RESUMEN
Biofouling on marine surfaces causes immense material and financial harm for maritime vessels and related marine industries. Previous reports have shown the effectiveness of amphiphilic coating systems based on poly(dimethylsiloxane) (PDMS) against such marine foulers. Recent studies on biofouling mechanisms have also demonstrated acidic microenvironments in biofilms and stronger adhesion at low-pH conditions. This report presents the design and utilization of amphiphilic polymer coatings with buffer functionalities as an active disruptor against four different marine foulers. Specifically, this study explores both neutral and zwitterionic buffer systems for marine coatings, offering insights into coating design. Overall, these buffer systems were found to improve foulant removal, and unexpectedly were the most effective against the diatom Navicula incerta.
Asunto(s)
Biopelículas , Incrustaciones Biológicas , Diatomeas , Dimetilpolisiloxanos , Incrustaciones Biológicas/prevención & control , Diatomeas/fisiología , Dimetilpolisiloxanos/química , Animales , Tampones (Química) , Propiedades de Superficie , Concentración de Iones de HidrógenoRESUMEN
Two types of amphiphilic random terpolymers, poly(ethylene glycol methyl ether methacrylate)-ran-poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)-ran-poly(polydimethyl siloxane methacrylate) (PEGMEMA-r-PTMA-r-PDMSMA), were synthesized and evaluated for antifouling (AF) and fouling-release (FR) properties using diverse marine fouling organisms. In the first stage of production, the two respective precursor amine terpolymers containing (2,2,6,6-tetramethyl-4-piperidyl methacrylate) units (PEGMEMA-r-PTMPM-r-PDMSMA) were synthesized by atom transfer radical polymerization using various comonomer ratios and two initiators: alkyl halide and fluoroalkyl halide. In the second stage, these were selectively oxidized to introduce nitroxide radical functionalities. Finally, the terpolymers were incorporated into a PDMS host matrix to create coatings. AF and FR properties were examined using the alga Ulva linza, the barnacle Balanus improvisus, and the tubeworm Ficopomatus enigmaticus. The effects of comonomer ratios on surface properties and fouling assay results for each set of coatings are discussed in detail. There were marked differences in the effectiveness of these systems against the different fouling organisms. The terpolymers had distinct advantages over monopolymeric systems across the different organisms, and the nonfluorinated PEG and nitroxide combination was identified as the most effective formulation against B. improvisus and F. enigmaticus.
RESUMEN
Biofouling is a major disruptive process affecting the fuel efficiency and durability of maritime vessel coatings. Previous research has shown that amphiphilic coatings consisting of a siloxane backbone functionalized with hydrophilic moieties are effective marine antifouling and fouling-release materials. Poly(ethylene glycol) (PEG) has been the primary hydrophilic component used in such systems. Recently, the morpholine group has emerged as a promising compact alternative in antifouling membranes but is yet to be studied against marine foulants. In this work, the use of morpholine moieties to generate amphiphilicity in a poly(dimethylsiloxane) (PDMS)-based antifouling and fouling-release coating was explored. Two separate coating sets were investigated. The first set examined the incorporation of an N-substituted morpholine amine, and while these coatings showed promising fouling-release properties for Ulva linza, they had unusually high settlement of spores compared to controls. Based on those results, a second set of materials was synthesized using an N-substituted morpholine amide to probe the source of the high settlement and was found to significantly improve antifouling performance. Both coating sets included PEG controls with varying lengths to compare the viability of the morpholine structures as alternative hydrophilic groups. Surfaces were evaluated through a combination of bubble contact angle goniometry, profilometry, X-ray photoelectron spectroscopy (XPS), and marine bioassays against two soft fouling species, U. linza and Navicula incerta, known to have different adhesion characteristics.
Asunto(s)
Incrustaciones Biológicas , Diatomeas , Ulva , Incrustaciones Biológicas/prevención & control , Morfolinas , Polietilenglicoles/química , Propiedades de SuperficieRESUMEN
Polymers are commonly used in applications that require long-term exposure to water and aqueous mixtures, serving as water purification membranes, marine antifouling coatings, and medical implants, among many other applications. Because polymer surfaces restructure in response to the surrounding environment, in situ characterization is crucial for providing an accurate understanding of the surface chemistry under conditions of use. To investigate the effects of surface-active side chains on polymer surface chemistry and resultant interactions with interfacial water (i.e., water sorption), we present synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) studies performed on poly(ethylene oxide) (PEO)- and poly(dimethylsiloxane) (PDMS)-based polymer surfaces modified with amphiphilic polypeptoid side chains, previously demonstrated to be efficacious in marine fouling prevention and removal. The polymer backbone and environmental conditions were found to affect polypeptoid surface presentation: due to the surface segregation of its fluorinated polypeptoid monomers under vacuum, the PEO-peptoid copolymer showed significant polypeptoid content in both vacuum and hydrated conditions, while the modified PDMS-based copolymer showed increased polypeptoid content only in hydrated conditions due to the hydrophilicity of the ether monomers and polypeptoid backbone. Polypeptoids were found to bind approximately 2.8 water molecules per monomer unit in both copolymers, and the PEO-peptoid surface showed substantial water sorption that suggests a surface with a more diffuse water/polymer interface. This work implies that side chains are ideal for tuning water affinity without altering the base polymer composition, provided that surface-driving groups are present to ensure activity at the interface. These types of systematic modifications will generate novel polymers that maximize bound interfacial water and can deliver surface-active groups to the surface to improve the effectiveness of polymer materials.
RESUMEN
The buildup of organic matter and organisms on surfaces exposed to marine environments, known as biofouling, is a disruptive and costly process affecting maritime operations. Previous research has identified some of the surface characteristics particularly suited to the creation of antifouling and fouling-release surfaces, but there remains room for improvement against both macrofouling and microfouling organisms. Characterization of their adhesives has shown that many rely on oxidative chemistries. In this work, we explore the incorporation of the stable radical 2,2,6,6-tetramethylpipiderin-1-oxyl (TEMPO) as a component in an amphiphilic block copolymer system to act as an inhibitor for marine cements, disrupting adhesion of macrofouling organisms. Using polystyrene-b-poly(dimethylsiloxane-r-vinylmethysiloxane) block copolymers, pendent vinyl groups were functionalized with TEMPO and poly(ethylene glycol) to construct an amphiphilic material with redox active character. The antifouling and fouling-release performance of these materials was investigated through settlement and removal assays of three model fouling organisms and correlated to surface structure and chemistry. Surfaces showed significant antifouling character and fouling-release performance was increased substantially toward barnacles by the incorporation of stable radicals, indicating their potential for marine antifouling applications.
Asunto(s)
Incrustaciones Biológicas/prevención & control , Óxidos N-Cíclicos/química , Poliestirenos/química , Siliconas/química , Animales , Óxidos N-Cíclicos/síntesis química , Diatomeas/fisiología , Poliestirenos/síntesis química , Siliconas/síntesis química , Thoracica/fisiología , Ulva/fisiología , HumectabilidadRESUMEN
In marine industries, the accumulation of organic matter and marine organisms on ship hulls and instruments limits performance, requiring frequent maintenance and increasing fuel costs. Current coatings technology to combat this biofouling relies heavily on the use of toxic, biocide-containing paints. These pose a serious threat to marine ecosystems, affecting both target and nontarget organisms. Innovation in the design of polymers offers an excellent platform for the development of alternatives, but the creation of a broad-spectrum, nontoxic material still poses quite a hurdle for researchers. Surface chemistry, physical properties, durability, and attachment scheme have been shown to play a vital role in the construction of a successful coating. This review explores why these characteristics are important and how recent research accounts for them in the design and synthesis of new environmentally benign antifouling and fouling release materials.
Asunto(s)
Organismos Acuáticos/fisiología , Incrustaciones Biológicas/prevención & control , Polímeros/química , Ecosistema , Lubricantes/química , Polímeros/síntesis química , Propiedades de SuperficieRESUMEN
This work reports the first transient electrospun nanofiber mat triggered by UV-irradiation using poly(propylene carbonate) (PPC)/poly(phthalaldehyde) (cPPA) polymer blends. The ability to trigger room temperature transience of nanofiber mats without the need for additional heat or solvent expands its utility in nonbiological fields, especially for transient electronic devices. The addition of a photo-acid-generator to the system, working in combination with UV light, provides an acid source to enhance degradation because both polymer backbones are acid-sensitive. Electrospinning enables the production of PPC/cPPA composite nanofiber mats capable of significant degradation upon exposure to UV radiation while maintaining relatively high mechanical properties. An acid amplifier, an autocatalytically decomposing compound triggered by acid, was used to generate more acid and accelerate nanofiber degradation. The electrospun fiber mats can be post-annealed to achieve an improved mat with a mechanical strength of â¼170 MPa.
RESUMEN
Polymers with a triggered decomposition are attractive for an array of applications ranging from patterning to transient packaging materials, as well as for environmental protection. This work showed for the first time UV and thermally triggered transience in fiber mats using poly(propylene carbonate) (PPC) composites. The electrospun PPC-composite fiber mats combine excellent decomposition performance (because of the high surface to volume ratio) with high stiffness and thus represent a new class of materials enabling innovative applications, such as transient filter materials and short-time plant protection materials, as well as temporary lightweight materials for aerospace engineering. Thermally and UV-triggerable additives (protected acids or base) have been used in different concentrations to tune the transience performance of the fiber mats over a wide range (75-212 °C). The addition of organo-modified clay (OMMT) enhanced mechanical stability and prevented shrinkage at room temperature. Different annealing methods have been used to improve the mechanical properties even further (tensile strength = 2-12 MPa, Young's modulus = 55-747 MPa) making these fiber mats attractive for a broad field of applications. An Ashby plot of Young's modulus versus degradation temperature for electrospun fiber mats is shown, revealing much lower degradation temperatures with higher moduli for PPC composites compared to other electrospun polymers.
RESUMEN
A set of controlled surface composition films was produced utilizing amphiphilic block copolymers dispersed in a cross-linked poly(dimethylsiloxane) network. These block copolymers contained oligo(ethylene glycol) (PEGMA) and fluoroalkyl (AF6) side chains in selected ratios and molecular weights to control surface chemistry including antifouling and fouling-release performance. Such properties were assessed by carrying out assays using two algae, the green macroalga Ulva linza (favors attachment to polar surfaces) and the unicellular diatom Navicula incerta (favors attachment to nonpolar surfaces). All films performed well against U. linza and exhibited high removal of attached sporelings (young plants) under an applied shear stress, with the lower molecular weight block copolymers being the best performing in the set. The composition ratios from 50:50 to 60:40 of the AF6/PEGMA side groups were shown to be more effective, with several films exhibiting spontaneous removal of the sporelings. The cells of N. incerta were also removed from several coating compositions. All films were characterized by surface techniques including captive bubble contact angle, atomic force microscopy, and near edge X-ray absorption fine structure spectroscopy to correlate surface chemistry and morphology with biological performance.