CN116288347A - Method for reducing corrosive wear and marine environment surface corrosion wear resistant fluorocarbon base film - Google Patents
Method for reducing corrosive wear and marine environment surface corrosion wear resistant fluorocarbon base film Download PDFInfo
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- CN116288347A CN116288347A CN202310523841.XA CN202310523841A CN116288347A CN 116288347 A CN116288347 A CN 116288347A CN 202310523841 A CN202310523841 A CN 202310523841A CN 116288347 A CN116288347 A CN 116288347A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 66
- 230000007797 corrosion Effects 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 40
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 53
- 239000000919 ceramic Substances 0.000 claims abstract description 43
- 238000005299 abrasion Methods 0.000 claims abstract description 30
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 25
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 229920001661 Chitosan Polymers 0.000 claims description 53
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
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- 238000010329 laser etching Methods 0.000 claims description 13
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/046—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with at least one amorphous inorganic material layer, e.g. DLC, a-C:H, a-C:Me, the layer being doped or not
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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Abstract
The invention discloses a method for reducing corrosion and abrasion and a marine environment surface corrosion and abrasion resistant fluorocarbon base film, which relates to the technical field of material surface modification and comprises the following steps: textured TiO 2 The ceramic layer is formed on the surface of the titanium alloy matrix; F-DLC structure layer, modified by carbon fluoride film layer on textured TiO 2 Forming the surface of the ceramic layer; and corrosion inhibitionAgent, encapsulated in textured TiO 2 In the texture structure of the ceramic layer. The novel high-hydrophobicity corrosion-wear-resistant fluorocarbon-based film on the surface of the titanium alloy in the marine environment has more excellent wear resistance, obviously improves the bonding force with a substrate, and has continuous corrosion-wear resistance; and the fluorocarbon-based film shows more excellent antibacterial performance.
Description
Technical Field
The invention belongs to the technical field of material surface modification, and particularly relates to a method for reducing corrosion and abrasion and a marine environment surface corrosion and abrasion resistant carbon fluoride base membrane.
Background
The marine industry has become a national strategic high-tech industry. At present, various military and civil ocean equipment such as aircraft carriers, carrier-borne aircraft, nuclear submarines, ocean drilling platforms and the like are greatly developed in China, so that research on tribological properties of materials in a seawater environment is more and more focused, a layer of oxide passivation film is immediately generated on the surface of titanium alloy in a normal-temperature seawater environment, pitting corrosion and crevice corrosion are prevented, and the titanium alloy is known as ocean metal and is often used as a supporting part of the equipment. However, when the titanium alloy is used as a mechanical moving part, the surface oxide passivation film is easily damaged in the friction process, and at the moment, the titanium alloy can be severely corroded and worn due to interaction of factors such as mechanics, chemistry, electrochemistry and the like.
In recent years, carbon-based films show great application prospects in the antifriction and corrosion-resistant fields due to their excellent tribological properties and chemical stability. However, when the carbon-based film is actually applied in a marine environment, micro cracks are easily generated under the action of an applied load due to the large hardness and internal stress of the carbon-based film, and the carbon-based film is more hydrophilic, so that corrosion mediums such as seawater can accelerate the expansion of the micro cracks, and the corrosion mediums penetrate through the micro cracks to the film-based interface to cause the film to peel off and lose efficacy, so that the lasting protection characteristic is difficult to fully exert. On the other hand, for titanium alloy, the elastic modulus and microhardness of the titanium alloy are low, the difference between the titanium alloy and the carbon-based film is large, the high internal stress causes poor film-substrate binding force, and the long-term protection of the carbon-based film on the substrate is not facilitated. Therefore, to realize the long-term protection of the carbon-based film to the titanium alloy substrate under the corrosive wear condition, an effective method is needed to solve the technical bottleneck.
Disclosure of Invention
The invention aims to provide a method for reducing corrosion and abrasion and a marine environment surface corrosion and abrasion resistant carbon fluoride-based film, which has more excellent abrasion resistance, obviously improves the bonding force with a substrate and has continuous corrosion and abrasion resistance; and the fluorocarbon-based film shows more excellent antibacterial performance.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a highly hydrophobic corrosion wear resistant fluorocarbon-based film of a titanium alloy surface comprising: textured TiO 2 The ceramic layer is formed on the surface of the titanium alloy matrix;
F-DLC structure layer, modified by carbon fluoride film layer on textured TiO 2 Forming the surface of the ceramic layer;
and corrosion inhibitor, encapsulated in textured TiO 2 In the texture structure of the ceramic layer.
Firstly, constructing textured TiO on the surface of a titanium alloy substrate 2 Ceramic film as transition layer, tiO 2 The ceramic film and the titanium alloy have good bonding strength, are also good corrosion resistant materials, and play an important role in improving the bonding force and corrosion resistance of the whole coating; the bearing capacity of the coating can be improved, and the coating also has excellent corrosion and abrasion resistance under the condition of larger load; in addition, the high hardness of the surface F-DLC coating enables the surface F-DLC coating to have enough bearing capacity, the textured F-DLC coating can effectively improve the surface hydrophobicity of the coating, the contact angle can be increased to more than 140 degrees, and the unique non-wettability of the surface super-hydrophobic film can effectively prevent the infiltration of corrosive media on the surface, so that the corrosion resistance of the material is effectively improved; the textured pattern of the concave surface can enable friction to only occur on the edge where the patterns meet, so that abrasion of hydrophobic materials in the concave pit is reduced, the concave pit is kept hydrophobic for a long time, and a long-acting corrosion-resistant effect is achieved; meanwhile, the doping of fluorine can effectively reduce the internal stress of the carbon-based film. In addition, the invention encapsulates the proper corrosion inhibitor in the texture structure, is used as a buffer mechanism after the surface film is damaged due to friction, can be adsorbed in the texture structure when micropores and cracks are generated after the coating is corroded and worn for a long time, delays the further occurrence of corrosion, ensures that the film has continuous corrosion and wear resistance, and ensures the long service life of the coating.
In an embodiment, the TiO is textured 2 The ceramic layer is subjected to thermal oxidation or PVD vacuum coating to obtain TiO 2 And the ceramic layer is obtained by performing texturing treatment through laser etching.
In a specific embodiment, the F-DLC structural layer is formed by PECVD vacuum coating.
In a specific embodiment, the corrosion inhibitor comprises cellulose, chitosan or derivatives thereof.
In a specific embodiment, the chitosan derivative is obtained from 2-amino-4, 6-dimethoxypyrimidine modified chitosan. The derivative is prepared by adopting the 2-amino-4, 6-dimethoxy pyrimidine modified chitosan, has excellent corrosion inhibition performance, can be used as a corrosion inhibitor to be applied to the preparation process of the fluorocarbon-based film, can further improve the wear resistance of the film, and obviously reduces the friction coefficient and the wear rate; meanwhile, the film has more excellent antibacterial performance. The reason for this may be that the chitosan is modified by adopting the-amino-4, 6-dimethoxy pyrimidine, and more active functional groups such as oxygen-containing and nitrogen-containing groups are introduced into the chain structure, so that the adsorption effect can be better generated on the surface of the metal substrate, micropores and cracks generated after the corrosion and abrasion of the metal device can be better filled, the corrosion of the device can be better and effectively delayed, and the service life of the coating can be prolonged.
The invention also discloses a preparation method of the chitosan derivative, which comprises the following steps:
adding distilled water into chitosan, uniformly dropwise adding 30% hydrogen peroxide under the condition of a water bath kettle at 55-65 ℃ while stirring, and reacting for 5-7 h; then filtering, distilling at 60-65 ℃ under reduced pressure, adding absolute ethyl alcohol, standing, filtering, and carrying out vacuum drying and grinding on the obtained solid to obtain degraded chitosan with the molecular weight of 2000-4000;
taking degraded chitosan, and adding distilled water for dissolution; adding an equal volume of acetone solution of epichlorohydrin, stirring for 10-20 min at 25-35 ℃, heating to 55-65 ℃, and adding 2-amino-4, 6-dimethoxy pyrimidine for reaction for 8-10 h; rotary steaming, adding absolute ethyl alcohol for precipitation, vacuum filtering, washing with absolute ethyl alcohol, and vacuum drying to obtain chitosan derivative.
In the specific embodiment, the solid-to-liquid ratio of chitosan to distilled water is 1:12-15 mL; the solid-liquid ratio of chitosan and 30% concentration hydrogen peroxide is 1 g:3.5-4.5 mL.
In a specific embodiment, the solid-to-liquid ratio of the degraded chitosan to distilled water is 1 g:60-70 mL; the molar ratio of the epichlorohydrin to the degraded chitosan is 3.5-4.5:1; the volume ratio of the epichlorohydrin to the acetone is 1:30-35; the molar ratio of the 2-amino-4, 6-dimethoxy pyrimidine to the degraded chitosan is 2-4:1.
The invention also discloses a method for reducing the corrosive wear, which comprises the following steps: preparing a surface highly hydrophobic corrosion-wear-resistant fluorocarbon-based film on the surface of the titanium alloy matrix.
The fluorocarbon-based film with high hydrophobicity and corrosion and abrasion resistance on the surface is the fluorocarbon-based film with corrosion and abrasion resistance on the surface of the marine environment.
The preparation method of the high-hydrophobicity corrosion-wear-resistant fluorocarbon-based film on the surface of the titanium alloy comprises the following steps:
(1) TiO is prepared on the surface of titanium alloy by a thermal oxidation method or a PVD vacuum coating method 2 A ceramic layer;
(2) TiO by laser etching 2 The ceramic layer is textured to obtain textured TiO 2 A ceramic layer;
(3) Texturing TiO by PECVD vacuum coating method 2 F-DLC is prepared on the surface of the ceramic layer, and a high hydrophobic surface is obtained by modifying a low surface energy substance;
(4) And packaging the green corrosion inhibitor in the texture.
In an embodiment, tiO is prepared by thermal oxidation in step (1) 2 The ceramic layer is specifically:
mixing titanium alloy with mixed acid (HF: HNO) 3 2.8-3.2, v/v) for 4-6 min, removing the surface oxide film, sequentially ultrasonically cleaning with acetone and distilled water for 8-12 min, naturally drying, and then placing in a muffle furnace with a temperature controlled by a program, and heating from room temperature to a set temperature of 550-650 ℃ in an air atmosphere at a heating rate of 4-7 ℃/min; and (3) preserving heat for 1.5-2.5 hours at constant temperature, and naturally cooling to room temperature.
In an embodiment, the TiO 2 The thickness of the ceramic layer is 0.5-10 μm.
In an embodiment, tiO in step (2) 2 The ceramic layer texturing process specifically comprises the following steps: presetting a laser etching pattern; the surface prepared in the step (1) is provided with TiO 2 The titanium alloy of the ceramic layer is placed on a workbench of laser etching equipment and positioned; and controlling the laser etching equipment to etch the etched product according to the preset laser etching pattern.
In an embodiment, the etching pattern includes an inverted pyramid, an inverted cone, or an inverted trapezoid.
In an embodiment, the PECVD vacuum coating process in the step (3) specifically comprises:
taking the texture in the step (2)TiO of (C) 2 Ultrasonic cleaning the ceramic layer for 15-30 min, soaking and cleaning surface organic matters by acetone, soaking and cleaning by absolute ethyl alcohol, and drying; and then placing the film on a lower polar plate sample tray in a vacuum chamber of an instrument, and performing a film plating experiment.
In an embodiment, specific parameters of the PECVD vacuum coating process include: the source gases are carbon source and fluorine source, the total flow of the reaction gases is 16-20 sccm, the flow ratio (fluorine source/(carbon source+fluorine source)) is 0.5-0.7, the flow is kept unchanged in the experimental process, and the deposition background pressure is not lower than 2X 10 -3 Pa, the temperature is 130-150 ℃, the deposition time is 20-40 min, and the deposition power is 200-250W.
In an embodiment, the F-DLC structural layer has a thickness of 1 to 20 μm.
In an embodiment, the specific process of encapsulating the corrosion inhibitor in step (4) is: and (3) immersing the titanium alloy with the high hydrophobic surface obtained in the step (3) in a chitosan derivative solution with the concentration of 5-8 wt%, taking out after 2-5 h, and drying at room temperature.
The chitosan derivative solution is prepared from an acetone/water mixed solution, wherein the volume ratio of the acetone to the water mixed solution is 1:2-3.
In an embodiment, the source gases in the PECVD vacuum coating process include a carbon source and a fluorine source.
In an embodiment, the carbon source is selected from C 2 H 2 、CH 4 At least one of (a) and (b); the fluorine source is selected from CF 4 、C 2 H 2 F 4 At least one of them.
The invention also discloses application of the surface highly hydrophobic corrosion-wear-resistant fluorocarbon-based film in corrosion-wear-resistant treatment of marine component surfaces.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a concept of preparing a composite super-hydrophobic carbon film with corrosion and abrasion resistance, and a composite carbon fluoride-based film with durable corrosion resistance is prepared on the surface of a titanium alloy, so that on one hand, the hydrophobicity of the film can be remarkably improved, and on the other hand, the friction coefficient and the energy consumption are also reduced. And the micro-nano texture of the film is used as a container to contain a proper amount of corrosion inhibitor, so that the corrosion and abrasion resistance of the film is further improved. The invention provides a new thought for solving the problem of corrosion and abrasion of titanium alloy in the seawater environment, and can be better applied to the development of a new generation of high-performance materials which can be used for mechanical equipment in the seawater environment. Furthermore, the derivative is prepared by adopting the 2-amino-4, 6-dimethoxy pyrimidine modified chitosan, and can be used as a corrosion inhibitor in the preparation process of the fluorocarbon-based film, so that the wear resistance of the film can be further improved, and the friction coefficient and the wear rate of the film are obviously reduced; meanwhile, the film has more excellent antibacterial performance.
Therefore, the invention provides a method for reducing corrosion and abrasion and a marine environment surface corrosion and abrasion resistant carbon fluoride-based film, which has more excellent abrasion resistance, obviously improves the bonding force with a substrate and has continuous corrosion and abrasion resistance; and the fluorocarbon-based film shows more excellent antibacterial performance.
Drawings
FIG. 1 is a schematic structural view of a fluorocarbon-based film according to example 1 of the present invention;
FIG. 2 is an infrared spectrum of the chitosan derivative and chitosan thereof prepared in example 3 of the present invention;
FIG. 3 is a diagram of TiO according to the invention prepared in example 5, example 7 2 XRD pattern of the ceramic layer.
Reference numerals:
1-corrosion inhibitor, 2-F-DLC layer, 3-textured TiO 2 Ceramic layer, 4-titanium alloy.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following describes in detail various embodiments of the present invention with reference to the embodiments. However, those of ordinary skill in the art will understand that in various embodiments of the present invention, numerous technical details have been set forth in order to provide a better understanding of the present application. However, the technical solutions claimed in the present application can be implemented without these technical details and with various changes and modifications based on the following embodiments.
Example 1:
a structural schematic diagram of a highly hydrophobic corrosion-wear-resistant fluorocarbon-based film on the surface of a titanium alloy is shown in figure 1, and the preparation process comprises the following steps:
(1) TiO is prepared on the surface of titanium alloy by a thermal oxidation method 2 The ceramic layer is specifically:
titanium alloy (Ti) 6 Al 4 V) after mixing the acid (HF: HNO (HNO) 3 =1:3, v/v), removing the surface oxide film layer, sequentially ultrasonically cleaning with acetone and distilled water for 10min, naturally drying, and placing in a muffle furnace with a program temperature control, and heating from room temperature to a set temperature of 600 ℃ in an air atmosphere at a heating rate of 5 ℃/min; keeping the temperature at constant temperature for 2 hours, naturally cooling to room temperature, and obtaining TiO 2 The thickness of the ceramic layer is 7.6 mu m;
(2) TiO is mixed with 2 Texturing the ceramic layer, and obtaining an inverted trapezoid shape by adopting laser etching; the method comprises the following steps: presetting a laser etching pattern; the surface prepared in the step (1) is provided with TiO 2 The titanium alloy of the ceramic layer is placed on a workbench of laser etching equipment and positioned; controlling laser etching equipment to etch the etched product according to a preset laser etching pattern;
(3) In TiO 2 F-DLC (thickness is 15.4 mu m) is prepared on the surface of the ceramic layer, and the titanium alloy with the high hydrophobic surface is obtained by modifying the low surface energy substance, specifically:
taking the TiO textured in the step (2) 2 Ultrasonic cleaning the ceramic layer for 20min, soaking and cleaning surface organic matters with acetone, soaking and cleaning with absolute ethyl alcohol, and drying; then placing the sample on a sample tray of a lower polar plate in a vacuum chamber of an instrument, and carrying out a coating experiment; the specific parameters include: the source gas being CH 4 And CF (compact F) 4 The total flow rate of the reaction gas was 18sccm, the flow rate ratio (CF 4 /(CH 4 +CF 4 ) 0.65, the flow is kept unchanged in the experimental process, and the deposition background pressure is not lower than 2 multiplied by 10 -3 Pa, the temperature is 145 ℃, the deposition time is 30min, and the deposition power is 230W;
(4) And (3) packaging a green corrosion inhibitor in the texture, immersing the titanium alloy with the high hydrophobic surface obtained in the step (3) in a chitosan solution with the concentration of 6.4wt% (the solvent is acetone/water mixed solution, v/v, 1:2.5), taking out after 3.5h, and drying at room temperature.
Example 2:
the preparation of the highly hydrophobic corrosion abrasion resistant fluorocarbon-based film on the surface of titanium alloy is different from that of example 1 in that:
the specific parameters of the PECVD vacuum coating process in the step (3) are as follows: the source gas being a carbon source (C) 2 H 2 ) And a fluorine source (C) 2 H 2 F 4 ) The total flow rate of the reaction gas was 20sccm, the flow rate ratio (C 2 H 2 F 4 /( C 2 H 2 + C 2 H 2 F 4 ) 0.55, the flow is kept unchanged in the experimental process, and the deposition background pressure is not lower than 2 multiplied by 10 -3 Pa, the temperature is 140 ℃, the deposition time is 25min, and the deposition power is 250W.
The concentration of the chitosan solution in step (4) was 7.2wt%.
Example 3:
the preparation of the highly hydrophobic corrosion abrasion resistant fluorocarbon-based film on the surface of titanium alloy is different from that of example 1 in that:
in the step (4), chitosan derivatives are adopted to replace chitosan, and the chitosan derivatives are prepared in the embodiment.
Preparation of chitosan derivatives:
adding distilled water into chitosan according to the solid-to-liquid ratio of 1:13.6mL, uniformly dripping 30% hydrogen peroxide (the solid-to-liquid ratio of chitosan to 30% hydrogen peroxide is 1g:4.1 mL) under the condition of a water bath at 60 ℃ while stirring, and reacting for 6h; then filtering, distilling under reduced pressure at 60 ℃, adding absolute ethyl alcohol, standing, filtering, vacuum drying and grinding the obtained solid to obtain degraded chitosan with the molecular weight of 3200;
taking degraded chitosan according to the solid-to-liquid ratio of 1g to 64mL, and adding distilled water for dissolution; adding an equal volume of acetone solution (the volume ratio of the epoxy chloropropane to the acetone is 1:32) with the molar ratio of the epoxy chloropropane to the degraded chitosan being 4.2:1, stirring for 15min at 30 ℃, then heating to 60 ℃, and adding 2-amino-4, 6-dimethoxy pyrimidine (the molar ratio of the epoxy chloropropane to the degraded chitosan is 3.1:1) for reacting for 9h; rotary steaming, adding absolute ethyl alcohol for precipitation, vacuum filtering, washing with absolute ethyl alcohol, and vacuum drying to obtain chitosan derivative.
Example 4:
the preparation of the highly hydrophobic corrosion abrasion resistant fluorocarbon-based film on the surface of titanium alloy is different from that of example 3 in that:
the specific parameters of the PECVD vacuum coating process in the step (3) are as follows: the source gas being a carbon source (C) 2 H 2 ) And a fluorine source (C) 2 H 2 F 4 ) The total flow rate of the reaction gas was 17sccm, the flow rate ratio (C 2 H 2 F 4 /( C 2 H 2 + C 2 H 2 F 4 ) 0.7, the flow is kept unchanged in the experimental process, and the deposition background pressure is not lower than 2 multiplied by 10 -3 Pa, temperature 150 ℃, deposition time 25min, deposition power 220W.
The chitosan derivative prepared in the step (4) was prepared in this example, and the concentration of the solution thereof was 5.8wt%.
The chitosan derivative was prepared differently from example 3 in that: the molecular weight of the degraded chitosan is 2200; the molar ratio of the epichlorohydrin to the degraded chitosan is 3.6:1; the molar ratio of the 2-amino-4, 6-dimethoxy pyrimidine to the degraded chitosan is 2.3:1.
Example 5:
the preparation of the highly hydrophobic corrosion abrasion resistant fluorocarbon-based film on the surface of titanium alloy is different from that of example 1 in that:
preparation of TiO on the surface of titanium alloy 2 The ceramic layer is prepared by a micro-arc oxidation method, and specifically comprises the following steps:
step-by-step polishing the titanium alloy by using a grinder and water sand paper to level the surface of the titanium alloy, then ultrasonically cleaning the titanium alloy for 30min by using acetone, and drying to obtain pretreated titanium alloy;
preparing composite electrolyte and NaAlO as composite solution system 2 (8-12 g/L) +NaF (4-6 g/L) +KOH (4-6 g/L) +pyrrolidine dithioformate ammonium-copper (0.5-2 g/L); wherein, the preparation of pyrrolidine dithio-ammonium formate-copper: copper sulfate pentahydrate and pyrrolidine disulfideThe ammonium formate is prepared by mixing according to the mass ratio of 1:1-1.5;
taking a stainless steel electrolytic tank as a cathode and titanium alloy as an anode for micro-arc oxidation treatment, wherein specific experimental parameters are as follows: the pulse frequency is 550-650 Hz, the duty ratio is 35-45%, the oxidation time is 30-50 min, and the current density is 4-8A/dm 2 . The invention adopts pyrrolidine dithio ammonium formate as an additive, and adds the additive into electrolyte to prepare TiO by a micro-arc oxidation method 2 The ceramic layer is then subjected to the rest of steps to obtain the fluorocarbon-based film, so that better bonding capability is shown between the fluorocarbon-based film and the matrix, and the bonding force is further improved; the friction performance of the film is further enhanced, the friction coefficient is reduced, and the abrasion rate is further reduced; and simultaneously, better antibacterial capability is shown. The reason for this is probably that the addition of ammonium pyrrolidinedichioformate to the electrolyte results in the preparation of TiO 2 The ceramic layer structure has beneficial effects and forms more stable rutile phase TiO 2 Exhibits more excellent interfacial bonding ability, so that the friction performance of the film is improved.
Further, in this example, tiO was prepared on the surface of the titanium alloy 2 The method of the ceramic layer comprises the following steps:
step-by-step polishing the titanium alloy by using a grinder and water sand paper to level the surface of the titanium alloy, then ultrasonically cleaning the titanium alloy for 30min by using acetone, and drying to obtain pretreated titanium alloy;
preparing composite electrolyte and NaAlO as composite solution system 2 (9.5 g/L) +NaF (5 g/L) +KOH (4.5 g/L) +pyrrolidine dithioformate ammonium-copper (1.5 g/L); wherein, the preparation of pyrrolidine dithio-ammonium formate-copper: the copper sulfate pentahydrate and the pyrrolidine dithioformate are mixed according to the mass ratio of 1:1.5;
taking a stainless steel electrolytic tank as a cathode and titanium alloy as an anode for micro-arc oxidation treatment, wherein specific experimental parameters are as follows: pulse frequency 620Hz, duty ratio 38%, oxidation time 40min, current density 6A/dm 2 。
Example 6:
the preparation of the highly hydrophobic corrosion abrasion resistant fluorocarbon-based film on the surface of titanium alloy is different from that of example 5 in that:
in the step (4), chitosan derivatives are adopted to replace chitosan, and the chitosan derivatives are prepared in the embodiment.
The chitosan derivative was prepared as in example 3.
Example 7:
the preparation of the highly hydrophobic corrosion abrasion resistant fluorocarbon-based film on the surface of titanium alloy is different from that of example 5 in that:
no additive is added into the composite electrolyte in the micro-arc oxidation method.
Test example 1:
characterization of infrared properties
The resolution is 4cm by using a Fourier infrared spectrometer -1 Wavelength range 500-4000 cm -1 。
The chitosan derivative prepared in example 1 and chitosan were subjected to the above test, and the results are shown in fig. 2. From the analysis in the figure, it is found that 1570cm in the infrared spectrum of the chitosan derivative prepared in example 1, compared with the infrared test result of chitosan -1 The characteristic absorption peak of pyrimidine ring appears nearby, indicating successful preparation of chitosan derivative in example 1.
XRD characterization
The samples were characterized using an X-ray diffractometer.
For TiO prepared in example 5 and example 7 2 The ceramic layer was subjected to the above test, and the results are shown in fig. 3. From the analysis in the figure, it is understood that compared with the TiO prepared in example 7 2 XRD pattern of ceramic layer, tiO prepared in example 5 2 In XRD pattern of ceramic layer, rutile phase TiO 2 The intensity of diffraction peak of (C) is increased, and anatase phase TiO is formed 2 The diffraction peak of (2) disappeared. The results show that the addition of the pyrrolidine dithioformate in the electrolyte is more beneficial to anatase phase TiO 2 To high temperature stable phase rutile phase TiO 2 And (3) converting.
Test example 2:
water contact Angle measurement
And (3) testing the water contact angle of the surface of the sample to be tested, wherein the testing method is carried out according to a conventional testing method.
The films prepared in examples 1 to 7 were subjected to the above test, and the results are shown in table 1:
TABLE 1 Water contact Angle test results
| Sample of | Water contact angle (°) |
| Example 1 | 149.5 |
| Example 2 | 148.4 |
| Example 3 | 150.7 |
| Example 4 | 149.8 |
| Example 5 | 150.1 |
| Example 6 | 150.5 |
| Example 7 | 149.9 |
From the data analysis in Table 1, it is known that the highly hydrophobic corrosion-resistant abrasion-resistant fluorocarbon-based film on the surface of the titanium alloy prepared in examples 1 to 7 of the present invention has a higher water contact angle and shows excellent hydrophobic performance.
Test example 3:
measurement of film-based binding force: testing a sample by adopting a multifunctional material surface performance tester, wherein a hemispherical diamond conical head (the cone angle is 120 degrees, the tip radius is 0.2 mm), loading in a vertical mode and loading from zero to 20N at a speed of 100N/min; and then detecting and recording acoustic signals through an acoustic emission probe arranged near the conical head, and comprehensively analyzing and judging the binding force of the film and the matrix by combining the friction force change curve recorded by the instrument.
Measurement of wear Rate and coefficient of Friction: and testing the friction performance of the sample to be tested by using a multifunctional friction and wear testing machine at the temperature of 50 ℃. Wherein, the dual material adopts Al with the diameter of 6.0mm and the hardness RC=62 2 O 3 Bearing ball, load 2N, slip speed 0.15m/s, frequency 5Hz, test time 6h. After the friction experiment is finished, the depth of the grinding mark is measured by using a KLA-Tencor Alpha-Step IQ profiler.
The films prepared in examples 1 to 7 were subjected to the above test, and the results are shown in Table 2:
TABLE 2 fluorocarbon based film Properties
| Sample of | Film base binding force (N) | Coefficient of friction | Wear Rate (. Times.10) -14 m 3 /N·m） |
| Example 1 | 30 | 0.45 | 3.6 |
| Example 2 | 28 | 0.47 | 4.1 |
| Example 3 | 31 | 0.32 | 0.9 |
| Example 4 | 30 | 0.34 | 1.1 |
| Example 5 | 41 | 0.38 | 0.6 |
| Example 6 | 42 | 0.29 | 0.09 |
| Example 7 | 35 | 0.43 | 1.8 |
From the data analysis in table 2, it is seen that the highly hydrophobic, corrosion-resistant and abrasion-resistant fluorocarbon-based film on the surface of the titanium alloy prepared in example 1 exhibited excellent bonding force with the substrate. The effect of example 5 is obviously better than that of example 1, and the effect of example 6 is better than that of example 3, which shows that the prepared film and the substrate show better binding force by adopting the pyrrolidine dithio-formic acid ammonium as an additive and carrying out film layer modification on the surface of the substrate through a micro-arc oxidation process.
In addition, the high-hydrophobicity corrosion-wear-resistant fluorocarbon-based film on the surface of the titanium alloy prepared in the embodiment 1 has low friction coefficient and wear rate, and can effectively reduce energy consumption. The effect of example 3 is obviously better than that of example 1, and shows that the derivative is prepared by adopting 2-amino-4, 6-dimethoxy pyrimidine modified chitosan, and is packaged in a textured structure as a corrosion inhibitor, so that the friction performance of a film can be effectively improved, the friction coefficient is obviously reduced, the wear resistance is further improved, and the wear rate is obviously reduced. The effect of example 5 is obviously better than that of example 1, and the effect of example 6 is better than that of example 3, which shows that the wear resistance of the prepared film is further enhanced by adopting the pyrrolidine dithio-formate as an additive and carrying out film layer modification on the surface of the substrate through a micro-arc oxidation process.
Test example 4:
antibacterial performance test:
the test method specifically comprises the following steps: diluting the prepared staphylococcus aureus suspension to 2.5X10 by PBS 4 cfu/mL, evenly coating 0.1mL on the surface of the sample to be tested, placing the sample in a sterile plate, and carrying out contact culture at 37 ℃ for 24 hours. And repeatedly washing the surface of the sample with PBS for 8 times, centrifuging the washed solution (2000 r/min,3 min) to collect staphylococcus aureus, dissolving the staphylococcus aureus in 1mL of bacterial heavy suspension, counting the staphylococcus aureus by a plate colony counting method, and calculating bacterial attachment rate by the number of strains before and after treatment to characterize the antibacterial property of the surface of the sample.
The films prepared in examples 1 to 7 were subjected to the above test, and the results are shown in Table 3:
TABLE 3 antibacterial Property test results
| Sample of | Adhesion Rate (%) |
| Example 1 | 33 |
| Example 2 | 32 |
| Example 3 | 11 |
| Example 4 | 12 |
| Example 5 | 28 |
| Example 6 | 5 |
| Example 7 | 31 |
From the data analysis in Table 3, the adhesion rate of the high-hydrophobicity corrosion-wear-resistant fluorocarbon-based film on the surface of the titanium alloy prepared in example 3 to staphylococcus aureus is obviously lower than that of example 1, which shows that the derivative is prepared by adopting 2-amino-4, 6-dimethoxy pyrimidine to modify chitosan, and the derivative is packaged in a textured structure as a corrosion inhibitor, so that the antibacterial property of the film can be effectively improved, and the effect on staphylococcus aureus is obviously increased all the time. The effect of example 5 is obviously better than that of example 1, and the effect of example 6 is better than that of example 3, which shows that the antibacterial property of the prepared film is further improved by adopting the pyrrolidine dithio-formic acid ammonium as an additive and carrying out film modification on the surface of the substrate through a micro-arc oxidation process.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A marine environmental surface corrosion wear resistant fluorocarbon based film comprising: textured TiO 2 The ceramic layer is formed on the surface of the titanium alloy matrix;
F-DLC structure layer, modified by carbon fluoride film layer on textured TiO 2 Forming the surface of the ceramic layer;
and corrosion inhibitor, encapsulated in textured TiO 2 In the texture structure of the ceramic layer.
2. A marine environmental surface corrosion wear resistant fluorocarbon base film as set forth in claim 1, wherein said textured TiO 2 The ceramic layer is subjected to thermal oxidation or PVD vacuum coating to obtain TiO 2 And the ceramic layer is obtained by performing texturing treatment through laser etching.
3. The marine environmental surface corrosion and wear resistant fluorocarbon-based film of claim 1, wherein said F-DLC structure layer is formed by PECVD vacuum plating.
4. A marine environmental surface corrosion and wear resistant fluorocarbon-based film as claimed in claim 1, wherein said corrosion inhibitor comprises cellulose, chitosan or chitosan derivatives.
5. The marine environmental surface corrosion and wear resistant fluorocarbon base film as claimed in claim 4, wherein said chitosan derivative is obtained from 2-amino-4, 6-dimethoxy pyrimidine modified chitosan.
6. The method for preparing the marine environmental surface corrosion and abrasion resistant fluorocarbon base film as set forth in claim 1, comprising:
(1) TiO is prepared on the surface of titanium alloy by a thermal oxidation method or a PVD vacuum coating method 2 A ceramic layer;
(2) TiO by laser etching 2 The ceramic layer is textured to obtain textured TiO 2 A ceramic layer;
(3) Texturing TiO by PECVD vacuum coating method 2 F-DLC is prepared on the surface of the ceramic layer, and a high hydrophobic surface is obtained by modifying a low surface energy substance;
(4) And packaging the green corrosion inhibitor in the texture structure.
7. The method of claim 6, wherein the source gases in the PECVD vacuum coating process comprise a carbon source and a fluorine source.
8. The method of claim 7, wherein the carbon source is selected from the group consisting of C 2 H 2 And CH (CH) 4 At least one of (a) and (b); the fluorine source is selected from CF 4 And C 2 H 2 F 4 At least one of them.
9. Use of the marine environmental surface corrosion and wear resistant fluorocarbon base film of claim 1 for the corrosion and wear resistant treatment of marine component surfaces.
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| CN103160800A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院兰州化学物理研究所 | Method for preparing fluorine-containing carbon-based film on silicon substrate surface |
| CN103233260A (en) * | 2013-05-10 | 2013-08-07 | 中国石油大学(华东) | Preparation of antifouling ceramic membrane electrolyte for titanium alloy surface and micro-arc oxidation method |
| CN104480511A (en) * | 2014-12-12 | 2015-04-01 | 南京理工大学 | Composite wear-resistant antifriction coating on titanium alloy surface and preparation method thereof |
| CN106119846A (en) * | 2016-06-27 | 2016-11-16 | 湖南航天新材料技术研究院有限公司 | A kind of method preparing anticorrosive wear-resistant coating at Mg alloy surface |
| CN107460518A (en) * | 2017-06-22 | 2017-12-12 | 浙江工业职业技术学院 | A kind of metal nano ceramic coating preparation method |
| CN109576640A (en) * | 2018-11-28 | 2019-04-05 | 江苏大学 | One kind preparing TiO in titanium substrate2The method of multiple dimensioned micro-nano compound structure |
| CN210727894U (en) * | 2018-11-30 | 2020-06-12 | 深圳先进技术研究院 | Super-hydrophobic medical instrument |
| WO2020119680A1 (en) * | 2018-12-14 | 2020-06-18 | 深圳先进技术研究院 | Superhydrophobic diamond-like composite layer structure and preparation method therefor |
| CN113430616A (en) * | 2021-06-16 | 2021-09-24 | 常州大学 | Preparation method of black ceramic film on titanium alloy surface |
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