WO2021068506A1 - Water-based anticorrosive coating based on graphene oxide and preparation method therefor - Google Patents
Water-based anticorrosive coating based on graphene oxide and preparation method therefor Download PDFInfo
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- 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
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- the mass concentration of the PVA aqueous solution is 0.5-1.2 mol/L, and the time for mixing the aluminum powder with the PVA aqueous solution after ball milling is 15-20 min.
Abstract
Provided are a water-based anticorrosive coating based on graphene oxide and a preparation method therefor, relating to the field of surface engineering technology. The coating provided in the present invention comprises the following components in parts by mass: 40-45 parts of an aqueous resin, 10-12 parts of graphene oxide, 10-12 parts of silicon carbide, 6-8 parts of a dispersing agent, 3-5 parts of an aluminum powder, and 120-200 parts of water. By means of the combined action of the hexagonal honeycomb structure of graphene oxide and the aluminum powder, the corrosion resistance of the coating layer is improved in the present application. The aluminum powder and the silicon carbide are combined to form an aluminum-silicon hybrid structure, thereby further improving the compactness, high-temperature resistance and corrosion resistance of the coating layer. Therefore, the water-based anticorrosive coating based on graphene oxide provided in the present invention has an excellent anticorrosive capacity, and is water-based, such that same is environmentally friendly and is low in cost. In addition, by means of the preparation method provided in the present invention, the bonding strength of the graphene oxide and the aluminum powder is very high, thereby efficiently improving the anticorrosive capacity of the coating; and the method is simple and easy to control.
Description
本发明涉及表面工程技术领域，特别涉及一种基于氧化石墨烯的水基防腐涂料及其制备方法。The invention relates to the technical field of surface engineering, in particular to a graphene oxide-based water-based anticorrosive coating and a preparation method thereof.
目前，在工程基建过程中，对建筑、钢架结构、户外设施等表面工程的防腐要求越来越高，且由于轻量化高强度的需求，越来越多的金属结构被应用，包括能源运输管道、化工容器、建筑桥梁、沿海码头设施等，对其防锈抗蚀的要求也随之提高。At present, in the process of engineering infrastructure, the anti-corrosion requirements of surface engineering such as buildings, steel frame structures, outdoor facilities, etc. are getting higher and higher, and due to the demand for light weight and high strength, more and more metal structures are used, including energy transportation Pipelines, chemical containers, construction bridges, coastal wharf facilities, etc. have also increased their rust and corrosion resistance requirements.
传统的防腐涂料主要成分为树脂等，原理主要是通过涂刷凝结后对金属结构进行隔离，避免外部腐蚀介质的侵入。但现有的腐蚀中，存在较大部分的电腐蚀，由电位差形成电离分解等情况，加速了金属锈蚀，而传统的防腐涂料防腐功能较为单一，无法对电腐蚀进行有效阻隔，并对环境存在污染。Traditional anti-corrosion coatings are mainly composed of resin, etc. The principle is to isolate the metal structure after painting and condensing to avoid the intrusion of external corrosive media. However, in the existing corrosion, there is a large part of electric corrosion, ionization decomposition formed by potential difference, etc., which accelerates metal corrosion. However, the traditional anti-corrosion coating has a single anti-corrosion function, which cannot effectively block the electric corrosion and affect the environment. There is pollution.
石墨烯基防腐涂料是逐渐发展起来的新型防腐涂料，主要以纯石墨烯作为防腐填料。然而现有的石墨烯基防腐涂料对电腐蚀也只能起到一定的阻隔作用，防腐性能提高的并不明显，因而限制了其使用范围。专利CN105349017B公开了一种添加了石墨烯/锌复合材料的防腐涂料及其制备方法，其防腐涂料由以下组分构成(按质量百分含量计)：聚氨酯20～90％、石墨烯/锌复合材料5～15％、着色颜料1～10％、填料5～10％、分散剂0.1～3％、润湿剂0.1～3％、增稠剂0.1～3％、流平剂0.1～1％、消泡剂0.1～1％、杀菌剂0.1～1％、水1～35％。该防腐涂料的防腐性能有所提高，但是在制备过程需要将锌粉在高温下汽化成锌蒸汽复合在石墨烯表面，这种方法存在石墨烯和锌结合强度不足的情况，且工艺较为复杂。Graphene-based anti-corrosion coatings are new types of anti-corrosion coatings that are gradually developed, mainly using pure graphene as anti-corrosion fillers. However, the existing graphene-based anticorrosive coatings can only play a certain barrier against electric corrosion, and the anticorrosion performance is not significantly improved, thus limiting the scope of its use. Patent CN105349017B discloses an anticorrosive coating added with graphene/zinc composite material and a preparation method thereof. The anticorrosive coating consists of the following components (in terms of mass percentage): polyurethane 20～90%, graphene/zinc composite Material 5-15%, coloring pigment 1-10%, filler 5-10%, dispersant 0.1-3%, wetting agent 0.1-3%, thickener 0.1-3%, leveling agent 0.1-1%, 0.1 to 1% defoamer, 0.1 to 1% bactericide, and 1 to 35% of water. The anti-corrosion performance of the anti-corrosion coating is improved, but during the preparation process, the zinc powder needs to be vaporized at high temperature into zinc vapor to be compounded on the surface of graphene. This method has insufficient bonding strength between graphene and zinc, and the process is more complicated.
发明内容Summary of the invention
有鉴于此，本发明的目的在于提供一种基于氧化石墨烯的水基防腐涂料及其制备方法。本发明提供的基于氧化石墨烯的水基防腐涂料抗腐蚀能力优异，并且环保、成本低。In view of this, the purpose of the present invention is to provide a graphene oxide-based water-based anticorrosive coating and a preparation method thereof. The graphene oxide-based water-based anticorrosive coating provided by the invention has excellent corrosion resistance, environmental protection and low cost.
为了实现上述发明目的，本发明提供了以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种基于氧化石墨烯的水基防腐涂料，包括以下质量份的组分：The present invention provides a water-based anticorrosive coating based on graphene oxide, which includes the following components by mass:
优选地，所述分散剂为聚羧酸氨盐分散剂。Preferably, the dispersant is a polycarboxylic acid ammonium salt dispersant.
本发明提供了以上方案所述基于氧化石墨烯的水基防腐涂料的制备方法，包括以下步骤：The present invention provides a preparation method of the graphene oxide-based water-based anticorrosive coating described in the above scheme, which includes the following steps:
将氧化石墨烯与水混合进行超声处理，得到氧化石墨烯处理液；Mixing graphene oxide and water for ultrasonic treatment to obtain a graphene oxide treatment solution;
将铝粉球磨后与PVA水溶液混合，得到PVA改性铝粉；Ball mill the aluminum powder and mix it with the PVA aqueous solution to obtain PVA modified aluminum powder;
将所述PVA改性铝粉与水进行混合，得到粉末泥浆；Mixing the PVA modified aluminum powder with water to obtain a powder slurry;
对所述粉末泥浆外侧加载电场，并将所述氧化石墨烯处理液加入到粉末泥浆中，经过电解得到复合粉末；Load an electric field on the outside of the powder slurry, and add the graphene oxide treatment solution to the powder slurry to obtain a composite powder through electrolysis;
将所述复合粉末在保护气氛下进行烧结，然后与水性树脂、分散剂、水和碳化硅混合，得到基于氧化石墨烯的水基防腐涂料。The composite powder is sintered in a protective atmosphere, and then mixed with a water-based resin, a dispersant, water and silicon carbide to obtain a graphene oxide-based water-based anticorrosive coating.
优选地，所述超声处理的频率为28kHz，功率为1000W，时间为15min。Preferably, the frequency of the ultrasonic treatment is 28kHz, the power is 1000W, and the time is 15min.
优选地，所述球磨的转速为330～350rpm，铝粉球磨后的粒度为3～5μm。Preferably, the rotation speed of the ball mill is 330 to 350 rpm, and the particle size of the aluminum powder after ball milling is 3 to 5 μm.
优选地，所述PVA水溶液的质量浓度为0.5～1.2mol/L，铝粉球磨后与PVA水溶液混合的时间为15～20min。Preferably, the mass concentration of the PVA aqueous solution is 0.5-1.2 mol/L, and the time for mixing the aluminum powder with the PVA aqueous solution after ball milling is 15-20 min.
优选地，所述电场的强度为60～80V/m。Preferably, the intensity of the electric field is 60-80V/m.
优选地，所述烧结的温度为550～600℃，时间为1.5～2h。Preferably, the sintering temperature is 550-600°C, and the time is 1.5-2h.
优选地，所述烧结的升温速率为50～70℃/min。Preferably, the heating rate of the sintering is 50-70°C/min.
优选地，所述烧结后，还包括对所得烧结产物进行碾磨，碾磨后的粒度为20～30目。Preferably, after the sintering, it further includes milling the obtained sintered product, and the particle size after milling is 20-30 mesh.
本发明提供了一种基于氧化石墨烯的水基防腐涂料，包括以下质量份的组分：水性树脂40～45份，氧化石墨烯10～12份，碳化硅10～12份，分散剂6～8份，铝粉3～5份，水120～200份。本发明提供的基于氧化石墨烯的水基防腐涂料通过氧化石墨烯的六边形蜂窝结构和铝粉的联合作用，提高了涂层 耐腐蚀性能，可对外部腐蚀进行有效抑制；铝粉和碳化硅结合形成铝-硅混合结构，进一步有效提高了涂层的致密性、耐高温性和抗腐蚀性。因此，本发明提供的基于氧化石墨烯的水基防腐涂料具有优异的防腐能力，且采用水基，环保、成本低。实施例结果表明，与传统的环氧树脂涂料和现有的石墨烯基涂料相比，本发明提供的基于氧化石墨烯的水基防腐涂料具有良好的力学性能和优异的耐化学及耐腐蚀性能，可以很好地保护基体不被腐蚀。The present invention provides a water-based anticorrosive coating based on graphene oxide, comprising the following components in parts by mass: 40 to 45 parts of water-based resin, 10 to 12 parts of graphene oxide, 10 to 12 parts of silicon carbide, and 6 to 12 parts of dispersant. 8 parts, 3 to 5 parts of aluminum powder, 120 to 200 parts of water. The graphene oxide-based water-based anticorrosive coating provided by the present invention improves the corrosion resistance of the coating through the combined action of the hexagonal honeycomb structure of graphene oxide and aluminum powder, and can effectively inhibit external corrosion; aluminum powder and carbonization Silicon is combined to form an aluminum-silicon mixed structure, which further effectively improves the compactness, high temperature resistance and corrosion resistance of the coating. Therefore, the graphene oxide-based water-based anticorrosive coating provided by the present invention has excellent anticorrosion ability, and adopts water-based, environmental protection and low cost. The results of the examples show that, compared with traditional epoxy resin coatings and existing graphene-based coatings, the graphene oxide-based water-based anticorrosive coating provided by the present invention has good mechanical properties and excellent chemical and corrosion resistance. , Can well protect the matrix from being corroded.
本发明提供了所述基于氧化石墨烯的水基防腐涂料的制备方法。本发明以PVA作为铝粉表面改性剂，经过改性的铝粉颗粒表面形成氢氧键，能够被氧化石墨烯有效包裹；本发明通过超声处理将多层结构的氧化石墨烯剥落层单层结构，提高氧化石墨烯的利用率，并降低包裹在铝粉颗粒外的层膜厚度；本发明通过电场作用使氧化石墨烯包裹在铝粉颗粒上形成复合粉末，结合强度高，且水电解法环保、无污染、制取效率高；本发明通过在保护气氛下对包裹有氧化石墨烯的铝粉颗粒进行烧结，可稳固包裹形态。因此，本发明提供的制备方法氧化石墨烯和铝粉的结合强度非常高，从而有效提高了涂料的防腐能力，且方法简单，易于控制。The invention provides a preparation method of the graphene oxide-based water-based anticorrosive coating. The present invention uses PVA as the surface modifier of aluminum powder, and the modified aluminum powder particles form hydrogen-oxygen bonds on the surface, which can be effectively wrapped by graphene oxide; the present invention uses ultrasonic treatment to exfoliate the graphene oxide layer of multi-layer structure. The structure improves the utilization rate of graphene oxide and reduces the thickness of the layer film wrapped outside the aluminum powder particles; the present invention uses the electric field to wrap the graphene oxide on the aluminum powder particles to form a composite powder, which has high bonding strength and is environmentally friendly by the water electrolysis method. , No pollution, high production efficiency; the present invention sinters the graphene oxide-coated aluminum powder particles in a protective atmosphere, which can stabilize the packaging form. Therefore, the preparation method provided by the present invention has a very high bonding strength between the graphene oxide and the aluminum powder, thereby effectively improving the anti-corrosion ability of the coating, and the method is simple and easy to control.
本发明提供了一种基于氧化石墨烯的水基防腐涂料，包括以下质量份的组分：The present invention provides a water-based anticorrosive coating based on graphene oxide, which includes the following components by mass:
以质量份计，本发明提供的基于氧化石墨烯的水基防腐涂料包括水性树脂40～45份，优选为42～44份，更优选为43份。本发明对所述水性树脂没有特别的要求，采用本领域熟知的水性树脂即可，具体地如水性环氧树脂、水性丙烯酸树脂等。In terms of parts by mass, the graphene oxide-based water-based anticorrosive coating provided by the present invention includes 40-45 parts of water-based resin, preferably 42-44 parts, and more preferably 43 parts. The present invention has no special requirements on the water-based resin, and water-based resins well-known in the art can be used, such as water-based epoxy resins, water-based acrylic resins, and the like.
以水性树脂的质量份为基准，本发明提供的基于氧化石墨烯的水基防腐涂料包括氧化石墨烯10～12份，优选为10.5～11.5份，更优选为11份。本发明对所述氧化石墨烯没有特别的要求，采用本领域熟知的氧化石墨烯即可。在本发明具体实施例中，所述氧化石墨烯优选采用以石墨纸为原料，通过电解水进行氧化制备得到的氧化石墨烯。在本发明中，所述氧化石墨烯与纯石墨烯相比，含氧官能团数量更多，性质更加活跃，更易于与铝粉颗粒结合，提高涂料的性能。Based on the mass parts of the water-based resin, the graphene oxide-based water-based anticorrosive coating provided by the present invention includes 10-12 parts of graphene oxide, preferably 10.5-11.5 parts, and more preferably 11 parts. The present invention has no special requirements on the graphene oxide, and graphene oxide well-known in the art can be used. In a specific embodiment of the present invention, the graphene oxide preferably adopts graphene oxide prepared by using graphite paper as a raw material and oxidizing through electrolysis of water. In the present invention, compared with pure graphene, the graphene oxide has more oxygen-containing functional groups, has more active properties, is easier to combine with aluminum powder particles, and improves the performance of the coating.
以水性树脂的质量份为基准，本发明提供的基于氧化石墨烯的水基防腐涂料包括碳化硅10～12份，优选为10.5～11.5份，更优选为11份；所述碳化硅的粒径优选为20～35μm。本发明对所述碳化硅的来源没有特别的要求，采用本领域熟知的市售产品即可。Based on the mass parts of the water-based resin, the graphene oxide-based water-based anticorrosive coating provided by the present invention includes 10-12 parts of silicon carbide, preferably 10.5-11.5 parts, more preferably 11 parts; the particle size of the silicon carbide Preferably it is 20-35 micrometers. The present invention has no special requirements on the source of the silicon carbide, and commercially available products well known in the art can be used.
以水性树脂的质量份为基准，本发明提供的基于氧化石墨烯的水基防腐涂料包括分散剂6～8份，优选为6.5～7.5份，更优选为7份。在本发明中，所述分散剂优选为聚羧酸氨盐分散剂；本发明对所述聚羧酸氨盐分散剂的来源没有特别的要求，采用本领域熟知的市售产品即可。Based on the mass parts of the water-based resin, the graphene oxide-based water-based anticorrosive coating provided by the present invention includes 6-8 parts of the dispersant, preferably 6.5-7.5 parts, more preferably 7 parts. In the present invention, the dispersant is preferably a polycarboxylic acid ammonium salt dispersant; the present invention has no special requirements on the source of the polycarboxylic acid ammonium salt dispersant, and a commercially available product well-known in the art may be used.
以水性树脂的质量份为基准，本发明提供的基于氧化石墨烯的水基防腐涂料包括铝粉3～5份，优选为3.5～4.5份，更优选为4份。本发明对所述铝粉的来源没有特别的要求，采用本领域熟知的市售产品即可。Based on the mass parts of the water-based resin, the graphene oxide-based water-based anticorrosive coating provided by the present invention includes 3 to 5 parts of aluminum powder, preferably 3.5 to 4.5 parts, and more preferably 4 parts. The present invention has no special requirements on the source of the aluminum powder, and commercial products that are well known in the art can be used.
以水性树脂的质量份为基准，本发明提供的基于氧化石墨烯的水基防腐涂料包括水120～200份，优选为150～200份，更优选为180份。本发明对所述水没有特别的要求，采用本领域熟知的水即可；在本发明具体实施例中，所述水优选为去离子水。Based on the mass parts of the water-based resin, the graphene oxide-based water-based anticorrosive coating provided by the present invention includes 120-200 parts of water, preferably 150-200 parts, and more preferably 180 parts. The present invention has no special requirements on the water, and water well known in the art can be used; in the specific embodiment of the present invention, the water is preferably deionized water.
本发明提供了以上所述基于氧化石墨烯的水基防腐涂料，本发明通过氧化石墨烯的六边形蜂窝结构和铝粉的联合作用，提高了涂层耐腐蚀性能，可对外部腐蚀进行有效抑制；铝粉和碳化硅结合形成铝-硅混合结构，进一步有效提高了涂层的致密性、耐高温性和抗腐蚀性。因此，本发明提供的基于氧化石墨烯的水基防腐涂料具有优异的防腐能力，且采用水基，环保、成本低。The present invention provides the above-mentioned water-based anticorrosive coating based on graphene oxide. Through the combined action of the hexagonal honeycomb structure of graphene oxide and aluminum powder, the present invention improves the corrosion resistance of the coating and can effectively prevent external corrosion. Inhibition; aluminum powder and silicon carbide combine to form an aluminum-silicon mixed structure, which further effectively improves the compactness, high temperature resistance and corrosion resistance of the coating. Therefore, the graphene oxide-based water-based anticorrosive coating provided by the present invention has excellent anticorrosion ability, and adopts water-based, environmental protection and low cost.
本发明提供了以上方案所述基于氧化石墨烯的水基防腐涂料的制备方法，包括以下步骤：The present invention provides a preparation method of the graphene oxide-based water-based anticorrosive coating described in the above scheme, which includes the following steps:
将氧化石墨烯与水混合进行超声处理，得到氧化石墨烯处理液；Mixing graphene oxide and water for ultrasonic treatment to obtain a graphene oxide treatment solution;
将铝粉球磨后与PVA水溶液混合，得到PVA改性铝粉；Ball mill the aluminum powder and mix it with the PVA aqueous solution to obtain PVA modified aluminum powder;
将所述PVA改性铝粉与水进行混合，得到粉末泥浆；Mixing the PVA modified aluminum powder with water to obtain a powder slurry;
对所述粉末泥浆外侧加载电场，并将所述氧化石墨烯处理液加入到粉末泥浆中，经过电解得到复合粉末；Load an electric field on the outside of the powder slurry, and add the graphene oxide treatment solution to the powder slurry to obtain a composite powder through electrolysis;
将所述复合粉末在保护气氛下进行烧结，然后与水性树脂、分散剂、水和碳化硅混合，得到基于氧化石墨烯的水基防腐涂料。The composite powder is sintered in a protective atmosphere, and then mixed with a water-based resin, a dispersant, water and silicon carbide to obtain a graphene oxide-based water-based anticorrosive coating.
本发明将氧化石墨烯与水混合进行超声处理，得到氧化石墨烯处理液。在本发明中，所述氧化石墨烯和水的质量比优选为1∶8～12，更优选为1∶12。在本发明中，所述超声处理的频率优选为28kHz，功率优选为1000W，时间优选为15min。经过超声处理后，氧化石墨烯的水溶液被降解至棕色，即得所述氧化石墨烯处理液。本发明通过超声处理将多层结构的氧化石墨烯剥落层单层结构，可提高氧化石墨烯的利用率，并降低包裹在铝粉颗粒外的层膜厚度。In the present invention, graphene oxide is mixed with water for ultrasonic treatment to obtain a graphene oxide treatment solution. In the present invention, the mass ratio of the graphene oxide to water is preferably 1:8-12, more preferably 1:12. In the present invention, the frequency of the ultrasonic treatment is preferably 28kHz, the power is preferably 1000W, and the time is preferably 15min. After ultrasonic treatment, the aqueous solution of graphene oxide is degraded to brown to obtain the graphene oxide treatment solution. In the present invention, the single-layer structure of the graphene oxide exfoliation layer of the multilayer structure can be improved through the ultrasonic treatment, which can improve the utilization rate of the graphene oxide and reduce the thickness of the layer film wrapped outside the aluminum powder particles.
本发明将铝粉球磨后与PVA水溶液混合，得到PVA改性铝粉。在本发明中，所述球磨的转速优选为330～350rpm，更优选为340rpm；所述球磨优选采用大功率球磨机进行；铝粉球磨后的粒度优选为3～5μm，更优选为4μm。经过球磨后，铝粉由片状、多面体状变为球形。在本发明中，所述PVA(聚乙烯醇)水溶液的质量浓度优选为0.8～1.2mol/L，更优选为0.98mol/L；本发明对所述PVA水溶液的加入量没有特别的要求，能够将球磨后的铝粉完全浸湿即可。在本发明中，所述球磨后的铝粉与PVA水溶液混合的时间优选为15～20min，更优选为17min。本发明对所述混合的方法没有特别的要求，采用本领域熟知的方法能够保证铝粉在PVA水溶液中充分分散即可，具体地如搅拌混合。混合后，本发明优选将所得混合液进行固液分离，得到的固体即为所述PVA改性铝粉；本发明对所述固液分离的方法没有特别的要求， 采用本领域熟知的方法即可。本发明以PVA作为铝粉表面改性剂，在球磨后的球形铝粉表面形成亲水性的PVA膜，经过改性的铝粉颗粒表面形成氢氧键，能够被氧化石墨烯有效包裹。In the invention, the aluminum powder is ball-milled and mixed with the PVA aqueous solution to obtain the PVA modified aluminum powder. In the present invention, the rotation speed of the ball mill is preferably 330-350 rpm, more preferably 340 rpm; the ball mill is preferably performed by a high-power ball mill; the particle size of the aluminum powder after ball milling is preferably 3 to 5 μm, more preferably 4 μm. After ball milling, the aluminum powder changes from flake or polyhedron to spherical. In the present invention, the mass concentration of the PVA (polyvinyl alcohol) aqueous solution is preferably 0.8-1.2 mol/L, more preferably 0.98 mol/L; the present invention has no special requirements on the amount of the PVA aqueous solution added, which can be Soak the aluminum powder after ball milling completely. In the present invention, the time for mixing the ball-milled aluminum powder with the PVA aqueous solution is preferably 15-20 min, more preferably 17 min. The present invention has no special requirements on the mixing method, and a method well known in the art can be used to ensure that the aluminum powder is fully dispersed in the PVA aqueous solution, specifically, such as stirring and mixing. After mixing, the present invention preferably subject the obtained mixed liquid to solid-liquid separation, and the obtained solid is the PVA modified aluminum powder; the present invention has no special requirements on the solid-liquid separation method, and the method is well known in the art. can. The present invention uses PVA as an aluminum powder surface modifier to form a hydrophilic PVA film on the surface of the spherical aluminum powder after ball milling, and the modified aluminum powder particles form hydrogen-oxygen bonds on the surface, which can be effectively wrapped by graphene oxide.
得到PVA改性铝粉后，本发明将所述PVA改性铝粉与水进行混合，得到粉末泥浆。在本发明中，所述PVA改性铝粉与水的质量比优选为1∶0.5～0.8，更优选为1∶0.6。本发明对所述混合的方法没有特别的要求，能够保证将PVA改性铝粉与水混合均匀即可。After obtaining the PVA modified aluminum powder, the present invention mixes the PVA modified aluminum powder with water to obtain a powder slurry. In the present invention, the mass ratio of the PVA modified aluminum powder to water is preferably 1:0.5-0.8, more preferably 1:0.6. The present invention has no special requirements on the mixing method, as long as it can ensure that the PVA modified aluminum powder and water are uniformly mixed.
得到粉末泥浆后，本发明对所述粉末泥浆外侧加载电场，并将所述氧化石墨烯处理液加入到粉末泥浆中，经过电解得到复合粉末。在本发明中，电场的强度优选为60～80V/m，更优选为70V/m。本发明对所述电场的具体施加方法没有特别的要求，采用本领域熟知的方法即可。本发明优选在电解的过程中对混合浆液进行搅拌，促进氧化石墨烯和PVA改性铝粉的分散。在本发明中，所述电解的时间以混合浆液的棕色褪去为准；电解后，本发明优选对电解后的混合浆液进行水洗，得到复合粉末。本发明通过电场作用(即采用水电解法)使氧化石墨烯包裹在铝粉颗粒上形成复合粉末，其中，铝粉表面带正电荷，氧化石墨烯由于羧基和羟基离子化带有负电荷，铝粉和氧化石墨烯相互吸附，结合强度高，且水电解法环保、无污染、制取效率高。After the powder slurry is obtained, the present invention loads an electric field on the outside of the powder slurry, and adds the graphene oxide treatment solution to the powder slurry, and electrolysis obtains a composite powder. In the present invention, the intensity of the electric field is preferably 60 to 80 V/m, and more preferably 70 V/m. The present invention does not have any special requirements for the specific application method of the electric field, and a method well known in the art may be used. The present invention preferably stirs the mixed slurry during the electrolysis process to promote the dispersion of graphene oxide and PVA modified aluminum powder. In the present invention, the electrolysis time is based on the fading of the brown color of the mixed slurry; after electrolysis, the present invention preferably washes the electrolyzed mixed slurry with water to obtain a composite powder. In the present invention, graphene oxide is wrapped on aluminum powder particles to form a composite powder through the action of an electric field (ie, water electrolysis). The surface of the aluminum powder is positively charged, and the graphene oxide is negatively charged due to the ionization of carboxyl and hydroxyl groups. It adsorbs each other with graphene oxide, has high bonding strength, and the water electrolysis method is environmentally friendly, pollution-free, and high in production efficiency.
得到复合粉末后，本发明将所述复合粉末在保护气氛下进行烧结，然后与水性树脂、分散剂、水和碳化硅混合，得到基于氧化石墨烯的水基防腐涂料。在本发明中，所述烧结的温度优选为550～600℃，更优选为570℃，时间优选为1.5～2h，更优选为1.7h。在本发明中，所述烧结的升温速率优选为50～70℃/min，更优选为60℃/min。在本发明中，所述烧结的过程中持续通入保护气氛；所述保护气氛优选为氩气或氮气；当所述保护气氛优选为氩气时，所述氩气的流量优选为50cc/min；当所述保护气氛优选为氮气时，所述氮气的流量优选为100cc/min。在本发明中，所述烧结后，还优选包括对所得烧结产物进行碾磨，碾磨后的粒度优选为20～30目。本发明对所述碾磨的具体方法没有特别的要求，采用本领域熟知的方法即可。本发明通过在保护气氛下对包裹有氧化石墨烯的铝粉颗粒，即复合粉末进行烧结，可稳固包裹 形态。所述复合粉末在保护气氛下进行烧结之后，与水性树脂、分散剂、水和碳化硅混合。在本发明中，所述混合的顺序优选为：将复合粉末烧结之后先与水性树脂和分散剂混合，再向其中加入水进行混合；最后向所得混合水溶液中加入碳化硅进行混合。本发明优选在搅拌的条件下进行混合，本发明对所述搅拌的速度和时间没有特别的要求，保证各组分混合均匀即可。混合后，得到所述基于氧化石墨烯的水基防腐涂料。After the composite powder is obtained, the present invention sinters the composite powder in a protective atmosphere, and then mixes it with water-based resin, dispersant, water and silicon carbide to obtain a graphene oxide-based water-based anticorrosive coating. In the present invention, the sintering temperature is preferably 550-600°C, more preferably 570°C, and the time is preferably 1.5-2h, more preferably 1.7h. In the present invention, the heating rate of the sintering is preferably 50-70°C/min, more preferably 60°C/min. In the present invention, the protective atmosphere is continuously introduced during the sintering process; the protective atmosphere is preferably argon or nitrogen; when the protective atmosphere is preferably argon, the flow rate of the argon is preferably 50cc/min When the protective atmosphere is preferably nitrogen, the flow rate of the nitrogen is preferably 100 cc/min. In the present invention, after the sintering, it also preferably includes milling the obtained sintered product, and the particle size after milling is preferably 20-30 mesh. The present invention does not have any special requirements for the specific method of milling, as long as the method is well known in the art. The present invention sinters the graphene oxide-coated aluminum powder particles, that is, the composite powder, in a protective atmosphere, so that the package shape can be stabilized. After the composite powder is sintered in a protective atmosphere, it is mixed with an aqueous resin, a dispersant, water and silicon carbide. In the present invention, the mixing sequence is preferably: after sintering the composite powder, first mix with the water-based resin and the dispersant, then add water to it for mixing; finally, add silicon carbide to the resulting mixed aqueous solution for mixing. In the present invention, mixing is preferably carried out under stirring conditions. The present invention has no special requirements on the stirring speed and time, as long as the components are uniformly mixed. After mixing, the graphene oxide-based water-based anticorrosive coating is obtained.
下面结合实施例对本发明提供的基于氧化石墨烯的水基防腐涂料及其制备方法进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The graphene oxide-based water-based anticorrosive coating and the preparation method thereof provided by the present invention will be described in detail below with reference to examples, but they should not be understood as limiting the protection scope of the present invention.
实施例1Example 1
一种基于氧化石墨烯的水基防腐涂料，包括：水性树脂45份、氧化石墨烯10份、碳化硅12份、聚羧酸氨盐分散剂8份、铝粉3份、去离子水200份，上述组分为质量份配比。制备方法如下：A water-based anticorrosive coating based on graphene oxide, comprising: 45 parts of water-based resin, 10 parts of graphene oxide, 12 parts of silicon carbide, 8 parts of polycarboxylate dispersant, 3 parts of aluminum powder, and 200 parts of deionized water, The above-mentioned components are in parts by mass. The preparation method is as follows:
1)将上述组分中的氧化石墨烯投放入去离子水内，氧化石墨烯和去离子水的质量比为1∶12，溶液经超声波降解直至棕色；1) Put the graphene oxide in the above components into deionized water, the mass ratio of graphene oxide to deionized water is 1:12, and the solution is degraded by ultrasonic until it is brown;
2)将铝粉进行球磨，细化至5μm；所述铝粉球磨采用大功率球磨机进行，转速为330rpm；2) Ball mill the aluminum powder to refine it to 5 μm; the aluminum powder ball mill is performed by a high-power ball mill with a rotation speed of 330 rpm;
3)将步骤2)中球磨后的球形铝粉采用PVA水溶液进行处理，在表面形成亲水性的PVA膜；3) The spherical aluminum powder after ball milling in step 2) is treated with a PVA aqueous solution to form a hydrophilic PVA film on the surface;
4)将步骤3)中改性后的铝粉投入去离子水中进行混合，改性后的铝粉与去离子水的质量比为1∶0.6，形成粉末泥浆；4) Put the modified aluminum powder in step 3) into deionized water for mixing, and the mass ratio of the modified aluminum powder to the deionized water is 1:0.6 to form a powder slurry;
5)对步骤4)中的粉末泥浆外侧加载电场，电场能够使得铝粉和氧化石墨烯带电荷，进行相互吸引；5) Load an electric field on the outside of the powder slurry in step 4), the electric field can make the aluminum powder and graphene oxide charge and attract each other;
6)将步骤1)中得到的溶液逐步添加至置于电场中的粉末泥浆内，进行分散搅拌，通过机械搅拌直至浆液从棕色褪去；6) The solution obtained in step 1) is gradually added to the powder slurry placed in the electric field, and dispersed and stirred, and mechanically stirred until the slurry fades from the brown color;
7)将步骤6)中获取的粉末泥浆进行冲洗清洁，并以每分钟50摄氏度的加热速率加热至550摄氏度，保温，受热过程中，持续注入氩气，持续时间2小时；氩气为匀速流动状态，流量为每分钟50cc；7) Wash and clean the powder slurry obtained in step 6), and heat it to 550 degrees Celsius at a heating rate of 50 degrees Celsius per minute, and keep it warm. During the heating process, continue to inject argon for 2 hours; argon flows at a constant speed State, the flow rate is 50cc per minute;
8)将步骤7)中的烧结产物进行碾磨成粉末状，并和水性树脂、分散剂采用机械搅拌混合，加入水进行混合搅拌；8) The sintered product in step 7) is milled into a powder, and mixed with the water-based resin and dispersant by mechanical stirring, and water is added for mixing and stirring;
9)将碳化硅加入至步骤8)获取的溶液中，继续进行搅拌混合，得到基于氧化石墨烯的水基防腐涂料。9) Add silicon carbide to the solution obtained in step 8), continue to stir and mix, to obtain a graphene oxide-based water-based anticorrosive coating.
实施例2Example 2
一种基于氧化石墨烯的水基防腐涂料，包括：水性树脂40份、氧化石墨烯12份、碳化硅10份、聚羧酸氨盐分散剂6份、铝粉5份、去离子水180份，上述组分为质量份配比。制备方法如下：A water-based anticorrosive coating based on graphene oxide, comprising: 40 parts of water-based resin, 12 parts of graphene oxide, 10 parts of silicon carbide, 6 parts of polycarboxylate dispersant, 5 parts of aluminum powder, and 180 parts of deionized water, The above-mentioned components are in parts by mass. The preparation method is as follows:
1)将上述组分中的氧化石墨烯投放入去离子水内，氧化石墨烯和去离子水的质量比为1∶12，溶液经超声波降解直至棕色；1) Put the graphene oxide in the above components into deionized water, the mass ratio of graphene oxide to deionized water is 1:12, and the solution is degraded by ultrasonic until it is brown;
2)将铝粉进行球磨，细化至3μm；所述铝粉球磨采用大功率球磨机进行，转速为350rpm；2) Ball mill the aluminum powder and refine it to 3 μm; the aluminum powder ball mill is performed by a high-power ball mill with a rotation speed of 350 rpm;
3)将步骤2)中球磨后的球形铝粉采用PVA水溶液进行处理，在表面形成亲水性的PVA膜；3) The spherical aluminum powder after ball milling in step 2) is treated with a PVA aqueous solution to form a hydrophilic PVA film on the surface;
4)将步骤3)中改性后的铝粉投入去离子水中进行混合，改性后的铝粉和去离子水的质量比为1∶0.6，形成粉末泥浆；4) Put the modified aluminum powder in step 3) into deionized water for mixing, and the mass ratio of the modified aluminum powder to deionized water is 1:0.6 to form a powder slurry;
5)对步骤4)中的粉末泥浆外侧加载电场；5) Load an electric field on the outside of the powder slurry in step 4);
6)将步骤1)中得到的溶液逐步添加至置于电场中的粉末泥浆内，进行分散搅拌，通过机械搅拌直至浆液从棕色褪去；6) The solution obtained in step 1) is gradually added to the powder slurry placed in the electric field, and dispersed and stirred, and mechanically stirred until the slurry fades from the brown color;
7)将步骤6)中获取的粉末泥浆进行冲洗清洁，并以每分钟50摄氏度的加热速率加热至600摄氏度，保温，受热过程中，持续注入氮气，注入流量100cc/min，持续时间1.5小时；7) Wash and clean the powder slurry obtained in step 6), and heat it to 600 degrees Celsius at a heating rate of 50 degrees Celsius per minute, keep it warm, and continue to inject nitrogen during the heating process at a flow rate of 100cc/min and a duration of 1.5 hours;
8)将步骤7)中的烧结产物进行碾磨成粉末状，并和水性树脂、分散剂采用机械搅拌混合，将去离子水加入搅拌混合；8) The sintered product in step 7) is ground into powder, and mixed with the water-based resin and dispersant by mechanical stirring, and deionized water is added to the stirring and mixing;
9)将碳化硅加入至步骤8)获取的溶液中，继续进行搅拌混合，得到基于氧化石墨烯的水基防腐涂料。9) Add silicon carbide to the solution obtained in step 8), continue to stir and mix, to obtain a graphene oxide-based water-based anticorrosive coating.
实施例3Example 3
一种基于氧化石墨烯的水基防腐涂料，包括：水性树脂42份、氧化石 墨烯11份、碳化硅11份、聚羧酸氨盐分散剂7份、铝粉4份、去离子水120份，上述组分为质量份配比。制备方法如下：A water-based anticorrosive coating based on graphene oxide, comprising: 42 parts of water-based resin, 11 parts of graphene oxide, 11 parts of silicon carbide, 7 parts of polycarboxylate dispersant, 4 parts of aluminum powder, and 120 parts of deionized water, The above-mentioned components are in parts by mass. The preparation method is as follows:
1)将上述组分中的氧化石墨烯投放入去离子水内，氧化石墨烯和去离子水的质量比为1∶12，溶液经超声波降解直至棕色；1) Put the graphene oxide in the above components into deionized water, the mass ratio of graphene oxide to deionized water is 1:12, and the solution is degraded by ultrasonic until it is brown;
2)将铝粉进行球磨，细化至3.5μm；所述铝粉球磨采用大功率球磨机进行，转速为340rpm；2) Ball mill the aluminum powder and refine it to 3.5 μm; the aluminum powder ball mill is performed by a high-power ball mill with a rotation speed of 340 rpm;
3)将步骤2)中球磨后的球形铝粉采用PVA水溶液进行处理，在表面形成亲水性的PVA膜；3) The spherical aluminum powder after ball milling in step 2) is treated with a PVA aqueous solution to form a hydrophilic PVA film on the surface;
4)步骤3)中改性后的铝粉投入去离子水中进行混合，改性后的铝粉和去离子水的质量比为1∶0.6，形成粉末泥浆；4) In step 3), the modified aluminum powder is poured into deionized water for mixing, and the mass ratio of the modified aluminum powder to the deionized water is 1:0.6 to form a powder slurry;
5)对步骤4)中的粉末泥浆外侧加载电场；5) Load an electric field on the outside of the powder slurry in step 4);
6)将步骤1)中得到的溶液逐步添加至置于电场中的粉末泥浆内，进行分散搅拌，通过机械搅拌直至浆液从棕色褪去；6) The solution obtained in step 1) is gradually added to the powder slurry placed in the electric field, and dispersed and stirred, and mechanically stirred until the slurry fades from the brown color;
7)将步骤6)中获取的粉末泥浆进行冲洗清洁，并以每分钟60摄氏度的加热速率加热至580摄氏度，保温，受热过程中，持续注入惰性保护气体，持续时间1.8小时；7) Wash and clean the powder slurry obtained in step 6), and heat it to 580 degrees Celsius at a heating rate of 60 degrees Celsius per minute, keep it warm, and continue to inject inert protective gas during the heating process for 1.8 hours;
8)将步骤7)中的烧结产物进行碾磨成粉末状，并和水性树脂、分散剂采用机械搅拌混合，将去离子水加入搅拌混合；8) The sintered product in step 7) is ground into powder, and mixed with the water-based resin and dispersant by mechanical stirring, and deionized water is added to the stirring and mixing;
9)将碳化硅加入至步骤8)获取的溶液中，继续进行搅拌混合，得到基于氧化石墨烯的水基防腐涂料。9) Add silicon carbide to the solution obtained in step 8), continue to stir and mix, to obtain a graphene oxide-based water-based anticorrosive coating.
实施例1～3制备的基于氧化石墨烯的水基防腐涂料固化成膜后为银灰色，表面有颗粒感，带有金属光泽；观察它们的微观结构发现均存在独立的包裹有氧化石墨烯的铝粉颗粒，且在分散剂的作用下均匀分布在各处，形成的是球粒状复合涂层。The graphene oxide-based water-based anticorrosive coatings prepared in Examples 1 to 3 are silver-grey after curing into a film, with a grainy surface and metallic luster; observing their microstructures, it is found that there are independent coatings coated with graphene oxide Aluminum powder particles are uniformly distributed everywhere under the action of the dispersant, forming a spherical granular composite coating.
对实施例1～3制备的基于氧化石墨烯的水基防腐涂料的性能分别进行测试，在测试的过程中，分别以防腐常用的环氧树脂涂料和某厂家石墨烯基涂料(金陵涂料HGM-10)作为对比例。The performances of the graphene oxide-based water-based anticorrosive coatings prepared in Examples 1 to 3 were tested. During the test, the epoxy resin coatings commonly used for anticorrosion and the graphene-based coatings of a certain manufacturer (Jinling Coatings HGM- 10) As a comparative example.
(1)耐腐蚀性能测试(1) Corrosion resistance test
将实施例1～3制备的涂料与作为对比例的环氧树脂涂料和某厂家石墨烯基涂料(金陵涂料HGM-10)分别涂覆在碳钢表面，涂覆厚度为220μm，固化成膜后分别对碳钢的腐蚀电位进行检测，结果见表1：The paint prepared in Examples 1 to 3, the epoxy resin paint as a comparative example and the graphene-based paint (Jinling paint HGM-10) of a certain manufacturer were respectively coated on the surface of carbon steel with a coating thickness of 220 μm. After curing and forming a film The corrosion potential of carbon steel was tested respectively, and the results are shown in Table 1:
表1实施例1～3制备的基于氧化石墨烯的水基防腐涂料的耐腐蚀性能Table 1 Corrosion resistance of graphene oxide-based water-based anticorrosive coatings prepared in Examples 1 to 3
(2)物理和化学性能测试(2) Physical and chemical performance test
对实施例1～3制备的涂料与作为对比例的环氧树脂涂料和某厂家石墨烯基涂料(金陵涂料HGM-10)形成的漆膜分别进行物理和化学性能测试，依照GB/T 13452.2-2008测定漆膜厚度，依照GB/T 9286-1998测定漆膜附着力，依照GB/T 6742-2007测定漆膜柔韧性，依照GB/T 1732-1993测定漆膜耐冲击性，依照GB/T 1733-1993测定漆膜耐水性，依照GB/T 6739-2006测定漆膜硬度，依照GB/T 1771-2007测定漆膜耐中性盐雾；测试结果如表2所示：表2实施例1～3制备的基于氧化石墨烯的水基防腐涂料的物理和化学性能Physical and chemical performance tests were carried out on the paint prepared in Examples 1 to 3, the epoxy resin paint as a comparative example and the paint film formed by a graphene-based paint (Jinling Paint HGM-10) from a certain manufacturer, respectively, according to GB/T13452.2- In 2008, the thickness of the paint film was measured, the adhesion of the paint film was measured in accordance with GB/T 9286-1998, the flexibility of the paint film was measured in accordance with GB/T 6742-2007, and the impact resistance of the paint film was measured in accordance with GB/T 1732-1993, in accordance with GB/T The water resistance of the paint film was measured in 1733-1993, the hardness of the paint film was determined in accordance with GB/T 6739-2006, and the neutral salt spray resistance of the paint film was determined in accordance with GB/T 1771-2007; the test results are shown in Table 2: Table 2 Example 1 ～3 Physical and chemical properties of water-based anticorrosive coating based on graphene oxide prepared
从表1和表2可以看出，与传统的环氧树脂涂料和现有的石墨烯基涂料相比，本发明提供的基于氧化石墨烯的水基防腐涂料具有良好的力学性能和优异的耐化学及耐腐蚀性能，可以很好地保护基体不被腐蚀。It can be seen from Table 1 and Table 2 that compared with traditional epoxy resin coatings and existing graphene-based coatings, the graphene oxide-based water-based anticorrosive coatings provided by the present invention have good mechanical properties and excellent resistance. Chemical and corrosion resistance, can well protect the matrix from being corroded.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications are also It should be regarded as the protection scope of the present invention.
Claims (10)
- 一种基于氧化石墨烯的水基防腐涂料，其特征在于，包括以下质量份的组分：A water-based anticorrosive coating based on graphene oxide, which is characterized in that it comprises the following components by mass:
- 根据权利要求1所述的基于氧化石墨烯的水基防腐涂料，其特征在于，所述分散剂为聚羧酸氨盐分散剂。The graphene oxide-based water-based anticorrosive coating according to claim 1, wherein the dispersant is a polycarboxylic acid ammonium salt dispersant.
- 权利要求1或2所述基于氧化石墨烯的水基防腐涂料的制备方法，其特征在于，包括以下步骤：The method for preparing a graphene oxide-based water-based anticorrosive coating according to claim 1 or 2, characterized in that it comprises the following steps:将氧化石墨烯与水混合进行超声处理，得到氧化石墨烯处理液；Mixing graphene oxide and water for ultrasonic treatment to obtain a graphene oxide treatment solution;将铝粉球磨后与PVA水溶液混合，得到PVA改性铝粉；Ball mill the aluminum powder and mix it with the PVA aqueous solution to obtain PVA modified aluminum powder;将所述PVA改性铝粉与水进行混合，得到粉末泥浆；Mixing the PVA modified aluminum powder with water to obtain a powder slurry;对所述粉末泥浆外侧加载电场，并将所述氧化石墨烯处理液加入到粉末泥浆中，经过电解得到复合粉末；Load an electric field on the outside of the powder slurry, and add the graphene oxide treatment solution to the powder slurry to obtain a composite powder through electrolysis;将所述复合粉末在保护气氛下进行烧结，然后与水性树脂、分散剂、水和碳化硅混合，得到基于氧化石墨烯的水基防腐涂料。The composite powder is sintered in a protective atmosphere, and then mixed with a water-based resin, a dispersant, water and silicon carbide to obtain a graphene oxide-based water-based anticorrosive coating.
- 根据权利要求3所述的制备方法，其特征在于，所述超声处理的频率为28kHz，功率为1000W，时间为15min。The preparation method according to claim 3, wherein the frequency of the ultrasonic treatment is 28kHz, the power is 1000W, and the time is 15min.
- 根据权利要求3所述的制备方法，其特征在于，所述球磨的转速为330～350rpm，铝粉球磨后的粒度为3～5μm。The preparation method according to claim 3, wherein the rotation speed of the ball mill is 330-350 rpm, and the particle size of the aluminum powder after ball milling is 3-5 μm.
- 根据权利要求3所述的制备方法，其特征在于，所述PVA水溶液的质量浓度为0.5～1.2mol/L，铝粉球磨后与PVA水溶液混合的时间为15～20min。The preparation method according to claim 3, wherein the mass concentration of the PVA aqueous solution is 0.5 to 1.2 mol/L, and the time for mixing the aluminum powder with the PVA aqueous solution after ball milling is 15 to 20 minutes.
- 根据权利要求3所述的制备方法，其特征在于，所述电场的强度为 60～80V/m。The preparation method according to claim 3, wherein the intensity of the electric field is 60-80 V/m.
- 根据权利要求3所述的制备方法，其特征在于，所述烧结的温度为550～600℃，时间为1.5～2h。The preparation method according to claim 3, wherein the sintering temperature is 550-600°C, and the time is 1.5-2h.
- 根据权利要求3或8所述的制备方法，其特征在于，所述烧结的升温速率为50～70℃/min。The preparation method according to claim 3 or 8, characterized in that the heating rate of the sintering is 50-70°C/min.
- 根据权利要求3所述的制备方法，其特征在于，所述烧结后，还包括对所得烧结产物进行碾磨，碾磨后的粒度为20～30目。The preparation method according to claim 3, characterized in that, after the sintering, it further comprises grinding the obtained sintered product, and the particle size after grinding is 20-30 mesh.
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