Antibacterial Agents for Concrete

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1		Maria Rosaria Plutino	+ 1803 word(s)	1803	2022-01-07 07:05:42	\|
2	The format is correct	Lindsay Dong	Meta information modification	1803	2022-01-10 03:13:18	\|

This entry is adapted from the peer-reviewed paper 10.3390/gels8010026

Concrete is the most used material for the construction of millions of structures around the world. Cementitious structures are often exposed to high humidity environments and the attack of atmospheric agents, such as acid rain, which make them vulnerable to microbial attachment with consequent colonization and deterioration over time. In the light of these considerations, the researchers turned their attention to designing green and sustainable alternative materials that exhibit similar characteristics to the traditional concrete by using nanotechnologies.

antifouling coatings sol–gel technique antibacterial activity cultural heritage conservation

1. Introduction

Concrete is the most used material for the construction of millions of structures around the world. Although it plays a crucial role in building development, it is considered an environmental pollutant due to the CO₂ emissions resulting from its production ^[1]^[2]. Furthermore, cementitious structures are often exposed to high humidity environments and the attack of atmospheric agents, such as acid rain, which make them vulnerable to microbial attachment with consequent colonization and deterioration over time. In the light of these considerations, the researchers turned their attention to designing green and sustainable alternative materials that exhibit similar characteristics to the traditional concrete by using nanotechnologies ^[1]. It is well known that stains on concrete walls and building facades are due to biodegradation phenomena and cement structures for irrigation and sewerage, which usually arise from the growth of cyanobacteria, fungi, and algae ^[3]^[4]. The microbial growth and microorganism present on the concrete surface are closely related to pH values, climatic exposure, and nutrient availability ^[5]. In addition, as previously mentioned, acid rains and air pollution can promote microbial development due to the formation of nitrogen or sulfur-containing compounds ^[6]^[7]. Some different mechanisms in which microorganisms can contribute to concrete deterioration are reported ^[8]. Physical deterioration caused by the bacteria proliferation, which leads to the mechanical breakage of concrete structures, aesthetic worsening due to biofilm formation on building surfaces, and chemical corrosion, deriving from the elimination of metabolites, were considered the main routes of degradation ^[6]. All these factors that negatively affect aesthetic characteristics, mechanical properties, and the stability of concretes also involve additional costs for repairing and renovating constructions. For these reasons, researchers tried to develop alternative and innovative cementitious materials that could show antimicrobial, antibacterial, and antifouling properties by using additives to the cement paste having antimicrobial properties against one or more microorganisms without affecting the mechanical properties of the concrete material.

2. Antibacterial Agents for Concrete

All antibacterial agents for concrete protection mentioned are summarized in Table 1.

Table 1. List of the common antibacterial agents used to preserve cement structures.

Antibacterial Agents	Authors	Ref.
ZnO and MgO NPs	Singh et al.	^[1]
Metal zeolites and antibacterial polymeric fibers	De Muynck et al.	^[9]
Epoxy resins	Kong et al.	^[10]
Quaternary ammonium compounds	Javaherdashti et al.	^[11]
Halogenated complex	Qiu et al.	^[12]
Metal oxide, silver, and tungsten powder	Plutino et al.	^[13]
CuO, Cu₂O, ZnO, TiO₂, Al₂O₃, and Fe₃O₄ nanoparticles	Sikora et al.	^[14]
Silver nanoparticles in commercial silica-based coating	Nam, K.Y.	^[15]
ZnO, TiO₂, SiO₂ nanoparticles	Dyshlyuk et al.	^[16]
SiO₂–Ag nanohybrid compounds in acrylic coatings	Le et al.	^[17]
Silver nanoparticles in N-SiO₂ nanocarriers	Dominguez et al.	^[18]
BiOCl_xBr_1−x micro flowers	Gao et al.	^[19]
TiO₂ nanoparticles, fluorine silicon sol	Zhu et al.	^[20]
TiO₂ nanoparticles	Verdier et al.	^[21]
TiO₂ modified with carbon and nitrogen	Janus et al.	^[22]
TiO₂ and ZnO nanoparticles in addition to polyethylene glycol (PEG)	Dehkordi et al.	^[23]
Fe₂O₃ contained in steel slag of an industrial induction furnace	Baalamurugan et al.	^[24]
Fly ashes recycled by alkali activation process supported with Zn	Rodwihok et al.	^[25]
Metakaolin-based geopolymer cement loaded with 5-chloro-2-(2,4-Dichlorophenoxy) phenol	Rubio-Avalos, J.C.	^[26]
Metakaolin-based geopolymer cement loaded with glass waste	Dal Poggetto et al.	^[27]
Zinc particles or zinc doped clay particles	Roghanian et al.	^[28]
Granular activated carbon and fundamental oxygen furnace steel slag particles, copper, and cobalt as inhibitory metals	Justo-Reinoso et al.	^[29]

2.1. Polymers and Inorganic Biocidal Additives as Antibacterial Agents

In the past years, scientists tried to reduce bacterial degradation by treating the surfaces of concrete structures with biocidal agents or antimicrobial polymers added directly to the cement mix. In work presented by De Muynck et al. in 2009, metal zeolites and antibacterial polymeric fibers were used on the concrete surface of sewers to prevent biogenic sulfuric acid corrosion ^[9]. Despite the presence of antibacterial compounds leading to a significant bacterial activity decrease, commercial surface treatments with epoxy and polyuria coatings showed better results. More recent studies performed by Kong et al. in 2019 confirmed the best protective effect of epoxy resins for cement exposed to the corrosion action of wastewater ^[10]. In their paper, the authors reported the investigations on an epoxy coal tar pitch coating, a cement-based capillary crystalline waterproofing coating, and a cement-based bacterial coating. The first one presented an excellent effect of shielding from wastewaters corrosion. It shows a low porosity structure and the same compressive strength as the untreated sample concrete immersed in water and cement-based biocides coatings, whose copper phthalocyanine, cuprous oxide, and potassium nitrate were functional components. Many other biocide agents suitable for concrete were described in the literature, such as quaternary ammonium compounds, halogenated complex, metal oxide, silver, and tungsten powder ^[11]^[12]^[13].

2.2. The Use of Nanotechnologies to Prevent Microbial Growth

In recent years the use of nanotechnologies to control the effect of microbial proliferation on concrete was investigated ^[30]^[31]. In particular, CuO, Cu₂O, ZnO, TiO₂, Al₂O₃, and Fe₃O₄ nanoparticles (NPs) incorporated in the cement paste, as reported by Sikora et al., showed biocide activity, although the colonies were able to re-proliferate ^[14]. In current technologies, silver nanoparticles are also added to the commercial silica-based coating to provide antimicrobial properties to the wall coverings ^[15]^[32]. The addition of these inorganic agents to paints, such as ZnO and MgO NPs, as described by Singh et al., promotes protecting the aesthetic properties of building surfaces, avoiding bacterial development ^[1]. Dyshlyuk et al. showed that zinc oxide nanoparticles with a size of 2–7 nm and a concentration between 0.1 and 0.25% in aqueous suspension decreased the proliferation of microorganisms that commonly attack building materials by 2–3 orders of magnitude. At the same time, TiO₂ and SiO₂ exhibited lower bactericidal activity ^[16]. Another strategy to improve the antimicrobial action, thermal resistance, and durability is developing and incorporating SiO₂–Ag nanohybrid compounds into acrylic coatings, as Le et al. ^[17] defined. The use of SiO₂ particles within the paints has the task of improving the adhesion of coatings to concrete walls of the buildings through chemical interactions with the components of the cement paste. A correct understanding of these interactions, which play a significant role in coatings’ biocidal activity, can help develop materials with improved antifouling properties. Recently, Dominguez et al. synthesized a coating of silver nanoparticles deposited on N-SiO₂ nanocarriers by using N-[3-(trimethoxysilyl) propyl] ethylenediamine and encapsulated in an organically modified silica matrix (ORMOSIL) by using the sol–gel method ^[18]. The -NHx groups, positively charged, linked to SiO₂ nanoparticles, lead to the interaction with the cell walls having a negative charge ^[33]. This coating showed better antifouling properties due to its ability to form a rough surface at the nanometer level, giving it superhydrophobic proprieties. Another study, illustrated by Gao et al., described the importance of hydrophobicity of coatings as a property that affects bacterial activity and as great potential for energy saving in buildings ^[19]. They synthesized coating based on BiOCl_xBr_1−x micro flowers featured by a high NIR reflectance. Once applied on the surface of building materials, such as concrete, they can decrease microbial growth at the inner temperature ^[19]. Zhu et al. also described the possibility of synthesizing hybrid silica coatings having, at the same time, heat reflective, antifouling, and weatherable properties. They prepared a superhydrophobic mortar for buildings by mixing black pigments, cement, sand, and TiO₂ nanoparticles and applied a fluorine silicon sol on the concrete surface ^[20]. The antibacterial activity of TiO₂ coatings was also investigated by Verdier et al. They evaluated the resistance of semi-transparent coverings to developing bacterial biofilms under amplified growing conditions on cementitious substrates ^[21]. Although titanium oxide showed high potential in the construction field, it presented a significant limitation due to its excitation when exposed to ultraviolet radiation. The most valid solution is to modify the TiO₂ photocatalyst structure with non-metallic elements or dope it with transition metal ions ^[34]. Janus et al. studied the microbial inactivation on concrete plates treated TiO₂ modified with carbon and nitrogen, describing an increase in the bacterial removal rate and enhancing the antimicrobial activity ^[22]. Mortars improved with modified titanium dioxide could be broadly used in buildings, which request high decontamination degrees, such as hospitals, schools, or water storage constructions. Dehkordi et al. suggested using TiO₂ and ZnO nanoparticles in addition to polyethylene glycol (PEG) as a new antibacterial coating applied on the surface of building materials ^[23]. PEG, used as a stabilizer to prevent the growth of common bacteria, i.e., E. coli, enhanced the stability of the white Portland cement samples under study. It is well known that also iron oxide shows antibacterial activity ^[14]. Baalamurugan et al. demonstrated that Fe₂O₃ contained in steel slag of an industrial induction furnace owns antibacterial activity and can be used to produce construction materials to enhance the resistance against microbial deterioration ^[24].

2.3. Hybrid Geopolymer-Based Materials with Antimicrobial Properties

Fly ashes, a waste product of the thermal power plants featured by a large amount of SiO₂ and Al₂O₃, can also be exploited to produce innovative materials with antibacterial properties. In this regard, Rodwihok et al. reported a study where fly ashes were recycled by an alkali activation process supported with Zn, which enhanced the microbial growth inhibitory properties ^[25]. These waste materials can also be used as primary resources to prepare and synthesize innovative hybrid geopolymer-based materials. These matrix components with strong antibacterial properties can be added, thus developing new protective concretes for buildings. Recently, in the literature, the antiseptic efficiency of metakaolin-based geopolymer cement loaded with organic and inorganic compounds, such as 5-chloro-2-(2, 4-Dichlorophenoxy) phenol and glass waste towards Gram-positive and negative bacteria, was described ^[26]^[27]. Another critical aspect of being assessed concerns concretes and cements relating to the masonry structures of buildings and those about civil infrastructures and urban wastewater drainage systems. In this regard, Roghanian et al. studied three types of coatings to prevent bio-corrosion in wastewater pipes due to the formation of sulfuric acid by microorganisms ^[28]. They investigated the effect on microbial growth by applying different coatings between the concrete and the pipes surface obtained from the adding of zinc particles or zinc doped clay particles, demonstrating a higher resistance to the degradations concerning the ordinary cement-based and geopolymer-based coverings. Justo-Reinoso et al. suggested replacing fine aggregates traditionally used in cement mixtures with granular activated carbon and fundamental oxygen furnace steel slag particles, copper, and cobalt as inhibitory metals towards the acidogenic microbial development in concrete sewer pipes ^[29]. This study also described improved mechanical properties, such as compressive and flexural strength for the cement-treated, concerning the conventional ones.

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