WO2020119680A1 - 超疏水类金刚石复合层结构及其制备方法 - Google Patents

超疏水类金刚石复合层结构及其制备方法 Download PDF

Info

Publication number
WO2020119680A1
WO2020119680A1 PCT/CN2019/124312 CN2019124312W WO2020119680A1 WO 2020119680 A1 WO2020119680 A1 WO 2020119680A1 CN 2019124312 W CN2019124312 W CN 2019124312W WO 2020119680 A1 WO2020119680 A1 WO 2020119680A1
Authority
WO
WIPO (PCT)
Prior art keywords
nano
diamond
fluorine
layer
substrate
Prior art date
Application number
PCT/CN2019/124312
Other languages
English (en)
French (fr)
Inventor
唐永炳
项磊
石磊
蒋春磊
Original Assignee
深圳先进技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳先进技术研究院 filed Critical 深圳先进技术研究院
Publication of WO2020119680A1 publication Critical patent/WO2020119680A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/0605—Carbon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of diamond-like coatings, and particularly relates to a super-hydrophobic diamond-like composite layer structure and a preparation method thereof.
  • Diamond-like carbon is an amorphous carbon material with sp 2 and sp 3 bonding characteristics. Due to its high hardness and high elastic modulus, low friction factor, wear resistance and good vacuum tribological characteristics, it is very suitable As a wear-resistant coating, it has attracted the attention of the tribological community, and has a broad application prospect in the fields of tools, molds, parts and biomedical devices. However, the lack of hydrophobicity greatly limits the industrial application of diamond coatings.
  • the purpose of the present invention is to provide a super-hydrophobic diamond-like carbon composite layer structure and a preparation method thereof, aiming to solve the problem that the existing diamond-like carbon coating does not have hydrophobicity.
  • a first aspect of the present invention provides a diamond-like carbon composite layer structure including a polymer substrate and a fluorine-doped diamond-like carbon layer disposed on the surface of the self-supporting substrate, wherein the fluorine-doped The surface of the diamond-like layer facing away from the polymer substrate is a micro-nano array surface.
  • the thickness of the fluorine-doped diamond-like layer is 0.5 microns to 1.2 microns.
  • the thickness of the polymer substrate is 200 microns to 800 microns.
  • the polymer substrate is a polyvinylidene fluoride-hexafluoropropylene substrate, and nano-silica and/or nano-alumina are dispersed in the polyvinylidene fluoride-hexafluoropropylene substrate.
  • a second aspect of the present invention provides a method for preparing a diamond-like composite layer structure, including the following steps:
  • the self-supporting substrate After the self-supporting substrate is sequentially subjected to glow cleaning and ion etching cleaning, it is placed in a deposition chamber, a tetrafluoromethane gas is introduced, a high-purity carbon target is turned on, and fluorine doping is deposited on the surface of the self-supporting substrate Miscellaneous diamond layer;
  • the ion source is turned on to etch the fluorine-doped diamond-like layer to prepare a fluorine-doped diamond-like layer with a micro-nano structure array on the surface.
  • the organic solution of polyvinylidene fluoride-hexafluoropropylene is an acetone solution of polyvinylidene fluoride-hexafluoropropylene.
  • the organic solution of polyvinylidene fluoride-hexafluoropropylene is an N-methylpyrrolidone solution of polyvinylidene fluoride-hexafluoropropylene.
  • the concentration of polyvinylidene fluoride-hexafluoropropylene is 0.01 ⁇ 0.1g/ml.
  • the concentration of the dibutyl phthalate in the mixed slurry is 0.05 ⁇ 0.2g/ml.
  • the concentration of the nano silica is 0.01 ⁇ 0.08g/ml; when the nano oxide is nano aluminum oxide , The concentration of the nano-alumina is 0.01 ⁇ 0.08g/ml; when the nano-oxide is nano-silica and nano-alumina, the total of the nano-silica and the nano-alumina The concentration is 0.01 ⁇ 0.08g/ml.
  • argon gas and tetrafluoromethane gas are introduced into the deposition chamber, the flow rate of argon gas is controlled to be 100 ⁇ 400sccm, tetrafluoromethane The flow rate of the gas is 50 ⁇ 200sccm, and the pressure of the vacuum chamber is adjusted to 0.7 ⁇ 1.3 Pa, control the target power of the high-purity carbon target to be 0.6-1.4 KW, the base bias voltage is 0-150 V, and deposit a fluorine-doped diamond-like layer on the surface of the self-supporting substrate.
  • the ion source voltage is controlled to be 50-90 V
  • the argon flow rate is 200-500 sccm
  • the working pressure is 0.5-1.7 Pa
  • the substrate is biased. It is -50 ⁇ -500 V.
  • the particle size of the nano silica is 10 nm to 100 nm.
  • the particle size of the nano aluminum oxide is 10 nm to 100 nm.
  • the diamond-like composite layer structure provided by the present invention contains a fluorine-doped diamond-like layer having a micro-nano structure array on the surface.
  • the fluorine-doped diamond-like carbon layer acts as a hydrophobic layer, which can improve the hydrophobic performance of the diamond-like carbon layer.
  • the surface of the fluorine-doped diamond-like layer has a micro-nano structure array, which can further improve the hydrophobic effect of the diamond-like layer.
  • the diamond-like composite layer structure has excellent hydrophobic properties.
  • the contact angle experiment shows that the contact angle (surface of the diamond-like layer) of the diamond-like composite layer structure is 151.5° to 155.0°.
  • the polymer substrate has good toughness, and has a high binding force with the diamond-like carbon layer, thus the diamond-like carbon composite layer structure formed can be used as a wetting material with high toughness and hydrophobic performance requirements Use, thereby expanding the industrial application prospects of diamond-like carbon.
  • the present invention improves the hydrophobicity of the diamond-like composite layer structure by preparing a hydrophobic surface.
  • a self-supporting substrate of polyvinylidene fluoride-hexafluoropropylene is prepared first, and the self-supporting substrate has a pore structure. Therefore, when the self-supporting substrate further prepares a diamond-like layer, it can be formed Diamond-like layer with uneven surface.
  • the obtained diamond-like layer is etched to enlarge the uneven structure of the diamond-like layer, forming a hydrophobic surface with a micro-nano structure array on the surface.
  • the present invention further improves the hydrophobic effect by doping through multiple layers.
  • at least one of nano-silica and nano-alumina is added.
  • Dispersing nano-silica and/or nano-alumina in polyvinylidene fluoride-hexafluoropropylene can improve the micro-roughness of the surface and reduce the surface energy, thereby further improving the hydrophobic effect of the diamond-like layer.
  • the addition of the nano-silica and nano-alumina can also improve the mechanical properties of the self-supporting substrate.
  • by doping the diamond-like carbon layer with fluorine the hydrophobic performance of the diamond-like carbon layer is improved.
  • the contact angle experiment shows that the diamond-like composite layer structure prepared by the method of the present invention has excellent hydrophobic properties.
  • the contact angle experiment shows that the contact angle (surface of the diamond-like layer) of the diamond-like composite layer structure is 151.5° to 155.0°.
  • FIG. 1 is a schematic structural diagram of a diamond-like composite layer structure provided by an embodiment of the present invention.
  • Example 2 is a graph of the contact angle test results of the diamond-like composite layer structure provided in Example 1 of the present invention.
  • first and second are used for description purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
  • the features defined as “first” and “second” may explicitly or implicitly include one or more of the features.
  • the meaning of “plurality” is two or more, unless otherwise specifically limited.
  • Diamond-like coatings due to their excellent properties, especially high hardness and good scratch resistance, have been increasingly used in various industries, from machinery manufacturing to optical electronics, from medical to aerospace field. However, it is precisely because of the material properties of diamond-like materials that diamond-like materials do not possess hydrophobic properties and are difficult to use in technologies that require better hydrophobic properties.
  • the present invention aims to provide a method for preparing a diamond-like composite layer structure with super-hydrophobic capacity, and a corresponding diamond-like composite layer structure with super-hydrophobic capacity.
  • a first aspect of an embodiment of the present invention provides a diamond-like carbon composite layer structure including a polymer substrate 10 and a fluorine-doped diamond-like carbon layer 20 disposed on the surface of the self-supporting substrate Wherein the surface of the fluorine-doped diamond-like carbon layer 20 facing away from the polymer substrate 10 is a micro-nano array surface.
  • the diamond-like composite layer structure includes a two-layer structure, specifically, a polymer substrate 10 and a fluorine-doped diamond-like carbon layer 20 provided on the surface of the polymer substrate 10. Each layer is described in detail below.
  • the polymer substrate 10 has good toughness.
  • the carrier layer of the hardness diamond-like composite layer structure it has good bonding force with the bonding force of the fluorine-doped diamond-like layer 20 and can be transformed Shaping the fluorine-doped diamond-like layer 20 to expand the application range of the diamond-like composite layer structure.
  • the polymer substrate 10 contains a microporous structure, especially the surface of the polymer substrate 10 in contact with the fluorine-doped diamond-like carbon layer 20, the microporous structure is evenly distributed, and has a microporous structure or
  • the polymer substrate 10 on the surface of the microporous structure serves as a carrier layer of the fluorine-doped diamond-like carbon layer 20, and can transfer the surface-distributed microporous structure to the fluorine-doped diamond-like carbon layer 20, thereby providing the fluorine-doped diamond-like carbon layer 20
  • the uneven surface improves the hydrophobicity of the fluorine-doped diamond-like layer 20.
  • the polymer substrate 10 is a polyvinylidene fluoride-hexafluoropropylene substrate.
  • the polyvinylidene fluoride-hexafluoropropylene is a copolymer of vinylidene fluoride and hexafluoropropylene.
  • the copolymer of vinylidene fluoride and hexafluoropropylene not only has good self-will, but also has a good binding force with the fluorine-doped diamond-like carbon layer 20.
  • the polyvinylidene fluoride-hexafluoropropylene substrate is a polyvinylidene fluoride-hexafluoropropylene substrate in which nano silicon dioxide and/or nano aluminum oxide are dispersed in the film layer, that is, the polyvinylidene fluoride Nano silicon dioxide and/or nano aluminum oxide are dispersed in the vinyl fluoride-hexafluoropropylene substrate.
  • nano-silica and/or nano-alumina By doping nano-silica and/or nano-alumina in the polyvinylidene fluoride-hexafluoropropylene substrate, the mechanical properties of the polyvinylidene fluoride-hexafluoropropylene substrate can be improved, and more importantly It is noted that adding nano-silica and/or nano-alumina into the polymer substrate 10 can improve the micro-roughness of the surface and reduce the surface energy, thereby further improving the hydrophobicity of the fluorine-doped diamond-like layer 20.
  • the particle size of the nano-silica and the nano-alumina should not be too large.
  • the particle size of the nano-silica and nano-alumina is too large, it is not conducive to the uniform dispersion of the nano-silica and the nano-alumina, thereby affecting the structure of the diamond-like composite layer Of hydrophobicity.
  • the particle diameter of the nano silica is 10 nm to 100 nm, more preferably 20 nm to 50 nm; the polymer substrate 10 is dispersed
  • the particle diameter of the nano aluminum oxide is 10 nm to 100 nm, and more preferably 20 nm to 50 nm.
  • the thickness of the polymer substrate 10 is 200 microns to 800 microns, and more preferably, the thickness of the self-supporting substrate is 400 microns to 600 microns.
  • the polymer substrate 10 with a suitable thickness can form a self-supporting structure, and at the same time, impart a good toughness to the diamond-like composite layer structure. If the thickness of the polymer substrate 10 is too thin, and the film layer is relatively brittle, it is insufficient to support the diamond-like layer with high hardness.
  • fluorine doping is performed in the diamond-like layer to improve the hydrophobicity of the diamond-like layer; on the other hand, the surface of the fluorine-doped diamond-like layer 20 facing away from the polymer substrate 10 is a micro-nano array Surface, thereby giving the fluorine-doped diamond-like carbon layer 20 excellent superhydrophobic properties.
  • the fluorine doping content is 10 wt% to 35 wt%.
  • Doping fluorine in diamond-like carbon can increase the sp 2 hybridization level, reduce the polarization strength of the film, deteriorate the wettability with water, and increase the contact angle.
  • the amount of fluorine doped in the fluorine-doped diamond-like layer 20 is too low, the effect on improving the hydrophobicity of the diamond-like layer is not obvious; if the fluorine-doped diamond-like layer 20 is doped with fluorine If the amount is too high, a larger fluorine content will lead to larger particles on the surface of the film, and the surface energy will increase, resulting in a lower contact angle.
  • the thickness of the fluorine-doped diamond-like layer 20 is 0.5 microns to 1.2 microns.
  • This thickness range has good general adaptability and can basically meet the industry requirements for using diamond-like coatings.
  • this thickness range can be passed Deposited and prepared, so as to ensure that the obtained fluorine-doped diamond-like coating has good quality.
  • the height of the micro-nano array is 0.5 ⁇ m-1.2 ⁇ m, and the spacing between adjacent micro-nano cells in the micro-nano array is 0.1 ⁇ m-1.2 ⁇ m.
  • the fluorine-doped diamond-like layer 20 has a good surface structure, and thus has excellent superhydrophobic properties.
  • the ratio of the height of the micro-nano cell to the pitch of the adjacent micro-nano cell is 1: (0.5 ⁇ 1.5), at this time, the fluorine is doped
  • the diamond-like carbon layer 20 has more excellent superhydrophobic performance, and the contact angle is between 153° and 155°.
  • the diamond-like composite layer structure is composed of a polymer substrate 10 and a fluorine-doped diamond-like carbon layer 20 provided on the surface of the polymer substrate 10.
  • the diamond-like composite layer structure provided by the embodiment of the present invention includes a fluorine-doped diamond-like layer 20 having an array of micro-nano structures on the surface.
  • the fluorine-doped diamond-like carbon layer 20 serves as a hydrophobic layer, which can improve the hydrophobic performance of the diamond-like carbon layer.
  • the surface of the fluorine-doped diamond-like carbon layer 20 has a micro-nano structure array, which can further improve the hydrophobic effect of the diamond-like carbon layer.
  • the diamond-like composite layer structure has excellent hydrophobic properties.
  • the contact angle experiment shows that the contact angle (surface of the diamond-like layer) of the diamond-like composite layer structure is 151.5° to 155.0°.
  • the polymer substrate 10 has good toughness, and has a high binding force with the diamond-like carbon layer.
  • the resulting diamond-like carbon composite layer structure can be used as a wetting that requires high toughness and hydrophobic properties
  • the use of materials has expanded the industrial application prospects of diamond-like carbon.
  • the diamond-like composite layer structure provided by the embodiment of the present invention can be prepared by the following method.
  • the second aspect of the embodiments of the present invention provides a method for preparing a diamond-like composite layer structure, including the following steps:
  • the self-supporting substrate After the self-supporting substrate is sequentially subjected to glow cleaning and ion etching cleaning, it is placed in a deposition chamber, PTFE gas is introduced, a high-purity carbon target is turned on, and the surface of the self-supporting substrate is deposited Fluorine-doped diamond-like layer;
  • the embodiments of the present invention improve the hydrophobicity of the diamond-like composite layer structure by preparing a hydrophobic surface.
  • a self-supporting substrate of polyvinylidene fluoride-hexafluoropropylene is prepared first, and the self-supporting substrate has a pore structure. Therefore, when the self-supporting substrate further prepares a diamond-like layer, it can be formed Diamond-like layer with uneven surface.
  • the obtained diamond-like layer is etched to enlarge the uneven structure of the diamond-like layer, forming a hydrophobic surface with a micro-nano structure array on the surface.
  • the embodiments of the present invention further improve the hydrophobic effect by doping through multiple layers.
  • at least one of nano-silica and nano-alumina is added.
  • Dispersing nano-silica and/or nano-alumina in polyvinylidene fluoride-hexafluoropropylene can improve the micro-roughness of the surface and reduce the surface energy, thereby further improving the hydrophobic effect of the diamond-like layer.
  • the addition of the nano-silica and nano-alumina can also improve the mechanical properties of the self-supporting substrate.
  • by doping the diamond-like carbon layer with fluorine the hydrophobic performance of the diamond-like carbon layer is improved.
  • the contact angle experiment shows that the diamond-like composite layer structure prepared by the method of the embodiment of the present invention has excellent hydrophobic properties.
  • the contact angle experiment shows that the contact angle (surface of the diamond-like layer) of the diamond-like composite layer structure is 151.5° to 155.0°.
  • an organic solution of polyvinylidene fluoride-hexafluoropropylene is provided.
  • the organic solution of polyvinylidene fluoride-hexafluoropropylene is polyvinylidene fluoride-hexafluoropropylene. Acetone solution.
  • the organic solution of polyvinylidene fluoride-hexafluoropropylene is a solution of polyvinylidene fluoride-hexafluoropropylene in N-methylpyrrolidone.
  • the acetone and the N-methylpyrrolidone have good solubility in the polyvinylidene fluoride-hexafluoropropylene, and can also effectively dissolve dibutyl phthalate and disperse nano oxides to form a uniform The slurry, and can have good spreadability when the solution is formed into a film.
  • dibutyl phthalate and nano oxide to the organic solution, wherein the dibutyl phthalate as a pore-forming agent can be uniformly dispersed in the film-forming substance (polyvinylidene fluoride-hexafluoro In propylene), it occupies a suitable site during the film formation process and is removed in subsequent steps to provide a microporous structure for the polyvinylidene fluoride-hexafluoropropylene self-supporting substrate.
  • the film-forming substance polyvinylidene fluoride-hexafluoro In propylene
  • the weight percentage of the dibutyl phthalate ranges from 20% ⁇ 60%, which can form a suitable number and size of microporous structure, to ensure that the microporous surface of the formed self-supporting substrate can be effectively transferred to the fluorine-doped diamond-like film layer. If the content of the dibutyl phthalate is too low, the micropore structure formed is too small, and the resulting microstructure of the surface of the self-supporting substrate is not obvious. Correspondingly, the fluorine-doped type formed on the self-supporting substrate The diamond layer does not have the corresponding micropore structure.
  • the nano oxide is selected from at least one of nano silicon dioxide and nano aluminum oxide.
  • the addition of the nano-silica and nano-alumina can improve the hydrophobicity of the fluorine-doped diamond-like layer.
  • the nano-oxide contains nano-silica
  • the nano-silica has a particle size of 10 nm to 100 nm.
  • the particle size of the nano aluminum oxide is 10 nm to 100 nm.
  • dibutyl phthalate and nano-oxide to the organic solution, you can add dibutyl phthalate and nano-oxide to the organic solution at the same time, you can also add dibutyl phthalate and nano-oxide
  • the oxide is added to the organic solution in tandem.
  • dibutyl phthalate is first added to the organic solution to form a uniform mixed solution, and then the nano oxide is added to the mixed solution, which is beneficial to improve the dispersibility of the nano oxide and further improve the diamond-like composite layer
  • the hydrophobic stability of the structure Further preferably, after the nano oxide is added to the mixed solution, the water bath is heated and stirred at 40-80°C for 2-8 hours to improve the dispersion performance of the nano oxide.
  • the concentration of polyvinylidene fluoride-hexafluoropropylene in the organic solution of polyvinylidene fluoride-hexafluoropropylene is 0.01 ⁇ 0.1g/ml, so as to ensure the formation of the film layer The compactness and ensure the appropriate film thickness.
  • the concentration of the dibutyl phthalate in the mixed slurry is 0.05 ⁇ 0.2g/ml. If the concentration of the dibutyl phthalate is too high, it will cause large surface pores , Destroy the surface micro-nano structure.
  • the concentration of the nano silica is 0.01 ⁇ 0.08g/ml; when the nano oxide is nano aluminum oxide , The concentration of the nano-alumina is 0.01 ⁇ 0.08g/ml; when the nano-oxide is nano-silica and nano-alumina, the total of the nano-silica and the nano-alumina The concentration is 0.01 ⁇ 0.08g/ml.
  • increasing the nano-oxide content can increase the surface roughness and increase the contact angle.
  • the concentration of the nano oxide is too large, the surface roughness will be too large, the contact angle will be reduced, and the film layer will become brittle.
  • the obtained mixed slurry is deposited on the substrate, and the deposition method is not strictly limited.
  • a doctor blade may be used to deposit the mixed slurry on the glass plate for uniform coating, but is not limited thereto.
  • the substrate deposited with the mixed slurry is dried to form a film.
  • the temperature of the dry film formation should not be too high. Excessively high temperature will not only damage the polymer in the film layer, but also easily lead to uneven thickness and curling of the obtained film layer. In view of this, drying the film deposited on the substrate on which the mixed slurry is deposited is performed under the conditions of 50° C.-80° C., preferably for 6-12 h.
  • the film layer obtained after drying is immersed in organic alcohol to dissolve the dibutyl phthalate, and the poly vinylidene fluoride-hexafluoropropylene in the film layer and the poly vinylidene fluoride in the dispersion are retained Nano-oxide in vinyl fluoride-hexafluoropropylene to prepare a self-supporting substrate with a pore structure.
  • the membrane layer obtained after drying is immersed in methanol for 12-48 h, then put the sample into a blast drying oven to dry at 80 ⁇ 120°C, and the self-supporting substrate is completed.
  • the self-supporting substrate is sequentially subjected to glow cleaning and ion etching cleaning, and through the glow cleaning and ion etching cleaning, moisture and gas remaining on the uneven surface of the self-supporting substrate such as scratches are removed In order to improve the adhesion effect of the coating.
  • glow cleaning and ion etching cleaning moisture and gas remaining on the uneven surface of the self-supporting substrate such as scratches are removed
  • moisture and gas remaining on the uneven surface of the self-supporting substrate such as scratches are removed
  • the coating has the best binding force on the self-supporting substrate after cleaning.
  • the self-supporting substrate after drying is fixedly clamped in a jig and fixed on a rotating frame in an ion source/arc ion plating composite coating equipment; vacuum is applied.
  • the pressure in the vacuum chamber reaches 3.2 ⁇ 10 -3 Pa, the self-supporting substrate starts to perform the glow cleaning.
  • the glow cleaning method is as follows: opening the main valve of the argon cylinder, the pressure reducing valve, the ion source valve, the arc valve and the target valve, and the mass flow meter, passing argon gas into the vacuum chamber to control the argon
  • the air flow is 300 ⁇ 500sccm
  • the working pressure is 1.0 ⁇ 1.7 Pa
  • the base bias voltage is -500 ⁇ -800V
  • the self-supporting substrate is subjected to glow cleaning
  • the cleaning time is 10 ⁇ 30min.
  • Glow cleaning under the above conditions can quickly remove the moisture and gas hidden in the microporous structure of the self-supporting substrate, preventing the adhesion of the film layer when the diamond-like layer is subsequently deposited by ion source magnetron sputtering To improve the bonding force of the film layer on the self-supporting substrate.
  • the self-supporting substrate is ion-etched and cleaned, and the self-supporting The uneven surface of the substrate, especially the moisture and gas in the microporous structure are completely removed.
  • the ion etching cleaning uses argon gas to ionize into plasma in the ion source, and ion bombardment cleaning is performed on the self-supporting liner.
  • the ion etching cleaning method is: after the glow cleaning is completed, the ion source is turned on to perform ion bombardment cleaning on the sample, wherein the ion source voltage is 50 ⁇ 90 V, argon flow rate 200 ⁇ 500sccm, working pressure 0.5 ⁇ 1.7Pa, base bias voltage -150 ⁇ -500V.
  • the cleaning time of the ion bombardment cleaning is 5-15 minutes.
  • the ion source-enhanced magnetron sputtering method is used to deposit a fluorine-doped diamond-like layer with a high-purity graphite target as a carbon source, which not only can obtain a film-stabilized fluorine-doped diamond-like layer, but also The microporous structure on the surface of the self-supporting substrate is copied to form an uneven surface of the fluorine-doped diamond-like layer. Specifically, a tetrafluoromethane gas is introduced into the deposition chamber, a high-purity carbon target is turned on, and a fluorine-doped diamond-like layer is deposited on the surface of the self-supporting substrate.
  • argon gas and tetrafluoromethane gas are introduced into the deposition chamber, and the flow rate of argon gas is controlled to be 100-400 sccm.
  • the flow rate of tetrafluoromethane gas is 50 ⁇ 200sccm, and the pressure of the vacuum chamber is adjusted to 0.7 ⁇ 1.3 Pa, control the target power of the high-purity carbon target to be 0.6-1.4 KW, the base bias voltage is 0-150 V, and deposit a fluorine-doped diamond-like layer on the surface of the self-supporting substrate.
  • the base bias affects the bonding force of the fluorine-doped diamond-like layer on the self-supporting substrate.
  • the base bias is 0 ⁇ -150 Under the condition of V, a fluorine-doped diamond-like carbon layer is deposited, and the obtained fluorine-doped diamond-like carbon layer has a better bonding force on the self-supporting substrate.
  • the target power of the high-purity carbon target and the flow rate of tetrafluoromethane gas jointly determine the fluorine content of the fluorine-doped diamond-like layer. If any one of the target power and the flow rate of tetrafluoromethane gas changes, it may affect the fluorine doping content.
  • the target power of the high-purity carbon target and the flow rate of tetrafluoromethane gas are within the above ranges, and the doping content of fluorine can be controlled between 10wt% and 35wt% Within the range, thereby obtaining a fluorine-doped diamond-like carbon layer with better hydrophobicity.
  • the pressure of the vacuum chamber has a certain influence on the quality of the fluorine-doped diamond-like layer.
  • the embodiment of the present invention adjusts the pressure of the vacuum chamber to 0.7 ⁇ 1.3 Pa, the resulting fluorine-doped diamond-like layer has a stronger binding force on the surface of the self-supporting substrate.
  • the pressure in the vacuum chamber is too high and the deposition speed is too fast, the obtained fluorine-doped diamond-like layer has a disordered lattice and irregular arrangement, which will reduce the binding force of the fluorine-doped diamond-like layer on the self-supporting substrate.
  • the deposition time is 30-60 minutes, thereby obtaining a fluorine-doped diamond-like layer having an appropriate thickness.
  • the thickness of the fluorine-doped diamond-like layer is 0.5 ⁇ m to 1.2 ⁇ m.
  • the ion source is turned on to etch the fluorine-doped diamond-like layer, and the surface defects (surface microporous structure) of the fluorine-doped diamond-like layer are strengthened by etching, thereby preparing an array with a micro-nano structure on the surface
  • the fluorine-doped diamond-like layer improves the hydrophobic properties of the diamond-like composite layer structure.
  • the ion source voltage is controlled to 50-90 V
  • the argon flow rate is 200-500 sccm
  • the working pressure is 0.5-1.7 Pa.
  • the substrate bias voltage is -50 ⁇ -500 V.
  • a method for preparing a diamond-like composite layer structure includes the following steps:
  • Glow cleaning open the main valve of the argon gas bottle, pressure reducing valve, ion source valve, arc valve and target valve, and mass flow meter, inject argon gas into the vacuum chamber, the flow rate of argon gas is 500 sccm, the working pressure is 1.0 Pa, the substrate Bias voltage -800 V, glow cleaning the substrate, cleaning time 10 min;
  • Ion etching cleaning After the glow cleaning is completed, the ion source is turned on to perform ion bombardment cleaning on the sample.
  • the ion source voltage is 50 V
  • the argon flow rate is 300 sccm
  • the working pressure is 0.8 Pa
  • the substrate bias voltage is -150 V
  • the cleaning time is 15 min.
  • argon gas is introduced at a flow rate of 300 sccm, while PTFE gas is introduced at a flow rate of 50 sccm, the vacuum chamber pressure is adjusted to 0.9 Pa, the high-purity carbon target is turned on, and the target power is 1 KW, Substrate bias -50 V for deposition of diamond-like coatings, deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that:
  • argon gas is introduced at a flow rate of 200 sccm, and PTFE gas is simultaneously introduced at a flow rate of 100 sccm, the vacuum chamber pressure is adjusted to 0.9 Pa, the high-purity carbon target is turned on, and the target power is 1 KW, Substrate bias -50 V for deposition of diamond-like coatings, deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that:
  • argon gas is introduced at a flow rate of 220 sccm, while PTFE gas is introduced at a flow rate of 80 sccm, the vacuum chamber pressure is adjusted to 0.9 Pa, the high-purity carbon target is turned on, and the target power is 1 KW, Substrate bias -100 V for deposition of diamond-like coatings with a deposition time of 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that after the ion etching cleaning is completed, argon gas is introduced at a flow rate of 230 sccm, while tetrafluoromethane gas is introduced at a flow rate of 100 sccm. Adjust the vacuum chamber pressure to 1.5 Pa, turn on the high-purity carbon target, the target power is 1.2 KW, the substrate bias voltage is -80 V for the deposition of diamond-like coating, the deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that after the ion etching and cleaning, argon gas is introduced at a flow rate of 300 sccm, and tetrafluoromethane gas is introduced at a flow rate of 120 sccm. Adjust the pressure of the vacuum chamber to 1.1 Pa, turn on the high-purity carbon target, the target power is 0.9 KW, the substrate bias voltage is -120 V for the deposition of diamond-like coating, the deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that after the ion etching and cleaning, argon gas is introduced at a flow rate of 280 sccm, and tetrafluoromethane gas is introduced at a flow rate of 90 sccm. Adjust the pressure of the vacuum chamber to 0.8 Pa, turn on the high-purity carbon target, the target power is 1 KW, the substrate bias voltage is -130 V for the deposition of diamond-like coating, the deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that after ion etching and cleaning, argon gas is introduced at a flow rate of 260 sccm, and tetrafluoromethane gas is introduced at a flow rate of 150 sccm. Adjust the pressure of the vacuum chamber to 1.1 Pa, turn on the high-purity carbon target, the target power is 1.2 KW, the substrate bias voltage is -150 V for the deposition of diamond-like coating, the deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure is different from that in Example 1 in that after ion etching and cleaning, argon gas is introduced at a flow rate of 180 sccm, and tetrafluoromethane gas is introduced at a flow rate of 180 sccm. Adjust the vacuum chamber pressure to 0.8 Pa, turn on the high-purity carbon target, the target power is 1 KW, the substrate bias voltage is -140 V for the deposition of diamond-like coating, the deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that after ion etching and cleaning, argon gas is introduced at a flow rate of 280 sccm, and tetrafluoromethane gas is introduced at a flow rate of 120 sccm. Adjust the vacuum chamber pressure to 0.9 Pa, turn on the high-purity carbon target, the target power is 1.2 KW, and the substrate bias voltage is -150 V for the deposition of diamond-like coating, the deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a method for preparing a diamond-like composite layer structure differs from Example 1 in that after ion etching and cleaning, argon gas is introduced at a flow rate of 220 sccm, and tetrafluoromethane gas is introduced at a flow rate of 60 sccm. Adjust the vacuum chamber pressure to 0.8 Pa, turn on the high-purity carbon target, the target power is 1 KW, the substrate bias voltage is -150 V for the deposition of diamond-like coating, the deposition time is 60 min, prepare a fluorine-doped diamond-like layer.
  • a preparation method of diamond-like coating includes the following steps:
  • Glow cleaning open the main valve of the argon gas bottle, pressure reducing valve, ion source valve, arc valve and target valve, and mass flow meter, inject argon gas into the vacuum chamber, the flow rate of argon gas is 500 sccm, the working pressure is 1.0 Pa, the substrate Bias voltage -800 V, glow cleaning the substrate, cleaning time 10 min;
  • Ion etching cleaning After the glow cleaning is completed, the ion source is turned on to perform ion bombardment cleaning on the sample.
  • the ion source voltage is 50 V
  • the argon flow rate is 300 sccm
  • the working pressure is 0.8 Pa
  • the substrate bias voltage is -150 V
  • the cleaning time is 15 min.
  • argon gas is introduced at a flow rate of 300 sccm, while PTFE gas is introduced at a flow rate of 50 sccm, the vacuum chamber pressure is adjusted to 0.9 Pa, the high-purity carbon target is turned on, and the target power is 1 KW, Substrate bias -50 V for deposition of diamond-like coatings, deposition time is 60 min.
  • test results are shown in Table 1 below, wherein the test result graph of Example 1 is shown in FIG. 2.
  • Example 1 151.961 151.877 151.919
  • Example 2 152.281 152.714 152.498
  • Example 3 151.635 151.852 151.744
  • Example 4 152.153 152.394 152.274
  • Example 5 152.568 152.386 152.477
  • Example 6 151.886 151.986 151.936
  • Example 7 153.653 153.731 153.692
  • Example 8 152.653 152.139 152.396
  • Example 9 152.785 152.631 152.708
  • Example 10 151.900 151.800 151.850 Comparative Example 1 131.056 130.875 130.965

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

一种类金刚石复合层结构的制备方法，包括以下步骤：提供聚偏氟乙烯-六氟丙烯的有机溶液，在所述有机溶液中加入邻苯二甲酸二丁酯和纳米氧化物，加热处理形成混合浆料，将所述混合浆料沉积在基底上，干燥处理，将得到的膜层置于有机醇中浸泡处理，以溶解所述邻苯二甲酸二丁酯，制备具有孔隙结构的自支撑衬底，其中，所述纳米氧化物选自纳米二氧化硅、纳米三氧化二铝中的至少一种；将所述自支撑衬底依次进行辉光清洗和离子刻蚀清洗后，置于沉积室中，通入四氟甲烷气体，开启高纯碳靶，在所述自支撑衬底的表面沉积氟掺杂类金刚石层；开启离子源对所述氟掺杂类金刚石层进行刻蚀处理，制备表面具有微纳结构阵列的氟掺杂类金刚石层。

Description

超疏水类金刚石复合层结构及其制备方法 技术领域
本发明属于类金刚石涂层技术领域，尤其涉及一种超疏水类金刚石复合层结构及其制备方法。
 背景技术
近年来，具有特殊浸润性能的超疏水材料受到人们广泛关注，超疏水材料在医学生物、工农业生产和日常生活中，如自清洁材料、油水分离材料、抗污织布、减阻材料等都有着极其广阔的应用前景。然而目前研究的超疏水材料，制备工艺复杂、稳定性不好、成本高昂，且制备出的超疏水材料硬度不高，无法满足材料多样化的要求。因此，发展一种高硬、超疏水材料的方法对特殊浸润性能材料的广泛应用具有重要的促进作用和意义。
类金刚石（DLC）是一种含有sp 2和sp 3键合特征的非晶碳材料，由于具有高硬度和高弹性模量，低摩擦因数，耐磨损以及良好的真空摩擦学特性，很适合于作为耐磨涂层，从而引起了摩擦学界的重视，在刀具、模具、零部件以及生物医疗器件等领域有着广泛的应用前景。但是由于不具备疏水性，极大限制了金刚石涂层的工业应用。
技术问题
本发明的目的在于提供一种超疏水类金刚石复合层结构及其制备方法，旨在解决现有的类金刚石涂层不具备疏水性的的问题。
 技术解决方案
为实现上述发明目的，本发明采用的技术方案如下：
本发明第一方面提供一种类金刚石复合层结构，所述类金刚石复合层结构包括聚合物衬底，设置在所述自支撑衬底表面的氟掺杂类金刚石层，其中，所述氟掺杂类金刚石层背离所述聚合物衬底的表面为微纳阵列表面。
优选的，所述氟掺杂类金刚石层的厚度为0.5微米~1.2微米。
优选的，所述聚合物衬底的厚度为200微米~800微米。
优选的，所述聚合物衬底为聚偏氟乙烯-六氟丙烯衬底，且所述聚偏氟乙烯-六氟丙烯衬底中分散有纳米二氧化硅和/或纳米三氧化二铝。
本发明第二方面提供一种类金刚石复合层结构的制备方法，包括以下步骤：
提供聚偏氟乙烯-六氟丙烯的有机溶液，在所述有机溶液中加入邻苯二甲酸二丁酯和纳米氧化物，加热处理形成混合浆料，将所述混合浆料沉积在基底上，干燥处理，将得到的膜层置于有机醇中浸泡处理，以溶解所述邻苯二甲酸二丁酯，制备具有孔隙结构的自支撑衬底，其中，所述纳米氧化物选自纳米二氧化硅、纳米三氧化二铝中的至少一种；
将所述自支撑衬底依次进行辉光清洗和离子刻蚀清洗后，置于沉积室中，通入四氟甲烷气体，开启高纯碳靶，在所述自支撑衬底的表面沉积氟掺杂类金刚石层；
开启离子源对所述氟掺杂类金刚石层进行刻蚀处理，制备表面具有微纳结构阵列的氟掺杂类金刚石层。
优选的，所述聚偏氟乙烯-六氟丙烯的有机溶液为聚偏氟乙烯-六氟丙烯的丙酮溶液。
优选的，所述聚偏氟乙烯-六氟丙烯的有机溶液为聚偏氟乙烯-六氟丙烯的N-甲基吡咯烷酮溶液。
优选的，所述聚偏氟乙烯-六氟丙烯的有机溶液中，聚偏氟乙烯-六氟丙烯的浓度为0.01~0.1g/ml。
优选的，所述混合浆料中，所述邻苯二甲酸二丁酯的浓度为0.05~0.2g/ml。
优选的，所述混合浆料中，所述纳米氧化物为纳米二氧化硅时，所述纳米二氧化硅的浓度为0.01~0.08g/ml；所述纳米氧化物为纳米三氧化二铝时，所述纳米三氧化二铝的浓度为0.01~0.08g/ml；所述纳米氧化物为纳米二氧化硅和纳米三氧化二铝时，所述纳米二氧化硅和纳米三氧化二铝的总浓度为0.01~0.08g/ml。
优选的，在所述自支撑衬底的表面沉积氟掺杂类金刚石层的步骤中，往沉积室中通入氩气和四氟甲烷气体，控制氩气的流量为100~400sccm，四氟甲烷气体的流量为50~200sccm，调节真空室压强为0.7~1.3 Pa，控制所述高纯碳靶的靶功率为0.6-1.4KW，基底偏压0~-150 V，在所述自支撑衬底的表面沉积氟掺杂类金刚石层。
优选的，开启离子源对所述氟掺杂类金刚石层进行刻蚀处理的步骤中，控制离子源电压为50~90 V，氩气流量200~500sccm，工作压强0.5~1.7Pa，基底偏压为-50~-500 V。
优选的，所述纳米氧化物中含有纳米二氧化硅时，所述纳米二氧化硅的粒径为10nm~100nm。
优选的，所述纳米氧化物中含有纳米三氧化二铝时，所述纳米三氧化二铝的粒径为10nm~100nm。
本发明提供的类金刚石复合层结构，含有表面具有微纳结构阵列的氟掺杂类金刚石层。首先，氟掺杂类金刚石层作为疏水层，可以提高类金刚石层的疏水性能。在此基础上，氟掺杂类金刚石层表面具有微纳结构阵列，可以进一步提高类金刚石层的疏水效果。综上，通过氟掺杂和表面微纳结构阵列的双层改性，所述类金刚石复合层结构具有优异的疏水性能。经接触角实验显示，所述类金刚石复合层结构的接触角（类金刚石层表面）为151.5°至155.0°。此外，所述聚合物衬底具有较好的韧性，且与所述类金刚石层具有较高的结合力，由此形成的类金刚石复合层结构能够作为对韧性和疏水性能要求较高的浸润材料使用，从而拓展了类金刚石的工业应用前景。
 有益效果
本发明提供的类金刚石复合层结构的制备方法，具有以下优点：
首先，本发明通过制备疏水表面来提高类金刚石复合层结构的疏水性。具体的，一方面，先制备聚偏氟乙烯-六氟丙烯的自支撑衬底，所述自支撑衬底具有孔隙结构，因此，在所述自支撑衬底进一步制备类金刚石层时，可以形成表面不平整的类金刚石层。另一方面，在自支撑衬底作为模板形成不平整表面的基础上，对得到的类金刚石层进行刻蚀，从而放大类金刚石层的不平整结构，形成表面具有微纳结构阵列的疏水表面。
其次，本发明通过多膜层进行掺杂进一步提高疏水效果。具体的，一方面，在制备聚偏氟乙烯-六氟丙烯的自支撑衬底时，添加有纳米二氧化硅、纳米三氧化二铝中的至少一种。在聚偏氟乙烯-六氟丙烯中分散纳米二氧化硅和/或纳米三氧化二铝，提高表面的微观粗糙结构和降低表面能，从而进一步提高类金刚石层的疏水效果。此外，所述纳米二氧化硅、纳米三氧化二铝的添加，还能提高自支撑衬底的力学性能。另一方面，通过对类金刚石层进行氟掺杂，提高类金刚石层的疏水性能。
经接触角实验显示，经本发明方法制备的类金刚石复合层结构，具有优异的疏水性能。经接触角实验显示，所述类金刚石复合层结构的接触角（类金刚石层表面）为151.5°至155.0°。
 附图说明
图1是本发明实施例提供的类金刚石复合层结构的结构示意图；
图2是本发明实施例1提供的类金刚石复合层结构的接触角测试结果图。
 本发明的实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
在本发明的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
类金刚石涂层，由于其优异的性质，特别是高硬度和良好的耐刮磨性能，已越来越多地应用于各行业中，从机械制造领域到光学电子领域，从医学领域到航空航天领域。然而，也正是由于类金刚石材料本身的物质属性，类金刚石材料不具备疏水性能，难以用于对疏水性能要求较好的技术中。鉴于此，本发明旨在提供一种具有超疏水能力的类金刚石复合层结构的制备方法，以及对应的具有超疏水能力的类金刚石复合层结构。
结合图1，本发明实施例第一方面提供一种类金刚石复合层结构，所述类金刚石复合层结构包括聚合物衬底10，设置在所述自支撑衬底表面的氟掺杂类金刚石层20，其中，氟掺杂类金刚石层20背离所述聚合物衬底10的表面为微纳阵列表面。
所述类金刚石复合层结构包括两层结构，具体的，包括聚合物衬底10，以及设置所述聚合物衬底10表面的氟掺杂类金刚石层20。下面对各层进行详细描述。
聚合物衬底10
本发明实施例中，聚合物衬底10具有较好的韧性，作为硬度类金刚石复合层结构的承载层，与氟掺杂类金刚石层20的结合力之间具有较好的结合力，可以变相为氟掺杂类金刚石层20塑形，拓展类金刚石复合层结构的应用范围。
进一步的，本发明实施例中，聚合物衬底10含有微孔结构，特别是聚合物衬底10与氟掺杂类金刚石层20接触的表面，均匀分布有微孔结构，具有微孔结构或微孔结构表面的聚合物衬底10作为氟掺杂类金刚石层20的承载层，可以将表面分布的微孔结构传递给氟掺杂类金刚石层20，从而为氟掺杂类金刚石层20提供不平整的表面，提高氟掺杂类金刚石层20的疏水性。
优选的，所述聚合物衬底10为聚偏氟乙烯-六氟丙烯衬底。所述聚偏氟乙烯-六氟丙烯为偏氟乙烯和六氟丙烯的共聚物。优选的，偏氟乙烯和六氟丙烯的共聚物不仅具有很好的任性，而且与氟掺杂类金刚石层20之间具有很好的结合力。进一步的，所述聚偏氟乙烯-六氟丙烯衬底为膜层中分散有纳米二氧化硅和/或纳米三氧化二铝的聚偏氟乙烯-六氟丙烯衬底，即所述聚偏氟乙烯-六氟丙烯衬底中分散有纳米二氧化硅和/或纳米三氧化二铝。通过在所述聚偏氟乙烯-六氟丙烯衬底中掺杂纳米二氧化硅和/或纳米三氧化二铝，可以提高所述聚偏氟乙烯-六氟丙烯衬底的力学性能，更重要的是，在聚合物衬底10中添加纳米二氧化硅和/或纳米三氧化二铝，可以提高表面的微观粗糙结构和降低表面能，从而进一步提高氟掺杂类金刚石层20的疏水性。
当所述聚合物衬底10中添加纳米二氧化硅和/或纳米三氧化二铝时，所述纳米二氧化硅、所述纳米三氧化二铝的粒径不宜过大。当所述所述纳米二氧化硅、所述纳米三氧化二铝的粒径过大，不利于所述纳米二氧化硅、所述纳米三氧化二铝的均匀分散，进而影响类金刚石复合层结构的疏水性。鉴于此，所述聚合物衬底10中分散有纳米二氧化硅时，所述纳米二氧化硅的粒径为10nm~100nm，更优选为20nm~50nm；所述聚合物衬底10中分散有纳米三氧化二铝时，所述纳米三氧化二铝的粒径为10nm~100nm，更优选为20nm~50nm。
优选的，聚合物衬底10的厚度为200微米~800微米，更优选的，所述自支撑衬底的厚度为400微米~600微米。合适厚度的聚合物衬底10，可以形成自支撑结构，同时，赋予类金刚石复合层结构良好的韧性。若聚合物衬底10的厚度过薄，且膜层较脆，不足以支撑硬度很高的类金刚石层。
氟掺杂类金刚石
本发明实施例中，一方面，在类金刚石层中进行氟掺杂，提高类金刚石层的疏水性；另一方面，氟掺杂类金刚石层20背离聚合物衬底10的表面为微纳阵列表面，从而赋予氟掺杂类金刚石层20优异的超疏水性能。
在一些实施例中，以所述氟掺杂类金刚石层20的总重量为100%计，氟的掺杂含量为10wt%~35wt%。类金刚石中掺杂氟元素可以提高sp 2杂化水平，薄膜极化强度减小，与水的浸润性变差，接触角增大。但若所述氟掺杂类金刚石层20中，氟的掺杂量过低，则对改善类金刚石层的疏水性影响不明显；若所述氟掺杂类金刚石层20中，氟的掺杂量过高，较大的氟含量会导薄膜表面的颗粒较大，表面能增加，导致接触角降低。
优选的，氟掺杂类金刚石层20的厚度为0.5微米~1.2微米，该厚度范围，具有较好的普遍适应性，基本能满足使用类金刚石涂层的行业要求，此外，该厚度范围可以通过沉积制备，从而可以保证得到的氟掺杂类金刚石涂层具有较好的质量。
在一些实施例中，氟掺杂类金刚石层20的微纳阵列表面中，微纳阵列的高度为0.5微米~1.2微米，微纳阵列中相邻微纳单元的间距为0.1微米~1.2微米。此时，氟掺杂类金刚石层20具有较好的表面结构，从而具有优异的超疏水性能。在优选的实施例中，氟掺杂类金刚石层20的微纳阵列结构中，微纳单元的高度和相邻微纳单元的间距的比为1：（0.5~1.5），此时氟掺杂类金刚石层20具有更优异的超疏水性能，接触角在153°至155°之间。
在上述实施例的基础上，作为一种具体优选实施方式，所述类金刚石复合层结构由聚合物衬底10以及设置所述聚合物衬底10表面的氟掺杂类金刚石层20组成。
本发明实施例提供的类金刚石复合层结构，含有表面具有微纳结构阵列的氟掺杂类金刚石层20。首先，氟掺杂类金刚石层20作为疏水层，可以提高类金刚石层的疏水性能。在此基础上，氟掺杂类金刚石层20表面具有微纳结构阵列，可以进一步提高类金刚石层的疏水效果。综上，通过氟掺杂和表面微纳结构阵列的双层改性，所述类金刚石复合层结构具有优异的疏水性能。经接触角实验显示，所述类金刚石复合层结构的接触角（类金刚石层表面）为151.5°至155.0°。此外，所述聚合物衬底10具有较好的韧性，且与所述类金刚石层具有较高的结合力，由此形成的类金刚石复合层结构能够作为对韧性和疏水性能要求较高的浸润材料使用，从而拓展了类金刚石的工业应用前景。
本发明实施例提供的类金刚石复合层结构，可以通过下述方法制备获得。
相应的，本发明实施例第二方面提供一种类金刚石复合层结构的制备方法，包括以下步骤：
S01.提供聚偏氟乙烯-六氟丙烯的有机溶液，在所述有机溶液中加入邻苯二甲酸二丁酯和纳米氧化物，加热处理形成混合浆料，将所述混合浆料沉积在基底上，干燥处理，将得到的膜层置于有机醇中浸泡处理，以溶解所述邻苯二甲酸二丁酯，制备具有孔隙结构的自支撑衬底，其中，所述纳米氧化物选自纳米二氧化硅、纳米三氧化二铝中的至少一种；
S02.将所述自支撑衬底依次进行辉光清洗和离子刻蚀清洗后，置于沉积室中，通入四氟甲烷气体，开启高纯碳靶，在所述自支撑衬底的表面沉积氟掺杂类金刚石层；
S03.开启离子源对所述氟掺杂类金刚石层进行刻蚀处理，制备表面具有微纳结构阵列的氟掺杂类金刚石层。
本发明实施例提供的类金刚石复合层结构的制备方法，具有以下优点：
首先，本发明实施例通过制备疏水表面来提高类金刚石复合层结构的疏水性。具体的，一方面，先制备聚偏氟乙烯-六氟丙烯的自支撑衬底，所述自支撑衬底具有孔隙结构，因此，在所述自支撑衬底进一步制备类金刚石层时，可以形成表面不平整的类金刚石层。另一方面，在自支撑衬底作为模板形成不平整表面的基础上，对得到的类金刚石层进行刻蚀，从而放大类金刚石层的不平整结构，形成表面具有微纳结构阵列的疏水表面。
其次，本发明实施例通过多膜层进行掺杂进一步提高疏水效果。具体的，一方面，在制备聚偏氟乙烯-六氟丙烯的自支撑衬底时，添加有纳米二氧化硅、纳米三氧化二铝中的至少一种。在聚偏氟乙烯-六氟丙烯中分散纳米二氧化硅和/或纳米三氧化二铝，提高表面的微观粗糙结构和降低表面能，从而进一步提高类金刚石层的疏水效果。此外，所述纳米二氧化硅、纳米三氧化二铝的添加，还能提高自支撑衬底的力学性能。另一方面，通过对类金刚石层进行氟掺杂，提高类金刚石层的疏水性能。
经接触角实验显示，经本发明实施例方法制备的类金刚石复合层结构，具有优异的疏水性能。经接触角实验显示，所述类金刚石复合层结构的接触角（类金刚石层表面）为151.5°至155.0°。
具体的，上述步骤S01中，提供聚偏氟乙烯-六氟丙烯的有机溶液，在一些实施例中，所述聚偏氟乙烯-六氟丙烯的有机溶液为聚偏氟乙烯-六氟丙烯的丙酮溶液。在另一些实施例中，所述聚偏氟乙烯-六氟丙烯的有机溶液为聚偏氟乙烯-六氟丙烯的N-甲基吡咯烷酮溶液。所述丙酮、所述N-甲基吡咯烷酮对所述聚偏氟乙烯-六氟丙烯具有较好的溶解性，同时也能够有效溶解邻苯二甲酸二丁酯、分散纳米氧化物，从而形成均匀的浆料，并能够在溶液成膜时具有较好的铺展性。
在所述有机溶液中加入邻苯二甲酸二丁酯和纳米氧化物，其中，所述邻苯二甲酸二丁酯作为造孔剂，能够均匀分散在成膜物质（聚偏氟乙烯-六氟丙烯）中，在成膜过程中占据合适的位点，并经后续步骤中去除，为聚偏氟乙烯-六氟丙烯自支撑衬底提供微孔结构。以所述聚偏氟乙烯-六氟丙烯、邻苯二甲酸二丁酯和纳米氧化物的总重量为100%计，所述邻苯二甲酸二丁酯的重量百分含量范围为20%~60%，由此可以形成合适数量和大小的微孔结构，保证形成的自支撑衬底的微孔表面能够有效传递给氟掺杂的类金刚石膜层。若所述邻苯二甲酸二丁酯的含量过低，则形成的微孔结构过少，得到的自支撑衬底表面微结构不明显，对应的，在自支撑衬底形成的氟掺杂类金刚石层也就不具备对应的微孔结构。
所述纳米氧化物选自纳米二氧化硅、纳米三氧化二铝中的至少一种。所述纳米二氧化硅、纳米三氧化二铝的添加，能够提高氟掺杂类金刚石层的疏水性。所述纳米氧化物中含有纳米二氧化硅时，所述纳米二氧化硅的粒径为10nm~100nm。所述纳米氧化物中含有纳米三氧化二铝时，所述纳米三氧化二铝的粒径为10nm~100nm。
在所述有机溶液中加入邻苯二甲酸二丁酯和纳米氧化物，可以将邻苯二甲酸二丁酯和纳米氧化物同时加入有机溶液中，也可以将邻苯二甲酸二丁酯和纳米氧化物一前一后加入有机溶液中。在优选实施例中，先将邻苯二甲酸二丁酯加入有机溶液形成均匀的混合溶液，然后在混合溶液中加入纳米氧化物，有利于提高纳米氧化物的分散性，进而提高类金刚石复合层结构的疏水稳定性。进一步优选的，在混合溶液中加入纳米氧化物后，在40-80℃下水浴加热搅拌2-8 小时，提高纳米氧化物的分散性能。
在上述实施例的基础上，优选的，所述聚偏氟乙烯-六氟丙烯的有机溶液中，聚偏氟乙烯-六氟丙烯的浓度为0.01~0.1g/ml，从而保证形成的膜层的致密性，并保证合适的膜层厚度。
优选的，所述混合浆料中，所述邻苯二甲酸二丁酯的浓度为0.05~0.2g/ml，若所述邻苯二甲酸二丁酯的浓度过高，会导致表面孔较大，破坏表面的微纳结构。
优选的，所述混合浆料中，所述纳米氧化物为纳米二氧化硅时，所述纳米二氧化硅的浓度为0.01~0.08g/ml；所述纳米氧化物为纳米三氧化二铝时，所述纳米三氧化二铝的浓度为0.01~0.08g/ml；所述纳米氧化物为纳米二氧化硅和纳米三氧化二铝时，所述纳米二氧化硅和纳米三氧化二铝的总浓度为0.01~0.08g/ml。在此范围内，增纳米氧化物的含量可以提高表面粗糙度，增加接触角。但纳米氧化物的浓度太大，会导致表面粗糙度过大，降低接触角，且会导致膜层变得较脆。
将得到的混合浆料沉积在基底上，沉积方式没有严格的限定，在一些实施例中，可采用刮刀将混合浆料沉积在玻璃板上涂覆均匀，但不限于此。进一步的，将在沉积有混合浆料的基底进行干燥成膜。优选的，所述干燥成膜的温度不宜过高，过高的温度不仅会破坏膜层中的聚合物被破坏，而且容易导致得到的膜层厚度不均、卷曲。鉴于此，将在沉积有混合浆料的基底进行干燥成膜在50℃-80℃的条件下进行，优选干燥6-12 h。
进一步的，将干燥后得到的膜层置于有机醇中浸泡处理，以溶解所述邻苯二甲酸二丁酯，保留膜层中的提供聚偏氟乙烯-六氟丙烯以及分散中提供聚偏氟乙烯-六氟丙烯中的纳米氧化物，制备具有孔隙结构的自支撑衬底。具体优选的，将干燥后得到的膜层放入甲醇中浸泡12-48 h，然后将样品放入鼓风干燥箱中80~120℃烘干，自支撑衬底制作完成。
上述步骤S02中，将所述自支撑衬底依次进行辉光清洗和离子刻蚀清洗，通过辉光清洗和离子刻蚀清洗去除自支撑衬底表面不平整处如刮痕中残留的水分、气体等，从而为提高涂层的附着效果。通过逐步清洗，达到最佳的清洗效果，涂层在清洗后的自支撑衬底上具有最好的结合力。
在一些实施例中，将烘干后的自支撑衬底固装夹定在夹具中，并固定在离子源/电弧离子镀复合镀膜设备中的转架上；抽真空。当真空室压强达到3.2×10 -3 Pa时，开始对所述自支撑衬底进行辉光清洗。
在具体实施例中，所述辉光清洗的方法为：打开氩气瓶主阀、减压阀、离子源阀、弧阀和靶阀以及质量流量计，向真空室内通入氩气，控制氩气流量300~500sccm，工作压强为1.0~1.7 Pa，基底偏压-500~-800V，对自支撑衬底进行辉光清洗，清洗时间10~30min。在上述条件下进行辉光清洗，可以将藏留在所述自支撑衬底微孔结构中的水分、气体快速清除，防止后续通过离子源磁控溅射沉积类金刚石层时膜层附着力不够，提高膜层在所述自支撑衬底上的结合力。
为了进一步保证所述自支撑衬底微孔结构中的水分、气体被充分去除，在辉光清洗结束后，对所述自支撑衬底进行离子刻蚀清洗，通过相对柔和的方式，将自支撑衬底不平整表面特别是微孔结构中的水分、气体完全去除。其中，所述离子刻蚀清洗采用氩气在离子源中离化成等离子体，对自支撑衬进行离子轰击清洗。
在一些具体实施例中，所述离子刻蚀清洗的方法为：辉光清洗结束后，开启离子源对样品进行离子轰击清洗，其中，离子源电压为50~90 V，氩气流量200~500sccm，工作压强0.5~1.7Pa，基底偏压为-150~-500 V。在上述条件下，可以将辉光清洗过程中没有去除的水分和气体完全去除。优选的，所述离子轰击清洗的清洗时间为5~15min。
本发明实施例通过对所述自支撑衬底依次进行辉光清洗和离子刻蚀清洗，可以逐级、不同力度地去除所述自支撑衬底表面的各种附着物，提高涂层在所述自支撑衬底表面的附着力；同时，按照该方法对所述自支撑衬底进行表面清洁，还具有很好的时效性。
本发明实施例中，采用离子源增强型磁控溅射的方法，以高纯石墨靶为碳源沉积氟掺杂类金刚石层，不仅可以得到膜层稳定的氟掺杂类金刚石层，而且可以复制所述自支撑衬底表面的微孔结构，形成不平整的氟掺杂类金刚石层表面。具体的，在沉积室中通入四氟甲烷气体，开启高纯碳靶，在所述自支撑衬底的表面沉积氟掺杂类金刚石层。
在优选实施例中，在所述自支撑衬底的表面沉积氟掺杂类金刚石层的步骤中，往沉积室中通入氩气和四氟甲烷气体，控制氩气的流量为100~400sccm，四氟甲烷气体的流量为50~200sccm，调节真空室压强为0.7~1.3 Pa，控制所述高纯碳靶的靶功率为0.6-1.4KW，基底偏压0~-150 V，在所述自支撑衬底的表面沉积氟掺杂类金刚石层。
制备氟掺杂类金刚石层的步骤中，基底偏压影响氟掺杂类金刚石层在自支撑衬底上的结合力，本发明实施例在基底偏压为0~-150 V的条件下，沉积氟掺杂类金刚石层，得到的氟掺杂类金刚石层在自支撑衬底上的结合力较好。
制备氟掺杂类金刚石层的步骤中，所述高纯碳靶的靶功率和四氟甲烷气体的流量，共同决定了氟掺杂类金刚石层的氟含量。若所述靶功率和四氟甲烷气体的流量中的任意一项发生变化，都可能影响氟的掺杂含量。本发明实施例提供的氟掺杂类金刚石层的制备方法，所述高纯碳靶的靶功率和四氟甲烷气体流量在上述范围内，能够控制氟的掺杂含量在10wt%~35wt%的范围内，从而得到疏水性更好的氟掺杂类金刚石层。
此外，制备氟掺杂类金刚石层的步骤中，真空室的压强对得到氟掺杂类金刚石层的质量有一定影响。本发明实施例调节真空室压强为0.7~1.3 Pa，得到的的氟掺杂类金刚石层在所述自支撑衬底表面的结合力增强。而若真空室压强过高，沉积速度过快，得到的氟掺杂类金刚石层晶格混乱、排列不规整，会降低氟掺杂类金刚石层在所述自支撑衬底的结合力。
本发明实施例中，在所述自支撑衬底的表面沉积氟掺杂类金刚石层的步骤中，沉积时间为30-60分钟，由此获得合适厚度的氟掺杂类金刚石层。具体的，所述氟掺杂类金刚石层的厚度为0.5微米~1.2微米。
上述步骤S03中，开启离子源对所述氟掺杂类金刚石层进行刻蚀处理，通过刻蚀强化氟掺杂类金刚石层的表面缺陷（表面微孔结构），进而制备表面具有微纳结构阵列的氟掺杂类金刚石层，提高类金刚石复合层结构的疏水性能。
在优选实施例中，开启离子源对所述氟掺杂类金刚石层进行刻蚀处理的步骤中，控制离子源电压为50~90 V，氩气流量200~500sccm，工作压强0.5~1.7Pa，基底偏压为-50~-500 V。通过控制刻蚀处理的参数，使得刻蚀强度合适，能够尽可能的在原有的氟掺杂类金刚石层的表面形状的基础上进行深入，形成维纳结构阵列。
涂层沉积结束后，关闭离子源电源以及偏压电源，然后关闭气体质量流量计和气瓶主阀和减压阀；设置降温程序，待温度降到100℃以下后，关闭高阀，打开放气阀，待真空室内压强与外界气压一致时，打开真空室门，然后将样品取出。
下面结合具体实施例进行说明。
实施例1
一种类金刚石复合层结构的制备方法，包括以下步骤：
S11. 用分析天平称取0.6g PVDF-HFP( 聚偏氟乙烯-六氟丙烯 )溶解在 10ml 丙酮溶液中，添加1g DBP（邻苯二甲酸二丁酯），0.2g的SiO 2（粒径30nm），在60℃下水浴条件下加热搅拌4h 得到混合溶液，用1000um的刮刀将混合溶液在玻璃板上涂敷均匀，然后放入烘箱在80℃下干燥12小时之后，将制备的莫测放入甲醇中浸泡24h，然后将样品放入鼓风干燥箱中80~120℃烘干，制备具有孔隙结构的自支撑衬底。
S12. 将烘干后的自支撑衬底固装夹定在夹具中，并固定在离子源/电弧离子镀复合镀膜设备中的转架上；抽真空。当真空室压强达到3.2×10 -3 Pa时，开始进行辉光清洗，辉光清洗之后进行离子刻蚀清洗。具体的：
辉光清洗：打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀以及质量流量计，向真空室内通入氩气，氩气流量500 sccm，工作压强为1.0 Pa，基底偏压-800 V，对基底进行辉光清洗，清洗时间10 min；
离子刻蚀清洗：辉光清洗结束后，开启离子源对样品进行离子轰击清洗，离子源电压为50 V，氩气流量300 sccm，工作压强0.8 Pa，基底偏压为-150 V；清洗时间为15 min。
离子刻蚀清洗结束后，通入氩气，流量为300 sccm，同时通入四氟甲烷气体，流量为50 sccm，调节真空室压强为0.9 Pa，开启高纯碳靶，靶功率为1 KW，基底偏压-50 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为50 V，氩气流量350 sccm，工作压强0.8 Pa，基底偏压为-100 V；刻蚀时间为10 min。
实施例2
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：
离子刻蚀清洗结束后，通入氩气，流量为200 sccm，同时通入四氟甲烷气体，流量为100 sccm，调节真空室压强为0.9 Pa，开启高纯碳靶，靶功率为1 KW，基底偏压-50 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为50 V，氩气流量300 sccm，工作压强0.7 Pa，基底偏压为-100 V；刻蚀时间为10 min。）。
实施例3
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：
离子刻蚀清洗结束后，通入氩气，流量为220 sccm，同时通入四氟甲烷气体，流量为80 sccm，调节真空室压强为0.9 Pa，开启高纯碳靶，靶功率为1 KW，基底偏压-100 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为50 V，氩气流量300 sccm，工作压强0.7 Pa，基底偏压为-100 V；刻蚀时间为10 min。
实施例4
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：离子刻蚀清洗结束后，通入氩气，流量为230 sccm，同时通入四氟甲烷气体，流量为100 sccm，调节真空室压强为1.5 Pa，开启高纯碳靶，靶功率为1.2 KW，基底偏压-80 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为70 V，氩气流量400 sccm，工作压强0.9 Pa，基底偏压为-200 V；刻蚀时间为10 min。
实施例5
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：离子刻蚀清洗结束后，通入氩气，流量为300 sccm，同时通入四氟甲烷气体，流量为120 sccm，调节真空室压强为1.1 Pa，开启高纯碳靶，靶功率为0.9 KW，基底偏压-120 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为60 V，氩气流量200 sccm，工作压强1.5 Pa，基底偏压为-300 V；刻蚀时间为10 min。
实施例6
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：离子刻蚀清洗结束后，通入氩气，流量为280 sccm，同时通入四氟甲烷气体，流量为90 sccm，调节真空室压强为0.8 Pa，开启高纯碳靶，靶功率为1 KW，基底偏压-130 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为80 V，氩气流量250 sccm，工作压强0.9 Pa，基底偏压为-160 V；刻蚀时间为10 min。
实施例7
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：离子刻蚀清洗结束后，通入氩气，流量为260 sccm，同时通入四氟甲烷气体，流量为150 sccm，调节真空室压强为1.1 Pa，开启高纯碳靶，靶功率为1.2 KW，基底偏压-150 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为80 V，氩气流量320 sccm，工作压强0.7 Pa，基底偏压为-150 V；刻蚀时间为10 min。
实施例8
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：离子刻蚀清洗结束后，通入氩气，流量为180 sccm，同时通入四氟甲烷气体，流量为180 sccm，调节真空室压强为0.8 Pa，开启高纯碳靶，靶功率为1 KW，基底偏压-140 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为70 V，氩气流量350 sccm，工作压强0.8 Pa，基底偏压为-180 V；刻蚀时间为10 min。
实施例9
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：离子刻蚀清洗结束后，通入氩气，流量为280 sccm，同时通入四氟甲烷气体，流量为120 sccm，调节真空室压强为0.9 Pa，开启高纯碳靶，靶功率为1.2 KW，基底偏压-150 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为70 V，氩气流量340 sccm，工作压强0.8 Pa，基底偏压为-160 V；刻蚀时间为10 min。
实施例10
一种类金刚石复合层结构的制备方法，与实施例1的不同之处在于：离子刻蚀清洗结束后，通入氩气，流量为220 sccm，同时通入四氟甲烷气体，流量为60 sccm，调节真空室压强为0.8 Pa，开启高纯碳靶，靶功率为1 KW，基底偏压-150 V进行类金刚石涂层的沉积，沉积时间为60 min，制备氟掺杂类金刚石层。
S13. 开启离子源对氟掺杂类金刚石涂层进行刻蚀，控制离子源电压为70 V，氩气流量380 sccm，工作压强0.8 Pa，基底偏压为-180 V；刻蚀时间为10 min。
对比例1
一种类金刚石涂层的制备方法，包括以下步骤：
提供基底，将基底预处理后，固装夹定在夹具中，并固定在离子源/电弧离子镀复合镀膜设备中的转架上；抽真空。当真空室压强达到3.2×10 -3 Pa时，开始进行辉光清洗，辉光清洗之后进行离子刻蚀清洗。具体的：
辉光清洗：打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀以及质量流量计，向真空室内通入氩气，氩气流量500 sccm，工作压强为1.0 Pa，基底偏压-800 V，对基底进行辉光清洗，清洗时间10 min；
离子刻蚀清洗：辉光清洗结束后，开启离子源对样品进行离子轰击清洗，离子源电压为50 V，氩气流量300 sccm，工作压强0.8 Pa，基底偏压为-150 V；清洗时间为15 min。
离子刻蚀清洗结束后，通入氩气，流量为300 sccm，同时通入四氟甲烷气体，流量为50 sccm，调节真空室压强为0.9 Pa，开启高纯碳靶，靶功率为1 KW，基底偏压-50 V进行类金刚石涂层的沉积，沉积时间为60 min。
将实施例1-3制备的类金刚石复合层结构以及对比例1制备的类金刚石涂层进行水接触角测试实验，测试方法如下：
测试结果如下表1所示，其中，实施例1的测试结果图如图2所示。
表1
测试电池 L水接触角(°) R水接触角(°) CA(°)
实施例1 151.961 151.877 151.919
实施例2 152.281 152.714 152.498
实施例3 151.635 151.852 151.744
实施例4 152.153 152.394 152.274
实施例5 152.568 152.386 152.477
实施例6 151.886 151.986 151.936
实施例7 153.653 153.731 153.692
实施例8 152.653 152.139 152.396
实施例9 152.785 152.631 152.708
实施例10 151.900 151.800 151.850
对比例1 131.056 130.875 130.965
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种类金刚石复合层结构的制备方法，其特征在于，包括以下步骤：
    提供聚偏氟乙烯-六氟丙烯的有机溶液，在所述有机溶液中加入邻苯二甲酸二丁酯和纳米氧化物，加热处理形成混合浆料，将所述混合浆料沉积在基底上，干燥处理，将得到的膜层置于有机醇中浸泡处理，以溶解所述邻苯二甲酸二丁酯，制备具有孔隙结构的自支撑衬底，其中，所述纳米氧化物选自纳米二氧化硅、纳米三氧化二铝中的至少一种；
    将所述自支撑衬底依次进行辉光清洗和离子刻蚀清洗后，置于沉积室中，通入四氟甲烷气体，开启高纯碳靶，在所述自支撑衬底的表面沉积氟掺杂类金刚石层；
    开启离子源对所述氟掺杂类金刚石层进行刻蚀处理，制备表面具有微纳结构阵列的氟掺杂类金刚石层。
  2. 如权利要求1所述的类金刚石复合层结构的制备方法，其特征在于，所述聚偏氟乙烯-六氟丙烯的有机溶液为聚偏氟乙烯-六氟丙烯的丙酮溶液，或所述聚偏氟乙烯-六氟丙烯的有机溶液为聚偏氟乙烯-六氟丙烯的N-甲基吡咯烷酮溶液。
  3. 如权利要求2所述的类金刚石复合层结构的制备方法，其特征在于，所述聚偏氟乙烯-六氟丙烯的有机溶液中，聚偏氟乙烯-六氟丙烯的浓度为0.01~0.1g/ml。
  4. 如权利要求3所述的类金刚石复合层结构的制备方法，其特征在于，所述混合浆料中，所述邻苯二甲酸二丁酯的浓度为0.05~0.2g/ml，和/或
    所述混合浆料中，所述纳米氧化物为纳米二氧化硅时，所述纳米二氧化硅的浓度为0.01~0.08g/ml；所述纳米氧化物为纳米三氧化二铝时，所述纳米三氧化二铝的浓度为0.01~0.08g/ml；所述纳米氧化物为纳米二氧化硅和纳米三氧化二铝时，所述纳米二氧化硅和纳米三氧化二铝的总浓度为0.01~0.08g/ml。
  5. 如权利要求1至4任一项所述的类金刚石复合层结构的制备方法，其特征在于，在所述自支撑衬底的表面沉积氟掺杂类金刚石层的步骤中，往沉积室中通入氩气和四氟甲烷气体，控制氩气的流量为100~400sccm，四氟甲烷气体的流量为50~200sccm，调节真空室压强为0.7~1.3 Pa，控制所述高纯碳靶的靶功率为0.6-1.4KW，基底偏压0~-150 V，在所述自支撑衬底的表面沉积氟掺杂类金刚石层。
  6. 如权利要求1至4任一项所述的类金刚石复合层结构的制备方法，其特征在于，开启离子源对所述氟掺杂类金刚石层进行刻蚀处理的步骤中，控制离子源电压为50~90 V，氩气流量200~500sccm，工作压强0.5~1.7Pa，基底偏压为-50~-500 V。
  7. 如权利要求1至4任一项所述的类金刚石复合层结构的制备方法，其特征在于，所述纳米氧化物中含有纳米二氧化硅时，所述纳米二氧化硅的粒径为10nm~100nm；
    所述纳米氧化物中含有纳米三氧化二铝时，所述纳米三氧化二铝的粒径为10nm~100nm。
  8. 一种类金刚石复合层结构，其特征在于，所述类金刚石复合层结构包括聚合物衬底，设置在所述自支撑衬底表面的氟掺杂类金刚石层，其中，所述氟掺杂类金刚石层背离所述聚合物衬底的表面为微纳阵列表面。
  9. 如权利要求8所述的类金刚石复合层结构，其特征在于，所述氟掺杂类金刚石层的厚度为0.5微米~1.2微米；和/或
    所述聚合物衬底的厚度为200微米~800微米。
  10. 如权利要求8所述的类金刚石复合层结构，其特征在于，所述聚合物衬底为聚偏氟乙烯-六氟丙烯衬底，且所述聚偏氟乙烯-六氟丙烯衬底中分散有纳米二氧化硅和/或纳米三氧化二铝。
PCT/CN2019/124312 2018-12-14 2019-12-10 超疏水类金刚石复合层结构及其制备方法 WO2020119680A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811532808.9A CN111321380B (zh) 2018-12-14 2018-12-14 超疏水类金刚石复合层结构及其制备方法
CN201811532808.9 2018-12-14

Publications (1)

Publication Number Publication Date
WO2020119680A1 true WO2020119680A1 (zh) 2020-06-18

Family

ID=71076051

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/124312 WO2020119680A1 (zh) 2018-12-14 2019-12-10 超疏水类金刚石复合层结构及其制备方法

Country Status (2)

Country Link
CN (1) CN111321380B (zh)
WO (1) WO2020119680A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686807A (zh) * 2022-04-03 2022-07-01 浙江大学杭州国际科创中心 一种超薄四面体非晶碳膜的制备工艺
CN114959585A (zh) * 2022-06-14 2022-08-30 上海锐畅医疗科技有限公司 一种生物医用复合涂层及其制备方法
CN116288347A (zh) * 2023-03-01 2023-06-23 纳狮新材料有限公司杭州分公司 减少腐蚀磨损方法及海洋环境表面耐腐蚀磨损氟化碳基膜
CN116555907A (zh) * 2023-04-28 2023-08-08 哈尔滨工业大学 仿生自清洁多晶金刚石的制备方法
CN117966133A (zh) * 2024-03-22 2024-05-03 华中光电技术研究所(中国船舶集团有限公司第七一七研究所) 一种光学窗口低应力疏水保护薄膜及其制备方法
US12098892B2 (en) 2022-02-18 2024-09-24 Hyundai Motor Company Laminate for radiational cooling, and method for preparing the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7851045B2 (en) * 2000-07-06 2010-12-14 Saint-Gobain Glass France Transparent textured substrate and methods for obtaining same
CN102582137A (zh) * 2012-01-13 2012-07-18 苏州羿日新能源有限公司 自清洁防雾元件及其制造方法
CN103804708A (zh) * 2012-11-14 2014-05-21 海洋王照明科技股份有限公司 聚偏氟乙烯-六氟丙烯基凝胶聚合物膜及其制备和应用
US8741158B2 (en) * 2010-10-08 2014-06-03 Ut-Battelle, Llc Superhydrophobic transparent glass (STG) thin film articles
CN105549128A (zh) * 2014-10-22 2016-05-04 乐金显示有限公司 功能性单层膜和具有该功能性单层膜的显示装置
CN108948889A (zh) * 2017-05-18 2018-12-07 通用汽车环球科技运作有限责任公司 有纹理的自清洁膜系统以及用于形成该膜系统的方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW431003B (en) * 1999-05-31 2001-04-21 Ind Tech Res Inst Polycarbonate electrolyte and its application on lithium battery
CN102585280B (zh) * 2011-12-30 2013-08-07 黑龙江省科学院大庆分院 一种碳材料改性多孔聚合物电解质膜的制备方法
CN103474601A (zh) * 2013-08-23 2013-12-25 江苏华东锂电技术研究院有限公司 复合隔膜及其制备方法，以及锂离子电池
JP6176035B2 (ja) * 2013-09-30 2017-08-09 日産自動車株式会社 微細表面構造体及びその製造方法
US9809712B2 (en) * 2013-11-26 2017-11-07 Baker Hughes, A Ge Company, Llc Hydrophobic and oleophobic coatings
CN106809795A (zh) * 2015-11-27 2017-06-09 中国科学院苏州纳米技术与纳米仿生研究所 一种超疏水微结构及其制备方法
CN106756820B (zh) * 2016-12-01 2019-04-05 深圳先进技术研究院 含类金刚石复合涂层及其制备方法
CN106835011B (zh) * 2016-12-20 2019-06-25 深圳先进技术研究院 一种具有类金刚石阵列的结构件及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7851045B2 (en) * 2000-07-06 2010-12-14 Saint-Gobain Glass France Transparent textured substrate and methods for obtaining same
US8741158B2 (en) * 2010-10-08 2014-06-03 Ut-Battelle, Llc Superhydrophobic transparent glass (STG) thin film articles
CN102582137A (zh) * 2012-01-13 2012-07-18 苏州羿日新能源有限公司 自清洁防雾元件及其制造方法
CN103804708A (zh) * 2012-11-14 2014-05-21 海洋王照明科技股份有限公司 聚偏氟乙烯-六氟丙烯基凝胶聚合物膜及其制备和应用
CN105549128A (zh) * 2014-10-22 2016-05-04 乐金显示有限公司 功能性单层膜和具有该功能性单层膜的显示装置
CN108948889A (zh) * 2017-05-18 2018-12-07 通用汽车环球科技运作有限责任公司 有纹理的自清洁膜系统以及用于形成该膜系统的方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12098892B2 (en) 2022-02-18 2024-09-24 Hyundai Motor Company Laminate for radiational cooling, and method for preparing the same
CN114686807A (zh) * 2022-04-03 2022-07-01 浙江大学杭州国际科创中心 一种超薄四面体非晶碳膜的制备工艺
CN114686807B (zh) * 2022-04-03 2023-10-27 浙江大学杭州国际科创中心 一种超薄四面体非晶碳膜的制备工艺
CN114959585A (zh) * 2022-06-14 2022-08-30 上海锐畅医疗科技有限公司 一种生物医用复合涂层及其制备方法
CN114959585B (zh) * 2022-06-14 2023-12-01 上海锐畅医疗科技有限公司 一种生物医用复合涂层及其制备方法
CN116288347A (zh) * 2023-03-01 2023-06-23 纳狮新材料有限公司杭州分公司 减少腐蚀磨损方法及海洋环境表面耐腐蚀磨损氟化碳基膜
CN116555907A (zh) * 2023-04-28 2023-08-08 哈尔滨工业大学 仿生自清洁多晶金刚石的制备方法
CN116555907B (zh) * 2023-04-28 2024-05-03 哈尔滨工业大学 仿生自清洁多晶金刚石的制备方法
CN117966133A (zh) * 2024-03-22 2024-05-03 华中光电技术研究所(中国船舶集团有限公司第七一七研究所) 一种光学窗口低应力疏水保护薄膜及其制备方法

Also Published As

Publication number Publication date
CN111321380B (zh) 2023-05-26
CN111321380A (zh) 2020-06-23

Similar Documents

Publication Publication Date Title
WO2020119680A1 (zh) 超疏水类金刚石复合层结构及其制备方法
TWI834975B (zh) 超疏水膜層及其製備方法和產品
CN111254391B (zh) 超疏水类金刚石复合层及其制备方法
CN106637085A (zh) 一种疏水薄膜及其制备方法和应用
CN117448827B (zh) 用于人工关节摩擦表面的低粗糙度氮化钛涂层及制备方法
CN112030108B (zh) 一种有机-金属纳米复合薄膜及其制备方法和应用
CN108396306A (zh) 一种低温沉积硬度可控的类金刚石复合薄膜的方法
CN108893711B (zh) 利用离子束加厚非晶四面体碳涂层的方法及装置及涂层
CN210727894U (zh) 超疏水医疗器具
CN111155052A (zh) 一种Er2O3涂层的制备方法及应用
CN108645061B (zh) 多层复合太阳光谱选择性吸收涂层及其制备方法
CN116377405A (zh) 一种基于Ta元素掺杂的VO2薄膜的制备方法
WO2023279474A1 (zh) 超浸润涂层的制备方法
CN109338304A (zh) 一种透明超疏水薄膜、其制备方法及应用
CN108554745A (zh) 一种dlc膜层的表面处理方法
CN114082617A (zh) 一种与基底间强附着力的疏水涂层及其制备方法
CN108642446B (zh) 一种多孔CrN涂层及其制备方法和一种超级电容器
CN106186719A (zh) 一种利用高温处理制备石墨烯透明导电薄膜的方法
CN103811240A (zh) 碳纳米管阴极的制备方法
CN113564527B (zh) 一种抗辐照无氢碳膜聚合物润滑材料及其制备方法和应用
CN210506520U (zh) 一种在超级马氏体不锈钢表面制备dlc薄膜的装置
CN117779032A (zh) 一种高结合性耐高温复合涂层及其制备方法
WO2022217679A1 (zh) 一种碳纤维改性方法及其产品
CN114381709A (zh) 涂层、用途及制备方法
CN105331930B (zh) 一种采用磁控溅射及真空热处理制备耐酸碱纳米哈氏合金涂层的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19895311

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 19895311

Country of ref document: EP

Kind code of ref document: A1