WO2019119487A1 - 羟基石墨烯改性镀层封闭剂及其制备方法 - Google Patents

羟基石墨烯改性镀层封闭剂及其制备方法 Download PDF

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WO2019119487A1
WO2019119487A1 PCT/CN2017/118728 CN2017118728W WO2019119487A1 WO 2019119487 A1 WO2019119487 A1 WO 2019119487A1 CN 2017118728 W CN2017118728 W CN 2017118728W WO 2019119487 A1 WO2019119487 A1 WO 2019119487A1
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graphene
hydroxy
agent
film
sealant according
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PCT/CN2017/118728
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English (en)
French (fr)
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郭崇武
赖奂汶
李小花
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广州超邦化工有限公司
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Priority to US16/387,180 priority Critical patent/US10619055B2/en
Publication of WO2019119487A1 publication Critical patent/WO2019119487A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • the invention belongs to the field of electroplating, and particularly relates to a zinc-nickel alloy and a zinc-plated hydroxy graphene modified sealing agent and a preparation method thereof.
  • Graphene is a nano-scale carbon material with special functions such as surface effect, small size effect, quantum size effect and macroscopic quantum effect. It also has good corrosion resistance, electrical conductivity and excellent mechanical properties. From graphene in 2004 It has been attracting attention since its discovery, and this material has great application prospects in many fields.
  • Zinc and zinc-nickel alloys have been widely used as anti-corrosion coatings.
  • the coatings are often subjected to sealing treatment after passivation treatment to meet the technical requirements of high-end products in the manufacturing industry.
  • sealing treatment As China moves from a manufacturing power to a manufacturing powerhouse, the existing coating sealants and properties cannot meet the growing technical needs of the electroplating industry.
  • the invention patent No. CN 106318200 A discloses a plating composite sealing agent, which comprises: 50-80 parts of methyl silicone resin, 10 to 30 parts of tetrafluoroethylene, 50 to 60 parts of silica sol, 3 to 10 parts of graphene, 0.5 to 2 parts of a catalyst, 1 to 3 parts of a film-forming agent, 1 to 3 parts of a lubricant, and 3 to 5 parts of a promoter, 5 to 8 parts of the metal corrosion inhibitor, 3 to 5 parts of the surfactant, 1 to 3 parts of the silane coupling agent, 15 to 20 parts of the lower alcohol, and 30 to 50 parts of the water.
  • the composite sealing agent prepared according to the above scheme and then the sealing agent is prepared by adding water with the composite blocking agent, and it is found that the redox graphene will completely sink into the bottom of the blocking liquid after the prepared blocking liquid is left for a period of time, thereby losing the graphite.
  • the properties of the olefin, the formulated blocking solution is reduced to the performance of the ordinary blocking solution.
  • redox graphene generally contains only a small amount of hydrophilic groups, and redox graphene (RGO) prepared by using sodium borohydride as a reducing agent cannot be dissolved in water without an emulsifier.
  • Methyl silicone and silica sol have a large specific surface area and are capable of adsorbing a large amount of surfactant molecules. Therefore, when the composite blocking agent is formulated, the added hydrophobic surfactant is mostly adsorbed on the surface of the silica sol and the methyl silicone colloidal particles, and the remaining surfactant is insufficient to make the redox graphene.
  • the solid particles form a stable emulsion.
  • the redox graphene Due to the high viscosity of the composite blocking agent, the redox graphene does not precipitate from the blocking agent, but after the blocking agent is diluted with water to form a blocking solution, the redox graphene will slowly aggregate and finally precipitate from the blocking solution. come out. If an excessive amount of surfactant is added to emulsify graphene, the surfactant will completely surround the silica sol and the methyl silicone resin particles, and the silica sol and the methyl silicone resin particles cannot be effectively crosslinked during the film formation process, resulting in a closed film. Deterioration in properties such as hardness, wear resistance, and corrosion resistance.
  • the above patent application does not teach the use of the composite sealant. If the composite sealant is not required to be diluted with water, but is directly used for coating, the sealant is used in the application of the coating, and plating. Blocking agents have different meanings. In the electroplating production line, the plated part is directly immersed in the composite sealing agent, and the surface of the plated part will be left with marks and nodules after the trough is dried, and a defective product appears; in addition, the coating formed thereby is thick, and often This results in an oversize of the plated part; therefore, the composite sealant cannot be directly used as a sealer on an electroplating line.
  • the method for preparing redox graphene described in the above patent application is as follows: the graphene is oxidized with concentrated sulfuric acid and concentrated nitric acid, and then reduced with sodium borohydride in an ice bath to obtain a redox graphene suspension, and the redox graphite is used.
  • the composite suspension is formulated directly from the olefin suspension.
  • the redox graphene suspension contains a large amount of nitrate and sulfate, and the corrosive substances are present in the composite sealing agent, which seriously affects the corrosion resistance of the prepared sealing coating, which is one of the above patent applications. Serious technical flaws.
  • the Chinese invention patent “A Highly Efficient and Environmentally Friendly Composite Sealant” with the publication number CN 106085218 A discloses a coating composite sealing agent comprising 50-80 parts of methyl silicone resin, 10-30 parts of alkyd resin, alumina sol. 50 to 60 parts, redox graphene 3 to 10 parts, catalyst 0.5 to 2 parts, film former 1 to 3 parts, lubricant 1 to 3 parts, accelerator 3 to 5 parts, metal corrosion inhibitor 5 to 8 parts 3 to 5 parts of a surfactant, 1 to 3 parts of a silane coupling agent, 15 to 20 parts of a lower alcohol, and 30 to 50 parts of water.
  • the blocking agent is substantially the same as the composite blocking agent disclosed in the invention patent No.
  • CN 106318200 A a modified aqueous composite sealing agent and a preparation method thereof, and the surfactant is adsorbed in a large amount on methyl silicon.
  • the resin colloidal particles On the surface of the resin colloidal particles, there is also a problem that redox graphene is precipitated in the blocking liquid, and nitrate and sulfate corrosive substances are also present in the redox graphene, and the redox graphene suspension is not given.
  • the blocking agent does not give any substance to the catalyst, a film-forming agent, a lubricant, and a promoter, and no specific component is given to the hydrophobic surfactant and the silane coupling agent.
  • the present invention provides a hydroxyl graphene modified plating sealant and a preparation method thereof.
  • a hydroxy graphene modified coating sealant prepared by the following components including the following parts by weight:
  • the resist is an aqueous solution of nano-sized graphene oxide having a mass fraction of 3.5% to 4.0%, and has a pH of 8.0 to 9.5.
  • the resist is a nanometer aqueous solution of hydroxyl graphene having a mass fraction of 3.8%.
  • the film forming material is a mixture of a silica sol and a water soluble silane polymer, the silica sol comprising from 30% to 70% by mass of the film forming material.
  • the silica sol comprises from 50% to 65% by mass of the film forming material.
  • the silica sol is industrial grade, having a silica mass fraction of 40%, a particle size of nanometers, and a pH of 9.0 to 9.5.
  • the water-soluble silane polymer is a water-soluble silane polymer of the product model PU 113 produced by Daikin Chemical of Taiwan.
  • the hydroxy graphene is prepared by adding concentrated sulfuric acid and graphite to the reactor, using potassium permanganate as an oxidant, and preparing the graphene oxide by three-step oxidation at a low temperature, a medium temperature, and a high temperature, using hydrogen peroxide. Reducing excess potassium permanganate, removing the acid and salt in the reaction product by electrodialysis, and then adding 20% sodium hydroxide solution to pH 11-12 to convert the sulfate-based graphene into hydroxyl graphene. The electrodialysis method removes excess sodium hydroxide so that the pH of the hydroxygraphene paste liquid is 8.0 to 9.5.
  • the antifoaming agent is a TANAFOAM S silicone antifoaming agent produced by Dutch Tana Company, and has an effective content of 46% to 49%.
  • the leveling agent is a LA13-863 silicone leveling agent manufactured by the Netherlands Starr Company, and has an effective content of 25%.
  • the blocking agent is prepared by mixing the materials together according to the composition and content of the blocking agent, and uniformly stirring to obtain the blocking agent product to be produced.
  • the method of using the blocking agent is:
  • the blocking agent is diluted 2.5 to 3.5 times with deionized water in a closed tank to obtain a blocking solution
  • the present invention has the following beneficial effects:
  • the blocking agent of the present invention uses hydroxygraphene as a resist, and the hydroxyl group on the surface of the hydroxy graphene in the drying process can dehydrate and condense with the hydroxyl group on the surface of the silica colloid in the silica sol.
  • the hydroxyl group on the surface of the graphene can also be condensed with the hydroxyl group on the silane polymer molecule to form a closed film with high strength, and the sealing of the hydroxyl graphene modified sealer is compared with graphene or redox graphene.
  • the film has higher corrosion resistance and wear resistance;
  • the hydroxy graphene used in the present invention is a nano material and can be uniformly distributed in the three-dimensional network structure of the sealing film. When other components on the surface of the sealing film are etched, the hydroxygraphene will uniformly cover the surface of the sealing layer. Preventing corrosive substances from further destroying the sealing film;
  • the nano-hydroxy graphene used in the invention has high permeability to the pores of the metal plating layer, has strong sealing ability, and can penetrate into the inner part of the pores of the metal plating layer, and the hydroxyl group on the hydroxygraphene can be stably formed with the metal. a compound capable of further increasing the corrosion resistance of the sealing film;
  • the hydroxy graphene used in the present invention has water solubility, and it is not required to emulsify hydroxygraphene with a surfactant as compared with redox graphene, thereby reducing the adverse effect of the surfactant on the performance of the sealing film;
  • the alcohol group in the silane polymer used in the present invention and the metal zinc and nickel can form a stable compound to protect the plating layer, and when the sealing film is scratched, the alcohol groups can spontaneously Cross-linking to form a new sealing film, making the sealing film self-healing;
  • a mixture of a silica sol and a water-soluble silane polymer is used as a film-forming agent, which can increase the flexibility of the sealing film.
  • Example 1 A Hydroxyl Graphene Modified Coating Blocker
  • the film-forming substance comprises a silica sol and a water-soluble silane polymer, the silica sol accounts for 60% of the film-forming substance, and the water-soluble silane polymer accounts for 40% of the mass of the film-forming substance;
  • the silica sol industrial grade, silica mass fraction 40%, particle size nanometer, pH 9.0-9.5;
  • the water-soluble silane polymer Taiwan Daikin Chemical production model is PU 113 water solubility Silane polymer;
  • the resist is made of hydroxygraphene: a 3.8% by weight aqueous solution of hydroxygraphene, having a particle size of nanometers and a pH of 8.0 to 9.5.
  • the defoaming agent is a TANAFOAM S silicone defoaming agent produced by Dutch Tana Company, and the effective content is 46% to 49%.
  • the leveling agent is LA13-863 silicone leveling agent produced by the Netherlands Starr Company, and the effective content is 25%.
  • the materials were mixed together according to the above-mentioned components and content requirements of the blocking agent, and stirred uniformly to obtain a hydroxyl graphene modified blocking agent as described in the present example.
  • the plating part is prepared and sealed by using the hydroxy graphene modified sealing agent of the embodiment, and the specific process is as follows:
  • the blocking agent is diluted 3 times with deionized water in a closed tank to prepare a blocking solution
  • a M8.0 ⁇ 30 screw is rolled by a cyanide-free alkaline zinc bath.
  • the screw material is A3 steel, and the galvanized layer has a thickness of 10 to 12 ⁇ m.
  • the plated parts are passivated with trivalent chromium blue white passivation solution, washed with water and immersed in the blocking liquid for 20s, and dripped after the trough;
  • Example 2 A Hydroxyl Graphene Modified Coating Blocker
  • the film-forming substance comprises a silica sol and a water-soluble silane polymer, the silica sol accounts for 60% of the film-forming substance, and the water-soluble silane polymer accounts for 40% of the mass of the film-forming substance.
  • the silica sol industrial grade, silica mass fraction 40%, particle size nanometer, pH 9.0-9.5.
  • the water-soluble silane polymer a water-soluble silane polymer produced by Taiwan Daikin Chemical Co., Ltd. model number PU 113.
  • the resist is made of hydroxygraphene: a 3.8% by weight aqueous solution of hydroxygraphene, having a particle size of nanometer and having a pH of 8.0 to 9.5.
  • the defoaming agent is a TANAFOAM S silicone defoaming agent produced by Dutch Tana Company, and the effective content is 46% to 49%.
  • the leveling agent is LA13-863 silicone leveling agent produced by the Netherlands Starr Company, and the effective content is 25%.
  • the materials were mixed together according to the above-mentioned composition and content of the blocking agent, and stirred uniformly to obtain the inventive hydroxyl graphene modified blocking agent.
  • the plating part is prepared and sealed by using the hydroxy graphene modified sealing agent of the embodiment, and the specific process is as follows:
  • the blocking agent is diluted 3 times with deionized water in a closed tank to prepare a blocking solution
  • the plated parts are passivated with trivalent chromium blue white passivation solution, washed with water and immersed in the blocking liquid for 20s, and dripped after the trough;
  • the neutral salt spray test was carried out for 320 h according to GB/T 10125-1997 "Artificial Atmosphere Corrosion Test Salt Spray Test". White corrosion occurred on the surface of the coating, and red corrosion occurred on the surface of the coating at 672 h.
  • the conventional plating sealant containing no hydroxyl graphene as described in the comparative example is made of the following materials:
  • the materials used in the blocking agent of this comparative example were the same as in Example 1, and the preparation method was also the same as in Example 1.
  • the plating preparation and sealing process was the same as in Example 1.
  • Neutral salt spray test was carried out for 72 h according to GB/T 10125-1997 "Artificial Atmosphere Corrosion Test Salt Spray Test", and white corrosion was observed on the surface of the coating.
  • Comparative Example 1 The results of Examples 1 and 2 show that the neutral salt spray test of the plated part sealed with the hydroxy graphene modified sealer has a white corrosion time of 312-320 h, which can be seen by using hydroxy graphene.
  • the resist can significantly increase the corrosion resistance of the plated workpiece.
  • the graphene-added plating sealant of the present comparative example was prepared from the following raw materials:
  • the resist is made of graphene: sodium dodecylsulfonate is used as an emulsifier to prepare a graphene paste aqueous solution having a mass fraction of 3.8%, and the particle diameter is nanometer, and the pH is 6.5-7.0.
  • Example 1 The other components were the same as in Example 1, and the preparation method was the same as in Example 1, and the plating member preparation and sealing process was the same as in Example 1.
  • Neutral salt spray test was carried out for 224 h according to GB/T 10125-1997 "Artificial Atmosphere Corrosion Test Salt Spray Test", and white corrosion was observed on the surface of the coating.
  • Comparative Example 2 and Example 2 show that the time of white corrosion of the plated part of the plated part treated with graphene blocking agent is 320 h, and the time of occurrence of white corrosive substance of Comparative Example 2 is 224 h.
  • the use of hydroxy graphene as a resist can significantly increase the corrosion resistance of the plated workpiece.

Abstract

提供一种羟基石墨烯改性镀层封闭剂及其制备方法。该封闭剂包括成膜物质、抗蚀剂、消泡剂、流平剂、去离子水；抗蚀剂为质量分数为3.5％～4％的纳米级羟基石墨烯水溶液，pH值8.0～9.5。该封闭剂使用纳米级羟基石墨烯作为抗蚀剂，羟基石墨烯上的羟基能与成膜物质硅溶胶以及硅烷聚合物中的羟基发生缩合反应，从而显著提高封闭膜的性能，与石墨烯或氧化还原石墨烯相比，封闭膜具有更高的耐蚀性和耐磨性。

Description

羟基石墨烯改性镀层封闭剂及其制备方法 技术领域
本发明属于电镀领域，特别涉及一种锌镍合金及锌镀层羟基石墨烯改性封闭剂及其制备方法。
背景技术
石墨烯为纳米级碳材料，具有表面效应、小尺寸效应、量子尺寸效应、宏观量子效应等特殊功能，又具有良好的耐蚀性、导电性以及优秀的机械性能等特性，从2004年石墨烯被发现以来就一直备受瞩目，而且这种材料在很多领域有着极大的应用前景。
以镀锌和锌镍合金用作防腐镀层已经获得了广泛的应用，为了提高镀层的耐腐蚀性能，镀层钝化处理后往往还需要进行封闭处理，才能满足制造业高端产品的技术要求。随着我国从制造大国向制造强国的迈进，现有的镀层封闭剂及性能已不能满足电镀行业日益增长的技术需求。
申请公布号为CN 106318200 A的中国发明专利《一种改性水性复合封闭剂及其制备方法》公开了一种镀层复合封闭剂，所述封闭剂含有：甲基硅树脂50～80份、聚四氟乙烯10～30份、硅溶胶50～60份、石墨烯3～10份、催化剂0.5～2份、成膜剂1～3份、润滑剂1～3份、促进剂3～5份、金属缓蚀剂5～8份、表面活性剂3～5份、硅烷偶联剂1～3份、低碳醇15～20份、水30～50份。
按上述方案配制的复合封闭剂，然后用所述复合封闭剂加水配制封闭液，试验发现，所配制的封闭液放置一段时间后氧化还原石墨烯会全部沉入封闭液的底部，从而丧失了石墨烯的特性，所配制封闭液降至普通封闭液的性能。
众所周知，氧化还原石墨烯一般只含有少量的亲水基团，用硼氢化钠作还原剂制备的氧化还原石墨烯(RGO)，在没有乳化剂作用下不能够溶于水中。甲基硅树脂和硅溶胶具有很大的比表面积，能吸附大量的表面活性剂分子。因此，所述复合封闭剂在配制时，所加憎水性表面活性剂大部分吸附在硅溶胶和甲基硅树脂胶体微粒的表面上，所剩余的表面活性剂不足以使所述氧化还原石墨烯固体微粒形成稳定的乳状液。由于所述复合封闭剂粘度大，氧化还原石墨烯还不至于从封闭剂中沉淀出来，但将封闭剂加水稀释配成封闭液后，氧化还原石墨烯则会缓慢聚集，最后从封闭液中沉淀出来。如果加入过量的表面活性剂乳化石墨烯，表面活性剂将完全包围硅溶胶和甲基硅树脂微粒，在成膜过程中硅溶胶及甲基硅树脂微粒不能有效交联在一起，导致封闭膜的硬度、耐磨性、耐蚀性等性能的下降。
上述专利申请文件没有给出所述复合封闭剂的使用方法，如果所述复合封闭剂不需加水稀释，而是直接用于镀层涂覆，则所述封闭剂在涂料的应用范畴内，与电镀用封闭剂有着不同的含义。在电镀生产线直接将镀件浸渍在所述复合封闭剂中，出槽烘干后镀件表面将会产生留痕和结瘤，出现不良品；另外，由此形成的涂层较厚，往往会导致镀件尺寸超差；因此，所述复合封闭剂不能直接用作电镀生产线上的封闭剂。
上述专利申请文件所述氧化还原石墨烯制备方法为：将石墨烯用浓硫酸和浓硝酸氧化后，再用硼氢化钠在冰浴下还原得到氧化还原石墨烯悬浮液，并用这种氧化还原石墨烯悬浮液直接配制所述的复合封闭剂。所述氧化还原石墨烯悬浮液中含有大量的硝酸根和硫酸根，这些腐蚀性物质存在于所述复合封闭剂中，会严重影响所制备封闭镀层的耐蚀性，这是上述专利申请中一个严重的技术缺陷。
上述专利申请文件没有给出所述石墨烯悬浮液中石墨烯的含量，也没有给出所述催化剂、成膜剂、润滑剂及促进剂是什么物质，对所述憎水类表面活性剂及硅烷偶联剂也没有给出具体成分，所述技术方案缺乏完整性。
申请公布号为CN 106085218 A的中国发明专利《一种高效环保复合封闭剂》公开了一种镀层复合封闭剂，含有甲基硅树脂50～80份、醇酸树脂10～30份、氧化铝溶胶50～60份、氧化还原石墨烯3～10份、催化剂0.5～2份、成膜剂1～3份、润滑剂1～3份、促进剂3～5份、金属缓蚀剂5～8份、表面活性剂3～5份、硅烷偶联剂1～3份、低碳醇15～20份、水30～50份。所述封闭剂与申请公布号为CN 106318200 A公开的发明专利《一种改性水性复合封闭剂及其制备方法》所述复合封闭剂大体相同，所述表面活性剂会大量吸附在甲基硅树脂胶体微粒的表面上，同样存在氧化还原石墨烯在封闭液中沉淀的问题，所述氧化还原石墨烯中同样存在硝酸根和硫酸根腐蚀性物质，也没有给出所述氧化还原石墨烯悬浮液中石墨烯的含量。所述封闭剂没有给出所述催化剂、成膜剂、润滑剂及促进剂是什么物质，对所述憎水类表面活性剂及硅烷偶联剂也没有给出具体成分。
发明内容
基于此，为了克服上述现有技术的缺陷，本发明提供了一种羟基石墨烯改性镀层封闭剂及其制备方法。
为了实现上述发明目的，本发明采取了以下技术方案：
一种羟基石墨烯改性镀层封闭剂，所述封闭剂由包括以下重量份的组分制备而得：
Figure PCTCN2017118728-appb-000001
Figure PCTCN2017118728-appb-000002
所述抗蚀剂为质量分数为3.5％～4.0％的纳米级羟基石墨烯水溶液，pH值8.0～9.5。
在其中一些实施例中，所述抗蚀剂为质量分数为3.8％的纳米级羟基石墨烯水溶液。
在其中一些实施例中，所述成膜物质为硅溶胶和水溶性硅烷聚合物的混合物，所述硅溶胶占成膜物质的质量分数为30％～70％。
在其中一些实施例中，所述硅溶胶占成膜物质的质量分数为50％～65％。
在其中一些实施例中，所述硅溶胶为工业级，二氧化硅质量分数40％，粒径为纳米级，pH值9.0～9.5。
在其中一些实施例中，所述水溶性硅烷聚合物为台湾大金化工生产的产品型号为PU 113的水溶性硅烷聚合物。
在其中一些实施例中，所述羟基石墨烯制备方法为：在反应器中加入浓硫酸和石墨，以高锰酸钾作氧化剂，经低温、中温、高温三步氧化制备氧化石墨烯，用双氧水还原过量的高锰酸钾，用电渗析法去除反应产物中的酸和盐，然后加入20％的氢氧化钠溶液至pH为11～12，使硫酸基石墨烯转化为羟基石墨烯，再用电渗析法去除过量的氢氧化钠，使羟基石墨烯糊状液的pH为8.0～9.5。
在其中一些实施例中，所述消泡剂为荷兰拓纳公司生产的TANAFOAM S有机硅消泡剂，有效含量为46％～49％。
在其中一些实施例中，所述流平剂为荷兰斯塔尔公司生产的LA13-863有机 硅流平剂，有效含量为25％。
在其中一些实施例中，所述封闭剂的制备方法为，按封闭剂成分及含量要求将各物质混合在一起，搅拌均匀，即可得到所要生产的封闭剂产品。
在其中一些实施例中，所述封闭剂的使用方法为：
(1)、于封闭槽中将封闭剂用去离子水稀释2.5～3.5倍，得到封闭液；
(2)、将锌镍合金或锌镀件钝化、水洗后浸入步骤(1)制得的封闭液中10～30s，出槽后滴干；
(3)、用高压空气吹掉镀件表面多余的封闭液，然后在70～90℃环境下烘烤30～60min。
与现有技术相比，本发明具有以下有益效果：
(1)、本发明的封闭剂使用羟基石墨烯作为抗蚀剂，封闭膜在烘干过程中羟基石墨烯表面上的羟基能与硅溶胶中二氧化硅胶体表面的羟基发生脱水缩合反应，羟基石墨烯表面上的羟基也能与硅烷聚合物分子上的羟基发生缩合反应，从而形成具有高强度的封闭膜，与石墨烯或氧化还原石墨烯相比，羟基石墨烯改性封闭剂制备的封闭膜具有更高的耐蚀性和耐磨性；
(2)、本发明所使用的羟基石墨烯为纳米材料，能够均匀分布在封闭膜的三维网状结构中，当封闭膜表面其它成分被腐蚀后，羟基石墨烯将均匀覆盖在封闭层的表面上，阻止腐蚀性物质进一步破坏封闭膜；
(3)、本发明所使用的纳米羟基石墨烯对金属镀层孔隙具有高渗透性，封孔能力强，可渗透至金属镀层孔隙内部深处，羟基石墨烯上的羟基还能与金属生成稳定的化合物，能够进一步增加封闭膜的耐蚀性；
(4)、本发明所使用的羟基石墨烯具有水溶性，与氧化还原石墨烯相比，不需要用表面活性剂乳化羟基石墨烯，从而降低了表面活性剂对封闭膜性能的不 良影响；
(5)、本发明所使用的所用硅烷聚合物中的醇基团与金属锌及镍能生成稳定的化合物，对镀层起到保护作用，当封闭膜划伤后，这些醇基团还能自发交联生成新的封闭膜，使封闭膜具有自修复性；
(6)、本发明使用硅溶胶与水溶性硅烷聚合物的混合物作为成膜剂，能够增加封闭膜的柔韧性。
具体实施方式
为更好地理解本发明，通过以下实施例对本发明作进一步具体的阐述，但不可理解为对本发明的限定，对于本领域的技术人员根据上述发明内容所作的一些非本质的改进与调整，也视为落在本发明的保护范围内。
实施例1一种羟基石墨烯改性镀层封闭剂
本实施例的羟基石墨烯改性镀层封闭剂包括以下各组分：
Figure PCTCN2017118728-appb-000003
所述成膜物质包含硅溶胶和水溶性硅烷聚合物，硅溶胶占成膜物质的质量分数为60％，水溶性硅烷聚合物占成膜物质的质量分数40％；
所述硅溶胶：工业级，二氧化硅质量分数40％，粒径为纳米级，pH为9.0～9.5；所述水溶性硅烷聚合物：台湾大金化工生产的产品型号为PU 113的水溶性硅烷聚合物；
所述抗蚀剂采用羟基石墨烯：质量分数为3.8％的羟基石墨烯糊状水溶液，粒径为纳米级，pH值8.0～9.5。
其中，所述羟基石墨烯的制备方法为：
(1)、低温氧化：在1000mL烧杯中加入浓硫酸115mL，在冰水浴中将浓硫酸的温度降2～5℃，加入5g质量分数大于99％的300目鳞片石墨粉，搅拌下缓慢加入高锰酸钾18g，控制反应温度在2～10℃范围内，搅拌下反应120min；
(2)、中温氧化：将冰水浴换成温水浴，控制反应温度在30～40℃之间、搅拌下反应90min；
(3)、高温氧化：中温反应后，将烧杯从水浴中取出，将烧杯中的糊状物加热至90℃，缓慢加水100mL，控制反应温度90～100℃，搅拌30min，向烧杯中缓慢加入30％的双氧水15mL，继续反应30min；
(4)、用电渗析法去除反应产物中的酸和盐，然后加入20％的氢氧化钠溶液至pH为11～12，使硫酸基石墨烯转化为羟基石墨烯，再用电渗析法去除过量的氢氧化钠，使羟基石墨烯糊状液的pH为8.0～9.5。
所述消泡剂为荷兰拓纳公司生产的TANAFOAM S有机硅消泡剂，有效含量为46％～49％。
所述流平剂为荷兰斯塔尔公司生产的LA13-863有机硅流平剂，有效含量为25％。
按上述封闭剂成分及含量要求将各物质混合在一起，搅拌均匀，得到本实施例所述的羟基石墨烯改性封闭剂。
镀件制备及利用本实施例的羟基石墨烯改性封闭剂进行封闭，具体过程为：
(1)、于封闭槽中将封闭剂用去离子水稀释3倍配制封闭液；
(2)、用无氰碱性锌槽滚镀M8.0×30的螺丝，螺丝材质为A3钢，镀锌层厚 度10～12μm。
(3)、镀件用三价铬蓝白色钝化液钝化、水洗后浸入封闭液中20s，出槽后滴干；
(4)、用高压空气吹掉镀件表面多余的封闭液，然后在80℃环境下烘烤40min。放置24h老化。
按GB/T10125–1997《人造气氛腐蚀试验盐雾试验》进行中性盐雾试验312h，镀层表面出现白色腐蚀物，648h时镀层表面出现红色腐蚀物。
实施例2一种羟基石墨烯改性镀层封闭剂
本实施例的羟基石墨烯改性镀层封闭剂包括以下各组分：
Figure PCTCN2017118728-appb-000004
所述成膜物质包含硅溶胶和水溶性硅烷聚合物，硅溶胶占成膜物质的质量分数为60％，水溶性硅烷聚合物占成膜物质的质量分数40％。
所述硅溶胶：工业级，二氧化硅质量分数40％，粒径为纳米级，pH为9.0～9.5。所述水溶性硅烷聚合物：台湾大金化工生产的产品型号为PU 113的水溶性硅烷聚合物。
所述抗蚀剂采用羟基石墨烯：质量分数为3.8％的羟基石墨烯糊状水溶液，粒径为纳米级，pH为8.0～9.5。
其中，羟基石墨烯的制备方法为：
(1)、低温氧化：在1000mL烧杯中加入浓硫酸115mL，在冰水浴中将浓硫酸的温度降2～5℃，加入5g质量分数大于99％的300目鳞片石墨粉，搅拌下缓慢加入高锰酸钾18g，控制反应温度在2～10℃范围内，搅拌下反应120min；
(2)、中温氧化：将冰水浴换成温水浴，控制反应温度在30～40℃之间、搅拌下反应90min；
(3)、高温氧化：中温反应后，将烧杯从水浴中取出，将烧杯中的糊状物加热至90℃，缓慢加水100mL，控制反应温度90～100℃，搅拌30min，向烧杯中缓慢加入30％的双氧水15mL，继续反应30min；
(4)、用电渗析法去除反应产物中的酸和盐，然后加入20％的氢氧化钠溶液至pH为11～12，使硫酸基石墨烯转化为羟基石墨烯，再用电渗析法去除过量的氢氧化钠，使羟基石墨烯糊状液的pH为8.0～9.5。
所述消泡剂为荷兰拓纳公司生产的TANAFOAM S有机硅消泡剂，有效含量为46％～49％。
所述流平剂为荷兰斯塔尔公司生产的LA13-863有机硅流平剂，有效含量为25％。
按上述封闭剂成分及含量要求将各物质混合在一起，搅拌均匀，得到所发明的羟基石墨烯改性封闭剂。
镀件制备及利用本实施例的羟基石墨烯改性封闭剂进行封闭，具体过程为：
(1)、于封闭槽中将封闭剂用去离子水稀释3倍配制封闭液；
(2)、用无氰碱性锌槽滚镀M8.0×30的螺丝，螺丝材质为A3钢，镀锌层厚度10～12μm。
(3)、镀件用三价铬蓝白色钝化液钝化、水洗后浸入封闭液中20s，出槽后滴干；
(4)、用高压空气吹掉镀件表面多余的封闭液，然后在80℃环境下烘烤40min。放置24h老化。
按GB/T 10125–1997《人造气氛腐蚀试验盐雾试验》进行中性盐雾试验320h，镀层表面出现白色腐蚀物，672h时镀层表面出现红色腐蚀物。
对比实施例1和2可知，当封闭剂中羟基石墨烯的含量从4份增加至10份，中性盐雾试验镀层出现白色腐蚀物时间增加8h，镀层出现红色腐蚀物时间增加24h。
对比例1不含羟基石墨烯的传统镀层封闭剂
该对比例所述的不含羟基石墨烯的传统镀层封闭剂，由以下原料制成：
Figure PCTCN2017118728-appb-000005
该对比例的封闭剂所使用的原料均与实施例1相同，制备方法也与实施例1相同。
镀件制备及封闭过程与实施例1相同。
按GB/T 10125–1997《人造气氛腐蚀试验盐雾试验》进行中性盐雾试验72h，镀层表面出现白色腐蚀物。
对比例1、实施例1～2的结果说明：采用羟基石墨烯改性封闭剂封闭的镀件中性盐雾试验出现白色腐蚀物的时间为312～320h，由此可见，用羟基石墨烯作抗蚀剂能显著增加电镀工件的耐蚀性。
对比例2添加石墨烯(GNP)的封闭剂
本对比例的添加石墨烯的镀层封闭剂，由以下原料制备而得：
Figure PCTCN2017118728-appb-000006
所述抗蚀剂采用石墨烯：用十二烷基磺酸钠作乳化剂，配制质量分数为3.8％的石墨烯糊状水溶液，粒径为纳米级，pH值6.5～7.0。
其他成分均与实施例1相同，制备方法与实施例1相同，镀件制备及封闭过程与实施例1相同。
按GB/T 10125–1997《人造气氛腐蚀试验盐雾试验》进行中性盐雾试验224h，镀层表面出现白色腐蚀物。
对比例2、实施例2的结果说明：采用石墨烯封闭剂进行封闭的镀件中性盐雾试验出现白色腐蚀物的时间为320h，对比例2出现白色腐蚀物的时间为224h，由此可见，用羟基石墨烯作抗蚀剂能显著增加电镀工件的耐蚀性。
对比例2的封闭液放置1星期后观察，石墨烯完全沉入封闭液的底部，说明对比例2的这种封闭液不稳定，不能用于工业生产。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细， 但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种羟基石墨烯改性镀层封闭剂，其特征在于，所述封闭剂由包括以下重量份的组分制备而得：
    Figure PCTCN2017118728-appb-100001
    其中，所述抗蚀剂为质量分数为3.5％～4.0％的纳米级羟基石墨烯水溶液，pH值8.0～9.5。
  2. 根据权利要求1所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述抗蚀剂为质量分数为3.8％的纳米级羟基石墨烯水溶液。
  3. 根据权利要求1或2所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述纳米级羟基石墨烯的制备方法为：在反应器中加入浓硫酸和石墨，以高锰酸钾作氧化剂，经低温、中温、高温三步氧化制备氧化石墨烯，用双氧水还原过量的高锰酸钾，用电渗析法去除反应产物中的酸和盐，然后加入20％的氢氧化钠溶液至pH为11～12，使硫酸基石墨烯转化为羟基石墨烯，再用电渗析法去除过量的氢氧化钠，使羟基石墨烯糊状液的pH为8.0～9.5。
  4. 根据权利要求1所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述成膜物质为硅溶胶和水溶性硅烷聚合物的混合物，所述硅溶胶占成膜物质的质量分数为30％～70％。
  5. 根据权利要求4所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述硅溶胶占成膜物质的质量分数为50％～65％。
  6. 根据权利要求4或5所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述硅溶胶的粒径为纳米级，其二氧化硅质量分数为40％，pH为9.0～9.5。
  7. 根据权利要求4或5所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述水溶性硅烷聚合物的产品型号为PU 113。
  8. 根据权利要求1所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述消泡剂为TANAFOAMS有机硅消泡剂，有效含量为46％～49％。
  9. 根据权利要求1所述的羟基石墨烯改性镀层封闭剂，其特征在于，所述流平剂为LA13-863有机硅流平剂，有效含量为25％。
  10. 权利要求1～9任一项所述的羟基石墨烯改性镀层封闭剂的制备方法，其特征在于，按封闭剂成分及含量要求将各原料混合在一起，搅拌均匀，即得。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113265180A (zh) * 2021-04-16 2021-08-17 清远慧谷新材料技术有限公司 一种硅改性石墨烯水性涂料及其制备方法
CN113340960A (zh) * 2021-07-16 2021-09-03 福建师范大学 一种基于硅溶胶检测莱克多巴胺的电化学传感器制备方法
CN113466300A (zh) * 2021-07-16 2021-10-01 福建师范大学 一种石墨烯改性硅溶胶负载沙丁胺醇抗体传感器制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976965A (zh) * 2018-07-18 2018-12-11 江苏卓岸电源科技有限公司 一种防腐电池箱
CN110724985B (zh) * 2019-11-13 2021-03-26 珠海市玛斯特五金塑胶制品有限公司 一种封闭处理液和透明耐腐蚀膜层及其制备方法
CN110952123A (zh) * 2019-12-21 2020-04-03 广州超邦化工有限公司 一种高耐蚀性铝合金阳极氧化防护层的制备方法
CN111005046B (zh) * 2019-12-24 2021-03-23 联泓(江苏)新材料研究院有限公司 一种石墨烯基镀镍封闭剂及其制备方法与应用
CN111778003B (zh) * 2020-08-06 2022-08-23 安徽陆海石油助剂科技有限公司 钻井液用封堵降滤失剂弹性石墨
CN112893059A (zh) * 2021-01-22 2021-06-04 江苏江南烯元石墨烯科技有限公司 一种增强石墨烯发热涂层与基材粘合力的方法
CN112962090A (zh) * 2021-02-03 2021-06-15 合肥华清方兴表面技术有限公司 一种锌铝镁合金自修复无铬钝化剂及其制备方法与应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103740153A (zh) * 2013-11-12 2014-04-23 宁波墨西科技有限公司 一种石墨烯改性的达克罗涂料
KR20140065174A (ko) * 2012-11-21 2014-05-29 이영림 방열층을 가지는 oled용 봉지필름
CN106085218A (zh) * 2016-08-17 2016-11-09 安徽红桥金属制造有限公司 一种高效环保复合封闭剂
CN106318200A (zh) * 2016-08-17 2017-01-11 安徽红桥金属制造有限公司 一种改性水性复合封闭剂及其制备方法
CN106590076A (zh) * 2016-12-15 2017-04-26 深圳大学 一种石墨烯改性无机涂料及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120277360A1 (en) * 2010-10-28 2012-11-01 Vorbeck Materials Corp. Graphene Compositions
US10213746B2 (en) * 2016-04-14 2019-02-26 Lockheed Martin Corporation Selective interfacial mitigation of graphene defects
US20160276056A1 (en) * 2013-06-28 2016-09-22 Graphene 3D Lab Inc. Dispersions for nanoplatelets of graphene-like materials and methods for preparing and using same
ES2534575B1 (es) * 2013-09-24 2016-01-14 Consejo Superior De Investigaciones Científicas (Csic) Exfoliación de grafito con disolventes eutécticos profundos
WO2015160764A1 (en) * 2014-04-14 2015-10-22 The Board Of Regents Of The University Of Texas System Graphene-based coatings
CN107033702B (zh) * 2017-06-09 2019-09-13 安徽工业大学 一种基于石墨烯复合的水性金属表面处理剂

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140065174A (ko) * 2012-11-21 2014-05-29 이영림 방열층을 가지는 oled용 봉지필름
CN103740153A (zh) * 2013-11-12 2014-04-23 宁波墨西科技有限公司 一种石墨烯改性的达克罗涂料
CN106085218A (zh) * 2016-08-17 2016-11-09 安徽红桥金属制造有限公司 一种高效环保复合封闭剂
CN106318200A (zh) * 2016-08-17 2017-01-11 安徽红桥金属制造有限公司 一种改性水性复合封闭剂及其制备方法
CN106590076A (zh) * 2016-12-15 2017-04-26 深圳大学 一种石墨烯改性无机涂料及其制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113265180A (zh) * 2021-04-16 2021-08-17 清远慧谷新材料技术有限公司 一种硅改性石墨烯水性涂料及其制备方法
CN113340960A (zh) * 2021-07-16 2021-09-03 福建师范大学 一种基于硅溶胶检测莱克多巴胺的电化学传感器制备方法
CN113466300A (zh) * 2021-07-16 2021-10-01 福建师范大学 一种石墨烯改性硅溶胶负载沙丁胺醇抗体传感器制备方法
CN113340960B (zh) * 2021-07-16 2023-04-14 福建师范大学 一种基于硅溶胶检测莱克多巴胺的电化学传感器制备方法
CN113466300B (zh) * 2021-07-16 2023-04-14 福建师范大学 一种石墨烯改性硅溶胶负载沙丁胺醇抗体传感器制备方法

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