Polymer Coatings Research Articles

Peeling of Polymer Coating from a Substrate: Analysis as a Binary Composite

Peeling of Polymer Coating from a Substrate: Analysis as a Binary Composite

Cryogenic quenching process enhancement through coating and microstructure optimization

In this work, we explore the impact of coatings and microstructures on heat transfer during a cryogenic quenching process. An easily reproducible quenching test is presented as a benchmark for testing different solutions. The study involves two different flat polymeric coatings as well as three porous microstructures. The results show that pairing a low-conductive coating with an appropriate porous surface microstructure on top of a stainless-steel plate can reduce the chill down time, accelerating the transition from room temperature to liquid nitrogen temperature, by a factor of five. High speed video recordings have been used to analyse the quenching process with different coatings and microstructures showing how the suppression of the film boiling regime is the key to enhancing the quenching process.

Metal oxide-dispersed PDMS nanocomposite films with enhanced heat-shielding ability and optical transparency

Coatings that transmit visible light and shield near-infrared (NIR) rays of sunlight have potential applications in smart windows, thermal camouflage, and heat shielding encapsulations. Here, we report metal oxide-dispersed polymer nanocomposites as potential coating materials that possess a combination of NIR reflection and visible light transmission. Film coatings (∼600 μm) comprising nanocrystalline zinc oxide (ZnO), titanium dioxide (TiO2), and cupric oxide (CuO) in the range of 0–2 wt% in polydimethylsiloxane (PDMS) matrix are fabricated. At optimal compositions, these coatings provided up to 52 % reduction in the interior air temperature, measured at distances ∼3 cm beneath the surface, while, at the same time, retaining up to 70 % of visible light transparency. The NIR reflection may be attributed to a combination of the band gap of the pigment material and the difference between the refractive indices of the pigments and the polymer matrix. We present a design map that highlights different regimes of heat-shielding and light transmission space for PDMS nanocomposite films. The performance, when compared with existing reports, suggests that films fabricated in this work outperform previously reported polymeric coatings in providing a combination of heat shielding and optical transparency.

Photo‐Arbuzov Reactions as a Broadly Applicable Surface Modification Strategy

AbstractChemical vapor deposition (CVD) polymerization is a commonly used approach in surface chemistry, providing a substrate‐independent platform for bioactive surface functionalization strategies. This work investigates the Arbuzov reaction of halogenated polymer coatings readily available via CVD polymerization, using poly(4‐chloro‐para‐xylylene) (Parylene C) as a model substance. Postpolymerization modification of these coatings via catalyst‐free and UV‐induced Arbuzov reaction using phosphites results in phosphonate‐functionalized polymers. The combination of infrared reflection‐absorption spectroscopy (IRRAS), X‐ray photoelectron spectroscopy (XPS), and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) provides detailed insights into the reaction progress. Time‐dependent studies suggest that the non‐polar phosphites penetrate deep into the CVD films and react with the polymer film. In addition, ToF‐SIMS, scanning electron microscopy (SEM), and atomic force microscopy (AFM) confirm spatial control of the reaction, resulting in localized chemical and topographical surface modification, recognizable by changes in interference color, fluorescence, and wettability. Preliminary 3D fluorescence spectroscopy investigations indicate tunable near‐infrared emission of these polymer films. This work is the first step toward generating multifunctional polymer coatings based on chemically modifiable, CVD polymers with potential applications in biomaterials, sensors, or optoelectronics.

Fiber Bragg Gratings Sensor Strain-Optic Behavior with Different Polymeric Coatings Subjected to Transverse Strain.

This research work is based on a previous study by the authors that characterized the behavior of FBG sensors with a polyimide coating in a structural monitoring system. Sensors applied to structural health monitoring are affected by the presence of simultaneous multidirectional strains. The previous study observed the influence of the transverse strain (εy) while keeping the longitudinal strain constant (εx), where the x direction is the direction of the optical fiber. The present study develops an experimental methodology consisting of a biaxial test plan on cruciform specimens with three embedded FBG sensors coated with polyimide, acrylate, and ORMOCER®. Applying the Strain-Optic Theory as a reference, a comparison of the experimental values obtained with the different coatings was studied. This experimental work made it possible to study the influence of the transverse strain (εy) on the longitudinal measurements of each FBGS and the influence of the coating material. Finally, the calibration procedure was defined as well as K (strain sensitivity factor) for each sensor.

Development of Microparticle Implanted PVDF-HF Polymer Coating on Building Material for Daytime Radiative Cooling.

A passive cooling method with great potential to lower space-cooling costs, counteract the urban heat island effect, and slow down worldwide warming is radiant cooling. The solutions available frequently require complex layered structures, costly products, or a reflective layer of metal to accomplish daytime radiative cooling, which restricts their applications in many avenues. Furthermore, single-layer paints have been used in attempts to accomplish passive daytime radiative cooling, but these usually require a compact coating or only exhibit limited cooling in daytime. In our study, we investigated and evaluated in daytime the surrounding cooling outcome with aid of one layer coating composed of BaSO4/TiO2 microparticles in various concentrations implanted in the PVDF-HF polymers on a concrete substrate. The 30% BaSO4/TiO2 microparticle in the PVDF-HF coating shows less solar absorbance and excessive emissivity. The value of solar reflectance is improved by employing micro-pores in the structure of PVDF polymers without noticeable effect on thermal emissivity. The 30% BaSO4/TiO2/PVDF coating is accountable for the hydrophobicity and proportionate solar reflection in the UV band, resulting in efficient solar reflectivity of about 95.0%, with emissivity of 95.1% and hydrophobicity exhibiting a 117.1° water contact angle. Also, the developed coating could cool to about 5.1 °C and 3.9 °C below the surrounding temperature beneath the average solar irradiance of 900 W/m-2. Finally, the results demonstrate that the 30% BaSO4/TiO2/PVDF-HF microparticle coating illustrates a typical figure of merit of 0.60 and is also capable of delivering outstanding dependability and harmony with the manufacturing process.

Modular Design of Functional Glucose Monomer and Block Co-Polymer toward Stable Zn Anodes.

Aqueous Zn batteries employing mildly acidic electrolytes have emerged as promising contenders for safe and cost-effective energy storage solutions. Nevertheless, the intrinsic reversibility of the Zn anode becomes a focal concern due to the involvement of acidic electrolyte, which triggers Zn corrosion and facilitates the deposition of insulating byproducts. Moreover, the unregulated growth of Zn over cycling amplifies the risk of internal short-circuiting, primarily induced by the formation of Zn dendrites. In this study, a class of glucose-derived monomers and a block copolymer are synthesized through a building-block assembly strategy, ultimately leading to uncover the optimal polymer structure that suppresses the Zn corrosion while allowing efficient ion conduction with a substantial contribution from cation transport. Leveraging these advancements, remarkable enhancements are achieved in the realm of Zn reversibility, exemplified by a spectrum of performance metrics, including robust cycling stability without voltage overshoot and short-circuiting during 3000 h of cycling, stable operation at a high depth of charge/discharge of 75% and a high current density, >95% Coulombic efficiency over 2000 cycles, successful translation of the anode improvement to full cell performance. These polymer designs offer a transformative path based on the modular synthesis of polymeric coatings toward highly reversible Zn anode.

Engineering Sulfur-Containing Polymeric Fire-Retardant Coatings for Fire-Safe Rigid Polyurethane Foam.

With the advantages of lightweight and low thermal conductivity properties, polymeric foams are widely employed as thermal insulation materials for energy-saving buildings but suffer from inherent flammability. Flame-retardant coatings hold great promise for improving the fire safety of these foams without deteriorating the mechanical-physical properties of the foam. In this work, four kinds of sulfur-based flame-retardant copolymers are synthesized via a facile radical copolymerization. The sulfur-containing monomers serve as flame-retardant agents including vinyl sulfonic acid sodium (SPS), ethylene sulfonic acid sodium (VS), and sodium p-styrene sulfonate (VSS). Additionally, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate are employed to enable a strong interface adhesion with polymeric foams through interfacial H-bonding. By using as-synthesized waterborne flame-retardant polymeric coating with a thickness of 600µm, the coated polyurethane foam (PUF) can achieve a desired V-0 rating during the vertical burning test with a high limiting oxygen index (LOI) of >31.5vol%. By comparing these sulfur-containing polymeric fire-retardant coatings, poly(VS-co-HEA) coated PUF demonstrates the best interface adhesion capability and flame-retardant performance, with the lowest peak heat release rate of 166kW m-2 and the highest LOI of 36.4vol%. This work provides new avenues for the design and performance optimization of advanced fire-retardant polymeric coatings.

NIR-triggered self-healing SiO2/melanin coatings with enhanced corrosion-resistant and mechanical robustness

Polymer coatings are inherently susceptible to deformation and irreversible damage when they are subjected to external forces during service. Self-healing coatings integrated with exceptional mechanical robustness and corrosion resistance are essential for industrial applications but have been deemed challenging. Here, we present a NIR-triggered self-healing coating by combining a toughness epoxy network with melanin-modified silica (MMS). Moreover, to investigate the impact of pore size and porosity of silica on the corrosion protection performance, three types of various silica particles are selected as building blocks. The melanin-modified fumed silica/epoxy coatings demonstrate superior elongation (275 %), outstanding tensile strength (5.31 MPa) and high toughness (7.37 MJ·m3). Moreover, the introduction of the MMS can not only improve the anticorrosion performance (|Z|0.01 Hz value of 1.24 × 1010 Ω·cm2) but also realize fast photo-thermal repair (60 s). Our strategy furnishes a universal layout prototype for the manufacture of robust self-healing coatings with a scalable and cost-effective preparation method.

Application of AIE luminogen-loaded core–shell fibers in self-warning and self-healing polymer coatings with enhanced corrosion resistance

Aggregation-induced emission (AIE) materials have been used for non-destructive visual detection of cracks and damages to prevent the final structural failure and increase the service life of coatings. In this study, a self-warning and self-healing core–shell fiber is synthesized for developing AIE composite coatings. In these core–shell fibers, a mixture of hmethylene diisocyanate (HDI) and tetraphenylethylene (TPE) is used as core constituent, and polyacrylonitrile (PAN) is used for preparing the shell, which are continuously wrapped with a high loading rate through coaxial electrospinning technology. The parameters of electrospinning process are optimized to achieve core–shell fibers with smooth surface and average diameter of 100 ± 50 nm. The composite coating reveals effective fluorescence in case of cracks in a corrosive environment. The maximum self-healing efficiency of the fiber coating is 94.8 % after soaking for 120 h. The introduced composite coating paves the way for improving the safety and reliability of critical engineering components.

Removing Aged Polymer Coatings from Porous Stone Surfaces Using the Gel Cleaning Method

Acrylic polymers were extensively used in past restoration practices, usually as consolidants or protecting agents. Their removal is often required because polymer coatings can improve some decay processes of stone substrates and, after ageing, may generate undesirable materials on the surface of artifacts. Therefore, the removal of old polymer coating from the surface of artifacts has become a common operation in the conservation of cultural heritage. As with other cleaning operations, it is a delicate process that may irreversibly damage the artifacts if not correctly carried out. The main aim of this study was to determine the appropriate cleaning procedure for efficiently removing old acrylic polymers (e.g., Paraloid B-72) from the surface of historical buildings. For this purpose, a polymer was applied to two different porous stone substrates (bio-calcarenite and arenaria stone). The hydrogel cleaning approach was used for the present study, as preliminary results suggested that it is the most promising polymer-removing method. The considered hydrogel (based on a semi-interpenetrating polymer network involving poly(2-hydroxyethyl methacrylate) and polyvinylpyrrolidone) was prepared and characterized using different techniques in order to assess the gel’s properties, including the gel content, equilibrium water content, retention capability, hardness, Young’s modulus, and morphology. After that, the hydrogel was loaded with appropriate amounts of nano-structured emulsions (NSEs) containing a surfactant (EcoSufTM), organic solvents, and H2O, then applied onto the coated surfaces. Moreover, plain EcoSurfTM in a water emulsion (EcoSurf/H2O) was also used to understand the polymer-removing behavior of the surfactant without any organic solvent. A comparative study was carried out on artificially aged and unaged polymer-coated samples to better understand the cleaning effectiveness of the considered emulsions for removing decayed polymer coatings. The experimental results showed that the NSE-loaded hydrogel cleaning method was more effective than other common cleaning procedures (e.g., cellulose pulp method). In fact, only one cleaning step was enough to remove the polymeric material from the stone surfaces without affecting their original properties.

Reducing Ice Adhesion to Polyelectrolyte Surfaces by Counterion-Mediated Nonfrozen Hydration Water.

Hydrophilic anti-icing coatings can be energy-effective passive solutions for combating ice accretion and reducing ice adhesion. However, their underlying mechanisms of action remain inferential and are ill-defined from a molecular perspective. Here, we systematically investigate the influence of the counterion identity on the shear ice adhesion strength to cationic polymer coatings having quaternary alkyl ammonium moieties as chargeable groups. Temperature-dependent molecular information on the hydrated polymer films is obtained using total internal reflection (TIR) Raman spectroscopy, complemented with differential scanning calorimetry (DSC) and ellipsometry. Ice adhesion measurements show a pronounced counterion-specific behavior with a sharp increase in adhesion at temperatures that depend on the anion identity, following the order Cl- < F- < SCN- < Br- < I-. Linked to the freezing of hydration water, the specific ordering results from differences in ion pairing and the amount of water present within the polymer film. Moreover, similar effects can be promoted by varying the cross-linking density in the coating while keeping the anion identity fixed. These findings shed new light on low ice adhesion mechanisms and may inspire novel approaches for improved anti-icing coatings.

Comparing industrial and analytical kraft lignins as biobased UV-protective additives in coatings

Lignin as the second most abundant biopolymer on Earth has the potential to become the alternative to petroleum-derived materials. It exhibits excellent UV absorption ability due to its aromatic structure and the presence of numerous phenolic, ketone, and intramolecular hydrogen bonds. Due to its complex nature, it is important to investigate its properties which is a very important step towards the valorization of lignin. Revealing its structural complexity allows for a better examination of its influence on the properties of the final lignin-based materials. In our research, we used two different kraft lignins: commercial analytical kraft lignin (AL) and industrial LignoBoost kraft lignin (KL) as UV-protect additives in BPA(Bisphenol A)-free polymer coatings based on diurethane dimethacrylate (DIUR). The maximum addition of KL and AL was 2 wt%. Both lignin samples were characterized in detail (composition analysis, ash content, molar mass and polydispersity, surface morphology, thermal properties, and quantitative measurement of hydroxyl group content). We investigated the influence of lignins on the textural and thermal properties of the coatings. Finally, we studied the application of lignin as a value-added UV-protective component by UV-Vis electronic absorption spectroscopy. KL with a higher purity and lower number of aliphatic OH had a better dispersion in the polymer matrix than AL lignin which had more agglomeration in the polymer matrix. The better dispersion resulted in producing a smoother surface in the coatings made from KL. Finally, a noticeable and significant impact of KL additive on the photoprotective properties of the coating material was demonstrated. These results showed a potential application and opportunity in the valorization of available industrial lignins toward sustainable and value-added products.

One-step rapid formation of wrinkled fractal antibiofouling coatings from environmentally friendly, waste-derived terpenes

Wrinkled coatings are a potential drug-free method for mitigating bacterial attachment and biofilm formation on materials such as medical and food grade steel. However, their fabrication typically requires multiple steps and often the use of a stimulus to induce wrinkle formation. Here, we report a facile plasma-based method for rapid fabrication of thin (<250 nm) polymer coatings from a single environmentally friendly precursor, where wrinkle formation and fractal pattern development are controlled solely by varying the deposition time from 3 s to 60 s. We propose a mechanism behind the observed in situ development of wrinkles in plasma, as well as demonstrate how introducing specific topographical features on the surface of the substrata can result int the formation of even more complex, ordered wrinkle patterns arising from the non-uniformity of plasma when in contact with structured surfaces. Thus-fabricated wrinkled surfaces show good adhesion to substrate and an antifouling activity that is not observed in the equivalent smooth coatings and hence is attributed to the specific pattern of wrinkles.

Creating Anti‐Biofouling Surfaces by Degradable Main‐chain Polyphosphoester Polymer Brushes

AbstractThe implementation of polymer brush coatings has proven crucial in biomedical and biotechnological applications for controlling biological interactions. Despite the extensive research and use of synthetic polymer coatings, concerns regarding their long‐term non‐biodegradability have arisen. This issue is significant as non‐degradable polymers can lead to complications such as inflammatory responses and bioaccumulation, highlighting the need for polymers that degrade in a controlled manner. To address this, polyphosphonate brushes are synthesized as anti‐biofouling coatings on silicon surfaces via controlled surface‐initiated organocatalytic ring‐opening polymerization (SI‐ROP) of cyclic phospholanes. 2‐Ethyl‐2‐oxo‐1,3,2‐dioxaphospholane and 2‐hexyl‐2‐oxo‐1,3,2‐dioxaphospholane are chosen as the monomers to prepare hydrophilic and hydrophobic brushes with thicknesses up to 55 nm, with a proven degradability in aqueous media. In addition, protein adsorption, bacterial adhesion, and biofilm formation are investigated as a function of the polyphosphonate side chain. Compared to non‐coated surfaces and polyester brushes, hydrophilic poly(2‐ethyl‐2‐oxo‐1,3,2‐dioxaphospholane) brushes have an enhanced resistance toward fouling of albumin, fibrinogen, and diluted human serum proteins, as well as toward Escherichia coli and Staphylococcus aureus bacteria. The stability and anti‐biofouling performance of hydrophilic polyphosphonate brushes position them as an attractive option as degradable materials for anti‐biofouling matrices on medical devices and/or lubricious coatings for artificial implant technologies.

Projecting the resiliency of nano-modified cementitious composites with hybrid BFP/PVA fibers in shear key joints

Effective bond strength at the interface between conventional concrete (CC) and high-performance fiber-reinforced cementitious composites (HPFRCC) is vital for applications like shear key for bridge joints. This study investigated the suitability of HPFRCC incorporating various constituents (cement, slag, as well as nano-silica), with only basalt fiber pellets (macro-BFP) or hybrid fiber systems including macro-BFP and micro-polyvinyl alcohol (PVA) fibers. BFP is a new emerging class of basalt fiber strands protected by a polymer coat. Experimental results (slant shear, pure shear, rebar pull-out, etc.) were used to develop modeling [homogenization/finite element modeling (FEM)] components to evaluate the effect of HPFRCC mixture design parameters on the mode of failure and bonding capacity with CC and steel rebar. After verification, these model components were integrated in a full-scale shear key joint model to project the field performance of the developed HPFRCC. The results revealed that nano-silica had a significant effect at improving the HPFRCC bonding strength capacity with CC and steel reinforcement. Whilst increasing BFP dosage (4.5%) in the nano-modified composites resulted in reduction of the interfacial bonding with CC, it significantly improved the rebar interfacial bonding and ultimate shear key capacity of the joint. Comparatively, the inclusion of 1% micro-PVA fibers in the nano-modified composites comprising macro-BFP resulted in the highest increase in shear resistance force, interfacial bonding with precast CC and shear reinforcement dowels, and ductility which suggests their promising potential to be employed in shear key jointing applications.

Antifouling efficiency of polymer coatings with SeNPs-loaded SiO2(rh)-PHMG composite as antimicrobial agent

Antifouling efficiency of polymer coatings with SeNPs-loaded SiO2(rh)-PHMG composite as antimicrobial agent

Surface Acoustic Wave Resonator Chip Setup for the Elimination of Interfering Conductivity Responses.

A surface acoustic wave (SAW) resonator chip setup is presented that eliminates interfering signal responses caused by changes in the electrical environment of the surrounding media. When using a two-port resonator, applying electrically shielding layers between the interdigital transducers (IDTs) can be challenging due to the limited dimensions. Therefore, a layered setup consisting of an insulating polymer layer and a conductive gold layer was preferred. The SAW resonators were provided with polycarbonate housings, resulting in SAW resonator chips. This setup enables easy application of a wide range of coatings to the active part of the resonator surface, while ensuring subsequent electrical and fluidic integration of the resonator chips into a microfluidic array for measurements. The signal responses of uncoated SAW resonators and those with polymer coatings with and without a gold layer were tested with aqueous potassium chloride (KCl) solutions up to 3 mol/L, corresponding to conductivities up to 308 mS/cm. The use of a polymer coating at the thickness of the first Love mode resonance and a conductive gold layer completely reduced the electrical impact on the SAW resonator signal response, making small signals resulting from changes in viscosity and density of the KCl solutions visible.

Influence of multilayered polymer coatings on the corrosion behaviour and microstructures of Al6061-T6 alloy

The influence of multilayered polymer coatings on the corrosion and microstructural properties of Al6061-T6 alloy was investigated. The electrochemical properties were determined in chloride solution via corrosion tests and electrochemical impedance spectroscopy (EIS) technique at room temperature. The microstructural properties and corrosion mechanism after polarization were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM)/Kelvin probe force microscopy (KPFM) techniques. From the corrosion tests and SEM-AFM/KPFM analysis, the multilayered polymer coated (using polyacrylic acid - PAA) Al6061-T6 alloy experienced a positive shift in the corrosion potential (-0.648 V), signifying a possible corrosion protection ability. With a charge transfer resistance of 2.506×10−6 Ω cm2, and lesser corrosion products featured on the coated sample, the present work demonstrates that the deposition of multilayered polymer PAA coating can enhance the corrosion resistance of Al6061-T6 alloy.

Unraveling Drug Delivery from Cyclodextrin Polymer-Coated Breast Implants: Integrating a Unidirectional Diffusion Mathematical Model with COMSOL Simulations.

Breast cancer ranks among the most commonly diagnosed cancers worldwide and bears the highest mortality rate. As an integral component of cancer treatment, mastectomy entails the complete removal of the affected breast. Typically, breast reconstruction, involving the use of silicone implants (augmentation mammaplasty), is employed to address the aftermath of mastectomy. To mitigate postoperative risks associated with mammaplasty, such as capsular contracture or bacterial infections, the functionalization of breast implants with coatings of cyclodextrin polymers as drug delivery systems represents an excellent alternative. In this context, our work focuses on the application of a mathematical model for simulating drug release from breast implants coated with cyclodextrin polymers. The proposed model considers a unidirectional diffusion process following Fick's second law, which was solved using the orthogonal collocation method, a numerical technique employed to approximate solutions for ordinary and partial differential equations. We conducted simulations to obtain release profiles for three therapeutic molecules: pirfenidone, used for preventing capsular contracture; rose Bengal, an anticancer agent; and the antimicrobial peptide KR-12. Furthermore, we calculated the diffusion profiles of these drugs through the cyclodextrin polymers, determining parameters related to diffusivity, solute solid-liquid partition coefficients, and the Sherwood number. Finally, integrating these parameters in COMSOL multiphysics simulations, the unidirectional diffusion mathematical model was validated.