Relationship between surface chemistry and surface energy of different shape pigment blend coatings

The influence of pigment shapes and pigment blends on the surface energy was investigated and compared with the surface chemistry of pigmented latex coatings. The coatings were made of different volume ratios of two pigments: plate-like kaolin clay pigment and prismatic precipitated calcium carbonate (PCC) pigment. These were mixed together with carboxylated styrene–butadiene–acrylonitrile latex (SBA), and applied over nonabsorbent substrates as well as absorbent substrates. The composition of the surface of the coatings was investigated by X-ray photoelectron spectroscopy (XPS). Two approaches were used to estimate the total surface energy and the components of the coatings: a conventional approach—“the Kaelble approach”—and a more modern approach—“the van Oss approach.” Pigment blends with different shapes and increments caused a change in the surface chemistry and the surface energy of the latex coatings. As the prismatic PCC pigment particles increased in the kaolin/SBA coating system, the SBA latex content at the coating surface increased and the total surface energy of the coating decreased. This is valid for both nonabsorbent as well as absorbent substrates. It was found that there was a strong correlation between the surface energy and the surface composition. The surface energy of the coatings estimated by the Van Oss approach was always lower than that estimated by the Kaelble approach. Colloidal interactions between pigment–pigment and/or pigment–binder were thought to play an essential role in determining the final coating surface energy and its components. Changes in the surface latex content and the surface energy due to the different pigment blends investigated were found to fit straight-line equations.     

Surface coating properties of different shape and size pigment blends

The effect of different shape and size of pigments in blends on latex coating surface properties was investigated. Two pigment blends were compared. Both blends were made of plate-like kaolin pigment but with different size prismatic precipitated calcium carbonate at different volume ratios. All coatings were applied on absorbent as well as non-absorbent substrates. Surface coating properties investigated include surface morphology, surface chemistry and surface energy. Surface morphology was characterized by measuring gloss and roughness, surface chemistry was characterized by X-ray Photoelectron Spectroscopy and surface energy was estimated by Kaelable approach.     

Heterogeneous latices as binders in porous particle structures

Heterogeneous carboxylated styrene-butadiene (S/Bu) latices were prepared by a two-stage polymerization process, using three seeds of polystyrene with different molecular weights. The second-stage polymer was a copolymer with a fixed S/Bu-ratio of 1 and a methacrylic acid (MAA) content of either 1 or 10 wt %. It has been found that the morphology of the films made from these latices influenced the modulus in the rubbery region of these films. The heterogeneous latices were used as binders in porous structures based on micron-sized kaolin particles. Such structures are typically employed as paper coatings. Polyester substrates were coated with aqueous suspensions containing the kaolin particles and the heterogeneous latex. The coatings were dried at room temperature, which corresponds to the rubbery region of the latex films. It was found that a higher modulus (which is determined here by the morphology of the latex film) in the rubbery region of the films was associated with coating layers with higher porosity, greater light scattering ability, and higher coating gloss. This is interpreted as being the result of a retarded shrinkage of the coating layers during the drying of these structures due to the increase in modulus of the latex films. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 661–670, 1997     

Drying and collapse of hollow latex

Hollow latex particles are used as white pigments for paints and paper coatings. In the coating dispersion, each hollow particle is filled with water. As the coating dries, water vacates the latex, leaving an air-filled void sized to scatter light (~0.5 μm) within each particle. Examinations of dried coatings reveal that hollow particles can collapse, decreasing their light scattering efficiency. Cryogenic scanning electron microscopy (cryoSEM) was used to characterize the microstructure of coatings containing hollow latex during drying. Images suggest latex voids empty after air invades into the coating interstitial space and collapse occurs late in the drying process. The effects of temperature (10–60°C), humidity (20–80%), and binder concentration (0–30 wt%) on particle collapse were also studied through SEM of dried coating surfaces. High drying temperature, high humidity, and low binder concentrations promoted collapse. For hollow latex particles with porous shell walls, temperature and humidity had little effect, whereas binder increased collapse. From these results, a theoretical model is proposed. During drying, diffusion of water from the particle creates a vacuum inside the latex. The vacuum is either relieved by nucleation of a gas bubble from the dissolved air in the water-filled particle or it causes the particle to collapse by buckling.     

Monte carlo approach to estimating the photodegradation of polymer coatings

The degradation of a polymer coating and predicting the coating lifetime based on physical properties and distribution within the coating of the polymer binder, pigments, and fillers are economically very important. As technologies advance and allow for control of coatings at the nanoscale level, methods such as Monte Carlo can be used not only to predict the behavior of a nanodesigned coating with time but also to design coatings, such as optimizing pigment particle distributions or optimum hard and soft phase distributions of the binders in multiphase systems for maintaining the desired property with time. Erosion of the coating surface was simulated using Monte Carlo techniques where terrestrial solar flux is the initiator for polymer segment cleavage and removal. The impact on the sensitivity of the polymer adjacent to the detached polymer segment can be increased or decreased in the model based on the chemistry and surface energy of the remaining polymer matrix. Multiple phases with varying sensitivity to degradation can be modeled. The Monte Carlo generates a statistically similar surface topography and chemistry of the coating. The results of the Monte Carlo model are compared to measurable properties such as gloss, fracture toughness, and wetting contact angle, using various published correlations of the property to the surface topology. The simulated properties change through the life-time of the coating in ways that are consistent with observed behavior. Apparently, complicated changes in many properties can be described by the repeated application of simple, random processes. Presented at the 79th Annual Meeting of the Federation of Societies for Coatings Technology, October 28–November 1, 2002, in New Orleans, LA.     

Dry sintering of latex particles in pigmented coatings. I. Influence on coating structure and properties

When a clay–latex coating, dried below the minimum film-forming temperature (MFT) of the latex, was subsequently heated above the MFT, its opacity and brightness were considerably enhanced. The improvement in optical properties was optimum in the latex content range of 20–40 parts per 100 parts of clay. The sintering of the latex particles, brought about by the thermal treatment, increased the average size of the microvoids to a diameter that is optimum for the scattering of light, without significantly affecting the total void content. Data on light-scattering coefficient, porosity, gloss, brightness, and oil permeability are discussed and compared to those of conventional coatings, i.e., of coatings dried above the MFT of the latex. Similar improvements in optical properties were obtained when coalescence of the latex particles was induced by exposure to a solvent.     

Interdiffusion and crosslinking in thermoset latex films

Thermoset latex systems represent an attractive approach to obtaining the high performance needed in many different kinds of industrial coatings, while satisfying the growing requirement for environmental friendliness. In these coatings in the dispersed state, the reactive groups are packaged inside of polymer particles. These latex particles deform as the coating dries to form a transparent binder phase. The useful properties of mechanical strength, as well as scrub and solvent resistance, develop over time. This paper focuses on the idea that to achieve the desired properties in a thermoset latex coating, one has to pay proper attention to the relative rates of polymer diffusion and crosslinking in the coating. Strength in these films develops as a consequence of chains that connect crosslink points on opposite sides of interface formed between adjacent particles in the film. Thus polymer diffusion must precede extensive bond formation created by the crosslinking chemistry. This paper reviews fundamental concepts and then describes experiments in three separate systems. These experiments show that the formulator has three main strategies to vary the relative rates of these processes: 1. Catalyst strength and concentration will affect the reaction rate. 2. Polymer chain length will affect the polymer diffusion rate. 3. Temperature changes will normally have a larger affect on the polymer diffusion rate than on the crosslinking reaction rate. Presented at the 79th Annual Meeting of the Federation of Societies for Coatings Technology, on November 3, 2001, in Atlanta, GA. Department of Chemistry, Toronto, Ont., M5S 3H6, Canada.     

Transparent,conductive polymer blend coatings from latex-based dispersions

Flexible, transparent and conductive polymer blend coatings were prepared from aqueous dispersions of poly(3,4-ethylenedixoythiophene)/poly(styrenesulfonate) [PEDOT/PSS] gel particles (∼80 nm) and latex (∼300 nm). The stable dispersions were deposited as wet coatings onto poly(ethylene terephthalate) substrates and dried at 80 °C. Microstructure studies using tapping mode atomic force microscopy (TMAFM) indicate that a network-like microstructure formed during drying at 0.03 volume fraction PEDOT/PSS loading. In this network-like structure, the PEDOT/PSS phase was forced into the boundary regions between latex. In addition, migration of the PEDOT/PSS particles towards coating surface is likely during drying of the aqueous dispersions. The addition of a small amount of dimethyl sulfoxide (DMSO) in dispersions altered the distribution of the PEDOT/PSS phase. As PEDOT/PSS concentration increases to 0.15 volume fraction, the coating surface is dominated by the PEDOT/PSS phase. The effect of DMSO on microstructure becomes less apparent as PEDOT/PSS concentration increases. The conductivity of the polymer blend coatings increases in a percolation-like fashion with a threshold of ∼0.02 volume fraction PEDOT/PSS. The addition of DMSO in dispersions enhanced the coating conductivity beyond the threshold by more than two orders of magnitude. The highest conductivity, ∼3 S/cm, occurs at 0.20 volume fraction PEDOT/PSS concentration. The polymer blend coatings have good transparency with only a weak dependence of transparency on wavelength due to the small refractive index difference between filler and matrix.     

Sintering of latex particles in pigmented coatings. II. Influence of the latex particle size

The light-scattering coefficient S of coatings formulated from a mixture of an inorganic pigment and polystyrene latex particles may be enhanced significantly when the dry coating is heated in order to cause sintering of the polystyrene spheres. The relative increase in S depends on the size and the amount of the latex particles and the type of the inorganic pigment. Of the latexes examined (0.5, 0.2, 0.1, and 0.03 μm in diameter) the 0.2μm latex is the most effective in blends with platelike delaminated clay. The coatings based on spherelike precipitated calcium carbonate are less responsive to the heat treatment. The gloss of the clay–latex coatings is not significantly altered by the heat treatment up to 20 pph of latex; the gloss of the calcium carbonate coatings generally decreases upon heating.     

Estimation of the effective particle sizes within a paper coating layer using a void network model

A range of calcium carbonate-based tablets and paper coating layers, with latex or starch as binder, were prepared. Their dry porous structures were analysed by mercury porosimetry. Some of these samples were also examined by electron microscopy. The porous space of these structures has been simulated using a network model named Pore-Cor, which creates network structures with percolation behaviour and porosity matching those of the experimental sample. Representative particles were grown between the cubic pores and cylindrical throats of the void network model until they touched up to four of the adjacent void features. The sizes of these representative particles, or skeletal elements, have been previously shown to be realistic for the case of unconsolidated sand and glass beads. The size distributions of these skeletal elements were compared with each other and with experiment using a Mann-Whitney test. The sizes of the skeletal elements were found to increase with the particle size of the calcium carbonate powder. The properties of the binders, used in the paper coating formulations, were found to have a major influence on the sizes of the skeletal elements, whose sizes also increased with coating thickness. These findings give insights into the wet structure and the drying process of paper coatings.     

Surface structure and properties of water‐based polymer coating materials prepared by the complexation of two polymer latices with chemically complementary structures

In this study, water‐based polymer coating materials used for the surface coating of substrates with lower surface energies were prepared by the complexation of two‐component polymer latices containing polydimethylsiloxane (PDMS) and having chemically complementary structures. The film‐forming performance of the polymer latices and the surface structures and properties of the coatings formed by the polymer latices were studied by means of scanning electron microscopy and by the measurement of mechanical strength, thermal performance, water absorbability, and contact angle. When the two‐component polymer latices [the poly(methyl methacrylate‐co‐butyl acrylate‐co‐methyl acrylic acid)/polydimethylsiloxane system (PA latex) and the poly(methyl methacrylate‐co‐butyl acrylate‐co‐pyrrolidone)/polydimethylsiloxane system (PB latex)] were compared, the complex polymer latex formed by the complexation of the PA latex with the PB latex had the best film‐forming performance, with formed coatings that were more smooth and had fewer less cracks. Also, compared to the two coatings formed by the two‐component polymer latices, the coatings formed by the complex polymer latex had a unique structure, a higher mechanical strength and elongation, a higher decomposing temperature, and better water resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1748–1754, 2003     

Optical and surface properties of whey protein isolate coatings on plastic films as influenced by substrate,protein concentration,and plasticizer type

Composite film structures of common plastic polymers including polypropylene (PP) or poly(vinyl chloride) (PVC) with whey protein isolate (WPI) coatings may be obtained by a casting method. Optical and surface properties of the resulting WPI‐coated plastic films, as affected by protein concentration and plasticizer type, were investigated to examine the biopolymer coating effects on surface modification with polymeric substrates of opposite polarity. The measured properties involved specular gloss, color, contact angle, and critical surface energy. Regardless of the substrates, WPI‐coated films possessed excellent gloss and no color, as well as good adhesion between the coating and the substrate when an appropriate plasticizer was added to the coating formulations. The protein concentration did not significantly affect gloss of WPI‐coated plastic films. Among five plasticizers applied, sucrose conferred the most highly reflective and homogeneous surfaces to the coated films. The WPI coatings were very transparent and the coated films with various protein concentrations and plasticizers showed no noticeable changes in color. Experimental results suggest that WPI coatings formulated with a proper plasticizer can improve the visual characteristics of the polymeric substrate and enhance water wettability of the coated plastic films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 335–343, 2004     

Effect of pigmentation on the surface chemistry and surface free energy of paper coating binders

The effect of the addition of clay and TiO₂ pigments on the surface energy and surface chemistry of films made from polymers used in paper coating formulations was evaluated. The polymers were carboxymethyl cellulose, polyvinyl alcohol and a protein-based polymer - all water-soluble - and two styrene-butadiene latexes of different carboxylation levels. The morphology of the surfaces was characterized by SEM examination, gloss measurement and stylus profilometry. Chemical composition was determined by EDS and XPS techniques. Surface energy and its Lifshitz-van der Waals and acid-base components were obtained from contact angle measurements using the van Oss et al. approach. Even though the addition of pigment increasingly upset the planar surface of the films, their surface chemistry and surface energy were only slightly affected over the pigmentation range studied (up to 40% by volume) and were dominated by the characteristics of the binder polymer.     

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     

Influences of WC-Co hard metal substrate pre-treatments with boron and silicon on low pressure diamond deposition

Diamond coatings were produced on WC-Co hard metal substrates. To improve the adhesion between the diamond coating and the substrate a substrate surface pre-treatment with boron or with silicon vapor was applied. This surface pre-treatment resulted in an increase in both the diamond nucleation density and the diamond growth rate. Simple adhesion tests confirmed an improved adhesion of thin diamond layers as compared with those on untreated hard metal substrates.Secondary ion mass spectroscopy (SIMS) depth profiles revealed an enrichment of B or of Si at the substrate-diamond interface due to the pre-treatment procedure. The correlation of the Co and W depth profiles in samples coated for 12 and 24 h supports the theory of diamond dissolution into the substrate. Co was detected only in the interface regions and on the surface of the diamond layers but not in the bulk of the thick layers. The SIMS results confirm X-ray examinations of the hard metal Co binder phase.     

A hybrid polyacrylate/OMMT nanocomposite latex: Synthesis,characterization and its application as a coating binder

Hybrid latex particles have an increasing importance in industrial applications especially for high performance waterborne coatings. They provide combined properties of different phase compositions for the final polymer which can also be enhanced by additives such as nanoclays. The present study describes the preparation of a hybrid polyacrylate/OMMT nanocomposite latex via two stage in situ emulsion polymerization with a low emulsifier content (1 wt%) which is usually a challenge for the preparation of stable polymer/OMMT nanocomposite latexes. The obtained nanocomposite latex was stable and had a fine average size diameter of 151 nm with a very narrow size distribution. The copolymer films exhibited a well exfoliated structure observed by WAXD and TEM. Other polymer properties were investigated by FTIR, DSC, TGA, DMTA and rheological measurements. The results indicated that the addition of clay even in low amount (2 wt%) yielded significantly improved mechanical and thermal properties of the final polymer. In addition, the nanocomposite latex was also applied on leathers as coating binder in a finishing formulation and the results of the performance tests revealed substantially increased rubbing and heat resistance whereas a slight decrease was observed at water vapor permeability of the coated leathers.     

Characterization of a plasma polymer coating from an organophosphorus silane deposited at atmospheric pressure for fire-retardant purposes

Protective coatings from diethylphosphatoethyltriethoxysilane (DEPETS) have been deposited on different polymer substrates in a plasma discharge operated at atmospheric pressure. Plasma polymer chemistry and structure were characterized by means of Fourier transform infrared spectroscopy (FTIR), laser desorption ionization-mass spectrometry (LDI-MS), nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). A chemical structure of the plasma polymer has been proposed based on the coating molecular characterization. Coatings were deposited on polycarbonate (PC) and polyamide 6 (PA6) substrates. The flame retardant properties of coated substrate samples were assessed using cone calorimetry and compared to those of bare substrates. A significant increase in the time to ignition (TTI), up to +143%, was recorded after coating deposition due to the formation of a high-performance barrier layer at the surface of both polymer substrates.     

Advances in emulsion polymerization for coatings applications: Latex blends and reactive surfactants

The utilization of latex blends to prepare zero-VOC coatings and the use of reactive surfactants in emulsion polymerization are two advances in waterborne technology that are of increasing interest to coatings formulators. The first part of this paper focuses on an investigation of the influence of the interface between high and low T_g latex particles on the gloss and surface morphologies offilms obtained from model latex blends. Gloss was influenced by the concentration of carboxyl groups present on the surface of the latex particles (optimal concentration for maximum gloss = 13% on the high T_g particles, the degree of neutralization of these groups (higher gloss with increased extent of neutralization), the type and concentration of the neutralizing base (higher gloss for stronger bases), and the presence of added surfactant (higher gloss with added surfactant). Gloss was found to be correlated with the surface smoothness of the film. The kinetics, partide size, molecular weight, and location of the reactive surfactant after polymerization, as well as the contact angle of films prepared from these latexes, are examined in the second part of this paper. The polymerization rate profiles were similar to those obtained using a conventional surfactant; however, the dependency of the rate on the number of particles was significantly lower. The amound bound increased and the molecular weight decreased with increasing surfactant concentration. Presented at the 78th Annual Meeting of the Federation of Societies for Coatings Technology, on October 16–20, 2000, in Chicago, IL. Emulsion Polymers Institute and Department of Chemical Engineering, 111 Research Dr., Bethlehem, PA, 18015-4791.     

Structure of polymer within the coating: an atomic force microscopy and small angle neutrons scattering study

Synthetic latex is widely used as a binder in waterbased paints. Upon dehydration of the dispersion, latex particles are brought into contact with mineral pigments: this process results in coating structuration and consolidation. This composite layer is described as a porous mineral structure, whose pores are covered by latex particles. Therefore, it is of fundamental interest to study the ordering of binder particles in the coating, and the wetting of pigments by polymer particles, toward understanding properties of coating such as: optical properties, adhesion, cohesion, sensitivity to water, etc. In this regard, we have used small angle neutron scattering and atomic force microscopy to study the ordering, the spreading, and the adhesion of latex particles on calcium carbonate within the coating. We discuss the structure of the coating.     

Effect of particle size distribution on stress development and microstructure of particulate coatings

The role of pigment particle size distribution on stress and microstructure development was studied for coatings prepared from aqueous suspensions of ground calcium carbonate (GCC) and latex binder. Stress development was monitored using a modified beam deflection technique under controlled environment. Microstructure was characterized by scanning electron microscopy (SEM) and cryogenic SEM. For coatings containing only GCC particles and no latex, a wide particle size distribution resulted in a significant particle size gradient in the cross-sectional microstructure and irregular stress development. With latex addition, uniform microstructures were observed in coatings with either wide or narrow GCC particle size distribution. GCC/latex coatings prepared using GCC with a wide particle size distribution developed a higher stress than those prepared using GCC with a similar average particle size but a narrow particle size distribution. The higher stress is related to the particle packing that results in smaller pore sizes and larger capillary pressures that drive compaction. In coatings prepared with the same GCC particles but different latex binders, the stress and cracking behavior of the coating depends on the latex properties.