Design novel three-dimensional network nanostructure for lubricant infused on titanium alloys towards long-term anti-fouling

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Highlights

Abstract

Titanium alloys, recognized as a marine material with great potential, are currently facing serious biofouling problems, which greatly limits its application range. To improve the antifouling performance of titanium alloys, three unique surface of three-dimensional network, grass-like and linear nanostructures were obtained on titanium alloys via hydrothermal treatment in this work. Further, slippery liquid-infused porous surfaces (SLIPSs) were fabricated on titanium alloys via infusing PFPE lubricant into these nanostructures. Water contact angles and sliding angles of SLIPSs were measured to evaluate the effect of nanostructures on the stability of PFPE lubricant layer. Anti-fouling capability of SLIPSs were investigated by quantifying the cells of chlorella and phaeodactylum tricornutum (P. tricornutum)adhered to titanium alloys. The results shows that all the SLIPSs exhibited remarkable inhibition capacity for the settlement of chlorella and P. tricornutum. Among them, the SLIPS with three-dimensional network nanostructure displayed the longest-term anti-fouling performance, and its reduction rate of P. tricornutum and chlorella reaching 77.2 % and 84.5 % after being cultivated for 21 days, respectively, indicating that there existed a positive correlation between the stability of lubricant layer in the artificial seawater and the antifouling effect.

Introduction

As we known, corrosion of metals in the marine environment causes serious economic losses. Simultaneously, the marine biofouling is a serious problem as critical as corrosion that cannot be ignored [[1], [2], [3], [4]]. Titanium alloys are the most widely used alloys in the marine environment for their excellent corrosion resistance and mechanical strength [[5], [6], [7], [8]]. However, marine organisms are easy to adhere and deposit on the surface of titanium alloys due to their good biocompatibility, which means they are particularly vulnerable to biofouling problems in the marine environment. This undesirable biofouling problem accelerates the corrosion damage of alloys, reduces its service life and disturbs the normal operation of the devices [9,10]. Hence, it is indispensable to advance the antifouling properties of titanium alloys to expand their application in marine environment.

Liquid-infused porous surface (SLIPS), inspired by the pitcher plant's predation of insects, was first proposed by Aizenberg et al. [11] and successfully prepared by infusing lubricant into the micro/nano-structure of substrate surface. This type of surface has many excellent properties, such as corrosion resistance [12], anti-icing [13], self-cleaning [14]and so on [15]. In particular, the SLIPS performs remarkable antifouling behavior in reducing the deposition and adhesion of fouling organisms like barnacle, bacteria and algae [[16], [17], [18], [19], [20], [21]]. Therefore, this kind of surface has attracted considerable interest and possessed broad application prospects in the antifouling field. Zhang et al. [22] reported that SLIPS prepared by infusing silicone oil into textured surface on stainless steel could decrease the soft tissue adhesion force by approximately 80 % at 250 ℃. Charpentier et al. [23] revealed that SLIPS fabricated via infusing 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide into microporous polypyrrole on stainless steel surface could reduce the calcium carbonate deposition by 95 % in comparison to untreated stainless steel. Howell et al. [24] proved that silicone oil-infused PDMS with 3D vascular systems exhibited a significant reduction in biofilm adhesion compared to PDMS and glass controls without any lubricant in the infectious bacteria and green microalgae. Wei et al. [25] used the self-assembly behavior of low-molecular-weight gelators to prepare a super-hydrophobic oil-injectable 3D network smooth surface, which performed liquid-repellency against water, low-surface-tension liquids, human serum and blood. Yuan et al. [26] prepared a liquid-infused poly(styrene-isobutylene-b-styrene) microfiber coating which could effectively suppress the attachment to blood cell and P. aeruginosa,reduce hemolysis and inhibit blood coagulation in vitro.

There are many methods for preparing the micro/nano-structures, including chemical etching [27], hydrothermal method [13], anodic oxidation [28], layer-by-layer self-assembly [29], free-radical polymerization [30]and so on [14,31,32]. Compared with micro-scale textures, nano-scale textures helps to stabilize lubricant layer under high shear conditions and does not hinder the sliding of liquid on the surface owing to its lower roughness [28,33]. Our previous work pointed out that the lubricant can be firmly locked in the surface microstructure through the powerful capillary force generated by the ordered nanotubes, thereby forming a stable lubricant layer [34]. Complex nanostructures with different shapes and sizes on metal surface constructed by hydrothermal method, except nanotubes, do not exhibit strong capillary force. Whereas, they are with a large specific surface area and can be used as a lubricant storage container because of different blocking mechanisms for lubricant [[35], [36], [37], [38], [39]]. Therefore, it is significant to investigate the influence of nanostructures tailored by hydrothermal method on the stability of lubricant layer.

In this work, three kinds of nanostructures (three-dimensional network, grass-like and linear) were constructed on the surface of titanium alloys by hydrothermal method. These nanostructures were further modified by 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) to reduce their surface energy and increase the compatibility of the PFPE lubricant and nanostructures. Due to the hydrophobic property of POTS, the surface of the microstructure will not be occupied by water [40]. The lubricant should meet the requirements of low surface energy, low viscosity, non-volatile to form a stable and slippery interface with environmental liquids [11]. Here, the PFPE lubricant(Krytox GPL 101) with good compatibility was selected and silicone oil (20 mPa·S) was used for comparison. The results from the studies carried out with silicone oil are given in the supplementary. The antifouling properties of SLIPSs with three kinds of nanostructures were investigated by observing the adhesion behavior of the chlorella and the P. tricornutum on the titanium alloys.

Section snippets

Materials and reagents

TC4 (Ti-6Al-4 V) titanium alloys with the dimension of 30 mm × 20 mm × 3 mm were purchased from Baoji Changzheng Metal Material Co., Ltd. Sodium hydroxide and anhydrous ethanol were supplied by Sinopharm Chemical Reagent Co., Ltd. 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) were obtained from Aladdin. Dupont PFPE lubricant (Krytox GPL 101) was purchased from Changsha Zhixuan Chemical Co., Ltd. P. tricornutum and chlorella was provided by Shanghai Guangyu Biological Technology Co., Ltd.

Preparation of SLIPS

The

Surface morphology and composition of hydrothermal coatings

Three kinds of nanostructures, including three-dimensional network nanostructure, grass-like nanostructure and linear nanostructure, were constructed on the surface of TC4 titanium alloys by hydrothermal method, as shown in Fig.1. By immersing the titanium alloys in 2 M NaOH solution at 150 °C for 1 h, the three-dimensional network nanostructure composed of some convex structures connected to each other with the roughness value of 0.117 μm was obtained (Fig.1(a, d)). The protrusions were

Conclusions

Three-dimensional network nanostructure, grass-like nanostructure and linear nanostructure were fabricated on TC4 titanium alloys by regulating hydrothermal conditions. PFPE lubricant was infused into three nanostructures to form SLIPSs to improve the antifouling performance of TC4 titanium alloys. The results showed that three SLIPSs could significantly reduce the adhesion of chlorella and P. tricornutum on titanium alloys. Three nanostructures showed different blocking mechanisms for

CRediT authorship contribution statement

Mingyu Xie: Writing - original draft. Yanjun Wang: Writing - review & editing. Wenjie Zhao: Conceptualization.

Declaration of Competing Interest

We affirm that the manuscript entitled "Design Novel Three-dimensional Network Nanostructure for lubricant infused on Titanium Alloys towards Long-term Anti-fouling" (co-authored by Mingyu Xie, Yanjun Wang, Wenjie Zhao) submitted to Colloids and Surfaces B: Biointerfaces is no competing financial interest.

Acknowledgements

This work is supported by the National Key Basic Research Program of China (973) (2014CB643305), the National Natural Science Foundation of China (51202263), and the Youth Innovation Promotion Association, CAS (2017338).

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