Biomimetic Approach to Self-Cleaning Surfaces of Natural Qingshi Stone

Abstract

Abstract: Self-cleaning surfaces have significant applications in the protection of natural stone surfaces. Based on the strong adhesion of polydopamine and the condensation reaction between the Al—OH on the surface of Al2O3 and the —P（O）（OH）2 group of
alkylphosphoric acid form P—O—Al covalent bond, Qingshi stone was soaked in Tris-HCl solution of dopamine to form the adhesion
layer on its surface. A layer of fluorinated Al2O3 nanoparticles was constructed on the surface of the Qingshi stone by a soaking in
absolute ethyl alcohol dispersion contains Al2O3 nanoparticles and fluorophosphonic acid C10（FPA）. Water static contact angles bigger than 160° and hysteretic angles smaller than 20° were obtained on the self-cleaning surfaces. The SEM images of as-prepared Qingshi stone surfaces show a micro/nanoscale roughness.

Key words: natural Qingshi stone, biomimetic method, micro/nanoscale roughness, self-cleaning

Duan Zhuoqi, Xie Zaixin, Zhao Zhanqiang, Zhou Bao, Li Ruheng, Zheng Xiaohong, Hu Yongmao. Biomimetic Approach to Self-Cleaning Surfaces of Natural Qingshi Stone[J]. Journal of Dali University, 2021, 6(6): 15-21.

References

〔1〕ZHANG H，LIU Q，LIU T，et al. The Preservation Damage
of Hydrophobic Polymer Coating Materials in Conservation
of Stone Relics〔J〕. Progress in Organic Coatings，2013，76
（7/8）：1127-1134.
〔2〕牟涛，竹文坤，段涛，等. 大理石表面微生物诱导碳酸钙
覆膜〔J〕. 非金属矿，2014，37（1）：11-13.
〔3〕DOHERTY B，PAMPLONA M，SELVAGGI R，et al. Effi⁃
ciency and Resistance of the Artificial Oxalate Protection
Treatment on Marble Against Chemical Weathering 〔J〕.
Applied Surface Science，2007，253（10）：4477-4484.
〔4〕PINNA D，SALVADORI B，PORCINAI S. Evaluation of the
Application Conditions of Artificial Protection Treatments
on Salt-Laden Limestones and Marble〔J〕. Construction
and Building Materials，2011，25：2723-2732.
〔5〕PATANKAR N A. Mimicking the Lotus Effect：Influence of
Double Roughness Structures and Slender Pillars〔J〕. Lang⁃
muir，2004，20（19）：8209-8213.
〔6〕BARTHLOTT W，NEINHUIS C. Purity of the Sacred Lotus
or Escape from Contamination in Biological Surfaces〔J〕.
Planta，1997，202（1）：1-8.
〔7〕NEINHUIS C，BARTHLOTT W. Characterization and Dis⁃
tribution of Water-Repellent，Self-Cleaning Plant Surfac⁃
es〔J〕. Annals of Botany，1997，79（6）：667-677.
〔8〕YU M E，HWANG J，DEMING T J. Role of L-3，4-dihy⁃
droxyphenylalanine in Mussel Adhesive Proteins〔J〕. Jour⁃
nal of the American Chemical Society，1999，121（24）：
5825-5826.
〔9〕ZHAO H，WAITE J H. Linking Adhesive and Structural
Proteins in the Attachment Plaque of Mytilus California⁃
nus〔J〕. Journal of Biological Chemistry，2006，281（36）：
26150-26158.
〔10〕LEE H，DELLATORE S M，MILLER W M，et al. Mussel -
Inspired Surface Chemistry for Multifunctional Coat⁃
ings〔J〕. Science，2007，318（5849）：426-430.
〔11〕XI Z Y，XU Y Y，ZHU L P，et al. A Facile Method of Sur⁃
face Modification for Hydrophobic Polymer Membranes
Based on the Adhesive Behavior of Poly（dopa）and Poly
（Dopamine）〔J〕. Journal of Membrane Science，2009，327
（1/2）：244-253.
〔12〕李小林，朱利平，易砖，等. 以聚多巴胺为分离层的复合
纳滤膜制备与表征〔J〕. 功能材料，2010（S）：45-48.
〔13〕PAN F S，JIA H P，QIAO S Z，et al. Bioinspired Fabrica⁃
tion of High Performance Composite Membranes with Ul⁃
trathin Defect-Free Skin Layer〔J〕. Journal of Membrane
Science，2009，341（1/2）：279-285.
〔14〕陈铭忆，温变英，张扬. 聚多巴胺修饰固体材料表面研
究进展〔J〕. 中国塑料，2013，27（6）：7-12.
〔15〕BURZIO L A，WAITE J H. Cross-Linking in Adhesive
Quinoproteins：Studies with Model Decapeptides〔J〕. Bio⁃
chemistry，2000，39（36）：11147-11153.
〔16〕许枭然，周璘，孙雪，等. 银纳米粒子/聚多巴胺微球的
制备及催化性能〔J〕. 浙江理工大学学报（自然科学
版），2016，35（4）：548-553.
〔17〕LEE H，SCHERER N F，MESSERSMITH P B. Single-
Molecule Mechanics of Mussel Adhesion〔J〕. Proceedings
of the National Academy of Sciences，2006，103（35）：
12999-13003.
〔18〕LEE H，LEE B P，MESSERSMITH P B. A Reversible
Wet/Dry Adhesive Inspired by Mussels and Geckos〔J〕.
Nature，2007，448（7151）：338-341.
〔19〕徐又一，蒋金泓，朱利平，等. 多巴胺的自聚-附着行为与

膜表面功能化〔J〕. 膜科学与技术，2011，31（3）：32-38.

〔20〕SEVER M J，WEISSER J T，MONAHAN J，et al. Metal-
Mediated Cross-Linking in the Generation of a Marine-
Mussel Adhesive〔J〕. Angewandte Chemie International
Edition，2004，43（4）：448-450.
〔21〕赵晨旭，谢银红，廖芝建，等. 聚多巴胺对材料表面功能化
的研究及应用进展〔J〕. 高分子通报，2015（12）：28-37.
〔22〕MCINTYRE N S，NIE H Y，GROSVENOR A P，et al. XPS
Studies of Octadecylphosphonic Acid（OPA） Monolayer
Interactions with Some Metal and Mineral Surfaces〔J〕.
Surface and Interface Analysis，2005，37（9）：749-754.
〔23〕NIE H Y，WALZAK M J，MCINTYRE N S. Delivering
Octadecylphosphonic Acid Self-Assembled Monolayers
on a Si Wafer and Other Oxide Surfaces〔J〕. Journal of
Physical Chemistry B，2006，110（42）：21101-21108.
〔24〕ZHU Y，HU Y M，NIE H Y，et al. Superhydrophobicity via
Organophosphonic Acid Derivatised Aluminium Films〔J〕.
Surface Engineering，2016，32（2）：114-118.
〔25〕HU Y M，LI R H，ZHANG X Q，et al. Aluminium Films
Roughened by Hot Water Treatment and Derivatized by
Fluoroalkyl Phosphonic Acid：Wettability Studies〔J〕. Sur⁃
face Engineering，2020，36（6）：589-600.
〔26〕BHURE R，MAHAPATRO A，BONNER C，et al. In vitro
Stability Study of Organophosphonic Self-Assembled
Monolayers（SAMs）on Cobalt Chromium（Co-Cr）Alloy
〔J〕. Materials Science and Engineering C，2013，33（4）：
2050-2058.
〔27〕GUVENDIREN M，MESSERSMITH P B，SHULL K R.
Self-Assembly and Adhesion of DOPA-Modified Meth⁃
acrylic Triblock Hydrogels〔J〕. Biomacromolecules，2008，
9（1）：122-128.
〔28〕BERNSMANN F，BALL V，ADDIEGO F，et al. Dopa⁃
mine-Melanin Film Deposition Depends on the Used Oxi⁃
dant and Buffer Solution〔J〕. Langmuir，2011，27（6）：
2819-2825.
〔29〕张庆瑞，李奕璇，陈贺，等. 多巴胺功能材料在环境保护
中的应用进展〔J〕. 燕山大学学报，2018，42（1）：1-10.
〔30〕贺武，帅韬，高明阳，等. 聚多巴胺形成的机理及影响
因素〔J〕. 江西化工，2017（4）：4-10.
〔31〕WENZEL R N. Surface Roughness and Contact Angle〔J〕.
The Journal of Physical and Colloid Chemistry，1949，53
（9）：1466-1467.
〔32〕WENZEL R N. Resistance of Solid Surface to Wetting by
Water〔J〕. Industrial & Engineering Chemistry，1936，28
（8）：988-994.
〔33〕CASSIE A B D. Contact Angles〔J〕. Discussions of the
Faraday Society，1948，3：11-16.
〔34〕CASSIE A B D，BAXTER S. Wettability of Porous Sur⁃
face〔J〕. Transactions of the Faraday Society，1944，40：
546-550.
〔35〕TUTEJA A，CHOI W，MA M L，et al. Designing Super⁃
oleophobic Surfaces〔J〕. Science，2007，318（5856）：
1618-1622.
〔36〕DENG R，HU Y M，WANG L，et al. An Easy and Environ⁃
mentally-Friendly Approach to Superamphiphobicity of
Aluminum Surfaces〔J〕. Applied Surface Science，2017，
402：301-307.