WO2014161214A1 - 一种石墨烯无机涂料及其使用方法 - Google Patents
一种石墨烯无机涂料及其使用方法 Download PDFInfo
- Publication number
- WO2014161214A1 WO2014161214A1 PCT/CN2013/075229 CN2013075229W WO2014161214A1 WO 2014161214 A1 WO2014161214 A1 WO 2014161214A1 CN 2013075229 W CN2013075229 W CN 2013075229W WO 2014161214 A1 WO2014161214 A1 WO 2014161214A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- graphene
- inorganic coating
- coating
- inorganic
- coatings
- Prior art date
Links
Classifications
-
- 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
- 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
-
- 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
Definitions
- the invention relates to the technical field of inorganic coating production, in particular to a graphene inorganic coating and a using method thereof.
- Inorganic coatings mainly refer to coatings prepared by adding various kinds of pigments, fillers, auxiliaries and curing agents with silicate and pity acid compounds as binders.
- the silicate polymer compounds can be divided into alkalis. Metal silicates and silica sols.
- the coating material using the inorganic binder as a film-forming substance has a low film forming temperature, excellent weather resistance of the coating film, very stable under ultraviolet light, good heat resistance, incombustible fire, and good resistance. It has a wide range of industrial applications, such as polluting, not easy to absorb ash, able to maintain a bright decorative effect, no volatile organic matter produced during production and use, no pollution to the environment, abundant raw material resources, low cost, etc.
- the preparation process of inorganic coatings is similar to organic coatings.
- the solid materials such as pigments and fillers are first dispersed or ground to prepare a color paste, and then the base materials, color pastes and other auxiliary ingredients are mixed according to the formulation, and then ball milled, filtered, and packaged. If it is a coating containing a curing agent, the curing agent must be packaged separately from the base.
- the pigments and fillers commonly used in the preparation of coatings include titanium dioxide, zinc oxide, calcium carbonate, talc, kaolin, mica powder, quartz, etc. (Zhou Xirong et al. Preparation and application of new inorganic coatings, Shandong Ceramics, February 2004, Vol. 27 No. 1, 17-20).
- the metal surface when the metal surface is protected, if the inorganic coating is used, the metal surface needs to be roughened, such as sandblasting, and then the inorganic coating is sprayed, so that the inorganic coating can be firmly adhered to the metal surface.
- corrosion of the metal surface to achieve surface roughening treatment is also an effective method to improve the adhesion of inorganic coatings.
- the object of the present invention is to overcome the problem of poor adhesion of existing inorganic coatings on metal surfaces, and to provide a graphene inorganic coating, which improves the adhesion of inorganic coatings on metal surfaces by modifying existing inorganic coatings by graphene. , to achieve the same effect as the adhesion of the metal surface after sandblasting or corrosion roughening treatment.
- the invention also provides a method for using the graphene inorganic coating, which does not need to blast the metal surface or perform corrosion roughening treatment, that is, can improve the inorganic coating after the sandblasting treatment or the corrosion roughening treatment with the metal surface Focusing on the same effect greatly simplifies the construction.
- the adhesion of the inorganic coating to the metal is significantly higher than that of the existing inorganic coating and the metal surface by sandblasting or roughening.
- the adhesion of the treated metal provides a new way to achieve high quality construction.
- the technical solution adopted by the present invention to solve the technical problem thereof is:
- Graphene has the characteristics of softness, planar structure and high strength.
- the planar structure of graphene can improve the adsorption capacity, and the flexibility of graphene can inhibit the inorganic matter under the action of drying and external heating field. Shrinkage, thereby suppressing cracking, high strength properties of graphene along the plane direction Increase the overall strength of the inorganic film after film formation.
- the invention adopts graphene to modify the existing inorganic coating, can greatly improve the adhesion of the inorganic coating on the metal surface, and achieve the same effect of improving the adhesion of the inorganic coating after the metal surface is subjected to sand blasting or corrosion roughening treatment. There is no need to sandblast the metal surface or roughen the corrosion, which greatly simplifies the construction.
- Controlling the amount of graphene added is extremely critical. If the amount of graphene added is less than 0.001%, the effect of improving the adhesion of the existing inorganic coating on the metal surface cannot be achieved. If the amount of graphene added is more than 5%, It will affect the film-forming properties of existing inorganic coatings and reduce the film-forming quality of existing inorganic coatings.
- the graphene is added in an amount of from 0.1% to 1% by mass based on the mass of the inorganic coating.
- the amount of graphene added is controlled to be 0.1% to 1%, which is the best effect of modification.
- the graphene is a single-layer sheet structure, or the graphene has a layer number of 2-50 layers, and the carbon atoms in the layer are composed of a sp 2 hybrid orbital to form a hexagonal honeycomb lattice, and the interlayer is The carbon atoms are bonded by a ⁇ bond.
- the mass ratio of the carbon element to the non-carbon element is greater than 4: 1, and the non-carbon element is selected from one or more of fluorine, nitrogen, oxygen, sulfur, hydrogen, chlorine, bromine, and iodine.
- the graphene is added in the form of a graphene powder or a graphene slurry.
- the inorganic coating material is one selected from the group consisting of alkali metal silicate coatings, silica sol coatings, and dimethic acid coatings.
- Alkali metal silicate coatings, silica sol coatings, and dimethic acid coatings are conventional conventional inorganic coatings, The selection of a commercially available product can also be carried out by referring to the existing published patent documents or the formulations disclosed in the paper.
- Alkali metal silicate coatings also known as water glass based inorganic coatings, are a class of coatings based on potassium silicate and sodium silicate, usually composed of an adhesive, a curing agent, a pigment, a filler, and various additives. The coating is divided into two components, one group is divided into an alkali metal silicate aqueous solution, and the other component is a powder or slurry which is uniformly mixed with a pigment filler, a curing agent and an auxiliary agent.
- one group may be divided into an alkali metal silicate aqueous solution, a pigment filler, an auxiliary agent, and the other component is a curing agent.
- the two components are mixed prior to application and then applied to the substrate in a suitable process.
- the main products in China are roughly classified into potassium water glass paint, sodium water glass paint, potassium and sodium water glass paint, depending on the type of water glass.
- the silica sol coating is an inorganic coating which is obtained by mixing an aqueous dispersion of colloidal silica as a film-forming substance and mixing and dispersing a pigment, a filler and a flux.
- the dilute acid coating is mainly formed by using an acid-type aqueous solution of diacid salt (generally dihydroaluminum dihydroaluminum) as a film-forming material, with a pigment, a filler and a curing agent.
- diacid salt generally dihydroaluminum dihydroaluminum
- the pour acid coating has good heat resistance and bonding properties, but the gloss is low, so it is generally only used as a coating on industrial equipment, such as heat-resistant protective coating on the boiler pipe wall.
- a method for using a graphene inorganic coating which directly applies a graphene inorganic coating to a metal surface, and is dried at room temperature to 200 ° C for 1 minute to 24 hours.
- the metal surface is sandblasted.
- the drying treatment is further carried out at a high temperature baking at a baking temperature of from 200 ° C to 1000 ° C and a baking time of from 1 to 60 minutes. Further high temperature baking improves the adhesion of the inorganic coating to the metal surface.
- the graphene inorganic coating of the invention is used, and the adhesion of the inorganic coating to the metal is significantly higher than that of the existing inorganic coating and the metal surface by sandblasting or roughening.
- the adhesion of the treated metal provides a new way to achieve high quality construction.
- the alkali metal silicate coating, the silica sol coating and the diacid salt coating which are involved in the invention are all existing inorganic coatings, and may be selected from commercially available products, and may also refer to the patent documents disclosed in the prior publication or the formulations disclosed in the paper. Prepared.
- Graphene raw materials Graphene powder and graphene slurry are commercially available, and all of them are purchased from Ningbo Moxi Technology Co., Ltd.
- Graphene is a single-layer sheet structure, or the graphene has a layer number of 2-50 layers, a carbon atom in the layer is a hexagonal honeycomb lattice formed by sp 2 hybrid orbital, and a carbon atom is ⁇ bond between layers. Combine.
- the mass ratio of carbon element to non-carbon element is greater than 4:1, and the non-carbon element is selected from one or more of fluorine, nitrogen, oxygen, sulfur, hydrogen, chlorine, bromine and iodine.
- the inorganic coating is a pour acid coating, and the formulation of the dilute coating is referred to the CN1618887A invention patent (2005).
- Example 1-3 disclosed in the May 25th the graphene is added (in the form of graphene powder) during or after the preparation of the dilute acid coating, and the mixture is uniformly mixed, and the amount of graphene is added.
- the mass percentage of the inorganic coating is 0.001% to 5%, and 0.001% is used in this embodiment.
- the inorganic coating is a pour acid coating (commercially available, Yangzhou Meitu Shiling Special Coating Co., Ltd., the product name is inorganic p-zinc-rich zinc coating, model ET-98), and graphene is added to the diacid coating.
- the olefin powder form is added), and the mixture is uniformly mixed.
- the amount of graphene added is 0.001% to 5% by mass of the inorganic coating, and 5% is used in this embodiment.
- the inorganic coating is an alkali metal silicate coating (commercially available, Xinhuayan Refractory Insulation Materials Co., Ltd., the product name silicate coating), and graphene (with graphite) is added during the preparation of the alkali metal silicate coating or after the preparation.
- the olefin powder form is added), and the mixture is uniformly mixed.
- the amount of graphene added is 0.001%-5% by mass of the inorganic coating, and 1% is used in this embodiment.
- Inorganic coatings are alkali metal silicate coatings (potassium water glass composite exterior wall coatings, see Zhang Xueqin, etc., research and development of inorganic architectural coatings, “New Building Materials”, 2004, No. 7, 2.2.2). Adding graphene (added as graphene powder) during or after the preparation of the alkali metal silicate coating, and mixing uniformly, the amount of graphene added is 0.001%-5% by mass of the inorganic coating. The example uses 0.5%.
- the inorganic coating is silica sol coating (silica sol composite exterior wall coating, see Zhang Xueqin, etc., research and development of inorganic architectural coatings, “New Building Materials”, 2004, No. 7, Section 2.2.1).
- Graphene is added during the preparation of the silica sol coating or after the preparation is completed (added as a graphene slurry, the graphene content in the graphene slurry is 5%, and the amount of addition is calculated after conversion), and the mixture is uniformly mixed, and the amount of graphene is added.
- the mass percentage of the inorganic coating is 0.001% to 5%, and 0.1% is used in this embodiment.
- the inorganic coating is silica sol coating (commercially available, Shangyu Yinyu Silicon Products Co., Ltd.), and graphene (added as graphene powder) is added during the preparation of the alkali metal silicate coating or after the preparation, and the mixture is uniformly mixed. That is, the amount of graphene added is 0.001% to 5% by mass of the inorganic coating, and 0.8% is used in this embodiment.
- the following embodiment specifically describes the timing of addition of graphene, and the inorganic coating is a silica sol coating using tetraethyl orthosilicate as a raw material.
- the conventional procedure is to hydrolyze ethyl orthosilicate to obtain a silica sol, which is aged at 80 ° C for 5 hours to obtain a silica gel coating.
- the solution is obtained by hydrolyzing ethyl orthosilicate to obtain a silica sol, adding graphene and mixing, and aging at 80 ° C for 5 hours to obtain a graphene inorganic coating.
- ethyl orthosilicate is hydrolyzed to obtain a silica sol, which is aged at 80 ° C for 5 h, and graphene is added to obtain a graphene inorganic coating.
- the graphene inorganic coating of the present invention is directly applied to the surface of a metal (aluminum plate) at room temperature to 200 ° C Drying treatment for 1 minute to 24 hours, in order to improve the film forming properties of the inorganic material on the metal surface, and then baking at a high temperature, the baking temperature is 200 ° C to 1000 ° C, and the baking time is 1-60 minutes.
- the surface of the aluminum plate may be sandblasted and then coated with the graphene inorganic coating of the present invention.
- the graphene inorganic coating of the invention is applied to the surface of the aluminum plate (unsurface treated), dried at 80 ° C for 20 min, and then baked at 600 ° C for 20 min, according to the adhesion test of GB/T 9286-88. The method was applied to determine the adhesion of the coating. The results are as follows (Table 1):
- Example 2 As a control, the existing inorganic coatings of Examples 1-6 were applied to the surface of an aluminum plate (unsurface treated), dried at 80 ° C for 20 min, and baked at 600 ° C for 20 min (Comparative Examples 1-6 ), according to The adhesion test method of GB/T9286-88 was used to determine the adhesion of the coating. The results are as follows (Table 2):
- the inorganic coating is easy to fall off and has a weak cracking phenomenon.
- the surface layer appears more cracking phenomenon, the film formation is incomplete. Compared with the 4th grade spraying process, the inorganic coating is easy to fall off, and there is a weak cracking phenomenon.
- the present invention uses graphene to modify the existing inorganic coating, which can greatly improve the adhesion of the inorganic coating on the metal surface, and after the metal surface is subjected to sand blasting or corrosion roughening treatment. Improve the adhesion of inorganic coatings. There is no need to sandblast the metal surface or roughen the corrosion, which greatly simplifies the construction.
Abstract
一种石墨烯改性的无机涂料及其使用方法，其中所述石墨烯的加入量占无机涂料的质量百分比为0.001%-5%。石墨烯改性的无机涂料能大大提高无机涂料在金属表面的附着力，达到与金属表面经过喷砂处理或进行腐蚀粗糙化处理后提高无机涂料附着力相同的效果，无需对金属表面喷砂处理或进行腐蚀粗糙化处理，大大简化了施工难度。
Description
一种石墨烯无机涂料及其使用方法
技术领域
本发明涉及无机涂料生产技术领域， 特别涉及一种石墨烯无机涂料及其使 用方法。
背景技术
无机涂料主要是指以硅酸盐和憐酸盐类化合物作为粘结剂， 加入各种颜、 填料、 助剂、 固化剂配制而成的涂料， 其中硅酸盐高分子化合物又可分为碱金 属硅酸盐和硅溶胶。 这种以无机粘结剂作为成膜物质的涂料具有成膜温度低、 其涂膜具有优良的耐候性、 在紫外光作用下非常稳定、 良好的耐热性、 遇火不 燃、 较好的耐污染性、 不易吸灰、 能保持明快的装饰效果、 在制作与使用过程 中无挥发性有机物产生、 不会污染环境、 原材料资源丰富、 成本低廉等一系列 优点， 因而得到了广阔的工业应用， 其市场前景， 社会、 经济效益十分诱人。 无机涂料的制备工艺与有机涂料类似。 先将颜、 填料等固体物料经分散或研磨 制成色浆， 然后把基料、 色浆及其他辅助成分按配方规定混合， 再经过球磨、 过滤、 包装。 如果是含有固化剂的涂料， 则须将固化剂与基料分开包装。 配制 涂料常用的颜填料有钛白粉、 氧化锌、 碳酸钙、 滑石粉、 高岭土、 云母粉、 石 英等（周锡荣等， 新型无机涂料的制备及其应用， 山东陶瓷， 2004年 2月， 第 27 卷第 1期， 17-20 ) 。
通常金属表面防护时， 若采用无机涂料， 则需要对金属表面进行粗糙化处 理， 如喷砂处理， 然后喷涂无机涂料， 如此方能使无机涂层牢固附着于金属表 面。 然而对于大型建筑及装备， 对金属表面进行喷砂处理难度较大， 因此寻找 合适的材料， 提高无机涂料在金属表面的附着力意义重大。
为提高无机涂料在金属表面的附着力问题， 人们通常在无机涂料中加入有 机涂料， 或在金属表面预先涂覆黏胶层。 此外， 对金属表面进行腐蚀， 达到表 面粗糙化处理的效果， 也是提高无机涂料附着力的有效方法。
然而含有机物的涂层存在耐高温效果差的问题，金属表面预腐蚀存在与喷 砂一样的难操作的困难， 寻找新的材料， 以求突破现有工艺的困难， 非常重要。 发明内容
本发明的目的在于克服现有无机涂料在金属表面存在的附着力差的问题， 提供一种石墨烯无机涂料， 通过石墨烯改性现有无机涂料， 大大提高了无机涂 料在金属表面的附着力， 达到与金属表面经过喷砂处理或进行腐蚀粗糙化处理 后提高无机涂料附着力相同的效果。
本发明还提供了一种石墨烯无机涂料的使用方法， 无需对金属表面喷砂处 理或进行腐蚀粗糙化处理， 即能达到与金属表面经过喷砂处理或进行腐蚀粗糙 化处理后提高无机涂料附着力相同的效果， 大大简化了施工难度。 此外， 对金 属表面喷砂处理或进行腐蚀粗糙化处理后再使用本发明的石墨烯无机涂料， 无 机涂料与金属的附着力明显高于现有无机涂料与金属表面经过喷砂处理或进行 腐蚀粗糙化处理后的金属的附着力， 为实现优质施工质量提供了新的途径。 本发明解决其技术问题所采用的技术方案是：
一种石墨烯无机涂料，采用石墨烯改性无机涂料而得，所述石墨烯的加入量占 无机涂料的质量百分比为 0.001%-5%。
石墨烯具有柔软、 平面状结构、 强度高等特征， 均匀分散在无机物中时， 平面状结构的石墨烯可提高吸附能力， 石墨烯的柔软性可抑制无机物在干燥及 外加热场作用下的收縮性， 从而抑制龟裂， 石墨烯沿平面方向的高强度特性可
增加无机物成膜后的整体强度。
本发明采用石墨烯改性现有的无机涂料， 能大大提高无机涂料在金属表面 的附着力， 达到与金属表面经过喷砂处理或进行腐蚀粗糙化处理后提高无机涂 料附着力相同的效果。 无需对金属表面喷砂处理或进行腐蚀粗糙化处理， 大大 简化了施工难度。
控制石墨烯的加入量异常关键， 若石墨烯的加入量低于 0.001%, 则无法起 到提高现有无机涂料在金属表面的附着力的效果， 若石墨烯的加入量高于 5%， 则会影响现有无机涂料的成膜性能， 降低现有无机涂料的成膜质量。
作为优选， 所述石墨烯的加入量占无机涂料的质量百分比为 0.1%-1%。 控制石墨烯的加入量在 0.1%-1%， 这样改性的效果最佳。
作为优选， 所述石墨烯为单层片状结构， 或所述石墨烯为层数在 2-50层， 层内为碳原子以 sp2杂化轨道组成六角形蜂巢状晶格、 层间为碳原子以 π键结 合。 作为优选， 所述石墨烯中， 碳元素与非碳元素质量比大于 4: 1， 非碳元素 选自氟、 氮、 氧、 硫、 氢、 氯、 溴、 碘中一种或几种。 通常的石墨烯都采用化 学法制备， 因此， 不可避免的会带入一些杂质元素如氟、 氮、 氧、 硫、 氢、 氯、 溴、 碘等。 碳元素与非碳元素质量比大于 4:1， 保证了石墨烯能起到良好的提 高无机涂料在金属表面附着力的改性效果。
作为优选， 所述石墨烯以石墨烯粉或石墨烯浆料的形式添加。
作为优选， 所述无机涂料选自碱金属硅酸盐涂料、 硅溶胶涂料、 憐酸盐涂 料中的一种。
碱金属硅酸盐涂料、 硅溶胶涂料、 憐酸盐涂料为现有的常规无机涂料， 可
选择市售产品， 也可参考现有公开的专利文件或论文上公开的配方制备而来。 碱金属硅酸盐涂料又可称为水玻璃基无机涂料， 它是以硅酸钾和硅酸钠为 胶粘剂的一类涂料， 通常由胶粘剂、 固化剂、 颜料、 填料及各种助剂组成。 涂 料采用双组分， 一组分为碱金属硅酸盐水溶液， 另一组分为颜填料、 固化剂、 助剂混合均匀的粉剂或浆状物。 此外也可以是一组分为碱金属硅酸盐水溶液、 颜填料、 助剂， 另一组分为固化剂。 两组分在施工前混合， 然后以适当的工 艺涂刷于基体上。 目前国内主要产品随着水玻璃的类型不同， 大致可分为钾水 玻璃涂料， 钠水玻璃涂料， 钾、 钠水玻璃涂料 3 种。
硅溶胶涂料是以胶体二氧化硅的水分散液为成膜物质， 混以颜、 填料、 助 剂搅拌分散而成的一种无机涂料。
憐酸盐涂料主要是以酸式憐酸盐水溶液 （一般是憐酸二氢铝） 为成膜物， 配以颜、 填料， 固化剂而成。憐酸盐涂料具有很好的耐热性能和粘结性能， 但 光泽度低， 因此一般只用作工业设备上的涂料， 如锅炉管道壁的耐热保护涂料 等。
一种石墨烯无机涂料的使用方法，将石墨烯无机涂料直接涂覆于金属表面， 室温至 200 °C干燥处理 1分钟至 24小时。
作为优选， 所述金属表面经喷砂处理。
作为优选，干燥处理后进一步进行高温烘烤，烘烤温度为 200 °C至 1000°C， 烘烤时间为 1-60分钟。进一步进行高温烘烤可提高无机涂料在金属表面的附着 力。
本发明的有益效果是：
1、 采用石墨烯改性现有的无机涂料， 能大大提高无机涂料在金属表面的
附着力， 达到与金属表面经过喷砂处理或进行腐蚀粗糙化处理后提高无机涂料 附着力相同的效果。 无需对金属表面喷砂处理或进行腐蚀粗糙化处理， 大大简 化了施工难度。
2、 对金属表面喷砂处理或进行腐蚀粗糙化处理后再使用本发明的石墨烯 无机涂料， 无机涂料与金属的附着力明显高于现有无机涂料与金属表面经过喷 砂处理或进行腐蚀粗糙化处理后的金属的附着力， 为实现优质施工质量提供了 新的途径。
具体实施方式
下面通过具体实施例， 对本发明的技术方案作进一步的具体说明。
本发明中， 若非特指， 所采用的原料和设备等均可从市场购得或是本领域 常用的。 下述实施例中的方法， 如无特别说明， 均为本领域的常规方法。
本发明中涉及到的碱金属硅酸盐涂料、 硅溶胶涂料、 憐酸盐涂料均为现有 的无机涂料， 可选择市售产品， 也可参考现有公开的专利文件或论文上公开的 配方制备而来。
石墨烯原料： 石墨烯粉、 石墨烯浆料为市售， 均购自宁波墨西科技有限公 司。
石墨烯为单层片状结构， 或所述石墨烯为层数在 2-50层，层内为碳原子以 sp2杂化轨道组成六角形蜂巢状晶格、层间为碳原子以 π键结合。石墨烯中， 碳 元素与非碳元素质量比大于 4:1， 非碳元素选自氟、 氮、 氧、 硫、 氢、 氯、 溴、 碘中一种或几种。
实施例 1：
无机涂料为憐酸盐涂料，憐酸盐涂料配方参见 CN1618887A发明专利 (2005
年 5月 25日公开） 的实施例 1-3， 在该憐酸盐涂料配制过程中或配制完成后加 入石墨烯（以石墨烯粉形式加入）， 混合均匀即可， 石墨烯的加入量占无机涂料 的质量百分比为 0.001%-5%， 本实施例采用 0.001%。
实施例 2:
无机涂料为憐酸盐涂料 （市售， 扬州美涂士金陵特种涂料有限公司，产品 名无机憐酸盐富锌涂料， 型号 ET-98 ) , 在该憐酸盐涂料中加入石墨烯（以石墨 烯粉形式加入）， 混合均匀即可， 石墨烯的加入量占无机涂料的质量百分比为 0.001%-5%, 本实施例采用 5%。
实施例 3 :
无机涂料为碱金属硅酸盐涂料 （市售， 新华燕耐火保温材料有限公司， 产 品名硅酸盐涂料），在该碱金属硅酸盐涂料配制过程中或配制完成后加入石墨烯 (以石墨烯粉形式加入），混合均匀即可，石墨烯的加入量占无机涂料的质量百 分比为 0.001%-5%， 本实施例采用 1%。
实施例 4:
无机涂料为碱金属硅酸盐涂料 （钾水玻璃复合外墙涂料， 配方参见张雪芹 等，无机建筑涂料的研究与发展， 《新型建筑材料》 2004年 第 7期， 2.2.2节）， 在该碱金属硅酸盐涂料配制过程中或配制完成后加入石墨烯 （以石墨烯粉形式 加入），混合均匀即可，石墨烯的加入量占无机涂料的质量百分比为 0.001%-5%， 本实施例采用 0.5%。
实施例 5 :
无机涂料为硅溶胶涂料 （硅溶胶复合外墙涂料， 配方参见张雪芹等， 无机 建筑涂料的研究与发展， 《新型建筑材料》 2004年 第 7期， 2.2.1节） ， 在该
硅溶胶涂料配制过程中或配制完成后加入石墨烯 （以石墨烯浆料形式加入， 石 墨烯浆料中石墨烯含量 5%， 换算后计算加入量）， 混合均匀即可， 石墨烯的加 入量占无机涂料的质量百分比为 0.001%-5%， 本实施例采用 0.1%。
实施例 6:
无机涂料为硅溶胶涂料 （市售， 上虞市殷宇硅制品有限公司生产） ， 在该 碱金属硅酸盐涂料配制过程中或配制完成后加入石墨烯 （以石墨烯粉形式加 入）， 混合均匀即可， 石墨烯的加入量占无机涂料的质量百分比为 0.001%-5%， 本实施例采用 0.8%。 以下实施方式以具体说明石墨烯的加入时机， 无机涂料为以正硅酸乙酯为 原料的硅溶胶涂料。
常规步骤为将正硅酸乙酯水解得到二氧化硅溶胶， 于 80°C熟化 5h得硅溶 胶涂料。
本发明改进后：
1、 水解前加入： 将石墨烯分散在水中后， 加入正硅酸乙酯水解， 于 80°C 熟化 5h得石墨烯无机涂料。
2、 水解后加入： 将正硅酸乙酯水解得到二氧化硅溶胶， 加入石墨烯混匀， 于 80°C熟化 5h得石墨烯无机涂料。
3、 熟化后加入： 将正硅酸乙酯水解得到二氧化硅溶胶， 于 80°C熟化 5h， 加入石墨烯混匀得石墨烯无机涂料。 将本发明的石墨烯无机涂料直接涂覆于金属 （铝板） 表面， 室温至 200°C
干燥处理 1分钟至 24小时，为提高无机物在金属表面的成膜特性再进行高温烘 烤， 烘烤温度为 200°C至 1000°C， 烘烤时间为 1-60分钟。
为了获得优质的施工质量， 可对铝板表面喷砂处理， 然后再涂覆本发明的 石墨烯无机涂料。
为了便于测试， 将本发明石墨烯无机涂料涂覆于铝板（未表面处理）表面， 80°C干燥处理 20min，再 600°C高温烘烤 20min，按照 GB/T9286-88的涂层附着 力测试方法测定涂层附着力， 结果如下 （表 1 ):
表 1本发明石墨烯无机涂料涂层附着力测试结果
表 2现有无机涂料涂层附着力测试结果 （金属表面未处理)
烘烤， 表层出现一些龟裂现象， 成膜不完整 对 比 4级 喷涂过程中， 无机涂料易于脱落， 有微弱的开裂现象， 经高温 例 3
烘烤， 表层出现较多龟裂现象， 成膜不完整 对 比 4级 喷涂过程中， 无机涂料易于脱落， 有微弱的开裂现象， 经高温 例 4
烘烤， 表层出现较多龟裂现象， 成膜不完整 对 比 4级 喷涂过程中， 无机涂料易于脱落， 有微弱的开裂现象， 经高温 例 5
烘烤， 表层出现较多龟裂现象， 成膜不完整 对 比 4级 喷涂过程中， 无机涂料易于脱落， 有微弱的开裂现象， 经高温 例 6
烘烤， 表层出现较多龟裂现象， 成膜不完整
作为对照， 将实施例 1-6中的现有无机涂料涂覆于铝板（经表面喷砂处理) 表面， 80°C干燥处理 20min， 再 600°C高温烘烤 20min (对比例 7-12 )， 按照 GB/T9286-88的涂层附着力测试方法测定涂层附着力， 结果如下 （表 3 ) :
表 3现有无机涂料涂层附着力测试结果 （金属表面已处理）
以上所述的实施例只是本发明的一种较佳的方案， 并非对本发明作任何形 式上的限制， 在不超出权利要求所记载的技术方案的前提下还有其它的变体及 改型。
Claims
1. 一种石墨烯无机涂料， 其特征在于： 采用石墨烯改性无机涂料而得， 所述石 墨烯的加入量占无机涂料的质量百分比为 0.001%-5%。
2. 根据权利要求 1所述的一种石墨烯无机涂料，其特征在于：所述石墨烯的加 入量占无机涂料的质量百分比为 0.1%-1%。
3. 根据权利要求 1或 2所述的一种石墨烯无机涂料，其特征在于：所述石墨烯 为单层片状结构， 或所述石墨烯为层数在 2-50层， 层内为碳原子以 sp2杂化轨 道组成六角形蜂巢状晶格、 层间为碳原子以 π键结合。
4. 根据权利要求 3所述的一种石墨烯无机涂料， 其特征在于： 所述石墨烯中， 碳元素与非碳元素质量比大于 4: 1， 非碳元素选自氟、 氮、 氧、 硫、 氢、 氯、 溴、 碘中一种或几种。
5. 根据权利要求 1或 2所述的一种石墨烯无机涂料，其特征在于：所述石墨烯 以石墨烯粉或石墨烯浆料的形式添加。
6. 根据权利要求 1或 2所述的一种石墨烯无机涂料，其特征在于：所述无机涂 料选自碱金属硅酸盐涂料、 硅溶胶涂料、 憐酸盐涂料中的一种。
7. 一种如权利要求 1所述的石墨烯无机涂料的使用方法，其特征在于：将石墨 烯无机涂料直接涂覆于金属表面， 室温至 200°C干燥处理 1分钟至 24小时。
8. 根据权利要求 7所述的使用方法， 其特征在于： 所述金属表面经喷砂处理。
9. 根据权利要求 7或 8所述的使用方法，其特征在于：干燥处理后进一步进行 高温烘烤， 烘烤温度为 200°C至 1000°C， 烘烤时间为 1-60分钟。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310110824 | 2013-04-01 | ||
| CN201310110824.X | 2013-04-01 | ||
| CN201310131419.6 | 2013-04-16 | ||
| CN201310131419.6A CN103275542B (zh) | 2013-04-01 | 2013-04-16 | 一种石墨烯无机涂料及其使用方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014161214A1 true WO2014161214A1 (zh) | 2014-10-09 |
Family
ID=49058175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2013/075229 WO2014161214A1 (zh) | 2013-04-01 | 2013-05-07 | 一种石墨烯无机涂料及其使用方法 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103275542B (zh) |
| WO (1) | WO2014161214A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116426148A (zh) * | 2023-04-25 | 2023-07-14 | 合肥微晶材料科技有限公司 | 一种基于硅钛复合石墨烯树脂的高效防腐达克罗涂料 |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101510805B1 (ko) * | 2013-10-22 | 2015-04-08 | 현대자동차주식회사 | 그래핀-세라믹 하이브리드 코팅막, 및 이의 제조 방법 |
| CN103555016B (zh) * | 2013-11-07 | 2016-05-11 | 珠海市乐通化工股份有限公司 | 一种耐高温耐磨石墨烯涂料及其制备方法 |
| CN103740192B (zh) * | 2013-11-12 | 2016-02-03 | 宁波墨西新材料有限公司 | 一种石墨烯改性的氟树脂涂料 |
| CN103740158B (zh) * | 2013-11-12 | 2015-10-28 | 宁波墨西科技有限公司 | 一种石墨烯改性的建筑涂料 |
| CN103897446B (zh) * | 2014-04-21 | 2016-04-06 | 江苏同创节能科技有限公司 | 一种高性能的复合石墨烯导电涂料 |
| CN105086571A (zh) * | 2015-04-29 | 2015-11-25 | 宁波职业技术学院 | 一种添加石墨烯的涂料助剂 |
| CN105003945A (zh) * | 2015-06-12 | 2015-10-28 | 苏州邦多纳碳纤维科技有限公司 | 一种石墨烯导热地板及其制造方法 |
| CN105419413A (zh) * | 2015-12-25 | 2016-03-23 | 常州大学 | 一种含有石墨烯/氧化锌/氧化钛复合材料的防腐涂料及制备方法 |
| CN105647247B (zh) * | 2016-02-25 | 2018-04-10 | 中国科学院福建物质结构研究所 | 海洋装备用石墨烯基涂层的制备方法及其应用 |
| CN105754383B (zh) * | 2016-02-25 | 2018-04-10 | 中国科学院福建物质结构研究所 | 海洋装备用石墨烯基涂层的制备方法及其应用 |
| CN107033634A (zh) * | 2016-11-02 | 2017-08-11 | 张俊跃 | 石墨烯基涂料、制备方法及其应用 |
| CN106590252A (zh) * | 2016-12-15 | 2017-04-26 | 深圳大学 | 一种石墨烯改性的建筑外墙隔热涂料及其制备方法 |
| 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 |
| CN107189505B (zh) * | 2017-06-30 | 2020-08-28 | 广东美的厨房电器制造有限公司 | 一种高抗静电性能涂料及其制备方法 |
| CN108264851A (zh) * | 2018-01-31 | 2018-07-10 | 燕园众欣纳米科技（北京）有限公司 | 一种石墨烯型耐高温磷酸盐胶粘剂及制备方法 |
| CN108610673A (zh) * | 2018-04-18 | 2018-10-02 | 刘勤 | 一种石墨烯改性高温防腐涂料及其制备方法 |
| CN109943106A (zh) * | 2019-02-25 | 2019-06-28 | 北京碧海舟腐蚀防护工业股份有限公司 | 水性无机防腐涂料、防腐涂层及其应用 |
| CN110218469B (zh) * | 2019-06-25 | 2021-04-20 | 东方电气集团东方汽轮机有限公司 | 一种耐高温石墨烯导电水性防腐涂料 |
| CN110467837A (zh) * | 2019-08-02 | 2019-11-19 | 中国航发北京航空材料研究院 | 一种石墨烯无机磷酸盐铝涂料及其涂层制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474899A (zh) * | 2009-01-16 | 2009-07-08 | 南开大学 | 石墨烯-无机材料复合多层薄膜及其制备方法 |
| KR20110093970A (ko) * | 2011-07-13 | 2011-08-19 | 이재환 | 나노 복합체 조성물 |
| CN102199372A (zh) * | 2011-04-12 | 2011-09-28 | 合肥云荣机电科技有限公司 | 用于多晶硅铸锭炉的石墨烯- La2Ti2O7/锌-铝-锆系耐腐蚀涂层 |
| KR20120050078A (ko) * | 2010-11-10 | 2012-05-18 | 박은수 | 나노다공성을 갖는 전기전도성 고분자 나노복합체 충진제를 이용한 전자기차폐 내수성 규산염계 무기질 수성도료 및 그 제조방법 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134410B (zh) * | 2010-01-27 | 2015-11-25 | 张国庆 | 一种高性能水性防腐蚀涂料及其制备方法 |
| JP5777701B2 (ja) * | 2010-04-22 | 2015-09-09 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | グラフェンに基づいた２次元サンドウィッチナノ材料の製造方法 |
| KR101184443B1 (ko) * | 2010-10-15 | 2012-09-20 | 주식회사 썬닉스 | 방열코팅용 조성물 및 이를 이용한 반도체 제조 장치 |
| CN102208598B (zh) * | 2011-05-12 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | 石墨烯涂层改性的锂二次电池的电极极片及其制作方法 |
| CN102586775B (zh) * | 2012-01-18 | 2014-05-21 | 上海交通大学 | 用于航空铝合金材料的表面防腐处理方法 |
| CN102649896B (zh) * | 2012-05-29 | 2015-11-04 | 安顿雷纳(上海)纤维材料科技有限公司 | 一种新型高导热散热涂料及其制造方法 |
-
2013
- 2013-04-16 CN CN201310131419.6A patent/CN103275542B/zh active Active
- 2013-05-07 WO PCT/CN2013/075229 patent/WO2014161214A1/zh active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474899A (zh) * | 2009-01-16 | 2009-07-08 | 南开大学 | 石墨烯-无机材料复合多层薄膜及其制备方法 |
| KR20120050078A (ko) * | 2010-11-10 | 2012-05-18 | 박은수 | 나노다공성을 갖는 전기전도성 고분자 나노복합체 충진제를 이용한 전자기차폐 내수성 규산염계 무기질 수성도료 및 그 제조방법 |
| CN102199372A (zh) * | 2011-04-12 | 2011-09-28 | 合肥云荣机电科技有限公司 | 用于多晶硅铸锭炉的石墨烯- La2Ti2O7/锌-铝-锆系耐腐蚀涂层 |
| KR20110093970A (ko) * | 2011-07-13 | 2011-08-19 | 이재환 | 나노 복합체 조성물 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116426148A (zh) * | 2023-04-25 | 2023-07-14 | 合肥微晶材料科技有限公司 | 一种基于硅钛复合石墨烯树脂的高效防腐达克罗涂料 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103275542A (zh) | 2013-09-04 |
| CN103275542B (zh) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014161214A1 (zh) | 一种石墨烯无机涂料及其使用方法 | |
| CN103289450B (zh) | 一种碳纳米管无机涂料及其使用方法 | |
| CN103319919B (zh) | 一种云母和石墨烯共改性无机涂料及其使用方法 | |
| WO2018108030A1 (zh) | 一种石墨烯改性的建筑外墙隔热涂料及其制备方法 | |
| CN103740158B (zh) | 一种石墨烯改性的建筑涂料 | |
| CN103333539B (zh) | 硅酸盐系无机水性高温耐热涂料及其制备方法 | |
| CN111534131B (zh) | 一种保温涂料及其制备方法 | |
| CN1709988A (zh) | 高温保温、防腐蚀纳米涂料及其制备方法 | |
| JP6704516B2 (ja) | 親水型沈降防止遠赤外線波吸収材料及びその製造方法、並びにキッチン電気製品及びその製造方法 | |
| WO2008098421A1 (fr) | Adhésif composite inorganique résistant à des températures élevées | |
| WO2021068506A1 (zh) | 一种基于氧化石墨烯的水基防腐涂料及其制备方法 | |
| CN104817858A (zh) | 一种防雾、自洁纳米材料的制备方法 | |
| KR100852392B1 (ko) | 액상무기 바인더의 제조방법과 이를 이용한 콘크리트구조물 및 강구조물의 내구성 도막형성공법 | |
| CN103319978B (zh) | 一种防脱粉耐火涂料 | |
| CN103289467B (zh) | 一种云母无机涂料及其使用方法 | |
| WO2022198961A1 (zh) | 一种石墨烯改性的水性弹性涂料组合物及其制备方法 | |
| CN103773170A (zh) | 一种添加黑云母粉的防火涂料 | |
| CN105925177A (zh) | 一种水性有机无机杂化耐高温涂料及其制备方法 | |
| CN113248946A (zh) | 用于制作类陶瓷涂层的涂料组合物及其制备方法和应用 | |
| CN112210261A (zh) | 一种水性防火涂料及其制备方法 | |
| CN114736545B (zh) | 一种具有吸湿降燥功能的无机涂料 | |
| CN111909577B (zh) | 一种隔热保温涂料及其制备方法 | |
| CN107760133A (zh) | 一种纳米六硼化镧协同增强隔热效果的有机无机复合涂料的制备方法 | |
| CN110157252B (zh) | 一种用于外墙的反射隔热涂料 | |
| KR20120130545A (ko) | 진공중공캡슐을 함유한 단열, 내화, 방음 특성이 향상된 수성 무기도료 및 그 제조방법 |
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: 13881311 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 13881311 Country of ref document: EP Kind code of ref document: A1 |