The colloidal properties of alkaline‐soluble waterborne polymers

Waterborne polymer dispersions are widely used in coatings and graphic arts markets as environmentally friendly and more sustainable alternatives to solvent borne binders. Traditionally, waterborne (meth)acrylic dispersions are prepared by emulsion polymerization using low molar mass surfactants as a key ingredient to control particle size. However, these surfactants can have a negative influence on the performance of coatings such as reduced water resistance and adhesion. To mitigate the negative effects of surfactants, polymer latexes have been developed that employ alkaline‐soluble polymers as the sole stabilizer for a subsequent emulsion polymerization step. In this way surfactant‐free polymer dispersions are obtained. Despite the high commercial impact and relevance of this technology, fundamental studies regarding the physicochemical properties of the alkaline‐soluble polymers are lacking. In this article, the synthesis and colloidal properties of alkaline‐soluble waterborne methacrylic copolymers are reported. The dissolution behavior and colloidal properties of these alkaline‐soluble polymers were studied as function of molar mass, acid content, and pH. The dissolving polymer particles were characterized using static and dynamic light scattering, static and dynamic surface tension measurements, and cryogenic‐transmission electron microscopy analysis. It is concluded that the dissolution mechanism of alkaline‐soluble polymers follows a gradual process. As the pH increases deprotonation of the carboxylic acid groups swells the particle enhancing the further swelling with water. At a certain amount of base, the particles disintegrate into small polymer aggregates while the most water‐soluble polymer chains are dissolved in the water phase. An important learning is that part of the alkaline‐soluble polymer resides in very small particles (<5 nm). The formation of these polymer particles below 5 nm was not reported previously and offers a new insight into the dissolution mechanism of alkaline soluble polymers. The most important parameter steering this process is the acid value of the polymer, while the molar mass plays a modest role. The understanding gained in this study can be used to further advance alkaline‐soluble polymers as stabilizer in surfactant‐free emulsion polymerization technology, improving the performance of a wide range of industrially relevant coatings. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46168.     

Hydroresin dispersions: new emulsifier free binders for aqueous coatings

Hydroresin dispersions are a new class of emulsifier free polyacrylate secondary dispersions. One advantage over conventional secondary dispersions is the fact that they are not only water dilutable but free of organic solvents. Another advantage is the extremely low content of hydrophilic salt groups in the polymer molecules, which leads to very hydrophobic films. The application properties of these aqueous systems are more similar to those of organic polymer solutions than to conventional emulsion polymers. Applications of these surfactant free binders are in areas such as road marking paints without solvents and corrosion protection coatings without active pigments. Hydroresin dispersions also show very interesting perspectives for applications in the field of solar energy conversion.     

分散剂对红色颜料分散体系稳定性的影响及其在白板笔墨水中的应用

以高分子化合物——聚乙烯醇缩丁醛(PVB)、聚氧乙烯聚氧丙烯嵌段共聚物(F68)、聚乙烯吡咯烷酮(PVP)及其分别与非离子型表面活性剂脂肪醇聚氧乙烯醚(AEO-6)复配作为分散剂,研究不同分散剂对醇溶性白板笔墨水红色颜料分散体系稳定性的影响。通过离心分离-吸光度测试、粒径分析判断其稳定性;通过流变性测试探究高分子化合物与AEO-6之间的作用关系。将稳定性好的分散剂用于制备红色白板笔墨水,并通过流变性测试、粒径分析表征墨水的稳定性能。结果表明,采用3种高分子分散剂的红色颜料分散体系稳定性好,且添加质量分数为1%PVB的体系稳定性最佳。在高分子分散剂与AEO-6复配分散的颜料体系中,高分子分散剂对体系稳定性起主导作用,AEO-6并没有起到明显的作用。在红色白板笔墨水中,PVB分散的墨水体系稳定性最佳,此结果与红色颜料分散体系相一致。     

The fine dispersion of functionalized carbon nanotubes in acrylic latex coatings

Nanocomposites of a polymer and carbon nanotubes exhibit high electrical and thermal conductivity and enhanced mechanical properties in comparison to the polymer alone. Film formation from latex dispersions is an ideal way to create nanocomposite coatings with the advantages of solvent-free processing and a high uniformity of dispersion. It is shown here that carbon nanotubes functionalised with poly(vinyl alcohol) (PVA) can be blended with two types of acrylic latex to create stable colloidal dispersions without the need for added surfactant or emulsifier. Waterborne nanocomposite films with optical transparency can be formed. Microscopic analysis shows that the PVA-functionalized nanotubes are finely and uniformly dispersed in the polymer matrix.     

Multiphase coatings from complex radiation curable polyurethane dispersions

The waterborne nature of radiation curable polyurethane dispersions largely respond to the current environmental concerns and do not require any additional coalescent since the film formation (drying) and hardening (photo-curing) take place in distinct steps. It is possible to design aqueous dispersions with distinct polymer particle populations resulting in micro-structured coatings with optimized properties over a wide range of curing conditions. Mixed dispersions based on hard and soft acrylated polyurethane particles were used as model systems for the present study. The minimum film formation temperature has been investigated as a function of the hard:soft polymer ratio. The elastic modulus of the dry coatings shows a reinforcing effect consistent with the inclusion of hard domains in a soft continuous matrix. However, the level of reinforcement is not properly predicted by the usual mechanical models and it is qualitatively accounted for by assuming a composition gradient (interphase) between the hard domains and the matrix. The multiple-phase structure was clearly established by Atomic Force Microscopy in agreement with thermal analysis data. Furthermore the local nanoscale mechanical properties were mapped using a new imaging mode based on real-time force–distance curve analysis. Finally, the coatings prepared using this multiple-phase pattern present a clear benefit over conventional homogeneous coatings by offering an improved balance of chemical and mechanical resistance in pigmented systems applied on melamine-coated MDF panels.     

Studies on Silicon Containing Nano-hybrid Epoxy Coatings for the Protection of Corrosion and Bio-Fouling on Mild Steel

An epoxy nano-composite coating was developed using amine functionalized nZnO (in the amount of 2.5 %, 5.0 % and 7.5 wt %) as the dispersed phase and a commercially available epoxy resin as the matrix phase. The structural features of these materials were ascertained by FT-IR spectral studies. The anti-corrosive properties of the epoxy/nZnO hybrid coatings in comparison with a virgin coating were investigated by a salt spray test and electrochemical impedance spectroscopy technique. The surface morphology determined by SEM, indicates that nZnO particles were dispersed homogenously through the epoxy polymer matrix. The results showed improved antifouling and anticorrosive properties for epoxy-nZnO hybrid coatings.     

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.     

Anticorrosive properties of an epoxy-Meldrum acid cured system catalyzed by erbium III trifluromethanesulfonate

New low curing temperature powder epoxy coatings cured with Meldrum's acid and catalyzed by the use of erbium III trifluoromethanesulfonate have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin) and with an epoxy powder coating homopolymerized by erbium III trifluoromethanesulfonate. Three different tests of anticorrosive properties (EIS, AC/DC/AC and salt fog spray) have been used together with an adherence test, in order to establish the best system. Results show that systems crosslinked with Meldrum's acid and catalyzed with erbium triflate present very fast curing kinetics and very good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings.     

Anticorrosive properties of an epoxy-Meldrum acid cured system catalyzed by erbium III trifluromethanesulfonate

New low curing temperature powder epoxy coatings cured with Meldrum's acid and catalyzed by the use of erbium III trifluoromethanesulfonate have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin) and with an epoxy powder coating homopolymerized by erbium III trifluoromethanesulfonate. Three different tests of anticorrosive properties (EIS, AC/DC/AC and salt fog spray) have been used together with an adherence test, in order to establish the best system. Results show that systems crosslinked with Meldrum's acid and catalyzed with erbium triflate present very fast curing kinetics and very good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings.     

Preparation and characterization of acrylic polymer nanocomposite films obtained from aqueous dispersions

A functionalized fumed silica was dispersed in water using a nonionic surfactant, yielding a stable nanodispersion. This was blended with an aqueous acrylic polymer dispersion to produce hybrid nanocomposite films. The silica particles were shown to be well dispersed in the polymer matrix, with little agglomeration. Further evidence of good compatibility between the silica and acrylic polymer was given by the improved thermal stability of the nanocomposite compared with the pristine polymer. The nanocomposite films exhibited significantly lower dirt pick‐up behavior, which seems to be associated to the nanoroughness of the composite film surface observed in AFM analysis. This decreases the contact area between film and micrometric dirt particles. Surface tension and hardness do not seem to be significantly different in the composite and noncomposite materials. This approach may provide a strategy to obtain hybrid coatings with self‐cleaning properties, taking advantage of the relatively low cost, and large availability of fumed silica. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Application of electrochemical techniques to study the effect on the anticorrosive properties of the addition of ytterbium and erbium triflates as catalysts on a powder epoxy network

New low curing temperature epoxy powder coatings cured with o-tolylbiguanide and catalyzed by the use of erbium(III) and ytterbium(III) trifluoromethanesulfonates have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin). Three different tests for measuring anticorrosive properties (EIS, AC/DC/AC, and salt fog spray) have been used together with an adherence test, in order to establish the ideal system. Results show that a system using 1 phr of ytterbium triflate presents good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings with similar results.     

Development of polyorganosilazane–silicone marine coatings

The objective of the present work is the development and characterization of marine coatings based on polyorganosilazanes (PSZ). Two types of coatings containing silicone oils and biocidal compounds were investigated as anticorrosive and antifouling coatings. The flexibility, hydrophobicity and adhesion properties of the PSZ-based coatings on aluminum substrates were studied. Static immersions in natural seawater were investigated to evaluate the antifouling performances of these coatings. The corrosion properties were studied by salt spray tests. Results demonstrated that coatings based on silicone oils appeared to be the most efficient coatings in terms of antifouling and anticorrosive properties. Ten-month antifouling efficiency was revealed for biocide-free polydimethylsiloxane-based PSZ coatings in natural seawater static immersion. The adjunction of dicopper oxide as biocidal pigments was shown to decrease the stability in cans of the corresponding paints and therefore decreasing the flexibility of coatings. In addition, this pigment affected badly the anticorrosive properties of the coatings together with a short antifouling efficiency time. Thus, the silicone oil-based PSZ displayed remarkable advantages in addition to their dual antifouling and anticorrosive properties which are the absence of biocidal compounds released in marine environment and the absence of volatile solvent.     

Surface modification of sepiolite particles with polyurethane and polyvinyl alcohol

Sepiolite is a clay mineral that has many industrial applications due to its advantageous properties such as white color, low specific gravity, high absorption capacity, chemical composition and low thermal conductivity. In this study, the effect of the addition of polymers, polyvinyl-alcohol and polyurethane, on the rheological properties of the sepiolite dispersions have been investigated. The rheological parameters of clay suspensions can be used to examine particle–particle interactions. The polymers that have been added to the clay suspensions interact with clay particles, depending on their ionic or non-ionic character. Firstly, the sepiolite dispersions were characterized by the rheological properties, mineral structure and content. Then the effect of the polymers on the flow, structural, and surface properties of sepiolite dispersions was investigated by rheological, electrokinetical, and scanning electron microscopy (SEM) measurements. The measurements showed that polymer molecules bind on the surface of sepiolite particles and changed the flow properties of the dispersions as stable dispersions at some certain concentrations. It is also determined that PU polymer covered the surface of the sepiolite faster than PVA, but the coverage of the PVA was much more smoothly. The thermal properties of the sepiolite improved with PVA more than PU, as a result of the homogenous surface coverage.     

PAni/SBR composite as anticorrosive coating for carbon steel,part II: electrochemical characterization

Conducting polymer composites have gained popularity into the field of organic anticorrosive coatings research due to their low environmental and health impact. In this work, the effect of the conducting polymer/elastomer ratio and the PAni doping method on the electrochemical behavior of polyaniline/styrene butadiene rubber films (PAni/SBR) has been studied in order to evaluate the performance of the proposed coatings for carbon steel corrosion prevention. According to open circuit potential measurements, linear polarization resistance tests, electrochemical impedance spectroscopy and polarization curves, the use of dodecyl benzene sulfonic acid as doping agent and the reduction of the PAni content in the composite enhance the anticorrosive behavior of PAni/SBR composites by inducing carbon steel passivation process.     

Characterization of structure and corrosion resistivity of polyurethane/organoclay nanocomposite coatings prepared through an ultrasonication assisted process

In this study, a series of castor oil based polyurethane/organically modified montmorillonite (OMMT) clay nanocomposite coatings have been successfully prepared by effective dispersing of OMMT nano-layers in polyurethane matrix through an ultrasonication assisted process. Effectiveness of ultrasonication process in de-agglomeration of clay stacks in castor oil dispersions was evaluated by optical microscopy and sedimentation test. Structure of nanocomposite coatings was investigated by wide angle X-ray diffraction (WAXD) and Fourier-transform infrared spectroscopy (FT-IR). The anticorrosive properties of nanocomposite coatings were characterized by electrochemical impedance spectroscopy (EIS), Tafel polarization study, water absorption and pull-off adhesion tests. The experimental results showed that PU/OMMT nanocomposite coatings were superior to the neat PU in corrosion protection effects. Also, it was observed that the corrosion protection of polyurethane organoclay nanocomposite coatings is improved as the clay loading is increased up to 3 wt.%.     

Hydroresin dispersions: tailoring morphology of latex particles and films

Hydroresin dispersions are a new class of emulsifier free polyacrylate secondary dispersions. They are prepared by the emulsification of self-emulsifying polymer blends in water. The blends typically consist of two polymers, one is a salt group containing copolymer, the other is a hydrophobic polymer without salt groups. The particle diameters can be controlled by the amount of salt group containing polymer and the concentration of salt groups in this polymer. One advantage over conventional secondary dispersions is the fact that they are not only water dilutable but free of organic solvents. Another advantage is the extremely low content of hydrophilic salt groups in the resulting polymer mixture, which leads to very hydrophobic films. The application properties of these aqueous systems are more similar to those of organic polymer solutions than to conventional emulsion polymers. Applications of these surfactant free binders are in areas such as solvent face road marking paints and corrosion protection coatings without active pigments. The technique for the preparation of hydroresin dispersions is also useful for the creation of latex particles with core-shell structures. Two examples are given, which differ in the glass transition temperature of both the cores and the shells. From these dispersions, films with defined morphology can be prepared. A blending of the polymers with hydrophobic low molecular weight compounds, before the emulsification step, is also possible. It can be used for the incorporation of additional functions into the latex particles. As an example, the loading of latexes with a hydrophobic fluorescent dye is given.     

水性聚氨酯涂料光泽控制——理论与实践

光泽作为涂料的一个重要的美学价值体现,很大程度上影响涂装产品的客户需求。为了控制水性聚氨酯涂料的光泽,需要从理论上了解涂料光泽与树脂结构的关系。文章首先介绍了涂料光泽的基本理论,在理论基础上探讨了水性聚氨酯结构(聚合物结构的反射率、折射率、分散体粒径、涂膜表面粗糙度以及成膜过程)对涂料光泽的影响。     

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     

Development of Poly(aniline-co-o-toluidine)/TiO2 nanocomposite coatings for low carbon steel corrosion in 3.5% NaCl solution

Chemical oxidative polymerization of aniline (AN) and o-toluidine (OT) for the synthesis of copolymer, Poly(AN-co-OT) and its composite with TiO₂ nanoparticles, Poly(AN-co-OT)/TiO₂ employing ammonium persulfate as an oxidant and HCl as an external dopant were carried out. The homopolymers, Polyaniline and Poly(o-toluidine) were also prepared by following similar method. The synthesized polymers were characterized with FTIR spectroscopy, XRD/SEM/TEM analysis. The anticorrosive coatings were synthesized in dimethyl sulfoxide solution by dissolving synthesized polymers, and then were applied on low-carbon steel (LCS) samples using epoxy binder. The anticorrosive potential of the polymer coatings containing copolymer, copolymer-nanocomposite and homopolymers on LCS was evaluated in 3.5% NaCl at a temperature of 30?°C by open circuit potential, electrochemical impedance spectroscopy and potentiodynamic polarization measurements. It was observed that the nanocomposite coating increases the protection efficacy by providing better barrier properties against corrosion as compared with neat copolymer and homopolymers coatings. The morphology of the coatings before and after 60 days LCS immersion in 3.5% NaCl solution was determined using SEM.     

Novel water-dispersible glycidyl carbamate (GC) resins and waterborne amine-cured coatings

Water-dispersible glycidyl carbamate (GC) functional resins were synthesized and crosslinked using a water-dispersible amine to form coatings. GC functional resins are synthesized by the reaction of an isocyanate functional compound with glycidol to yield a carbamate (urethane) linkage (–NHCO–) and reactive epoxy group. The combination of both functionalities in a single resin structure imparts excellent mechanical and chemical properties to the coatings. Previous studies on the development of GC coatings have focused on solvent-borne coating systems. In this study, GC resins were modified by incorporating nonionic hydrophilic groups to produce water-dispersible resins. To determine the influence of the content of hydrophilic groups on dispersion stability, aqueous dispersions were made from a series of hydrophilically modified GC resins and characterized for particle size and dispersion stability. The composition of a typical, dispersed GC resin particle was predicted using Monte Carlo simulations. Stable GC dispersions were used to prepare amine-cured coatings. The coatings were characterized for solvent resistance, water resistance, hardness, flexibility, adhesion, and surface morphology. It was observed that GC resins were able to be dispersed in water without using any surfactant and by minimal mixing force (hand mixing) and produced coating films with good properties when crosslinked with a compatible waterborne amine crosslinker.