Advanced materials for smart protective coatings: Unleashing the potential of metal/covalent organic frameworks, 2D nanomaterials and carbonaceous structures.

The detrimental impact of corrosion on metallic materials remains a pressing concern across industries. Recently, intelligent anti-corrosive coatings for safeguarding metal infrastructures have garnered significant interest. These coatings are equipped with micro/nano carriers that store corrosion inhibitors and release them when triggered by external stimuli. These advanced coatings have the capability to elevate the electrochemical impedance values of steel by 2-3 orders of magnitude compared to the blank coating. However, achieving intelligent, durable, and reliable anti-corrosive coatings requires careful consideration in the design of these micro/nano carriers. This review paper primarily focuses on investigating the corrosion inhibition mechanism of various nano/micro carriers/barriers and identifying the challenges associated with using them for achieving desired properties in anti-corrosive coatings. Furthermore, the fundamental aspects required for nano/micro carriers, including compatibility with the coating matrix, high specific surface area, stability in different environments, stimuli-responsive behavior, and facile synthesis were investigated. To achieve this aim, we explored the properties of micro/nanocarriers based on oxide nanoparticles, carbonaceous and two-dimensional (2D) nanomaterials. Finally, we reviewed recent literature on the application of state-of the art nanocarriers based on metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs). We believe that the outcomes of this review paper offer valuable insights for researchers in selecting appropriate materials that can effectively enhance the corrosion resistance of coatings.

Synthesis of Mesoporous Silica Particles as Inhibitor Containers for Anticorrosive Applications.

Herein, we introduce an innovative experimental assembly based on a high-speed disperser and a water recirculator connected to a double-wall stainless steel container as a new and effective pathway for an eco-friendly and controlled synthesis of mesoporous silica particles (MSPs). With the setup, we demonstrated a one-pot encapsulation of the particles with an inhibitor benzotriazole (BTA) to produce a smart nano/microcontainer for potential use in anticorrosive coatings. One advantage of the experimental setup is the high volume of reactant solution that can be used, yet with good control of solution temperature and stirring conditions, which increases the yield and saves laboratory time. The results obtained from the modified Stöber method show the successful preparation of near-spherical and "bean-shaped" nanometer-size (∼310 nm) MSPs with high benzotriazole encapsulation capacity (46 wt %). More so, the one-pot BTA encapsulated mesoporous silica approach revealed monodispersed spherical particles at optimal temperature and stirring conditions with a mean diameter of ∼1.1 µm and a BTA encapsulation of 23 wt %. The synthesized particles show pH responsiveness and can be further optimized and applied as nanocarriers in smart anticorrosive coatings. The experimental assembly adopted in this work represents a new, scalable approach for the synthesis of mesoporous silica particles.

Encapsulated Corrosion Inhibitive Pigment for Smart Epoxy Coating Development: An Investigation of Leaching Behavior of Inhibitive Ions.

A comparative study between the leaching behavior of inhibitive ions from conventionally pigmented and smart (with encapsulated pigments) epoxy coatings has been conducted. Leaching of calcium phosphate as an inhibitive pigment from epoxy coatings was tested in 3.5 wt % NaCl solution. The results showed that pigment encapsulation contributed to a more uniform and stable coating microstructure based on the Scanning Electron Microscopy-Energy-Dispersive X-ray Spectroscopy (SEM-EDX) analysis and a higher leaching rate of the inhibitive pigment via the Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) analysis, thereby enhancing both the active corrosion protection and the barrier properties of the coating film. This was further verified by the Electrochemical Impedance Spectroscopy (EIS) measurements. After 7 days of immersion in 3.5 wt % NaCl solution, the coating resistance of the smart epoxy coating with mesoporous silica nanoparticle encapsulated calcium phosphate (MSN-CP3%) was 2 × 109 Ω·cm2 compared to 1.1 × 106 Ω·cm2 and 2.6 × 106 Ω·cm2 for the conventional epoxy coatings pigmented with 3 wt % and 5 wt % calcium phosphate (CP3% and CP5%), respectively.

Assessment of Anticorrosion Performance of Zinc-Rich Epoxy Coatings Added with Zinc Fibers for Corrosion Protection of Steel.

The effect of adding 0.5 wt % zinc fibers on the anticorrosion performance of zinc-rich epoxy (ZRE) coatings with 85, 75, and 65 wt % of zinc dust was investigated. The salt spray testing, scanning electron microscopy, open circuit potential, and electrochemical impedance spectroscopy measurements were used to characterize the corrosion protection performance of coatings. The results indicate that the ZRE coating containing 85 wt % zinc dust showed superior cathodic protection, while the coating with 65 wt % zinc dust provided neither cathodic protection nor good barrier protection. No significant improvement in the anticorrosion performance was observed for both coatings with the addition of 0.5 wt % zinc fibers. In contrast, the ZRE coating containing 75 wt % zinc dust, which provided short-term cathodic protection followed by barrier protection, showed remarkably improved anticorrosion performance with the addition of zinc fibers.

Characterization and Release Mechanisms of Aerogel-Encapsulated Biocide Crystals for Low-Loading and High-Utilization Antifouling Coatings.

Silica aerogel-encapsulated biocide crystals can potentially enhance the protection efficiency of antifouling coatings, thereby lowering the impact on nontarget aquatic life. In the present study, copper pyrithione (CuPT) crystals are encapsulated by silica aerogel to obtain loadings of 50-80 wt % CuPT. For optimal design of the heterogeneous particles and mapping of the underlying biocide release mechanisms, the aerogel-encapsulated biocide crystals are characterized by scanning (transmission) electron microscopy, energy-dispersive X-ray spectroscopy, thermal gravimetric analysis, mercury intrusion porosity, Brunauer-Emmett-Teller analysis, and light scattering. The microscopic examination demonstrates that the elongated CuPT crystals are encapsulated by a thin highly porous silica layer. When varying the CuPT loading of the aerogels, it is possible to tune the particle size, pore volume, and specific surface area of the aerogels. Furthermore, this study suggests that the hydrophilic aerogel-encapsulated CuPT, when used in antifouling coatings, attracts seawater and contributes to an efficient controlled release of active CuPT.

A Tunable Hyperspectral Imager for Detection and Quantification of Marine Biofouling on Coated Surfaces.

Fouling control coatings (FCCs) are used to prevent the accumulation of marine biofouling on, e.g., ship hulls, which causes increased fuel consumption and the global spread of non-indigenous species. The standards for performance evaluations of FCCs rely on visual inspections, which induce a degree of subjectivity. The use of RGB images for objective evaluations has already received interest from several authors, but the limited acquired information restricts detailed analyses class-wise. This study demonstrates that hyperspectral imaging (HSI) expands the specificity of biofouling assessments of FCCs by capturing distinguishing spectral features. We developed a staring-type hyperspectral imager using a liquid crystal tunable filter as the wavelength selective element. A novel light-emitting diode illumination system with high and uniform irradiance was designed to compensate for the low-filter transmittance. A spectral library was created from reflectance-calibrated optical signatures of representative biofouling species and coated panels. We trained a neural network on the annotated library to assign a class to each pixel. The model was evaluated on an artificially generated target, and global accuracy of 95% was estimated. The classifier was tested on coated panels (exposed at the CoaST Maritime Test Centre) with visible intergrown biofouling. The segmentation results were used to determine the coverage percentage per class. Although a detailed taxonomic description might be complex due to spectral similarities among groups, these results demonstrate the feasibility of HSI for repeatable and quantifiable biofouling detection on coated surfaces.

A review of blasting waste generation and management in the ship repair industry.

Solid blasting waste generated from coating removal during ship repair and maintenance poses environmental challenges. This paper presents a review of the generation, characterization, and treatment of blasting waste in the ship repair industry. The quantities, properties, and environmental impacts of the generated blasting waste are summarized and analyzed, and the results indicate that blasting waste has a high generation rate and/or high toxicity. As alternatives to landfill, available blasting waste treatment methods include hydrometallurgical leaching, physical/physicochemical separation, thermal treatment, and direct utilization in the production of building materials. The advantages and disadvantages of these treatments are reviewed and compared. The production of building materials from blasting waste is currently attractive owning to its economic benefits and technical simplicity, whereas recycling blasting waste for high-value applications is gradually gaining research interest. The high dependence of the choice and performance of treatment methods on the waste type and characteristics is highlighted. The results emphasize the interest in conducting more research on physiochemical and thermal properties and the environmental effects of blasting waste. This review suggests that future research should focus more on paint waste management because of the restricted application of dry abrasive blasting and the development of nonabrasive blasting methods in the ship repair industry.

Reliable Condensation Curing Silicone Elastomers with Tailorable Properties.

The long-term stability of condensation curing silicone elastomers can be affected by many factors such as curing environment, cross-linker type and concentration, and catalyst concentration. Mechanically unstable silicone elastomers may lead to undesirable application failure or reduced lifetime. This study investigates the stability of different condensation curing silicone elastomer compositions. Elastomers are prepared via the reaction of telechelic silanol-terminated polydimethylsiloxane (HO-PDMS-OH) with trimethoxysilane-terminated polysiloxane ((MeO)3Si-PDMS-Si(OMe)3) and ethoxy-terminated octakis(dimethylsiloxy)-T8-silsesquioxane ((QMOEt)8), respectively. Two post-curing reactions are found to significantly affect both the stability of mechanical properties over time and final properties of the resulting elastomers: Namely, the condensation of dangling and/or unreacted polymer chains, and the reaction between cross-linker molecules. Findings from the stability study are then used to prepare reliable silicone elastomer coatings. Coating properties are tailored by varying the cross-linker molecular weight, type, and concentration. Finally, it is shown that, by proper choice of all three parameters, a coating with excellent scratch resistance and electrical breakdown strength can be produced even without an addition of fillers.

Analytical performance of the Hologic Aptima HBV Quant Assay and the COBAS Ampliprep/COBAS TaqMan HBV test v2.0 for the quantification of HBV DNA in plasma samples.

BACKGROUND: Quantification of HBV DNA is used for initiating and monitoring antiviral treatment. Analytical test performance consequently impacts treatment decisions. OBJECTIVES: To compare the analytical performance of the Aptima HBV Quant Assay (Aptima) and the COBAS Ampliprep/COBAS TaqMan HBV Test v2.0 (CAPCTMv2) for the quantification of HBV DNA in plasma samples. STUDY DESIGN: The performance of the two tests was compared on 129 prospective plasma samples, and on 63 archived plasma samples of which 53 were genotyped. Linearity of the two assays was assessed on dilutions series of three clinical samples (Genotype B, C, and D). RESULTS: Bland-Altman analysis of 120 clinical samples, which quantified in both tests, showed an average quantification bias (Aptima - CAPCTMv2) of -0.19 Log IU/mL (SD: 0.33 Log IU/mL). A single sample quantified more than three standard deviations higher in Aptima than in CAPCTMv2. Only minor differences were observed between genotype A (N = 4; average difference -0.01 Log IU/mL), B (N = 8; -0.13 Log IU/mL), C (N = 8; -0.31 Log IU/mL), D (N = 25; -0.22 Log IU/mL), and E (N = 7; -0.03 Log IU/mL). Deming regression showed that the two tests were excellently correlated (slope of the regression line 1.03; 95% CI: 0.998-1.068). Linearity of the tests was evaluated on dilution series and showed an excellent correlation of the two tests. Both tests were precise with %CV less than 3% for HBV DNA ≥3 Log IU/mL. CONCLUSIONS: The Aptima and CAPCTMv2 tests are highly correlated, and both tests are useful for monitoring patients chronically infected with HBV.

Analytical and clinical performance of the Hologic Aptima HCV Quant Dx Assay for the quantification of HCV RNA in plasma samples.

BACKGROUND: Chronic hepatitis C virus (HCV) infection can be effectively treated with directly acting antiviral (DAA) therapy. Measurement of HCV RNA is used to evaluate patient compliance and virological response during and after treatment. OBJECTIVES: To compare the analytical performance of the Aptima HCV Quant Dx Assay (Aptima) and the COBAS Ampliprep/COBAS TaqMan HCV Test v2.0 (CAPCTMv2) for the quantification of HCV RNA in plasma samples, and compare the clinical utility of the two tests in patients undergoing treatment with DAA therapy. STUDY DESIGN: Analytical performance was evaluated on two sets of plasma samples: 125 genotyped samples and 172 samples referred for quantification of HCV RNA. Furthermore, performance was evaluated using dilutions series of four samples containing HCV genotype 1a, 2b, 3a, and 4a, respectively. Clinical utility was evaluated on 118 plasma samples obtained from 13 patients undergoing treatment with DAAs. RESULTS: Deming regression of results from 187 plasma samples with HCV RNA >2 Log IU/mL indicated that the Aptima assay quantified higher than the CAPCTMv2 test for HCV RNA >4.9 Log IU/mL. The linearity of the Aptima assay was excellent across dilution series of four HCV genotypes (slope of the regression line: 1.00-1.02). The Aptima assay detected significantly more replicates below targeted 2 Log IU/mL than the CAPCTMv2 test, and yielded clearly interpretable results when used to analyze samples from patients treated with DAAs. CONCLUSIONS: The analytical performance of the Aptima assay makes it well suited for monitoring patients with chronic HCV infection undergoing antiviral treatment.

Comparison of the Hologic Aptima HIV-1 Quant Dx Assay to the Roche COBAS Ampliprep/COBAS TaqMan HIV-1 Test v2.0 for the quantification of HIV-1 RNA in plasma samples.

BACKGROUND: HIV-RNA is the most important parameter for monitoring antiviral treatment in individuals infected with HIV-1. Knowledge of the performance of different tests for the quantification of HIV-1 RNA is therefore important for clinical care. OBJECTIVES: To compare the analytical performance of the Aptima HIV-1 Quant Dx Assay (Aptima) and the COBAS Ampliprep/COBAS TaqMan HIV-1 Test v2.0 (CAPCTMv2) for the quantification of HIV-1 RNA in plasma samples. STUDY DESIGN: The performance of the two tests was compared on 216 clinical plasma samples, on dilutions series in seven replicates of five clinical samples of known subtype and on ten replicates of the Acrometrix High and Low Positive Control. RESULTS: Bland-Altman analysis of 130 samples that quantified in both tests did not show indications of gross mis-quantification of either test. A tendency of the Aptima assay to quantify higher at high viral load compared to the CAPCTMv2 was observed in Bland-Altman analysis, by Deming regression (Slope 1.13) and in dilution series of clinical samples. Precision evaluated using the Acrometrix Positive Controls was similar for the High Control (CV: 1.2% vs. 1.3%; Aptima assay vs. CAPCTMv2 test, respectively), but differed for the Low control (CV: 17.9% vs. 7.1%; Aptima assay vs. CAPCTMv2 test, respectively). However, this did not impact clinical categorization of clinical samples at neither the 50 cp/mL nor 200 cp/mL level. CONCLUSION: The Aptima assay and the CAPCTMv2 test are highly correlated and are useful for monitoring HIV-infected individuals.

Reactor design for minimizing product inhibition during enzymatic lignocellulose hydrolysis: II. Quantification of inhibition and suitability of membrane reactors.

Product inhibition of cellulolytic enzymes affects the efficiency of the biocatalytic conversion of lignocellulosic biomass to ethanol and other valuable products. New strategies that focus on reactor designs encompassing product removal, notably glucose removal, during enzymatic cellulose conversion are required for alleviation of glucose product inhibition. Supported by numerous calculations this review assesses the quantitative aspects of glucose product inhibition on enzyme-catalyzed cellulose degradation rates. The significance of glucose product inhibition on dimensioning of different ideal reactor types, i.e. batch, continuous stirred, and plug-flow, is illustrated quantitatively by modeling different extents of cellulose conversion at different reaction conditions. The main operational challenges of membrane reactors for lignocellulose conversion are highlighted. Key membrane reactor features, including system set-up, dilution rate, glucose output profile, and the problem of cellobiose are examined to illustrate the quantitative significance of the glucose product inhibition and the total glucose concentration on the cellulolytic conversion rate. Comprehensive overviews of the available literature data for glucose removal by membranes and for cellulose enzyme stability in membrane reactors are given. The treatise clearly shows that membrane reactors allowing continuous, complete, glucose removal during enzymatic cellulose hydrolysis, can provide for both higher cellulose hydrolysis rates and higher enzyme usage efficiency (kg(product)/kg(enzyme)). Current membrane reactor designs are however not feasible for large scale operations. The report emphasizes that the industrial realization of cellulosic ethanol requires more focus on the operational feasibility within the different hydrolysis reactor designs, notably for membrane reactors, to achieve efficient enzyme-catalyzed cellulose degradation.

Reactor design for minimizing product inhibition during enzymatic lignocellulose hydrolysis: I. Significance and mechanism of cellobiose and glucose inhibition on cellulolytic enzymes.

Achievement of efficient enzymatic degradation of cellulose to glucose is one of the main prerequisites and one of the main challenges in the biological conversion of lignocellulosic biomass to liquid fuels and other valuable products. The specific inhibitory interferences by cellobiose and glucose on enzyme-catalyzed cellulose hydrolysis reactions impose significant limitations on the efficiency of lignocellulose conversion - especially at high-biomass dry matter conditions. To provide the base for selecting the optimal reactor conditions, this paper reviews the reaction kinetics, mechanisms, and significance of this product inhibition, notably the cellobiose and glucose inhibition, on enzymatic cellulose hydrolysis. Particular emphasis is put on the distinct complexity of cellulose as a substrate, the multi-enzymatic nature of the cellulolytic degradation, and the particular features of cellulase inhibition mechanisms and kinetics. The data show that new strategies that place the bioreactor design at the center stage are required to alleviate the product inhibition and in turn to enhance the efficiency of enzymatic cellulose hydrolysis. Accomplishment of the enzymatic hydrolysis at medium substrate concentration in separate hydrolysis reactors that allow continuous glucose removal is proposed to be the way forward for obtaining feasible enzymatic degradation in lignocellulose processing.

A passive apparatus for controlled-flux delivery of biocides: hydrogen peroxide as an example.

A new test method has been developed to estimate the required release rate of hydrogen peroxide (H2O2) to prevent marine biofouling. The technique exploits a well-defined concentration gradient of biocide across a cellulose acetate membrane. A controlled flux of H2O2, an environmentally friendly biocide, was obtained. Larvae of the barnacle, Balanus improvisus, were subjected to known release rates of H2O2 from a surface, under laboratory conditions. It was found that the distribution of settled larvae was not significantly different from the controls when H2O2 fluxes of 5-8 microg cm(-2) day(-1) were applied. However, release rates of 40 microg cm(-2) day(-1) significantly displaced the distribution of settled larvae towards the area of the chamber farthest away from the membrane. Membrane tests in seawater (Jyllinge Harbour, Denmark) for over 16 weeks showed that release rates of H2O2 of approximately 2800 microg cm(-2) day(-1) deterred biofouling efficiently. A H2O2 release rate of about 224 microg cm(-2) day(-1) resulted in some slime formation, but it was less than that on the H2O2-free control. It appears that to obtain efficient resistance to biofouling in natural seawater requires much higher membrane release rates of H2O2 (factor of between 5 and 50) than laboratory membrane exposure assays using barnacle larvae.

Effect and modeling of glucose inhibition and in situ glucose removal during enzymatic hydrolysis of pretreated wheat straw.

The enzymatic hydrolysis of lignocellulosic biomass is known to be product-inhibited by glucose. In this study, the effects on cellulolytic glucose yields of glucose inhibition and in situ glucose removal were examined and modeled during extended treatment of heat-pretreated wheat straw with the cellulolytic enzyme system, Celluclast 1.5 L, from Trichoderma reesei, supplemented with a beta-glucosidase, Novozym 188, from Aspergillus niger. Addition of glucose (0-40 g/L) significantly decreased the enzyme-catalyzed glucose formation rates and final glucose yields, in a dose-dependent manner, during 96 h of reaction. When glucose was removed by dialysis during the enzymatic hydrolysis, the cellulose conversion rates and glucose yields increased. In fact, with dialytic in situ glucose removal, the rate of enzyme-catalyzed glucose release during 48-72 h of reaction recovered from 20-40% to become approximately 70% of the rate recorded during 6-24 h of reaction. Although Michaelis-Menten kinetics do not suffice to model the kinetics of the complex multi-enzymatic degradation of cellulose, the data for the glucose inhibition were surprisingly well described by simple Michaelis-Menten inhibition models without great significance of the inhibition mechanism. Moreover, the experimental in situ removal of glucose could be simulated by a Michaelis-Menten inhibition model. The data provide an important base for design of novel reactors and operating regimes which include continuous product removal during enzymatic hydrolysis of lignocellulose.

Effects of substrate loading on enzymatic hydrolysis and viscosity of pretreated barley straw.

In this study, the applicability of a "fed-batch" strategy, that is, sequential loading of substrate or substrate plus enzymes during enzymatic hydrolysis was evaluated for hydrolysis of steam-pretreated barley straw. The specific aims were to achieve hydrolysis of high substrate levels, low viscosity during hydrolysis, and high glucose concentrations. An enzyme system comprising Celluclast and Novozyme 188, a commercial cellulase product derived from Trichoderma reesei and a beta-glucosidase derived from Aspergillus niger, respectively, was used for the enzymatic hydrolysis. The highest final glucose concentration, 78 g/l, after 72 h of reaction, was obtained with an initial, full substrate loading of 15% dry matter weight/weight (w/w DM). Conversely, the glucose yields, in grams per gram of DM, were highest at lower substrate concentrations, with the highest glucose yield being 0.53 g/g DM for the reaction with a substrate loading of 5% w/w DM after 72 h. The reactions subjected to gradual loading of substrate or substrate plus enzymes to increase the substrate levels from 5 to 15% w/w DM, consistently provided lower concentrations of glucose after 72 h of reaction; however, the initial rates of conversion varied in the different reactions. Rapid cellulose degradation was accompanied by rapid decreases in viscosity before addition of extra substrate, but when extra substrate or substrate plus enzymes were added, the viscosities of the slurries increased and the hydrolytic efficiencies decreased temporarily.

Presence and effects of marine microbial biofilms on biocide-based antifouling paints.

Marine microorganisms are capable of successfully colonizing toxic surfaces through the formation of biofilm structures. In this article, most of the literature reporting the presence of marine biofilms on chemically-active antifouling paints is briefly reviewed. Of special concern is the influence of the dense extracellular polymeric substances (EPS) matrix on the release rate of the compounds involved in antifouling paint performance (i.e. active compounds and controlled-release binder molecules). A deeper understanding of these phenomena is of interest for both environmental legislators and paint formulators.

Estimation of polishing and leaching behaviour of antifouling paints using mathematical modelling: a literature review.

The development of chemically active antifouling paints has traditionally been based on an empirical approach. Optimisation and evaluation of novel and existing products are frequently conducted by means of, for example, systematic paint rotary tests in the laboratory or at sea sites. In this review, the usefulness of combining rotary experiments with the development of detailed mathematical models of paint behaviour will be discussed with reference to the relevant literature. Mathematical models can generally be used in the design of suitable release systems for various active components such as proteins or biocides, as well as for the estimation of release rates from different compositions of paints under various seawater conditions. Insoluble matrix, soluble matrix and self-polishing paints will be considered. Simulations from recent publications that show the effects of dynamic changes in seawater on paint behaviour will be presented. Examples of potential uses of paint models for accelerated polishing and leaching tests and screening of novel paint components will also be discussed. Directions of future modelling work are suggested.

Controlled drug delivery from swellable hydroxypropylmethylcellulose matrices: model-based analysis of observed radial front movements.

This work is related to the on-going development of mathematical models describing transient drug delivery from hydroxypropylmethylcellulose (HPMC) matrices. Recently, experimental data providing a detailed mapping of radial swelling, diffusion, and erosion front movements in a high-viscosity HPMC matrix were published [J. Controlled Release 70 (2001) 383]. Using these and other data for verification of simulations, a detailed mathematical model, taking into account water-induced swelling, drug dissolution, and external and internal mass transport resistances of dissolved drug, has been developed. In contrast to earlier models, explicit equations for the rate of movement of the swelling, diffusion and erosion fronts, with the relevant physical properties of drug and HPMC matrix contained in the equations, were derived. Simulations have been compared to transient experimental data for three drugs of very different water solubility and a good agreement was found, taking into account the uncertainty of key input parameters. Furthermore, the model predicts the presence of the drug particle translocation phenomenon observed experimentally. However, continued swelling of the matrix, subsequent to the disappearance of the swelling front, could not be described by the present model. The front-tracking approach illustrated is of relevance in the development of detailed and accurate models of drug delivery from swellable cylindrical matrices involving both axial and radial diffusion.