Mono and bilayer coatings of alkanethiol and silane on copper: Prevents corrosion and regulate bacterial adhesion

Abstract

Self-assembling molecules (SAMs) provide a flexible system for surface modification of materials by forming films of molecular thickness. SAMs protect materials from corrosion and modify surface properties such as adhesion, adsorption and wetting due to their molecular composition and orientation. In this investigation, polished copper specimens were dip coated to form SAMs of alkanethiol and silane to study bacterial adhesion as well as for corrosion prevention. The SAM coated specimens were exposed to the log phase cultures of Pseudomonas aeruginosa (aerobic bacteria) and Desulfovibrio vulgaris (anaerobic bacteria) for 12, 24 and 48 hrs, to monitor cell adhesion and biofilm thickness by microscopy. The results showed that alkanethiols SAM promoted adhesion and biofilm formation. The biofilm thickness ranged from 10 to 38 µm for Pseudomonas and 9 – 25 µm for Desulfovibrio sp. Among the SAM coatings tested, octadecyl-trichlorosilane (ODTCS), alkane-thiol and ODTCS (bilayer SAM) showed no bacterial adhesion, however, solitary alkane-thiol SAM showed significant bacterial adhesion. The high hydrophobicity (contact angle ∼140°), antibacterial and anti-biofilm property of the ODTCS coating could have regulated bacterial adhesion. The constant climate test results showed that silane SAM prevented copper corrosion up to ∼160 days (3480 hrs), while the alkanethiol coating could protect up to 10 days (240 hrs). Confocal laser scanning microscopic images of the silane coated copper specimens showed initiation of the corrosion after 160 days of exposure, while at the end of 200 days significant copper corrosion was observed. Surface modification leads to specific biochemical interactions that regulate bacterial adhesion and prevent biofilm formation and corrosion of copper.

Introduction

In natural environments, biofilms are the predominant mode of bacterial growth [1], [2]. Biofilm formation happens in two stages; first the cells adhere to an inert surface which is a spontaneous and rapid action and in the second stage the formation of multi-layered bacterial cell aggregation happens, which is enmeshed in exopolymeric matrix produced by bacteria [3]. The initial bacterial cell adhesion process depends on different strains and species that interact with the inert surface [1]. Bacterial cell adhesion and biofilm control are an important aspect to food, pharmaceutical and medical sectors. The sessile bacterial consortium can become resistant to antimicrobial compounds and disinfectant agents due to horizontal gene transfer [4]. Surface modification if carefully tailored is capable of preventing cell adhesion and biofilm formation [5]. The surface properties can be practically modified to reduce bacterial adhesion and also reduce biofouling process of the surfaces [6]. Surface modification in case of metals refers to any alteration of physico-chemical properties of a surface (hydrophobicity, etc.). This, will lead to specific biochemical interactions that prevent bacterial attachment and thus hampering biofilm formation [7].

Copper is an important commercial material of use in various industries, it has very high conductivity, strength and excellent thermal property. Copper and its various alloys are widely used in cooling water systems, for potable water pipelines, industrial heating and in decorative metallic works [8]. The electronic industry also needs copper for its high value components manufacturing. Several studies on corrosion of copper and its alloys were carried out in varied conditions and were reported in literature [9], [10], [11], [12], [13]. Industrially, microbial biofilms cause several issues in cooling water systems and in distribution system pipelines, where the biofilm growth impairs the heat transfer efficiency, that reduces the function of condenser system resulting in the turbine back pressure as well as impairing the functioning of ancillary units [14], [15]. Microbes, that cause corrosion include algae, bacteria and fungi, primarily, there are five types of bacteria that are identified to cause corrosion. They include biopolymer producing bacteria, iron reducing, iron oxidizing, nitrate and sulphate reducing bacteria [16], [17]. The main factors/metabolites, which promote copper corrosion, are; slime (exopolymers), ammonia, hydrogen sulphide, and organic acids. The primary source of sulphide is from sulphate reducing bacteria (SRB), which grow under anaerobic conditions. In addition, putrefaction of plant and animal matter within the distribution system pipelines during periods of shutdown and stagnancy release organo-sulphur compounds and augment SRB growth. Furthermore, corrosion of copper-based alloys in water distribution systems is aggravated by the presence of exopolymer producing bacteria. Exopolymer producing bacteria (such as Pseudomonas sp) attach to the metal surfaces by forming a gel matrix that entrap other metal ions and create innumerable tiny galvanic corrosion cells, which act in syndicate corroding the metal [18].

Self-assembled molecules (SAMs) protect materials from corrosion and influence surface properties such as adhesion, adsorption and wetting [8]. One of the biggest advantages of SAMs are their molecular (crystalline) perfection, resistance to contamination and ease of preparation. The self-assembly monolayer formation depends on weaker van der Waals interactions and directional bonds such as ionic, hydrogen bonds organize atoms or molecules in an array [19]. The molecules or ions adjust their own atomic positions to reach a thermodynamic minimum to create stable films. The performance of the SAM monolayer is based on its ability to stop electron transmission from the metal substrate to the reducing molecules present in the surrounding medium [20]. The alkanethiol (R-SH) SAMs interact with metals to form self-assembled monolayers, this molecular interaction has attracted considerable interest [21].

Among the various molecular coatings organo-functional silanes are a probable candidate for surface modification. Silanes can be used to modify the surface energy or wettability of substrates through the interaction of boundary layers of solids, effecting variable degrees of hydrophobicity or hydrophilicity [22], [23]. Monomeric silicon chemicals are known as silanes and when they contain at least one silicon carbon bond (e.g., Si-CH3) are called organo-silanes. Organo-functional silanes are molecules carrying two different reactive groups so that they can react with inorganic substrates such as glass and metals and form stable covalent bonds and organic substitution [24]. In addition, the organo-silane products were found to prevent the adhesion of the pathogenic bacteria on glass surfaces, however, their effect is relatively influenced by bacterial species [25].

Generally, silanes act as adhesion promoters between an inorganic substrate and an organic coating. Silanes are identified by the structure XnSiR4-n, where R is an organo ligand compatible with the organic layer and X forms a metal-siloxane bond (Si-O-metal). Silane molecules are bi-functional, the resulting direct and cross-linking bonds repel moisture and offer tremendous adhesion, as measured by salt spray, vapor humidity, condensing humidity, bending, and influence tests [26], [27]. Modification of surfaces with organo-silanes usually increases the hydrophobic quality and low surface free energy of native surfaces. Hydrophobicity of surfaces has been reported as an important factor affecting the attachment of bacteria on surfaces. Specifically, hydrophobicity seems to decrease the adhesion of microorganisms on to metallic surfaces [28] and in the same time enhances the detachment of sessile cells [24]. Recently, antifouling-coatings with SAM technology are being developed for antibacterial activity [29].

In this study the investigators assayed some SAM coatings for their antibacterial activity as well as in prevention of copper metal corrosion. Two important corrosion-causing bacteria were evaluated for their adhesion and biofilm formation properties with respect to SAM layers of alkanethiol and silane on copper. In addition, tests were conducted to study the hydrophobicity of the SAM monolayers and their corrosion resistant property.

Section snippets

Alkanethiol solution preparation

A stock solution of 0.1 M solution in pure ethanol was prepared by taking suitable volume of alkanethiol – Hexadecanethiol. A dilution of 10−3 M was used for the study.

Silane solution preparation

Silane solutions are prepared by dissolving the silane compounds in either Toluene or 1-Proponal. For the present study silane – Octadecyl-trichlorosilane, were dissolved in alcohol: acetic acid: water mixture as well as in Toluene. A dilution of 10−3 M was used for the study.

Bilayer SAM preparation

Bilayer SAM coating were prepared by initially coating

Contact angle

Contact angle (CA) data showed a maximum 140º for silane and 135º for bilayer SAM coatings. Fig. 1 illustrates the contact angle values, of the alkanethiol, silane and bilayer coated SAMs along with plain polished copper. The CA for polished copper was in the range 8–10º. Alkanethiol SAM showed a CA of 76–82º, while silane coated copper at different contact time had CA values of 84–90º for 10 mins, 115–125º for 20 mins contact time. While silane coating of 30 mins contact time and bilayer SAM

Discussion

The major advantages of SAMs are their molecular (crystalline) veracity and ease of preparation. The SAMs coating rely on van der Waals interactions, and ionic, hydrogen bonds to organize the atoms, molecules or ions to form a stable protective structure [8], [35]. The key to organize the type of monolayer synthesis, control the non-covalent interactions, to overcome entropy and to bring the molecules together to aggregate. The resulting cross-linking bonds of SAMs offer tremendous adhesion, as

Conclusions

Copper coupon finish (surface homogeneity), played a major role in SAM adsorption. Polished coupons showed better SAM adsorption when compared to unpolished (as received copper sheets). The SAM chain length played a key role in adsorption kinetics. Particularly, it was noticed with small chain alkanethiols. These compounds took more time for adsorption when compared to long chain alkanethiols. The wettability of the SAM coated copper is proportional to the adsorbed monolayer. Closely packed

Funding

This work was supported by Deutsches Zentrum für Luft- und Raumfahrt (DLR), Bonn, Germany.

CRediT authorship contribution statement

Toleti Subba Rao: Designed the study, Experimental work, Data analysis, Inference, Manuscript writing. Ralf Feser: Designed the study, Inference of data, Manuscript final checking.

Declaration of Competing Interest

The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Toleti Subba Rao reports administrative support was provided by Sai University. None.

Acknowledgement

The work was carried out under the Indo-German project DLR / IND 99 /039 of Deutsches Zentrum für Luft- und Raumfahrt (DLR), Bonn. The first author is grateful to the DLR for providing post-doctoral fellowship.

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