Combinatorial materials research applied to the development of new surface coatings XVI: fouling-release properties of amphiphilic polysiloxane coatings.

High-throughput methods were used to prepare and characterize the fouling-release (FR) properties of an array of amphiphilic polysiloxane-based coatings possessing systematic variations in composition. The coatings were derived from a silanol-terminated polydimethylsiloxane, a silanol-terminated polytrifluorpropylmethylsiloxane (CF3-PDMS), 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane (TMS-PEG), methyltriacetoxysilane and hexamethyldisilazane-treated fumed silica. The variables investigated were the concentration of TMS-PEG and the concentration of CF3-PDMS. In general, it was found that the TMS-PEG and the CF3-PDMS had a synergist effect on FR properties with these properties being enhanced by combining both compounds into the coating formulations. In addition, reattached adult barnacles removed from coatings possessing both TMS-PEG and relatively high levels of CF3-PDMS displayed atypical base-plate morphologies. The majority of the barnacles removed from these coatings exhibited a cupped or domed base-plate as compared to the flat base-plate observed for the control coating that did not contain TMS-PEG or CF3-PDMS. Coating surface analysis using water contact angle measurements indicated that the presence of CF3-PDMS facilitated migration of TMS-PEG to the coating/air interface during the film formation/curing process. In general, coatings containing both TMS-PEG and relatively high levels of CF3-PDMS possessed excellent FR properties.

Iron nanoparticles coated with amphiphilic polysiloxane graft copolymers: dispersibility and contaminant treatability.

Amphiphilic polysiloxane graft copolymers (APGCs) were used as a delivery vehicle for nanoscale zerovalent iron (NZVI). The APGCs were designed to enable adsorption onto NZVI surfaces via carboxylic acid anchoring groups and polyethylene glycol (PEG) grafts were used to provide dispersibility in water. Degradation studies were conducted with trichloroethylene (TCE) as the model contaminant. TCE degradation rate with APGC-coated NZVI (CNZVI) was determined to be higher as compared to bare NZVI. The surface normalized degradation rate constants, k(SA) (Lm(2-) h(-1)), for TCE removal by CNZVI and bare NZVI ranged from 0.008 to 0.0760 to 007-0.016, respectively. Shelf life studies conducted over 12 months to access colloidal stability and 6 months to access TCE degradation indicated that colloidal stability and chemical reactivity of CNZVI remained more or less unchanged. The sedimentation characteristics of CNZVI under different ionic strength conditions (0-10 mM) did not change significantly. The steric nature of particle stabilization is expected to improve aquifer injection efficiency of the coated NZVI for groundwater remediation.

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.

Remediation of alachlor and atrazine contaminated water with zero-valent iron nanoparticles.

Zero-valent iron nanoparticles (nZVI, diameter < 90 nm, specific surface area = 25 m(2) g(-1)) have been used under anoxic conditions for the remediation of pesticides alachlor and atrazine in water. While alachlor (10, 20, 40 mg L(-1)) was reduced by 92-96% within 72 h, no degradation of atrazine was observed. The alachlor degradation reaction was found to obey first-order kinetics very closely. The reaction rate (35.5 x 10(-3)-43.0 x 10(-3) h(-1)) increased with increasing alachlor concentration. The results are in conformity with other researchers who worked on these pesticides but mostly with micro ZVI and iron filings. This is for the first time that alachlor has been degraded under reductive environment using nZVI. The authors contend that nZVI may prove to be a simple method for on-site treatment of high concentration pesticide rinse water (100 mg L(-1)) and for use in flooring materials in pesticide filling and storage stations.

Assessment of molecularly imprinted polymers as phosphate sorbents.

Phosphorus (P) is a non-renewable natural resource which is used extensively in agriculture as a fertilizer. Phosphate (PO43-) rocks are mined to meet growing agricultural demands induced by rising global populations. Much of the P used in agricultural fields finds its way into surface waters where it permanently resides, leading to devastating effects on the aquatic ecosystem through eutrophication of the waterbodies. This research was aimed at developing a sorbent that can engender a P reuse cycle by utilizing eutrophic surface waters as viable P sources (mines). The goal was to develop a sorbent which can selectively recover low concentration (≤100 P µg L-1) typical of eutrophic waters. Molecularly imprinted polymers (MIPs) were identified as a potential technology for accomplishing this goal. Three MIPs were screened for viability by assessing their sorption capacities. After the initial screening, one MIP was selected for further studies. The selected MIP was found to have partial PO43- selectivity and tunable P sorption capacity. Adjusting the template:monomer ratio resulted in an increase in P sorption capacity from ∼11 to ∼28 mg PO43--P g-1, making this MIP competitive with existing technologies. The MIP was characterized to understand the polymer chemistry and mechanisms of P-removal. The possible mechanisms of aqueous P removal by the MIP were identified as selective chemical binding to the imprinted recognition sites and electrostatic attraction.

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.

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 microm), elastic modulus (0.08-1.3 MPa), and shear rate (2-22 microm 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 IX: an investigation of novel antifouling/fouling-release coatings containing quaternary ammonium salt groups.

Polysiloxane coatings containing chemically-bound ("tethered") quaternary ammonium salt (QAS) moieties were investigated for potential application as environmental-friendly coatings to control marine biofouling. A combinatorial/high-throughput approach was applied to the investigation to enable multiple variables to be probed simultaneously and efficiently. The variables investigated for the moisture-curable coatings included QAS composition, ie alkyl chain length, and concentration as well as silanol-terminated polysiloxane molecular weight. A total of 75 compositionally unique coatings were prepared and characterized using surface characterization techniques and biological assays. Biological assays were based on two different marine microorganisms, a bacterium, Cellulophaga lytica and a diatom, Navicula incerta, as well as a macrofouling alga, Ulva. The results of the study showed that all three variables influenced coating surface properties as well as antifouling (AF) and fouling-release (FR) characteristics. The incorporation of QAS moieties into a polysiloxane matrix generally resulted in an increase in coating surface hydrophobicity. Characterization of coating surface morphology revealed a heterogeneous, two-phase morphology for many of the coatings investigated. A correlation was found between water contact angle and coating surface roughness, with the contact angle increasing with increasing surface roughness. Coatings based on the QAS moiety containing the longest alkyl chain (18 carbons) displayed the highest micro-roughness and, thus, the most hydrophobic surfaces. With regard to AF and FR properties, coatings based on the 18 carbon QAS moieties were very effective at inhibiting C. lytica biofilm formation and enabling easy removal of Ulva sporelings (young plants) while coatings based on the 14 carbon QAS moities were very effective at inhibiting biofilm growth of N. incerta.

Nitrate removal by entrapped zero-valent iron nanoparticles in calcium alginate.

Zero-valent iron nanoparticles (nZVI) were successfully entrapped in calcium alginate beads. The potential use of this technique in environmental remediation using nitrate as a model contaminant was investigated. Kinetics of nitrate degradation using bare nZVI (approximately 35 nm dia) and entrapped nZVI were compared. Calcium alginate beads show promise as the entrapment medium for nZVI for possible use in permeable reactive barriers for groundwater remediation. Based on scanning electron microscopy images it can be inferred that the alginate gel cluster acts as a bridge that binds the nZVI particles together. Kinetic experiments with 100, 60, and 20 mg NO3--N L(-1) indicate that 50-73% nitrate-N removal was achieved with entrapped nZVI as compared to 55-73% with bare nZVI over a 2 h period. The controls ran simultaneously show little or no NO3--N removal. Statistical analysis indicates that there was no significant difference between the reaction rates of bare and entrapped nZVI. The authors have shown for the first time that nZVI can be effectively entrapped in Ca-alginate beads and no significant decrease in the reactivity of nZVI toward the model contaminant (nitrate here) was observed after the entrapment.

Combinatorial materials research applied to the development of new surface coatings VII: an automated system for adhesion testing.

An automated, high-throughput adhesion workflow that enables pseudobarnacle adhesion and coating/substrate adhesion to be measured on coating patches arranged in an array format on 4x8 in.(2) panels was developed. The adhesion workflow consists of the following process steps: (1) application of an adhesive to the coating array; (2) insertion of panels into a clamping device; (3) insertion of aluminum studs into the clamping device and onto coating surfaces, aligned with the adhesive; (4) curing of the adhesive; and (5) automated removal of the aluminum studs. Validation experiments comparing data generated using the automated, high-throughput workflow to data obtained using conventional, manual methods showed that the automated system allows for accurate ranking of relative coating adhesion performance.

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.

Combinatorial materials research applied to the development of new surface coatings XV: an investigation of polysiloxane anti-fouling/fouling-release coatings containing tethered quaternary ammonium salt groups.

As part of ongoing efforts aimed at the development of extensive structure−property relationships for moisture-curable polysiloxane coatings containing tethered quaternary ammonium salt (QAS) moieties for potential application as environmental friendly coatings to combat marine biofouling, a combinatorial/high-throughput (C/HT) study was conducted that was focused on four different compositional variables. The coatings that were investigated were derived from solution blends of a silanol-terminated polydimethylsiloxane (HO-PDMS-OH), QAS-functional alkoxysilane, and methyltriacetoxysilane. The compositional variables investigated were alkoxysilane functionality of the QAS-functional silane, chain length of the monovalent alkyl group attached to the QAS nitrogen atom, concentration of the QAS-functional alkoxysilane, and molecular weight of the HO-PDMS-OH. Of these variables, the composition of the alkoxysilane functionality of the QAS-functional silane was a unique variable that had not been previously investigated. The antifouling (AF) and fouling-release (FR) characteristics of the 24 unique coating compositions were characterized using HT assays based on three different marine microorganisms, namely, the two bacteria, Cellulophaga lytica and Halomonas pacifica, and the diatom, Navicula incerta. Coatings surfaces were characterized by surface energy, water contact angle hysteresis, and atomic force microscopy (AFM). A wide variety of responses were obtained over the compositional space investigated. ANOVA analysis showed that the compositional variables and their interactions significantly influenced AF/FR behaviors toward individual marine microorganisms. It was also found that utilization of the ethoxysilane-functional QASs provided enhanced AF character compared to coatings based on methoxysilane-functional analogues. This was attributed to enhanced surface segregation of QAS groups at the coating-air interface and confirmed by phase images using AFM.

Novel, UV-curable coatings containing a tethered biocide: Synthesis, characterization, and antimicrobial activity.

Cationic, UV -curable coatings containing the tethered biocide, triclosan, were produced and their antimicrobial activity toward Staphylococcus epidermidis and Escherichia coli determined. Two polysiloxanes functionalized with both cycloaliphatic epoxy and triclosan were synthesized using hydrosilylation. The functionalized polysiloxanes, with varied concentration of pendant triclosan, were used to produce UV-curable coatings with reasonably good coating properties. Fourier transform (FT)-Raman spectroscopy showed that the tethered triclosan moieties self-concentrate on the coating surface. Using biological assays, it was determined that the coatings possessed nearly 100% antimicrobial activity toward the Gram-positive bacterium, S. epidermidis, without leaching toxic components. For the Gram-negative bacterium, E. coli, 60-80% reduction in biofilm retention was observed for all the coatings. Interestingly, the coatings were lesser effective in reducing E. coli cell viability suggesting that the tethered triclosan were able to substantially reduce the production of the biofilm extracellular matrix with minimal adverse affect on the bacterial cells attached to the coating surfaces. The high specificity of the coatings toward S. epidermidis indicates that a novel mode of contact-active antimicrobial activity was achieved through the disruption of processes unique to the Gram-positive cell wall. These novel UV-curable coatings have potential applications in inhibiting implantable biomedical device associated infections.

Entrapment of iron nanoparticles in calcium alginate beads for groundwater remediation applications.

Zero-valent iron nanoparticles (nZVI) have been successfully entrapped in biopolymer, calcium (Ca)-alginate beads. The study has demonstrated the potential use of this technique in environmental remediation using nitrate as a model contaminant. Ca-alginate beads show promise as an entrapment medium for nZVI for possible use in groundwater remediation. Based on scanning electron microscopy images it can be inferred that the alginate gel cluster acts as a bridge that binds the nZVI particles together. Kinetic experiments with 100, 60, and 20mg NO(3)(-)-NL(-1) indicate that 50-73% nitrate-N removal was achieved with entrapped nZVI as compared to 55-73% with bare nZVI over a 2-h period. The controls ran simultaneously show little NO(3)(-)-N removal. Statistical analysis indicates that there was no significant difference between the reaction rates of bare and entrapped nZVI. The authors have shown for the first time that nZVI can be effectively entrapped in Ca-alginate beads and no significant decrease in the reactivity of nZVI toward the model contaminant (nitrate here) was observed after the entrapment.

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

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 microm and shear tests were performed at four different shear rates (2, 7, 12, and 22 microm 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 microm 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.

Mini-review: combinatorial approaches for the design of novel coating systems.

Combinatorial and high throughput experimental methods are being applied to the design and development of novel polymers and coatings used in a number of application areas. Methods have been developed for polymer synthesis and screening and for the development of polymer thin film and coating libraries and the screening of these libraries for key properties such as surface energy and modulus. Combinatorial and high throughput methods enable the efficient exploration of a large number of compositional variables over a wide range. In the development of coatings for use in the marine environment, the key challenge is in the development of screening methods that can predict good performance. A number of assays are under development that will permit the rapid screening of the interaction of coatings with representative marine organisms.

Combinatorial materials research applied to the development of new surface coatings I: a multiwell plate screening method for the high-throughput assessment of bacterial biofilm retention on surfaces.

Combinatorial, high-throughput capabilities have been established to aid in the rapid development of new and effective antifouling marine coatings for naval applications. A biological screening process involving marine bacteria was developed that allows for rapid and effective quantification of bacterial biofilm growth and retention on large numbers of coating surfaces in parallel. The screening process involves (1) multiwell plate modifications for coating deposition, (2) deposition of combinatorial coating libraries via an automated liquid dispensing robot, (3) coating thickness measurements of cured coatings, (4) preconditioning of coatings via immersion in deionized water, (5) bacterial incubation, (6) plate processing, and (7) data analysis for identification of promising candidates. The details of the method developed are described in this document.

Development of combinatorial chemistry methods for coatings: high-throughput weathering evaluation and scale-up of combinatorial leads.

Combinatorial screening of materials formulations followed by the scale-up of combinatorial leads has been applied for the development of high-performance coating materials for automotive applications. We replaced labor-intensive coating formulation, testing, and measurement with a "combinatorial factory" that includes robotic formulation of coatings, their deposition as 48 coatings on a 9x12-cm plastic substrate, accelerated performance testing, and automated spectroscopic and image analysis of resulting performance. This high-throughput (HT) performance testing and measurement of the resulting properties provided a powerful set of tools for the 10-fold accelerated discovery of these coating materials. Performance of coatings is evaluated with respect to their weathering, because this parameter is one of the primary considerations in end-use automotive applications. Our HT screening strategy provides previously unavailable capabilities of (1) high speed and reproducibility of testing by using robotic automation and (2) improved quantification by using optical spectroscopic analysis of discoloration of coating-substrate structure and automatic imaging of the integrity loss of coatings. Upon testing, the coatings undergo changes that are impossible to quantitatively predict using existing knowledge. Using our HT methodology, we have developed several cost-competitive coatings leads that match the performance of more costly coatings. These HT screening results for the best coating compositions have been validated on the traditional scales of coating formulation and weathering testing. These validation results have confirmed the improved weathering performance of combinatorially developed coatings over conventional coatings on the traditional scale.

Development of combinatorial chemistry methods for coatings: high-throughput screening of abrasion resistance of coatings libraries.

Design, validation, and implementation of an optical spectroscopic system for high-throughput analysis of combinatorially developed protective organic coatings are reported. Our approach replaces labor-intensive coating evaluation steps with an automated system that rapidly analyzes 8 x 6 arrays of coating elements that are discretely deposited on a single plastic substrate. Each coating element of the library is 10 mm in diameter and 2-5 microm thick. Performance of coatings is evaluated with respect to their resistance to wear abrasion because this parameter is one of the primary considerations in end-use applications. Upon testing, the coating materials undergo changes that are impossible to quantitatively predict using existing knowledge. Coatings are abraded using industry-accepted abrasion test methods at a single or multiple abrasion conditions followed by the high-throughput analysis of abrasion-induced light scatter. The developed automated system is optimized for the analysis of diffusively scattered light that corresponds to 0-30% haze. System precision of 0.1-2.5% relative standard deviation provides capability for the reliable ranking of coatings performance. Although the system was implemented for high-throughput screening of combinatorially developed organic protective coatings for automotive applications, it can be applied for a variety of other applications for which materials ranking can be achieved using optical spectroscopic tools.

Development of combinatorial chemistry methods for coatings: high-throughput adhesion evaluation and scale-up of combinatorial leads.

Coupling of combinatorial chemistry methods with high-throughput (HT) performance testing and measurements of resulting properties has provided a powerful set of tools for the 10-fold accelerated discovery of new high-performance coating materials for automotive applications. Our approach replaces labor-intensive steps with automated systems for evaluation of adhesion of 8 x 6 arrays of coating elements that are discretely deposited on a single 9 x 12 cm plastic substrate. Performance of coatings is evaluated with respect to their resistance to adhesion loss, because this parameter is one of the primary considerations in end-use automotive applications. Our HT adhesion evaluation provides previously unavailable capabilities of high speed and reproducibility of testing by using a robotic automation, an expanded range of types of tested coatings by using the coating tagging strategy, and an improved quantitation by using high signal-to-noise automatic imaging. Upon testing, the coatings undergo changes that are impossible to quantitatively predict using existing knowledge. Using our HT methodology, we have developed several coatings leads. These HT screening results for the best coating compositions have been validated on the traditional scales of coating formulation and adhesion loss testing. These validation results have confirmed the superb performance of combinatorially developed coatings over conventional coatings on the traditional scale.