James Bahr

Combinatorial materials research applied to the development of new surface coatings V. Application of a spinning water-jet for the semi-high throughput assessment of the attachment strength of marine fouling algae

Abstract In order to facilitate a semi-high throughput approach to the evaluation of novel fouling-release coatings, a ‘spinjet’ apparatus has been constructed. The apparatus delivers a jet of water of controlled, variable pressure into the wells of 24-well plates in order to facilitate measurement of the strength of adhesion of algae growing on the base of the wells. Two algae, namely, sporelings (young plants) of the green macroalga Ulva and a diatom (Navicula), were selected as test organisms because of their opposing responses to silicone fouling-release coatings. The percentage removal of algal biofilm was positively correlated with the impact pressure for both organisms growing on all the coating types. Ulva sporelings were removed from silicone elastomers at low impact pressures in contrast to Navicula cells which were strongly attached to this type of coating. The data obtained for the 24-well plates correlated with those obtained for the same coatings applied to microscope slides. The data show that the 24-well plate format is suitable for semi-high throughput screening of the adhesion strength of algae.

Adhesion study of silicone coatings: the interaction of thickness, modulus and shear rate on adhesion force.

Abstract Interactions between coating thickness, modulus and shear rate on pseudobarnacle adhesion to a platinum-cured silicone coating were studied using a statistical experimental design. A combined design method was used for two mixture components and two process variables. The two mixture components, vinyl end-terminated polydimethylsiloxanes (V21: MW = 6 kg mole−1 and V35: MW = 4 9.5 kg mole−1, Gelest Inc.) were mixed at five different levels to vary the modulus. The dry coating thickness was varied from 160 – 740 μm and shear tests were performed at four different shear rates (2, 7, 12, and 22 μm s−1). The results of the statistical analysis showed that the mixture components were significant factors on shear stress, showing an interaction with the process variable. For the soft silicone coating based on the high molecular weight polydimethylsiloxane (E = 0.08 MPa), shear stress significantly increased as coating thickness decreased, while shear rate slightly impacted shear force especially at 160 μm coating thickness. As the modulus was increased (E = 1.3 MPa), more force was required to detach the pseudobarnacle from the coatings, but thickness and rate dependence on shear stress became less important.

Release characteristics of reattached barnacles to non-toxic silicone coatings

Release mechanisms of barnacles (Amphibalanus amphitrite or Balanus amphitrite) reattached to platinum-cured silicone coatings were studied as a function of coating thickness (210–770 μm), elastic modulus (0.08–1.3 MPa), and shear rate (2–22 µm s−1). It was found that the shear stress of the reattached, live barnacles necessary to remove from the silicone coatings was controlled by the combined term (E/t)0.5 of the elastic modulus (E) and thickness (t). As the ratio of the elastic modulus to coating thickness decreased, the barnacles were more readily removed from the silicone coatings, showing a similar release behavior to pseudobarnacles (epoxy glue). The barnacle mean shear stress ranged from 0.017 to 0.055 MPa whereas the pseudobarnacle mean shear stress ranged from 0.022 to 0.095 MPa.

Combinatorial materials research applied to the development of new surface coatings XIII: an investigation of polysiloxane antimicrobial coatings containing tethered quaternary ammonium salt groups.

High-throughput biological assays were used to develop structure - antimicrobial relationships for polysiloxane coatings containing chemically bound (tethered) quaternary ammonium salt (QAS) moieties. The QAS-functional polysiloxanes were derived from solution blends of a silanol-terminated polydimethylsiloxane, a trimethoxysilane-functional QAS (QAS-TMS), and methylacetoxysilane. Since the QAS moieties provide antimicrobial activity through interaction with the microorganism cell wall, most of the compositional variables that were investigated were associated with the chemical structure of the QAS-TMS. Twenty different QAS-TMS were synthesized for the study and the antimicrobial activity of sixty unique polysiloxane coatings derived from these QAS-TMS determined toward Escherichia coli , Staphylococcus aureus , and Candida albicans . The results of the study showed that essentially all of the compositional variables significantly influenced antimicrobial activity. Surface characterization of these moisture-cured coatings using atomic force microscopy as well as water contact angle and water contact angle hysteresis measurements indicated that the compositional variables significantly affected coating surface morphology and surface chemistry. Overall, compositional variables that produced heterogeneous surface morphologies provided the highest antimicrobial activity suggesting that the antimicrobial activity was primarily derived from the relationship between coating chemical composition and self-assembly of QAS moieties at the coating/air interface. Using data modeling software, a narrow region of the compositional space was identified that provided broad-spectrum antimicrobial activity.

Living carbocationic polymerization of a vinyl ether monomer derived from soybean oil, 2-(vinyloxy)ethyl soyate

A novel vinyl ether monomer was produced from soybean oil by base-catalyzed transesterification of 2-(vinyloxy)ethanol with soybean oil. The cationic polymerization of this monomer, which is being referred to as 2-(vinyloxy)ethyl soyate (2-VOES), was investigated using a polymerization system involving a difunctional cationogen, ethylaluminum sesquichloride as the coinitiator, toluene as the solvent, and a polymerization temperature of 0 °C. With this polymerization system, the polymerization was first order with respect to monomer and molecular weight increased linearly with monomer conversion. Further, the molecular weight distribution of the polymers obtained were below 1.2. The addition of fresh monomer to a polymerization that had reach approximately 90 percent monomer conversion resulted in a further increase in molecular weight without an increase in molecular weight distribution. These results indicate that the polymerization was a living polymerization, which will enable well-defined polymer architectures, such as triblock copolymers, to be produced in the future.

Combinatorial Materials Research Applied to the Development of New Surface Coatings X: A High-Throughput Electrochemical Impedance Spectroscopy Method for Screening Organic Coatings for Corrosion Inhibition

The objective of the study was to develop a high-throughput electrochemical impedance spectroscopy (HT-EIS) method for rapid and quantitative evaluation of corrosion protective coatings. A 12-element, spatially addressable electrochemical platform was designed, fabricated, and validated. This platform was interfaced to a commercial EIS instrument through an automated electronic switching unit. The HT-EIS system enables four parallel EIS measurements to be run simultaneously, which significantly reduces characterization time compared to that of serial EIS measurements using a multiplexer. The performance of the HT-EIS system was validated using a series of model systems, including a Randles equivalent circuit, an electrochemical reaction (Ti/K4FeCN6, K3FeCN6), a highly uniform polymer film, and several polymer coatings. The results of the validation studies showed that the HT-EIS system enables a major reduction in characterization time and provides high quality data comparable to data obtained with conventional, single-cell EIS measurement systems.

Automated Image-Based Method for Laboratory Screening of Coating Libraries for Adhesion of Algae and Bacterial Biofilms

Assessment and down-selection of non-biocidal coatings that prevent the adhesion of fouling organisms in the marine environment requires a hierarchy of laboratory methods to reduce the number of experimental coatings for field testing. Automated image-based methods are described that facilitate rapid, quantitative biological screening of coatings generated through combinatorial polymer chemistry. Algorithms are described that measure the coverage of bacterial and algal biofilms on coatings prepared in 24-well plates and on array panels, respectively. The data are used to calculate adhesion strength of organisms on experimental coatings. The results complement a number of physical and mechanical methods developed to screen large numbers of samples.

High-Throughput Screening of Fouling-Release Properties: An Overview

Marine biofouling of ship hulls has significant cost, performance and environmental implications. Due to environmental concerns associated with traditional antifouling paints that mitigate fouling with the use of biocides, increasing research and development efforts have been made on fouling-release (FR) coatings. FR coatings do not actively deter settlement of marine organisms, but, instead, mitigate biofouling by minimizing the strength of adhesion. Ideally, an FR coating will allow the fouling community to be removed by simply running the vessel at relatively high speed. Traditional methods for characterizing FR properties involve immersion of relatively large samples in the ocean and waiting months for enough fouling to occur to enable reliable measurements to be made. To greatly enhance research and development relative to FR coatings, a combinatorial/high-throughput workflow was developed that includes a suite of FR laboratory assays involving marine bacteria, microalgae, and live, adult barnacles. The novel high-throughput FR measurement systems have been shown to allow for rapid screening of FR characteristics of miniaturized coating samples arranged in an array format.

Semicrystalline Polyamide Engineering Thermoplastics Based on the Renewable Monomer, 1,9-Nonane Diamine: Thermal Properties and Water Absorption

A series of poly(1,9-nonamethylene adipamide-co-1,9-nonamethylene terephthalamide) copolymers were produced using melt polymerization and the thermal properties, crystal structure, and moisture uptake characterized. The results confirmed that the copolymers exhibit isomorphism. As expected, glass transition temperature and the apparent melting temperature increased with increasing terephthalmide content. Using the difference in the apparent melting temperature to the crystallization temperature as a measure of relative crystallization rate, it was observed that crystallization rate decreased as the terephthalamide content of the copolymer was increased from 0 to 50 mole % but then sharply increased when increased beyond 50 mole %. This behavior may be the result of extensive inter- and intramolecular interactions in the melt associated with terephthalmide units in the polymer chain that nucleate crystallization upon cooling below the equilibrium melting temperature. Comparing the thermal properties of copolymers possessing an excess of terephthalmide units to the commodity polyamide Nylon 6,6, it is believed that these copolymers may have utility as partially renewable engineering thermoplastics.

Polymer Coating Materials and Their Fouling Release Activity: A Cheminformatics Approach to Predict Properties

A novel cheminformatics-based approach has been employed to investigate a set of polymer coating materials designed to mitigate the accumulation of marine biofouling on surfaces immersed in the sea. Specifically, a set of 27 nontoxic, amphiphilic polysiloxane-based polymer coatings was synthesized using a combinatorial, high-throughput approach and characterized for fouling-release (FR) activity toward a number of relevant marine fouling organisms, including bacteria, microalgae, and adult barnacles. In order to model these complex systems adequately, a new computational technique was used in which all investigated polymer-based coating materials were considered as mixture systems comprising several compositional variables at a range of concentrations. By applying a combination of methodologies for mixture systems and a quantitative structure-activity relationship approach (QSAR), seven unique QSAR models were developed that were able to successfully predict the desired FR properties. Furthermore, the developed models identified several significant descriptors responsible for FR activity of investigated polymer-based coating materials, with correlation coefficients ranging from rtest2 = 0.63 to 0.94. The computational models derived from this study may serve as a powerful set of tools to predict optimal combinations of source components to produce amphiphilic polysiloxane-based coating systems with effective, broad-spectrum FR properties.