CN107216473B - 基于多巴胺提高碳纤维增强复合材料表面涂装性能的方法 - Google Patents
基于多巴胺提高碳纤维增强复合材料表面涂装性能的方法 Download PDFInfo
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Abstract
本发明属于材料表面处理及涂装技术领域，涉及一种表面自由能较低的碳纤维增强树脂基复合材料，通过该方法可显著提高涂料在材料表面的附着能力。技术方案包括以下步骤：(1)脂肪醇聚氧乙烯醚AEO‑12，0.1‑2份，JFC，0.1‑3份，30wt％的H2O2溶液，0.01‑0.5份，余量为H2O，组成A液。(2)用硼砂和硼酸配制pH值为8.0‑8.5的缓冲溶液，将盐酸多巴胺溶于缓冲溶液，配制浓度为0.4‑0.6g/L的盐酸多巴胺溶液,得到B液。(3)将A液与B液等体积混合均匀，刷涂或喷涂至经过打磨处理后的碳纤维增强树脂基复合材料表面上，待干燥后进行涂料的涂装。本发明可显著提高涂料在碳纤维增强树脂基复合材料表面的附着力。
Description
技术领域
本发明属于碳纤维复合材料表面处理及涂装技术领域，提供了一种基于多巴胺的提高碳纤维增强复合材料(CFRP)和涂料附着力的方法。
背景技术
碳纤维是一种含碳量在95％以上的，具有高强度、高模量的新型纤维材料。碳纤维是由片状石墨微晶沿纤维轴向方向堆砌而成，经碳化及石墨化处理而得到的微晶石墨材料。碳纤维具有轴向强度和模量高，密度低，耐疲劳性和耐腐蚀性好，热膨胀系数小，且具有各向异性的特点，在国防军工和民用方面都具有重要的研究和应用价值。同传统的玻璃纤维和凯夫拉纤维相比，碳纤维具有更高的杨氏模量，同时，其在有机溶剂、酸、碱中不溶不胀，耐蚀性突出。碳纤维不仅具有碳材料的固有本征特性，同时还具有纺织纤维的柔软可加工性，是新一代增强纤维(沈真，碳纤维复合材料在飞机结构中的应用，高科技纤维与应用，2010，35(4)：1-4+24.)。
碳纤维的主要用途之一是与树脂、金属、陶瓷等基体复合，制备具有优异性能的碳纤维增强复合材料(CFRP)。CFRP具有质量轻、强度高、耐冲击、耐腐蚀的优点，可广泛应用于发动机罩、翼子板、车顶、行李箱盖、门板和底盘等零部件。CFRP由于受成形技术(固化时间长)和碳纤维价格昂贵等因素制约，多用于航空航天领域和少量高级轿车或跑车上。随着其技术进步和应用规模不断扩大，使用成本逐步下降，目前国外已经开始在量产车型上有所应用。
碳纤维增强复合材料本身为黑色，为了装饰和美观，需要在其表面进行相应的涂装。CFRP具有很低的表面能，给其表面涂装带来了困难，如何提高涂料在其表面的附着力显得尤为重要。可以通过对碳纤维增强复合材料基材进行表面处理来增加其表面的附着力，从而提高涂装性能。已经报道过的表面处理方法有：机械法、氧化液法、等离子体法、火焰处理法、紫外照射法等，上述各种方法都能在一定程度上提高碳纤维增强复合材料表面与涂料的黏附能力，但同时也存在一定的缺点。如，机械法是较为常用的方法，但处理力度难以掌握，若轻度打磨会造成表面的脱模剂未完全脱落，影响涂料的附着性能。打磨过度则会破坏复合材料内的碳纤维丝而降低碳纤维增强复合材料基材的力学性能，从而影响其使用功能。氧化液法用到Cr6+，因而存在一定的污染问题，等离子体法、火焰处理法、紫外照射法适合实验室或小零件的处理加工，难以实现工业化。因此，开发一种简单、环保而又能适合工业化生产的方法来提高碳纤维增强复合材料表面与涂料的黏附能力的方法非常必要。
据文献报道，海洋贻贝类生物可以分泌出黏附蛋白，在潮湿的环境下展现出了超强的黏附能力(Lee Haeshin,Dellatore Shara M.,Miller William M.,MessersmithPhilip B.,Mussel-inspired surface chemistry for multifunctional coatings,Science,2007,318:426-430.)。海洋贻贝黏附蛋白所具有的高强度，高韧性，防水性以及特殊的黏附性能，是目前其他黏合剂所无法比拟的。目前，通过模仿黏附蛋白分子结构和性能，开发和应用新型功能材料，是仿生领域研究的热点之一。
贻贝可以通过自身分泌出的粘液，将自己牢固的黏附在金属、玻璃、聚合物等材料表面，甚至在极难黏附的聚四氟乙烯表面均能达到牢固的黏附(Xi ZhenYu,Xu YouYi,ZhuLiPing,Wang Yue,Zhu BaoKu,A facile method of surface modification forhydrophobic polymer membranes based on the adhesive behavior of poly(DOPA)andpoly(dopamine),Journal of Membrane Science,2009,327:244-253.)
研究表明，贻贝分泌出的具有邻苯二酚基团的化合物，该种类型化合物与有机基材的表面相互作用，是通过不可逆的共价键来实现的，因此使其具有超乎寻常的黏附能力(Dalsin Jeffrey L.,Hu BiHuang,Lee Bruce P.,Messersmith Philip B.,Musseladhesive protein mimetic polymers for the prepartion of nonfouling surfaces,Journal of American Chemical Society,2003,125:4253-4258.)。
上述文献报道，虽然研究了多巴胺类化合物在有机、无机材料表面的附着情况，但未涉及碳纤维增强复合材料表面处理领域，而更多的是在生物领域和分离膜处理领域。
本发明通过简单易行的方法在CFRP与涂料底漆之间加入多巴胺类过渡层，该过渡层增强了碳纤维复合材料基材及底漆之间有较强粘合力，且具有低成本、低污染、易涂装等优点。
发明内容
本发明主要解决现有CFRP涂层附着力差、成本高，污染大、难以实现工业化等问题。在其基材表面引入多巴胺类过渡层，用于修饰碳纤维增强复合材料的表面结构，增加表面的极性，增大CFRP基材与涂料之间附着力，从而提高涂料与CFRP之间的附着性能。
本发明为实现上述目的采取以下技术方案：(1)脂肪醇聚氧乙烯醚AEO-12，0.1-2份，JFC，0.1-3份，30wt％的H2O2溶液0.01-0.5份，余量为H2O，组成A液。(2)用硼砂和硼酸配制pH值为8.0-8.5的缓冲溶液，将盐酸多巴胺溶于缓冲溶液，配制浓度为0.4-0.6g/L的盐酸多巴胺溶液，得到B液。(3)将A液与B液等体积混合均匀，刷涂或喷涂至经过打磨处理后的碳纤维增强复合材料表面上，待干燥后进行涂料的涂装。
其中所述(1)中的A液，AEO-12，0.1-2份，JFC，0.1-3份，30wt％的H2O2溶液0.01-0.5份，余量为H2O。(2)中的B液，首先用硼砂和硼酸配制成pH值为8.0-8.5的缓冲溶液，然后将盐酸多巴胺溶于该缓冲溶液，盐酸多巴胺的浓度为0.4-0.6mol/L。(3)预先将碳纤维增强复合材料表面进行打磨处理，使用前，A液与B液等体积混合，施工方式为刷涂或喷涂。
本发明中，所述步骤(1)中采用的AEO-12与JFC可以增加盐酸多巴胺溶液在打磨处理后的碳纤维增强复合材料表面的润湿性，H2O2的加入可以加速多巴胺的氧化聚合。步骤(2)中pH值为8.0-8.5的硼砂和硼酸缓冲溶液，可以为碳纤维增强复合材料表面的盐酸多巴胺的氧化聚合提供有利的反应条件。步骤(3)中，使用前，A液与B液混合，可以充分保持两种溶液的稳定性。
本发明与已有制备方法相比有益效果是：
(1)本发明中采用的原料盐酸多巴胺对环境不存在污染。
(2)本发明采用刷涂或喷涂法代替了原先的浸渍法，方法简单易行，利于工业化推广及应用，适用于大部件大规模的涂装。
(3)本发明有效地弥补了其他碳纤维增强复合材料涂装方法的缺陷，提高了CFRP基材与涂料之间的粘合力。
具体实施方式
下面结合实施例进一步叙述本发明所研制的复合过渡层对CFRP基材和涂料粘合力的大小。
实施例1：
取0.50g的AEO-12，0.8g的JFC，0.03g的30wt％的H2O2溶液，98.67g的H2O混合均匀得到A溶液。
取1.91g的硼砂，1.24g的硼酸，96.85g的H2O，配成pH值为8.0左右的缓冲溶液，向其中加入0.43g的盐酸多巴胺，得到B溶液。
将2.5mm厚的CFRP基材用300目的砂纸打磨至表面变为亲水后用蒸馏水冲洗，然后电吹风吹干。将上述A溶液与B溶液混合均匀后，刷涂至CFRP基材表面上，待其完全干燥后依次进行环氧底漆的正常涂装。待涂层完全干燥后对漆膜进行拉开法附着力测试。环氧底漆与碳纤维复合材料基材的附着力达到8.35MPa。作为对比样，未引入多巴胺过渡层，碳纤维复合材料基材同样打磨后直接刷涂涂料，测得环氧底漆与碳纤维复合材料基材的附着力为3.17MPa。
实施例2：
取0.41g的AEO-12，0.82g的JFC，0.07g的30wt％的H2O2溶液，98.70g的H2O混合均匀得到A溶液。
取0.98g的硼砂，0.62g的硼酸，98.40g的H2O，配成pH值为8.1左右的缓冲溶液，向其中加入0.47g的盐酸多巴胺，得到B溶液。
将2.5mm厚的CFRP基材用300目的砂纸打磨至表面变为亲水后用蒸馏水冲洗，然后电吹风吹干。将上述A溶液与B溶液混合均匀后，刷涂至CFRP基材表面上，待其完全干燥后依次进行环氧底漆的正常涂装。待涂层完全干燥后对漆膜进行拉开法附着力测试。环氧底漆与碳纤维复合材料基材的附着力达到9.15MPa。作为对比样，未引入多巴胺过渡层，碳纤维复合材料基材同样打磨后直接刷涂涂料，测得环氧底漆与碳纤维复合材料基材的附着力为3.17MPa。
实施例3：
取1.22g的AEO-12，0.63g的JFC，0.05g的30wt％的H2O2溶液，98.10g的H2O混合均匀得到A溶液。
取2.87g的硼砂，1.86g的硼酸，95.31g的H2O，配成pH值为8.0左右的缓冲溶液，向其中加入0.38g的盐酸多巴胺，得到B溶液。
将2.5mm厚的CFRP基材用300目的砂纸打磨至表面变为亲水后用蒸馏水冲洗，然后电吹风吹干。将上述A溶液与B溶液混合均匀后，刷涂至CFRP基材表面上，待其完全干燥后依次进行环氧底漆的正常涂装。待涂层完全干燥后对漆膜进行拉开法附着力测试。环氧底漆与碳纤维复合材料基材的附着力达到7.15MPa。作为对比样，未引入多巴胺过渡层，碳纤维复合材料基材同样打磨后直接刷涂涂料，测得环氧底漆与碳纤维复合材料基材的附着力为3.17MPa。
实施例4：
取0.83g的AEO-12，1.27g的JFC，0.09g的30wt％的H2O2溶液，97.81g的H2O混合均匀得到A溶液。
取0.76g的硼砂，0.47g的硼酸，98.77g的H2O，配成pH值为8.3左右的缓冲溶液，向其中加入0.51g的盐酸多巴胺，得到B溶液。
将2.5mm厚的CFRP基材用300目的砂纸打磨至表面变为亲水后用蒸馏水冲洗，然后电吹风吹干。将上述A溶液与B溶液混合均匀后，刷涂至CFRP基材表面上，待其完全干燥后依次进行环氧底漆的正常涂装。待涂层完全干燥后对漆膜进行拉开法附着力测试。环氧底漆与碳纤维复合材料基材的附着力达到9.65MPa。作为对比样，未引入多巴胺过渡层，碳纤维复合材料基材同样打磨后直接刷涂涂料，测得环氧底漆与碳纤维复合材料基材的附着力为3.17MPa。
Claims (4)
1.基于多巴胺提高碳纤维增强复合材料表面涂装性能的方法，可显著提高涂料在碳纤维增强树脂基复合材料表面之间的附着力，其特征在于包含以下步骤：(1)脂肪醇聚氧乙烯醚AEO-12，0.1-2份，JFC，0.1-3份，30wt％的H2O2溶液，0.01-0.5份，余量为H2O，组成A液；(2)用硼砂和硼酸配制pH值为8.0-8.5的缓冲溶液，将盐酸多巴胺溶于缓冲溶液，配制浓度为0.4-0.6g/L的盐酸多巴胺溶液,得到B液；(3)将A液与B液等体积混合均匀，刷涂或喷涂至经过打磨处理后的碳纤维增强复合材料表面上，待干燥后进行涂料的涂装；
其中，适用的基材为碳纤维增强树脂复合材料，基材表面需预先进行打磨处理。
2.根据权利要求1所述的基于多巴胺提高碳纤维增强复合材料表面涂装性能的方法，其特征在于：步骤(1)中采用了脂肪醇聚氧乙烯醚AEO-12及JFC为增加表面润湿性的表面活性剂，利于后面的多巴胺溶液在碳纤维增强树脂复合材料表面的分散，采用的H2O2溶液增加了碳纤维增强树脂复合材料表面的多巴胺溶液的氧化聚合速度，缩短反应时间。
3.根据权利要求1所述的基于多巴胺提高碳纤维增强复合材料表面涂装性能的方法，其特征在于：处理步骤(2)用硼砂和硼酸配制pH值为8.0-8.5的缓冲溶液，将盐酸多巴胺溶于缓冲溶液，盐酸多巴胺的浓度为0.4-0.6g/L。
4.根据权利要求1所述的基于多巴胺提高碳纤维增强复合材料表面涂装性能的方法，其特征在于：处理步骤(3)中，施工前，将A液与B液等体积混合，采用的施工工艺为刷涂或喷涂。
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