Advanced techniques for nanocharacterization of polymeric coating surfaces

Surface properties of a polymeric coating system have a strong influence on its performance and service life. However, the surface of a polymer coating may have different chemical, physical, and mechanical properties from the bulk. In order to monitor the coating property changes with environmental exposures from the early stages of degradation, nondestructive techniques with the ability to characterize surface properties with micro- to nanoscale spatial resolution are required. In this article, atomic force microscopy has been applied to study surface microstructure and morphological changes during degradation in polymer coatings. Additionally, the use of AFM with a controlled tip-sample environment to study nanochemical heterogeneity and the application of nanoindentation to characterize mechanical properties of coatings surfaces are demonstrated. The results obtained from these nanometer characterization techniques will provide a better understanding of the degradation mechanisms and a fundamental basis for predicting the service life of polymer coatings. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology on November 12–14, 2003, in Philadelphia, PA.     

超细粉体表面包覆技术综述

通过超细粉体的表面包覆以改善粉体的分散性及其表面性质,已经成为超细粉体制备和应用的关键技术。综述了超细粉体的表面包覆方法,包括机械化学法、气相沉积法、聚合物包裹法、液相化学法及微胶囊化法等,主要介绍了每种方法的基本原理及应用。     

Numerical Spray Model of the Fluidized Bed Coating Process

In this study, a new model for the batch top-spray fluidized bed coating process is presented. The model is based on the one-dimensional (axial) discretization of the bed volume into different control volumes, in which the dynamic heat and mass balances for air, water vapor, droplets, core particles, and coating material were established. The coupling of the droplet phase's mass and heat transfer terms with the gas and solid phases was established by means of a droplet submodel in which droplet trajectories were individually simulated.

The model calculation method combines a Monte Carlo technique for the simulation of the particle exchange with the first-order Euler's method for solving the heat and mass balances, enabling the prediction of both the dynamic coating mass distribution and the one-dimensional (axial) thermodynamic behavior of the fluidized bed during batch operation. The simulation results were validated using experimental two-dimensional spatial air temperature and air humidity distributions, which were measured in a fluidized bed pilot reactor using a scanning probe.

Sensitivity analysis was carried out to study the effect of controllable process variables, such as fluidization air and atomization air properties, as well as the properties of the spraying liquid upon the simulated dynamic temperature and humidity distributions. Also, the effects of relevant process variables on growth rate uniformity and process yield were studied. Based on these sensitivity studies it was concluded that nozzle parameters, such as air pressure and positioning with respect to the bed, are as important as the fluidization air properties (humidity, temperature, and flow rate) for the coating growth rate uniformity and process yield.     

The influence of substrate absorbency on coating surface chemistry

The composition of the top surface of a coating layer can influence its functional properties or subsequent processing steps. The effect of the substrate absorbency on the coating surface chemistry is reported. Different coating systems containing a kaolin clay pigment, fine or coarse precipitated calcium carbonates, and a common latex binder were examined. The influence of a soluble polymer added into the coating was characterized. The surface chemistry was measured with attenuated total internal reflectance (ATR) and X-ray photoelectron spectroscopy (XPS).

Absorbent substrates generate bulky coatings with high voids and low gloss. Rapid dewatering by the absorbent substrate pulls the small particles, like latex binder, away from the top layers causing a low latex concentration at the surface. On non-absorbent substrates, the addition of the soluble polymer generates coating layers with higher void volume, lower gloss, and lower latex concentrations at the coating surface. However, on absorbent substrates, polymer addition causes coatings with lower void volumes and higher gloss. In this case, the rapid dewatering and mobility of particles is reduced by the polymer, which helps to retain the small particles at the surface. As a result, latex concentration at the surface increases with polymer addition on absorbent substrates.     

Numerical Spray Model of the Fluidized Bed Coating Process

In this study, a new model for the batch top-spray fluidized bed coating process is presented. The model is based on the one-dimensional (axial) discretization of the bed volume into different control volumes, in which the dynamic heat and mass balances for air, water vapor, droplets, core particles, and coating material were established. The coupling of the droplet phase's mass and heat transfer terms with the gas and solid phases was established by means of a droplet submodel in which droplet trajectories were individually simulated.

The model calculation method combines a Monte Carlo technique for the simulation of the particle exchange with the first-order Euler's method for solving the heat and mass balances, enabling the prediction of both the dynamic coating mass distribution and the one-dimensional (axial) thermodynamic behavior of the fluidized bed during batch operation. The simulation results were validated using experimental two-dimensional spatial air temperature and air humidity distributions, which were measured in a fluidized bed pilot reactor using a scanning probe.

Sensitivity analysis was carried out to study the effect of controllable process variables, such as fluidization air and atomization air properties, as well as the properties of the spraying liquid upon the simulated dynamic temperature and humidity distributions. Also, the effects of relevant process variables on growth rate uniformity and process yield were studied. Based on these sensitivity studies it was concluded that nozzle parameters, such as air pressure and positioning with respect to the bed, are as important as the fluidization air properties (humidity, temperature, and flow rate) for the coating growth rate uniformity and process yield.     

On the electrochemical and structural behavior of biologically degraded automotive coatings; Part 1: Effect of natural and simulated bird droppings

Environmental factors can potentially deteriorate automotive coatings. These include UV radiation, humidity, hot–cold shocks as well as aggressive chemical compounds. In addition, natural occurring materials such as bird droppings and tree gums are also enable to affect the coatings. The present work aims to study the degradation of an automotive coating system exposed to natural and simulated bird droppings. To this end, structural analysis of samples was studied using FT-IR spectroscopy, optical and atomic force microscopes. Also, the mechanical and electrochemical behaviors of coatings were investigated by DMTA and electrochemical impedance spectroscopy (EIS). It was found that the biological materials significantly affect the mechanical and chemical properties of the coatings, resulting in a decrease in corrosion resistance. A two-time constant semicircle was observed for degraded coatings after a short time as a result of electrolyte diffusion into the coating/metal interface. The behavior of the coatings was then discussed based on the formation of surface defects.     

Electrochemical impedance spectroscopy response of water uptake in organic coatings by finite element methods

The corrosion of metals is a long standing topic of research which is of immense economic importance. One of the principal means of preventing surface corrosion of metals is thin polymer coatings, i.e. paint. These coatings often fail because of the passage of water or other active ionic species into and through the polymer coating. Since both the capacitance and the resistance of a polymer coating change as it absorbs water, electrochemical impedance spectroscopy (EIS) gives a general idea of how much water a polymer has been absorbed. Theories, such as the Brasher-Kingsbury approximation, are effective medium theories based on the assumption that the absorbed water is randomly distributed in spherical inclusions. The water in a coating may be distributed as spherical inclusions, as discrete channels, or as some combination that transports water from the coating surface until the water reaches the metal substrate and corrosion can begin.The resistance and the capacitance of a coating depend on both the amount of water (volume fraction) and the shape of the water inclusions. EIS gives only a general idea of how much water has been absorbed by a coating but does not provide the distribution or shape of the water inclusions. EIS circuit response is often modeled with the equivalent circuit elements describing the material properties for water inclusions that are implicitly assumed to be randomly distributed spherical inclusions. Numerical calculations using the finite element analysis (FEA) are reported here to solve Maxwell's equations for various shapes and sizes of water inclusions within the polymer. Calculations here have been based on the electrical properties of a polyvinyl fluoride film, as an exemplar, with water inclusions of different shapes and concentrations (water volume fraction). The Brasher-Kingsbury approximation gives the correct outcome only for a random distribution of spherical inclusions, as expected. Other shapes and distributions can vary from the Brasher-Kingsbury prediction of water volume fraction by more than 50% of the actual gravimetric water volume fraction. Results are presented here for spherical and cylindrical randomly distributed water inclusions. Understanding the sensitivity to different distributions and numbers of inclusions is an objective planned for future research.     

Simulations of nanoscale and macroscopic property changes on coatings with weathering

Coatings are designed for and applied on a surface for both aesthetics and protection of the substrate. Many properties are measured to indicate performance, and eventual failure, of a coating under these two broad categories. Monte Carlo simulations have shown success in predicting trends in macroscopic properties during exposure. The Central Limit Theorem (CLT) is applicable because damage made to a coating can come from the accumulation of a vast number of very small damage events. Application of the CLT to property equations has generated additional equations for the prediction of properties of a coating with exposure, including measurable properties such as gloss, color, fracture toughness, and contact angle. These equations, when fitted to measured data, provide in sight into the mechanisms of degradation processes, since the fitting parameters are physically based. They also offer a means to scale accelerated testing measurements to early field measurements of the property of interest for predicting lifetime in varied environments. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Statistical approaches for predicting weathering degradation and service life

Predicting the service lifetime of any material is very important. One of the major difficulties is relating individual, nanoscale, degradation events to the eventual deterioration in macroscopic properties. Monte Carlo simulations and the Central Limit theorem provide approaches to the kinetics of how general coating topology, or bulk morphology, changes during long term weathering. Results on structural changes, from these approaches, may then be translated, via well-known models, into the degradation of macroscopic, “use” properties. Thus service lifetime may be related to composition and degradation mechanisms. Results on pigmented, acrylic coatings demonstrate the applicability and utility of this statistical approach. Changes in gloss and contact angle were related, via these models and provide insights into the processes of degradation in pigmented coatings. Values of parameters for the models that relate surface roughening with exposure are consistent with results from atomic force microscopy. The models provide justification for using simple expressions for trends in non-destructive monitoring, e.g. gloss, or contact angle or for comparing different systems and estimating long-term changes in properties.     

Nylon 11/silica nanocomposite coatings applied by the HVOF process. II. Mechanical and barrier properties

Nylon 11 coatings filled with nominal 0–15 vol % of nanosized silica or carbon black were produced using the high velocity oxy‐fuel combustion spray process. The scratch and sliding wear resistance, mechanical, and barrier properties of nanocomposite coatings were measured. The effect of powder initial size, filler content, filler chemistry, coating microstructure, and morphology were evaluated. Improvements of up to 35% in scratch and 67% in wear resistance were obtained for coatings with nominal 15 vol % contents of hydrophobic silica or carbon black, respectively, relative to unfilled coatings. This increase appeared to be primarily attributable to filler addition and increased matrix crystallinity. Particle surface chemistry, distribution, and dispersion also contributed to the differences in coating scratch and wear performance. Reinforcement of the polymer matrix resulted in increases of up to 205% in the glass storage modulus of nanocomposite coatings. This increase was shown to be a function of both the surface chemistry and amount of reinforcement. The storage modulus of nanocomposite coatings at temperatures above the glass transition temperature was higher than that of unfilled coatings by up to 195%, depending primarily on the particle size of the starting polymer powder. Results also showed that the water vapor transmission rate through nanoreinforced coatings decreased by up to 50% compared with pure polymer coatings. The aqueous permeability of coatings produced from smaller particle size polymers (D‐30) was lower than the permeability of coatings produced from larger particles because of the lower porosities and higher densities achieved in D‐30 coatings. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2272–2289, 2000     

Influence of compositional variables on the morphological and dynamic mechanical behavior of fatty acid based self-crosslinking poly (urethane urea) anionomers

Fatty acid based self-crosslinking polyurethane urea (PUU) anionomers can find potential applications in coatings field due to enhanced chemical resistance properties. To optimize their performance in coatings, the molecular features that influence the microphase morphology and dynamic mechanical (DM) behavior of polymer films must be understood and exploited. In this work, comprehensive materials characterization of model PUU anionomers films with oxidative-crosslinking microstructure is addressed. For this, linoleic fatty acid based precursor (LPE) was included in polymer backbone which provides reactive sites for autooxidative polymerization. Three series of compositions were prepared with urea content of 8.4%, 13.2% and 18.1% where within each series LPE content has been increasing in same proportion. Different experimental techniques like FTIR, DSC, DMA and mechanical testing were utilized to study the effect of compositional variables on the extent of phase segregation, domain structure and mechanical properties of fully cured polymer samples. The extent soft segment (SS) oxidative crosslinking had marked effect on the microphase morphology and DM properties of materials of lowest urea content. Significant phase mixing was observed with evolvement of single heterogenous phase in the sample with highest LPE content. Samples with 13.2% urea shows less sensitivity toward increased SS crosslinking in their microphase morphology change. Their mechanical and DM properties were observed to be dominated by interlocked hard domains. With higher urea content, such kind of hard segment cohesion results due to greater strength of bidenate H-bonding among urea linkages. While samples with highest % urea, were clearly found to be well microphase separated compared to other two series with highest HS interconnectivity and have marginal effect of extent of SS crosslinking on microphase separation. This study gives an insight about effect of extent of complex oxidative crosslinking on the microphase separation and DM behavior of segmented PUU anionomers based films with different urea content which is useful in designing such materials in coating system with specific surface structure and function.     

Transport and related properties of paint films. II. Dynamic mechanical properties and humidity effects

A systematic four-stage investigation of eight unpigmented coating formulations, including three vinyl, two polyurethanes, and three epoxy systems was done to provide baseline structural information upon which an improved understanding and an optimization of protective coatings can be founded. First, the results from dynamic mechanical measurements are provided and discussed for the base polymer component in each coating system. Second, the effects of humidity on the dynamic mechanical properties of these base polymers were determined at room temperature. The extent of property degradation was monitored by calculating the T_g depression with increased humidity, assuming a temperature–humidity superposition. The extent of degradation, as monitored by the T_g, was found to correlate directly with the level of hydrogen bonding in these coatings. Third, the influence of typical coating additives (a TCP plasticizer and a rosin hardener) on the properties of two of the vinyl coating systems was investigated. In the final stage, the synergistic effects of absorbed moisture and these additives on the coatings properties were investigated at room temperature. Increases in the concentration of these additives was found to magnify the degradation effect of increased humidity. This magnified degradation has been assigned to increased water absorption with increases in the concentration of either of these additives.     

Preliminary investigation of the impact of polymer composition on electrochemical properties of coatings as determined by electrochemical impedance spectroscopy

The influence of structural and systematic compositional variations in glycidyl carbamate (GC) functional polymers on the electrochemical properties of their coatings was studied. There are few reports which focus on the correlation of structural and compositional variations in polymer films with their electrochemical barrier properties, diffusion properties with regards to water and aqueous electrolytes, and corrosion performance. To begin to fill this knowledge gap, two sets of GC functional polymers were studied. The polymer compositions were designed to vary the extent of polar hydrophilic groups, non-polar hydrophobic groups, and reactive epoxy groups in the final coatings. Impedance responses of the coatings were found to be closely related to the structural and compositional variations of these GC polymer films. In addition, single frequency EIS experiments were used in an attempt to understand the water uptake behavior of these polymer films using NaCl solution and ionic liquid under immersed condition. The resulting transport property data of the films was correlated to their polymer structure and composition. Moreover, a novel attempt at ranking the stability of coating using capacitance measurement during a cyclic wetting–drying condition was also attempted. The information obtained from this work can potentially be used to optimize the polymer for the specific performance properties needed in the protective coating applications, saving significant time and effort in the research and development stage.     

A family of multivariate non-gaussian time series models

In this article, we propose a class of multivariate non-Gaussian time series models which include dynamic versions of many well-known distributions and consider their Bayesian analysis. A key feature of our proposed model is its ability to account for correlations across time as well as across series (contemporary) via a common random environment. The proposed modeling approach yields analytically tractable dynamic marginal likelihoods, a property not typically found outside of linear Gaussian time series models. These dynamic marginal likelihoods can be tied back to known static multivariate distributions such as the Lomax, generalized Lomax, and the multivariate Burr distributions. The availability of the marginal likelihoods allows us to develop efficient estimation methods for various settings using Markov chain Monte Carlo as well as sequential Monte Carlo methods. Our approach can be considered to be a multivariate generalization of commonly used univariate non-Gaussian class of state space models. To illustrate our methodology, we use simulated data examples and a real application of multivariate time series for modeling the joint dynamics of stochastic volatility in financial indexes, the VIX and VXN.     

Low surface energy self-polishing polymer grafted MWNTs for antibacterial coating and controlled-release property of Cu2O

Marine biofouling had been a headache when engaging in marine activities. The most effective and convenient method for dealing with this problem was to apply antifouling coatings. But now a single anti-fouling system was hard to satisfy the requirement of anti-fouling simultaneously. Therefore, it was particularly important to develop novel multi-system anti-fouling technology. In the work, a novel polymer coatings with polydimethylsiloxane (PDMS) segments in the main chain and hydrolysable side chain was designed and synthesized which showed low surface energy and self-polishing performance, and then we creatively covalently immobilized the polyurethane on the surface of multi-carbon nanotubes (MWNTs) to form multisystem antifouling coating. The results showed that the polymer coating would produce hydrolysable regions in the hydrophobic PDMS segment to endure the polymer coating hydrophobic and hydrolysis properties when contacted with water. In addition, the self-polishing rate and the surface energy could be regulated by varying its copolymerization, and the addition of MWNTs could kill the microorganisms and endowed the polymer coating itself enhanced antibacterial effect. Furthermore, considering the high specific surface area and physicochemical characteristics of MWNTs, it could be combined with antifoulant Cu₂O through a polar or non-polar combination as a carrier to control the release rate of Cu₂O in coatings.     

Computer simulation of network formation processes,structure and mechanical properties of polymer networks

The possibilities offered by computer simulation for the investigation of polymer networks are discussed. Instantaneous crosslinking can be simulated by fixing the conformation of a set of linear macromolecules. Equilibrium crosslinking requires a complete rearrangement of the conformation after formation of each crosslink. The conformations of the lattice models of polymer networks with certain topologies can be constructed using a Monte Carlo procedure for obtaining the equilibrium configurations of the junction points, and the methods of generating conformations of polymer chains with fixed end-to-end distances. The deformational properties of polymer networks, taking into account the finite length of chains, can be investigated by the use of a model of interacting junction points, quasi-particles. The way of investigating the entanglement effects and the interchain interactions are proposed. Polymer chain mobility may be simulated by the molecular dynamics of the ‘pearl necklace’ model. Destruction processes in polymer networks can be simulated by a Monte Carlo method if the breakage of a strand connecting two junction points is regarded as an elementary event.     

共聚高分子吸附的Monte Carlo模拟

用MonteCarlo方法对选择性溶剂中两嵌段共聚高分子在固液界面的吸附进行了模拟 ,获得了吸附等温线以及吸附层厚度、链附着率、表面覆盖率、链节浓度分布等表征吸附层结构的信息 ,同时模拟获得了固液界面区吸附构型大小及分布等表征高分子构型的微观信息 ,考察了吸附性链节A所受的对比排斥能、链组成以及体相浓度等因素对这些参数的影响 .     

Nylon 11/silica nanocomposite coatings applied by the HVOF process. I. Microstructure and morphology

Nylon 11 coatings filled with nanosized silica and carbon black have been produced using the high velocity oxy‐fuel (HVOF) combustion spray process. The physical properties and microstructure of coatings produced from nylon 11 powders with starting particle sizes of 30 and 60 μm have been evaluated as a function of the filler content, filler chemistry, and processing conditions. The nominal filler content was varied from 5 to 20 vol %. Co‐milling of the nano‐sized fillers with the polymer powders produced an embedded 4–8 μm thick filler layer on the surfaces of the polymer particles. Optimization of the HVOF processing parameters based on an assessment of the degree of splatting of polymer particles was accomplished by varying the jet temperature (via hydrogen/oxygen ratio). Gas mixtures with low hydrogen contents minimized polymer particle degradation. The filler was found to be agglomerated at the splat boundaries in the final coating microstructures. Aggregates of silanated silica and carbon black were of the order of 50 nm in size, whereas the aggregates of untreated silica and hydrophilic silica were of the order of 100 nm. The morphology of the polymer and the microstructure of the coatings depended on the filler surface chemistry and the volume fraction of the filler, as well as the initial nylon 11 particle size. Although all filled coatings had higher crystallinities than pure nylon 11 coatings, coatings produced from a smaller starting polymer particle size exhibited improved spatial distribution of the silica in the matrix and lower crystallinity. In addition, coatings prepared from smaller polymer particles had a higher density and lower porosity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1684–1699, 2000     

Processing and characterization of elastomeric polycaprolactone triol–citrate coatings for biomedical applications

In this paper we describe the synthesis, processing and characterization of a novel elastic polyester coating created by carrying out catalyst-free polyesterification between biocompatible and non-toxic multifunctional reactants, namely polycaprolactone triol and citric acid. The physico-chemical and surface properties of the resulting polyester coatings and films have been investigated. This new material has been characterized by matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS), nuclear magnetic resonance spectroscopy (NMR), Fourier-transform infra-red spectroscopy (FTIR), water-in-air contact angle measurements, scanning electron microscopy (SEM), thermal analysis (DSC), mechanical tests and swelling experiments. The polymer structure, surface properties (morphology and chemistry), mechanical integrity and hydration of the elastomer can be controlled by simple variation of the initial citric acid concentration in the polymer formation. This feature of the novel polyester material presents a significant development in the production of advanced coatings for biomedical applications.     

Bio-Macromolecular Surface Coatings for Autohesive,Transparent, Elastomeric Foils

Thin materials made from elastomeric polymers such as polydimethylsiloxane (PDMS) and polyurethane (PU) can be both, compliant and resilient. Their mechanical robustness and flexibility will make them great candidates for applications in the human body where space is limited and repeated deformations occur. Nonetheless, current medical applications of elastomeric foil-like products are mainly restricted to inflatable balloon parts of stents or intubation tubes. Here, a key limiting factor is the autohesive behavior of those foils, that is, their propensity to stick to themselves. This property impedes handling and processing and can also interfere with the designated tasks of such foils. To mitigate this undesired behavior, different bio-macromolecular coatings are applied here and assess their influence on the autohesive behavior, flexibility, and transparency of the materials. A non-covalent, dopamine-assisted coating approach is compared to a covalent coating strategy employing carbodiimide chemistry and investigated both, anionic and cationic macromolecules as top layers. The results show that especially the carbodiimide-mediated mucin coating can efficiently suppress the autohesive behavior of the foils while maintaining the flexibility and transparency of the material. Thus, such coatings can not only broaden the medical application range of foil-based elastomeric devices but may also prove beneficial for applications in soft robotics.