據中國工程院侯保榮院士組織的中國腐蝕成本調查結果顯示，2014年我國腐蝕總成本約占當年GDP的3.34%，超過2.1萬億元，其中海洋腐蝕與污損損失約占總腐蝕損失的1/3以上。海洋生物污損（Marine Biofouling）是指海洋微生物、植物和動物在海洋設施表面吸附、生長和繁殖而形成的生物垢，它會造成濱海電廠海水冷卻管道管壁變厚甚至堵塞、加速鋼樁腐蝕而減少服役壽命、船舶航行阻力及油耗顯著增加、導致水下觀測設備測量結果失真、養殖網箱網衣的產量減少和形成生物入侵等一系列嚴重問題。全球每年由此造成損失達2000億美元以上，是困擾全球海洋各類工程設施和裝備的共性難題。傳統含殺生劑涂層雖有效卻危害生態，而污損脫附型有機硅低表面能防污涂層雖環保，卻面臨靜態防污能力弱、機械性能差等瓶頸。如何開發環境友好、長效耐用的防污解決方案，成為海洋材料領域的重大挑戰。
近日，中國科學院海洋研究所海洋環境腐蝕與生物污損重點實驗室、海洋關鍵材料全國重點實驗室段繼周研究員團隊在《Chemical Engineering Journal》上發表最新研究成果“Transparent hybrid coatings for marine antifouling: Synergizing amphiphilicity, nanocellulose lubrication, and electrostatic repulsion”。報道了一種兼具高透明度與優異防污性能的有機硅雜化涂層。該涂層通過兩親性分子設計、納米纖維素潤滑、靜電排斥三重機制協同作用，在180天實海試驗中保持90%以上的宏觀污損抵抗率，為開發綠色海洋防污涂層技術提供了新的思路。
三重協同：破解防污難題的“組合拳”
團隊前期在環保型有機硅基海洋防污涂層研究方面取得系列進展（J Mater Sci Technol, 2022, 124, 1-13; ?Appl Mater Today?, 2022, 28, 101551; Chem Eng J, 2024, 490, 151567; Prog Org Coat. 2024, 197, 108833.; Int J Biol Macromol, 2024, 278, 134885.; Prog Org Coat. 2025, 206, 109357）。在該研究中，團隊從海洋生物防污策略中獲得靈感，巧妙地將三種非釋放型防污機制整合于單一涂層系統：
1. 微觀兩親性表面：通過含氟疏水鏈段與親水丙烯酸鏈段的精確調控，形成納米級疏水/親水異質區，干擾微生物的識別與附著；
2. 納米潤滑界面：將蓖麻油修飾的纖維素納米晶（CO-CNs）共價錨定在涂層網絡，使摩擦系數從0.52驟降至0.08，減少微生物接觸面積；
3. 強化靜電排斥：引入膽酸（CA）賦予涂層表面-110.22 mV的高負電勢（pH 8時），與帶負電微生物產生強靜電斥力。
流體力顯微鏡（FluidFM）測試證明，該涂層對假單胞菌的粘附力（0.29 nN）比商用PDMS（7.29 nN）降低98%，從單細胞層面揭示了靜電排斥的主導作用；涂層在30天的實海浸泡后，16S rRNA基因測序結果表明，涂層表面的腐蝕性電活性微生物希瓦氏菌（Shewanella）的相對豐度從對照組的40.9%降至20.2%。
性能突破：透明、強韌與防污的優異平衡
1. 光學性能：平均可見光透過率>90%，優于商業化PDMS，適用于光學儀器和水下窗口；
2. 機械性能：涂層通過100次彎折/卷曲測試無裂紋，附著力高達3.93 MPa；
3. 防污性能：實驗室防污測試顯示細菌粘附減少99%，蛋白吸附抑制率達95%，硅藻附著面積減少99%，在青島海域實海掛板測試180天后仍能保持90%以上防污率。
該研究通過合理的材料設計實現了多種基于物理作用的防污機制的協同增效，為開發新型環境友好防污涂層提供了新思路。未來將優化涂層配方并擴大實海測試范圍，評估在不同海域、季節的防污表現，推動該透明雜化涂層在光學儀器、可折疊顯示器和海洋設施裝備等領域的實際應用。
論文第一作者為中科院海洋所助理研究員孫佳文，通訊作者為中科院海洋所段繼周研究員。該研究得到了國家自然科學青年基金（42406206），山東省自然科學青年基金（ZR2023QD117），國家重點研發計劃（2024YFF0510100），中科院2022年度特別研究助理資助項目和青島市博士后項目（QDBSH20230101017）等項目的共同支持。
Fig. 1. Hybrid coating design. (A) Synthetic route of the amphiphilic telomer. (B) Surface modification route of CN. (C) Preparation process of the hybrid coating.
Fig. 2. Characterization of hybrid coatings. (A) Water contact angles of CN, COOH-CN, and CO-CN. (B) Digital photographs and TEM images of CN and CO-CN. (C) FTIR spectra of the hybrid coatings. (D) Photograph of HC/CO-CN-0.3/CA-3 coated on a PET substrate. (E) Transmittance spectra of the PDMS and hybrid coatings with a thickness of ≈100 μm. (F) Photographs of the HC/CO-CN-0.3/CA-3 coating and its deformations presented by bends, twists, and rolls. (G) Hardness and elastic modulus. (H) Load-displacement curves of the hybrid coatings. (I) Adhesion strength of each coating adhered to the GFE and steel before and after immersion in ASW for 28 days.
Fig. 3. Analysis of surface properties. (A) WCA and SFE of coatings. (B) AFM profiles of HC/CO-CN-0.3/CA-3 evaluated in amplitude modulation mode in air (left to right: 3D topography image (20 × 20 μm2) and Rq (nm), 2D topography image (20 × 20 μm2), and height profile across the red line). (C) Friction coefficient curves, and (D) friction coefficient values of hybrid coatings. (E) Schematic diagram of the lubrication mechanism of the hybrid coatings. (F) Self-cleaning performance of HC/CO-CN-0.3/CA-3. (G) Amount of BSA adsorbed on the different coatings. (H) Pseudobarnacle removal strength of the coatings.
Fig. 4. Anti-biofouling performance tests. (A) Fluorescence images of P. sp., S. sp., E. coli, and S. aureus adhered to PDMS, HC and HC/CO-CN-0.3/CA-3 surface, relative bacteria adhesion (RBA) on different coatings. (B) P. sp. and S. sp. biofilms grown on PDMS, HC and HC/CO-CN-0.3/CA-3 surface stained with crystal violet, OD590 values against P. sp. and S. sp. on different coatings. (C) Fluorescence images of N. incerta adhered to PDMS, HC and HC/CO-CN-0.3/CA-3 surface after immersion in a diatom cell suspension for 1, 7, and 14 days, percent of the coverage area of N.incerta on different coatings.
Fig. 5. Analysis of antifouling mechanism. (A) Schematic diagram showing the repulsive effect of electrostatic forces between the microorganisms and coating surfaces. (B) Zeta potential on each coating surface. (C) Voltage-time curve demonstrating the temporal evolution of voltage as a single bacterium P. sp. approached, contacted, and subsequently detached from the PDMS coating surface. (D) Simplified schematic diagram of measuring adhesion forces between a single bacterium and coating surface based on FluidFM-based SCFS. (E) Typical adhesion force (Fad)-distance curves between a single bacterium and coating surface. The adhesion force was calculated by quantifying the difference between the lowest point (red circle) in a specific adhesion force curve and the corresponding point where the adhesion force finally reached a relatively steady state with time.
Fig. 6. Marine field tests and high-throughput pyrosequencing results. (A) Images of different tested panels following immersion in Qingdao Sea for durations of 0, 30, 60, 120, and 180 days from December 2023 to June 2024. (B) Composition of microbial communities shown in their relative abundance at the class level; and (C) genus level based on 16S rRNA gene amplicon analysis.
論文信息：
Jiawen Sun, Jizhou Duan*, Yimeng Zhang, Xiaofan Zhai, Yuqing Zhu, Xue Yang, Xingda Liu, Ruiyong Zhang, Baorong Hou. Transparent hybrid coatings for marine antifouling: Synergizing amphiphilicity, nanocellulose lubrication, and electrostatic repulsion. Chemical Engineering Journal, 2025, 521, 166869. DOI: 10.1016/j.cej.2025.166869.
原文鏈接：https://doi.org/10.1016/j.cej.2025.166869
