encloses and certain basis is provided.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the SEM figures and TEM figures of graphene oxide-cobalt nanocrystal-DLC film；
Fig. 2 is the adhesive tape test figure of graphene oxide-cobalt nanocrystal-DLC film；
Fig. 3 is the corrosive nature figure of graphene oxide-cobalt nanocrystal-DLC film；
Fig. 4 is the automatically cleaning behavior figure of graphene oxide-cobalt nanocrystal-DLC film；
Fig. 5 a are the contact angle size figures of graphene oxide-cobalt nanocrystal-DLC film；
Fig. 5 b are 6 contact angle size figures of embodiment；
Fig. 6 is the schematic diagram of graphene oxide-cobalt nanocrystal-DLC film.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, a concentration of 0.06mg/mL of acetylacetone cobalt (II) in the electrolytic solution, and electrolyte volume is
100mL；(3) silicon chip handled well is fixed on cathode graphite electrode, the platinized platinum of identical size is fixed on anode graphite electrode
On, two interelectrode distances of adjusting are 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, correct connection electricity
The positive and negative anodes of Xie Chi and the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control
In, temperature control is 55 DEG C；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, and voltage is
1200V, under electric field action, Co2+、CH3 +To movable cathode, it is deposited on silicon chip.The contact angle of prepared film is
137.10°。
Embodiment 2：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, a concentration of 0.10mg/mL of acetylacetone cobalt (II) in the electrolytic solution, and electrolyte volume is
100mL；(3) silicon chip handled well is fixed on cathode graphite electrode, the platinized platinum of identical size is fixed on anode graphite electrode
On, two interelectrode distances of adjusting are 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, correct connection electricity
The positive and negative anodes of Xie Chi and the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control
In, temperature control is 55 DEG C；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, and voltage is
1200V, under electric field action, Co2+、CH3 +To movable cathode, it is deposited on silicon chip.The contact angle of prepared film is
153.22°。
Embodiment 3：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, a concentration of 0.14mg/mL of acetylacetone cobalt (II) in the electrolytic solution, and electrolyte volume is
100mL；(3) silicon chip handled well is fixed on cathode graphite electrode, the platinized platinum of identical size is fixed on anode graphite electrode
On, two interelectrode distances of adjusting are 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, correct connection electricity
The positive and negative anodes of Xie Chi and the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control
In, temperature control is 55 DEG C；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, and voltage is
1200V, under electric field action, Co2+、CH3 +To movable cathode, it is deposited on silicon chip.The contact angle of prepared film is
133.68°。
Embodiment 4：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, and a concentration of 0.10mg/mL of acetylacetone cobalt (II) in the electrolytic solution, graphene oxide is being electrolysed
A concentration of 0.003mg/mL in liquid, electrolyte volume are 100mL, and ultrasonic disperse is for 24 hours in ultrasonic wave for electrolyte；It (3) will place
The silicon chip managed is fixed on cathode graphite electrode, and the platinized platinum of identical size is fixed on anode graphite electrode, adjusts two electrodes
Between distance be 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, the correct positive and negative anodes for connecting electrolytic cell
With the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control, and temperature control is
55℃；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, voltage 1200V, in electric field
Under effect, Co2+、CH3 +To movable cathode, although the graphene oxide in electrolyte is not involved in electrode reaction, but graphite oxide
Alkene is under the effect of the two poles of the earth high electric field, by CH3 +And Co2+Drive is deposited on silicon chip, and graphene oxide-cobalt nanocrystal-is prepared
DLC film.The contact angle size of obtained film is respectively 151.56 °, as shown in Figure 5 a.
Embodiment 5：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, and a concentration of 0.10mg/mL of acetylacetone cobalt (II) in the electrolytic solution, graphene oxide is being electrolysed
A concentration of 0.005mg/mL in liquid, electrolyte volume are 100mL, and ultrasonic disperse is for 24 hours in ultrasonic wave for electrolyte；It (3) will place
The silicon chip managed is fixed on cathode graphite electrode, and the platinized platinum of identical size is fixed on anode graphite electrode, adjusts two electrodes
Between distance be 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, the correct positive and negative anodes for connecting electrolytic cell
With the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control, and temperature control is
55℃；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, voltage 1200V, in electric field
Under effect, Co2+、CH3 +To movable cathode, although the graphene oxide in electrolyte is not involved in electrode reaction, but graphite oxide
Alkene is under the effect of the two poles of the earth high electric field, by CH3 +And Co2+Drive is deposited on silicon chip, and graphene oxide-cobalt nanocrystal-is prepared
DLC film.The contact angle size of obtained film is respectively 152.18 °, as shown in Figure 5 a.
Embodiment 6：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, and a concentration of 0.10mg/mL of acetylacetone cobalt (II) in the electrolytic solution, graphene oxide is being electrolysed
A concentration of 0.007mg/mL in liquid, electrolyte volume are 100mL, and ultrasonic disperse is for 24 hours in ultrasonic wave for electrolyte；It (3) will place
The silicon chip managed is fixed on cathode graphite electrode, and the platinized platinum of identical size is fixed on anode graphite electrode, adjusts two electrodes
Between distance be 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, the correct positive and negative anodes for connecting electrolytic cell
With the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control, and temperature control is
55℃；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, voltage 1200V, in electric field
Under effect, Co2+、CH3 +To movable cathode, although the graphene oxide in electrolyte is not involved in electrode reaction, but graphite oxide
Alkene is under the effect of the two poles of the earth high electric field, by CH3 +And Co2+Drive is deposited on silicon chip, and graphene oxide-cobalt nanocrystal-is prepared
DLC film.The contact angle size of obtained film is respectively 158.64 °, as shown in Figure 5 a.
Embodiment 7：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, and a concentration of 0.10mg/mL of acetylacetone cobalt (II) in the electrolytic solution, graphene oxide is being electrolysed
A concentration of 0.009mg/mL in liquid, electrolyte volume are 100mL, and ultrasonic disperse is for 24 hours in ultrasonic wave for electrolyte；It (3) will place
The silicon chip managed is fixed on cathode graphite electrode, and the platinized platinum of identical size is fixed on anode graphite electrode, adjusts two electrodes
Between distance be 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, the correct positive and negative anodes for connecting electrolytic cell
With the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control, and temperature control is
55℃；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, voltage 1200V, in electric field
Under effect, Co2+、CH3 +To movable cathode, although the graphene oxide in electrolyte is not involved in electrode reaction, but graphite oxide
Alkene is under the effect of the two poles of the earth high electric field, by CH3 +And Co2+Drive is deposited on silicon chip, and graphene oxide-cobalt nanocrystal-is prepared
DLC film.The contact angle size of obtained film is respectively 149.98 °, as shown in Figure 5 a.
Embodiment 8：
(1) silicon chip pre-processes：5 will be cleaned by ultrasonic in analyzing pure methanol for the silicon chip of long 30mm, wide 15mm, thickness 0.7mm
Minute, it is to corrode 5 minutes in 10%HF aqueous solutions to remove the oxidation of silicon chip surface that silicon chip extracting, which is then put into mass fraction,
Silicon chip is finally put into the pure methanol of analysis and is cleaned by ultrasonic 5 minutes, finally uses N by layer again2Drying；(2) electrolyte is prepared：Electrolysis
Liquid solvent is to analyze pure methanol, and a concentration of 0.10mg/mL of acetylacetone cobalt (II) in the electrolytic solution, graphene oxide is being electrolysed
A concentration of 0.011mg/mL in liquid, electrolyte volume are 100mL, and ultrasonic disperse is for 24 hours in ultrasonic wave for electrolyte；It (3) will place
The silicon chip managed is fixed on cathode graphite electrode, and the platinized platinum of identical size is fixed on anode graphite electrode, adjusts two electrodes
Between distance be 8mm, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, the correct positive and negative anodes for connecting electrolytic cell
With the positive and negative anodes of DC high-voltage power supply；(4) film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control, and temperature control is
55℃；It is passed through nitrogen 8h, sedimentation time control is 8h；Additional power source uses high-voltage DC power supply, voltage 1200V, in electric field
Under effect, Co2+、CH3 +To movable cathode, although the graphene oxide in electrolyte is not involved in electrode reaction, but graphite oxide
Alkene is under the effect of the two poles of the earth high electric field, by CH3 +And Co2+Drive is deposited on silicon chip, and graphene oxide-cobalt nanocrystal-is prepared
DLC film.The contact angle size of obtained film is respectively 142.20 °, as shown in Figure 5 a.
The structure of film is observed using transmission electron microscope (TEM) (FEI Tecnai G2-20), passes through field
Emit scanning electron microscope (SEM) (MLA650F, FEI, USA) to film surface appearance observation analysis, schemes from the SEM of Fig. 1 a
In as can be seen that G-Co/a-C:The surface texture of H films is fine and close, and it is multi-level micro- to can be seen that film surface shows from Fig. 1 b
Nanometer class petal design, is conducive to super-hydrophobic formation, because this structure can squeeze water in water droplet stored underneath air
Drop is so that water droplet quickly rolls off.Especially from the TEM of Fig. 1 c figures as can be seen that nano compound film has typical nanocrystalline edge
Embedding amorphous composite microstructure, and nanocrystal is evenly distributed in amorphous carbon.Fig. 1 d are the partial enlargements to Fig. 1 c, and Fig. 1 e are pair
The amplification of light circle in Fig. 1 d, Fig. 1 f are to find the cobalt in film with list by analysis the amplification of dark circle in Fig. 1 d
The form of matter exists, and nano cobalt granule and graphene uniform are inlayed in the film, can be obtained by Fig. 1 e, graphene oxide
Spacing of lattice be 0.34nm, can be obtained by Fig. 1 f, the spacing of lattice of cobalt is 0.20nm.The present invention successfully prepares on silicon chip
The cobalt granule of the phase containing polycrystalline and graphene oxide-cobalt nanocrystal-DLC film of graphene, and graphene oxide-
Cobalt nanocrystal-DLC film belongs to typical nanocrystalline/non crystalline structure.
Using adhesive tape test come the cohesive force of testing film and substrate, can be seen that from the adhesive tape test figure of Fig. 2 to oxidation
Graphene-cobalt nanocrystal-DLC film carries out adhesive tape and bonds test, graphene oxide-cobalt nanocrystal-DLC film
Initial contact angle is 158.64 °, and after being bonded by an adhesive tape, film surface contact angle is 157.11 °, is still shown excellent
Ultra-hydrophobicity, and film surface does not have particle to fall, and until the 7th adhesive tape test, film surface contact angle is
150.21°.Adhesive tape bonds test and shows that super-hydrophobic diamond-like carbon composite film has good adhesive property.
Using the corrosive nature of electrochemical workstation (CHI660E, China) test material, experiment is using three classical electricity
Polar body system is tested, and wherein reference electrode is saturation KCl electrodes, comparison electrode is platinum electrode, sample is working electrode.Pass through
The basic parameters such as open circuit potential, electrochemical impedance spectroscopy and dynamic potential polarization curve analyze the corrosion behavior of composite coating.
Electrochemical impedance spectroscopy test frequency ranging from 10-2~105Hz, amplitude 5mV.Area of Sample is controlled in 1 ± 0.1cm2, in quality
Start to measure after impregnating two hours in score 3.5%NaCl solution.It is obtained from Fig. 3, super-hydrophobic/corrosion resistant diamond is compound
G-Co/a-C:The corrosion electric current density of H films after measured is 3.19 × 10-10A/cm2, corrosion potential is -0.209V, is shown
Excellent corrosion resistance.
Using yellow chalk dust as pollutant, the deionized water of 0.05mL is then used to test self-cleaning performance, from Fig. 4
Self-cleaning-test figure can be seen that graphene oxide-cobalt nanocrystal-DLC film have excellent self-cleaning performance,
Graphene oxide-cobalt nanocrystal-DLC film is covered by yellow chalk dust in experiment, when water droplet drops in film surface,
The water droplet on graphene oxide-cobalt nanocrystal-DLC film surface carries chalk dust and tumbles rapidly, and surface recovery is initial
Ultra-hydrophobicity, it can be seen that, graphene oxide-cobalt nanocrystal-DLC film surface shows surprising automatically cleaning
Performance.Graphene oxide-cobalt nanocrystal-DLC film greatly expands it in drag reduction, corrosion-resistant, automatically cleaning etc.
Application, the related fields such as national defence, industrial and agricultural production can be applied to.
Material surface wetability is characterized by contact angle measurement, contact angle test is carried out to each embodiment, is obtained
The contact angle size of film is respectively 151.56 °, 152.18 °, 158.64 °, 149.98 ° and 142.20 °, as shown in Figure 5 a.Figure
5b is the contact angle figure that embodiment 6 prepares film, shows the excellent ultra-hydrophobicity of film.
The preparation process of graphene oxide-cobalt nanocrystal-DLC film is as shown in Figure 6.Using being electrochemically-deposited in
Silicon substrate surface constructs the film of multi-grade nano composite structure, to obtain the super hydrophobic surface with excellent properties.It is super thin
The formation of water surface is attributed to cobalt nano-particle and graphene oxide and shows a kind of stratiform micro-convex structure in film surface, such as schemes
Shown in circle in 6, structure is the structure shown by Fig. 1 a and Fig. 1 d, and this structure makes air be retained in water droplet and film table
Between the micro-convex structure of face, to be conducive to exclude the water droplet of film surface rapidly.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention
It is interior.
Claims (6)
1. the preparation method of graphene oxide-cobalt nanocrystal-DLC film, which is characterized in that specifically according to the following steps
It carries out：
Step S1, silicon chip pre-processes：Silicon chip is cleaned by ultrasonic 5 minutes in analyzing pure methanol, silicon chip extracting is then put into matter
Amount score is corrode 5 minutes in 10%HF aqueous solutions, is finally put into analyze silicon chip again and is cleaned by ultrasonic 5 minutes in pure methanol, most
After use N2Drying；
Step S2, electrolyte is configured：Electrolyte solvent is to analyze pure methanol, acetylacetone cobalt (II) in the electrolytic solution a concentration of
0.06mg/mL-0.14mg/mL, a concentration of 0.003mg/mL-0.011mg/mL of graphene oxide in the electrolytic solution；
Step S3, Preparatory work of experiment：The silicon chip handled well is fixed on cathode graphite electrode, platinized platinum is fixed on anode graphite electrode
On, addition electrolyte to electrode between liquid level at a distance from be 10-15mm, the correct positive and negative anodes and DC high-voltage for connecting electrolytic cell
The positive and negative anodes in source；
Step S4, film deposits：In preparation process, electrolytic cell is immersed in water bath with thermostatic control, and temperature control is 55 DEG C；It is passed through nitrogen
8h；Additional power source uses high-voltage DC power supply, and voltage 1200V, under electric field action, sedimentation time control is 8h, Co2+、CH3 +To movable cathode, graphene oxide is under the effect of the two poles of the earth high electric field, by CH3 +And Co2+Drive is deposited on silicon chip, is prepared
Graphene oxide-cobalt nanocrystal-DLC film.
2. the preparation method of graphene oxide-cobalt nanocrystal-DLC film according to claim 1, feature exist
In the long 30mm of silicon chip, width 15mm, thickness 0.7mm in the step S1.
3. the preparation method of graphene oxide-cobalt nanocrystal-DLC film according to claim 1, feature exist
In the preparation method of graphene oxide in the electrolytic solution is in the step S2, and graphene oxide is added in electrolyte in ultrasound
Ultrasonic disperse is for 24 hours in wave.
4. the preparation method of graphene oxide-cobalt nanocrystal-DLC film according to claim 1, feature exist
In the distance between the step S3 Anodics and cathode are 8mm.
5. the preparation method of graphene oxide-cobalt nanocrystal-DLC film according to claim 2, feature exist
In platinized platinum is identical as die size in the step S3.
6. the preparation method of graphene oxide-cobalt nanocrystal-DLC film according to claim 1, feature exist
In the graphene oxide-cobalt nanocrystal-DLC film being prepared in the step S4 is the more of 30~40 microns of thickness
First nano compound film, the polynary nanometer laminated film are that graphene oxide cooperates with the polynary nanometer of metallic cobalt particle implantation compound
GO-Co/a-C:H films.
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