CN108237063A - 一种金属防腐石墨烯复合涂层的制备方法 - Google Patents
一种金属防腐石墨烯复合涂层的制备方法 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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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
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- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
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Abstract
本发明涉及纳米材料领域，具体地，涉及一种金属防腐石墨烯复合涂层的制备方法。本发明的制备方法，包括以下步骤：(1)以石墨为原料并制得浓度为0.1wt％‑1wt％的石墨烯分散液；(2)将该石墨烯分散滴加在极性溶剂表面，在极性溶剂表面形成一层石墨烯薄膜层；(3)将单金属或合金进行清洗，使其形成亲水的表面；(4)将清洗后的单金属或合金插入到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，得到石墨烯涂层；(5)将覆盖有石墨烯涂层的金属片在惰性气体环境中高温处理2小时，得到金属防腐石墨烯涂层。本发明用界面转移方法将石墨烯涂覆在金属或合金表面，制备的石墨烯涂层具有稳定、高效、无毒、隔绝水和空气等优点。
Description
技术领域
本发明涉及纳米材料领域，具体地，涉及一种金属防腐石墨烯复合涂层的制备方法。
背景技术
金属腐蚀是一个非常严重的全球性问题，它对国民经济造成了直接的损失，因此，世界各国的科学家们都在努力地寻找有效的金属防护技术手段。腐蚀源于金属的表面同空气、水或其他物质发生了接触，目前普遍采用的防腐蚀方法是用惰性金属、导电聚合物、巯基的单分子层等保护层，但这些保护层材料都有其自身限制。自组装在金属表面的巯基单分子层不能耐100℃以上的温度；而聚合物涂层相对较厚，从而会显著改变下层金属的物理性质。
石墨烯是一种仅有单原子层厚度的新型碳材料，具有独特的结构和优异的物理化学性能。由于其具有超大的比表面积、优异的抗渗透性、高的热稳定性和化学稳定性等优点，故在金属材料的防腐领域也具有非常大的潜力。主要是由于石墨烯的层状结构使得其有快速的导电性，电子会通过石墨烯传递到金属涂层上，阴极电子不会直接发生在金属上，而是直接与涂层发生反应，这样就会降低对金属的溶解，从而实现对金属的保护。专利申请号201510785643.6公开了利用PECVD方法在锆合金表面原位生长垂直石墨烯的方法，该石墨烯层提高了锆合金的耐腐蚀性能和抗磨损能力。发明专利申请号为201610148083.8的专利公开了一种用于不锈钢表面的石墨烯防腐涂层。其是以石墨为原料，通过氧化还原法制备得到石墨烯粉末，然后对石墨烯粉末进行冷冻干燥，将石墨烯粉末放在压片机中压成石墨烯薄膜，然后石墨烯薄膜放在不锈钢基底上方作为离子溅射的靶材，经离子溅射后石墨烯薄膜被打碎从而沉积在不锈钢表面，得到石墨烯防腐涂层。Kang等通过自组装的方式，将氧化石墨烯旋涂在沉积有SiO2的硅片上，经热处理还原得到多层石墨烯薄膜，在Cu和Fe的基底上进行氧化实验测试，覆盖有石墨烯的金属表面得到有效保护。Liu等采用浸渍法在Al表面涂上氧化石墨烯，由于Al的活性，将氧化石墨烯还原为石墨烯，该涂层显示出高的抗腐蚀性。Chen等利用CVD法在纯金属Cu和Cu/Ni合金表面制备的石墨烯的抗氧化性能，电化学测试发现石墨烯在保护金属表面形成透明的导电惰性薄膜涂层，能有效防止金属在多种环境下(空气、溶液中)的氧化，同时发现石墨烯晶粒边界处会发生局部氧化，因此石墨烯的质量将是影响其抗氧化性的关键。澳大利亚的Nick Bribilis探索了石墨烯作为在Ni和Cu表面的防腐涂层的耐蚀性，先采用CVD方法在纯Ni和纯Cu表面沉积一层石墨烯，电化学研究表明，石墨烯在金属表面形成离子阻碍，能有效阻止金属在盐溶液中的电化学腐蚀。Prasai等采用CVD法在Cu和Ni表面制备石墨烯涂层，在Cu基底上生长石墨烯涂层使耐蚀性提高7倍，而在Ni基底上生长石墨烯涂层使耐蚀性提高20倍，并且建立了单层或多层石墨烯薄膜涂层的数量模型来描述其钝化机制。S.Raman等研究了CVD法制备Cu基石墨烯薄膜涂层在NaCl溶液中的腐蚀行为，发现电化学腐蚀的阳极和阴极电流都减小了1～2个数量级，交流阻抗谱显示石墨烯涂层显著提高了金属的阻抗。
综上所述，目前金属表面石墨烯涂层主要的制备方法是CVD法和氧化还原法，但是这些方法都难以实现大规模制备大面积的无缺陷石墨烯薄膜，仍然是制约其在金属防腐领域的发展的瓶颈。
发明内容
针对上述技术问题，本发明的目的在于提供一种用于金属表面的高隔绝防腐纳米涂层，同时提供高效防腐涂层的制备方法及用途。
本发明的金属防腐石墨烯涂层的制备方法，是在单一金属或合金的表面覆盖一层石墨烯，其中所述的金属或合金包括铜、铜合金、镍、镍合金、铝、铝合金等；所述的石墨烯涂层的厚度约为20nm-10μm。用界面转移方法将石墨烯涂覆在金属或合金表面，制备的石墨烯涂层具有稳定、高效、无毒、隔绝水和空气等优点，实现抗腐蚀的作用，可广泛应用于海洋、陆地以及地下工业生产环境和日常生活环境中使用的钢材等的腐蚀防护。
为实现上述目的，本发明的金属防腐石墨烯涂层的制备方法的具体工艺步骤如下：
本发明的金属防腐石墨烯涂层的制备方法，包括以下步骤：
(1)优选以天然石墨为原料通过机械剥层的方法得到是石墨烯片，并制得浓度为0.1wt％-1wt％的石墨烯分散液；
(2)将步骤(1)所述石墨烯分散液滴加在极性溶剂表面，在极性溶剂表面形成一层均匀的石墨烯薄膜层；
(3)将单金属或合金进行清洗，去除金属表面的油污，使其形成亲水的表面；
(4)将清洗后的单金属或合金插入到步骤(2)含石墨烯薄膜层的溶液中，进行薄膜的界面转移，在单金属或合金表面得到均匀的石墨烯涂层；
(5)将覆盖有石墨烯涂层的金属片在惰性气体环境中、在300-900℃下处理2-6小时，得到金属防腐石墨烯涂层。
根据本发明的制备方法，作为优选地，所述石墨烯片的厚度小于等于4nm，粒径为100-6000nm。
根据本发明的制备方法，作为优选地，所述石墨烯分散液的分散剂可以是环戊酮、环己酮、乙烯基吡咯烷酮、1,3-二甲基-2-咪唑啉苯甲基安息香酸、N,N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、环己基吡咯烷酮、N-辛基吡咯烷酮、乙酸乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜和四氢呋喃中的一种或多种。
作为优选地，步骤(2)所述极性溶剂是乙醇、甲醇、丙醇、异丙醇、水、丙酮、吡啶、乙酸和乙腈中的一种或多种。
根据本发明的制备方法，优选使用单金属片或合金片。所述单金属可以为但不限于铁、铜、镍或铝等，所述合金可以为但不限于铁合金(包括钢)、铜合金、镍合金或铝合金等。
根据本发明的制备方法，其中，步骤(5)得到的金属防腐石墨烯涂层的厚度可以达到20nm-10μm。
本发明的金属防腐石墨烯复合涂层的制备方法，与现有技术相比，具有以下优点：
(1)本发明采用的石墨烯分散液的原料是石墨，原料易得，成本低廉；
(2)本发明的石墨烯涂层采用界面转移技术，所得的石墨烯薄膜均匀，厚度可控，效率高，制备方法简单易于规模化制备；
(3)该方法可将石墨烯薄膜转移到任何形状的单一金属或合金表面，不受材料形状的限制；
(4)石墨烯防腐层在金属或合金表面堆积紧密，具有隔绝水和空气等优点，耐腐蚀性能强，石墨烯涂层的低频阻抗模值从10-2提高到10-7，能对基体起到更有效的保护作用；且在强腐蚀性溶液中浸泡多天，低频阻抗模值基本不变，显示出优异的耐腐蚀稳定性。
(5)可广泛应用于海洋、陆地以及地下工业生产环境和日常生活环境中使用的钢材等的腐蚀防护。
附图说明
图1为本发明石墨烯涂层的扫描电镜图。
图2为无涂层碳钢和有石墨烯涂层的碳钢在0.1mol L-1的硫酸溶液中的波特(Bode)图对比。
具体实施方式
下面结合实施例对本发明技术方案予以进一步的说明。
实施例1
制备金属防腐石墨烯涂层：
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为0.1wt％石墨烯环戊酮分散液，其中石墨烯片的厚度3nm，粒径为1000nm；
(2)将步骤(2)的石墨烯分散滴加在乙醇表面，在极性溶剂表面形成一层均匀的石墨烯薄膜；
(3)将碳钢片进行清洗，去除表面的油污，使其形成亲水的表面；
(4)将清洗后的碳钢片插入到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在碳钢表面得到均匀的石墨烯涂层；
(5)将覆盖有是石墨烯的碳钢片在氩气环境中在300℃下处理6小时，得到耐腐蚀的石墨烯涂层。
使用扫面电镜观察石墨烯涂层，所述石墨烯涂层厚度在100nm左右，如图1所示，从图1可以看出，石墨烯片尺寸约为500nm-1μm，这些石墨烯片紧密堆叠在一起，形成致密保护层。
将未涂层的碳钢和制作的有石墨烯涂层的碳钢在0.1mol L-1的硫酸溶液中，，进行腐蚀试验。二者的波特(Bode)图对比如图2所示，上线为纯碳钢的波特图、下线为覆盖有石墨烯的碳钢的波特图，从图中可以发现，石墨烯的碳钢在低频区和高频区都具有较大的阻抗，显示出较好的防腐效果。
实施例2
制备金属防腐石墨烯涂层：
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为1wt％石墨烯乙酸乙酯分散液，其中石墨烯片的厚度4nm，粒径为6000nm；
(2)将步骤(2)的石墨烯分散滴加在水表面，在极性溶剂表面形成一层均匀的石墨烯薄膜；
(3)将铜锌合金片进行清洗，去除表面的油污，使其形成亲水的表面；
(4)将清洗后的铜锌合金片插入到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在铜锌合金片表面得到均匀的石墨烯涂层；
(5)将覆盖有是石墨烯的铜锌合金片在氦气环境中在600℃下处理2小时，得到耐腐蚀的石墨烯涂层。
所制得的石墨烯涂层厚度在10μm左右，耐腐蚀性能良好。
实施例3
制备金属防腐石墨烯涂层：
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为0.5wt％石墨烯丙酮分散液，其中石墨烯片的厚度1nm，粒径为100nm；
(2)将步骤(2)的石墨烯分散滴加在丙酮表面，在极性溶剂表面形成一层均匀的石墨烯薄膜；
(3)将镍棒进行清洗，去除表面的油污，使其形成亲水的表面；
(4)将清洗后的镍棒插入到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在镍棒表面得到均匀的石墨烯涂层；
(5)将覆盖有是石墨烯的镍棒在氩气环境中在400℃下处理5小时，得到耐腐蚀的石墨烯涂层。
所制得的石墨烯涂层厚度在20nm左右，耐腐蚀性能良好。
实施例4
制备金属防腐石墨烯涂层：
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为0.8wt％石墨烯四氢呋喃分散液，其中石墨烯片的厚度2nm，粒径为500nm；
(2)将步骤(2)的石墨烯分散滴加在乙酸表面，在极性溶剂表面形成一层均匀的石墨烯薄膜；
(3)将铝片进行清洗，去除表面的油污，使其形成亲水的表面；
(4)将清洗后的铝片插入到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在铝片表面得到均匀的石墨烯涂层；
(5)将覆盖有是石墨烯的铝片在氩气环境中在900℃下处理2小时，得到耐腐蚀的石墨烯涂层。
所制得的石墨烯涂层厚度在50nm左右，耐腐蚀性能良好。
当然，本发明还可以有多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明的公开做出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明的权利要求的保护范围。
Claims (9)
1.一种金属防腐石墨烯复合涂层的制备方法，包括以下步骤：
(1)以石墨为原料通过机械剥层的方法得到石墨烯片，并制得浓度为0.1wt％-1wt％的石墨烯分散液；
(2)将步骤(1)所述石墨烯分散液滴加在极性溶剂表面，在极性溶剂表面形成一层石墨烯薄膜层；
(3)将单金属或合金进行清洗，去除金属表面的油污，使其形成亲水的表面；
(4)将清洗后的单金属或合金插入到步骤(2)含石墨烯薄膜层的溶液中，进行薄膜的界面转移，在单金属或合金表面得到石墨烯涂层；
(5)将覆盖有石墨烯涂层的金属片在惰性气体环境中、在300-900℃下处理2-6小时，得到金属防腐石墨烯复合涂层。
2.根据权利要求1所述的制备方法，其特征在于，所述石墨为天然石墨。
3.根据权利要求1或2所述的制备方法，其特征在于，所述石墨烯片的厚度小于等于4nm，粒径为100-6000nm。
4.根据权利要求1所述的制备方法，其特征在于，所述石墨烯分散液的分散剂是环戊酮、环己酮、乙烯基吡咯烷酮、1,3-二甲基-2-咪唑啉苯甲基安息香酸、N,N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、环己基吡咯烷酮、N-辛基吡咯烷酮、乙酸乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜和四氢呋喃中的一种或多种。
5.根据权利要求1所述的制备方法，其特征在于，步骤(2)所述极性溶剂是乙醇、甲醇、丙醇、异丙醇、水、丙酮、吡啶、乙酸和乙腈中的一种或多种。
6.根据权利要求1所述的制备方法，其特征在于，所述单金属或合金为片状。
7.根据权利要求1或6所述的制备方法，其特征在于，所述单金属为铁、铜、镍或铝，所述合金为铁合金、铜合金、镍合金或铝合金。
8.根据权利要求1所述的制备方法，其特征在于，步骤(5)得到的金属防腐石墨烯涂层的厚度为20nm-10μm。
9.根据权利要求1所述的制备方法，其特征在于，步骤(2)在极性溶剂表面形成一层均匀的石墨烯薄膜层；步骤(4)在单金属或合金表面得到均匀的石墨烯涂层。
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| CN111085416A (zh) * | 2019-12-02 | 2020-05-01 | 深圳石墨烯创新中心有限公司 | 一种石墨烯复合金属箔及其制备方法 |
| CN111321403B (zh) * | 2020-03-10 | 2022-03-11 | 河北北方学院 | 一种基于多巴胺的锌表面载镓-氧化石墨烯复合涂层的制备方法 |
| CN116262868B (zh) * | 2022-12-20 | 2024-02-13 | 华鸿画家居股份有限公司 | 一种高透明高导电石墨烯纳米铟防银变色涂层的制备方法 |
| CN115975423B (zh) * | 2023-02-08 | 2024-02-27 | 大连交通大学 | 还原氧化石墨烯/铝防腐蚀材料及其制备方法和应用 |
| CN116254013B (zh) * | 2023-02-14 | 2023-11-17 | 复旦大学 | 一种多功能石墨烯自组装膜及其制备方法 |
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| CN105195407B (zh) * | 2015-08-22 | 2018-05-11 | 江苏万源新材料有限公司 | 一种铝基石墨烯水性丙烯酸树脂复合材料及其制备方法 |
| CN105484016A (zh) * | 2015-12-28 | 2016-04-13 | 宁国市龙晟柔性储能材料科技有限公司 | 一种石墨烯复合导电纤维的制备方法 |
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| US20150367381A1 (en) * | 2014-06-19 | 2015-12-24 | Uchicago Argonne, Llc. | Low friction wear resistant graphene films |
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| CN109909131B (zh) * | 2019-03-26 | 2021-10-01 | 中铁建大桥工程局集团第四工程有限公司 | 一种石墨烯基钢材防腐涂层的制备方法 |
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