Marine paint fomulations: Conducting polymers as anticorrosive additives

Within coating technology, there is increasing interest in the development of efficient anticorrosive additives able to replace the conventional inorganic anticorrosive pigments usually added to paints, which may have detrimental effects on both environment and health. A number of recent studies have evidenced that the modification of a paint formulation by the addition of a low concentration of conducting polymer (0.2–0.3%, w/w) increases significantly the protective properties of the coating. Here we focus on the principles of anticorrosive additives based on conducting polymers for marine paints. The article reviews the most important findings achieved in recent studies. The relevant factors that are determinant for the anticorrosive protection imparted by conducting polymers, as the doping level, the miscibility with paint, the electrochemical stability, etc., are discussed in detail.     

Alkylated phenolic antioxidants for paints

Summary  Polymeric antioxidants based on p-cumyl phenol formaldehyde resin (PCPF), p-nonyl phenol formaldehyde (PNPF) and p-octyl phenol formaldehyde (POPF) were prepared by condensation reaction of respective phenols with formaldehyde in presence of an acid catalyst. The reactions were monitored by TLC and the melting point of the products was determined by open capillary method. Stabilising the action of PCPF, PNPF for protecting paint against thermal oxidation was tested using a QUV weatherometer. The effect of exposure on the properties of paints such as gloss, whiteness and yellowness were evaluated. Results show that paints containing these new polymeric antioxidants possess better stabilising effects against photo-oxidation than those employed in standard paints available in the market.     

Nanoparticles as antifungal additives for indoor water borne paints

There are nanotechnology-based materials that can be used as antimicrobial additives in different applications such as water-borne paints. Antimicrobial paints are important tool in order to avoid indoor biological colonization and therefore prevent paint bio-deterioration and health problems in people and pets. These paints would have application in kitchens, bathrooms and hospitals. The present study evaluated the incorporation of silver (of two different sizes), copper and zinc oxide nanoparticles in indoor waterborne paints and the bio-resistance imparted by them. The antifungal activity of nanoparticles is a less studied topic in relation to the antibacterial activity but is no less important from the environmental point of view. Molds that grow in indoor environments contribute significantly with bioaerosol formation and therefore on air contamination and human health deterioration. In this sense, this research evaluated the nanoparticles’ antifungal activity using previously isolated fungi, Chaetomium globosum and Alternaria alternata, on solid medium. Then, the bio-resistance of acrylic paints, with nanoparticles incorporated, was evaluated in Petri dishes and observations were made using scanning electron microscopy. The better results were obtained with the paint that contained silver with the smaller size (10 nm).     

Self‐segregating hyperbranched polymer/silver nanoparticle hybrids in thermoplastic polyurethane films

Self‐segregating hyperbranched polymer (HBP) additives have been utilized to concentrate silver nanoparticles (AgNPs) at the air interface of polyurethane films. The limited spontaneous surface migration of the AgNPs was enhanced through the addition of appropriately functionalized HBPs. Both amine and thiol terminated additives were employed to allow interaction of the HBP with the nanoparticles. Both types of additives increased surface concentration of silver modestly, though the thiol‐terminated HBPs demonstrated nearly a seven‐fold enhancement of surface migration. It was also found that wholly‐aliphatic HBPs demonstrated only slightly reduced ability to bias AgNP concentration as compared to HBPs functionalized with perfluorinated chains. In addition, films containing 1% total silver concentration were tested for antimicrobial activity using the ASTM‐E 2180 protocol. Significant reduction of the microorganisms was observed for all samples, 6‐log reduction was achieved for the gram‐negative bacteria P. aeruginosa, the gram‐positive bacteria S. aureus, and the fungi C. albicans. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Development of silver nanoparticles‐loaded calcium alginate beads embedded in gelatin scaffolds for use as wound dressings

Silver nanoparticles (AgNPs)‐loaded calcium alginate beads embedded in gelatin scaffolds were developed to sustain and maintain the release of silver (Ag⁺) ions over an extended time period. The UV irradiation technique was used to reduce Ag⁺ ions in alginate solution to AgNPs. The average sizes of AgNPs ranged between ca 20 and ca 22 nm. The AgNPs‐loaded calcium alginate beads were prepared by electrospraying of a sodium alginate solution containing AgNPs into calcium chloride (CaCl₂) solution. The AgNPs‐loaded calcium alginate beads were then embedded into gelatin scaffolds. The release characteristics of Ag⁺ ions from both the AgNPs‐loaded calcium alginate beads and the AgNPs‐loaded calcium alginate beads embedded in gelatin scaffolds were determined in either deionized water or phosphate buffer solution at 37 °C for 7 days. Moreover, the AgNPs‐loaded calcium alginate beads embedded in gelatin scaffolds were tested for their antibacterial activity and cytotoxicity. © 2014 Society of Chemical Industry     

Effect of plasma duty cycle on silver nanoparticles loading of cotton fabrics for durable antibacterial properties

A facile method for strongly anchoring silver nanoparticles (AgNPs) onto cotton fabrics was reported. It consists in loading AgNPs onto the cotton fiber preliminary coated with maleic anhydride plasma polymer layer. This results in hydrolyzis and ring opening of anhydride groups followed by electrovalent bonding of silver ions and reduction in NaBH₄. X‐ray photoelectron spectroscopy (XPS), infrared spectroscopy, and scanning electron microscope (SEM) were used to analyze changes in the surface chemical composition and morphology of the plasma modified fibers. The presence of AgNPs was confirmed by UV–Visible spectroscopy and atomic force microscopy (AFM) images. Remarkably, varying plasma duty cycle for plasma polymer deposition allowed tailoring the amount of loaded AgNPs. The highest amount of AgNPs was obtained with the lowest duty cycle values. Qualitative tests showed that silver containing plasma modified cotton displays significant antibacterial activity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41279.     

Comparison of release behaviour from microcapsules and microspheres

The plasticizing effect of core oil in the polymer shell of core–shell particles, so-called microcapsules, was here examined. The study involved release measurements of 4-nitroanisole into aqueous solution from two types of microparticles. In the first study, a microcapsule with PMMA shell and hexadecane core was examined. The second type of particle was a homogeneous PMMA microsphere containing no oil. Experimental data were compared to models that describe release by a diffusion mechanism out from core–shell particles as well as homogeneous spherical particles. Results clearly show that the alkane oil has a plasticizing effect on the PMMA shell, thereby generating a faster release of 4-nitroanisole. In both types of microparticles, the diffusion coefficients of 4-nitroanisole could be determined. The findings increase our understanding of important parameters in the microcapsule design with regard to tuning the release behaviour. Using microparticles, the ambition is to prolong the protection of paint and other coatings against fouling.     

Preparation and characterization of flame retardant solvent base and emulsion paints

In this research solvent base alkyd and emulsion paint formula were made flame retardant (FR) by incorporation of hexachlorodiphosh (V) azane of types (I–III). Elemental analysis was used to characterize the structure of these compounds. These additives are physically incorporated into the paint formula through grinding in a pebble mill until all particulates have a size below 38 μm. Experimental coatings were manufactured on a laboratory scale, applied by brush on wood and steel panels. Results of an oxygen index value indicated that coating with these compounds containing chlorine, nitrogen and phosphorus exhibit very good flame retardant effect when mixed with solvent base alkyd and emulsion paint. The physical, mechanical and corrosion resistance were studied to evaluate the additives drawbacks. The additives did not affect the flexibility and pinholes of paint formula. The gloss and the impact strength were decreased by the additives, the hardness and adhesion resistance increased by the additives. However, corrosion resistance was not significantly changed by these additives.     

Ag NPs改性鱼鳞明胶-琼脂复合膜的制备及性能表征

利用鱼鳞明胶作为还原剂和稳定剂制备银纳米颗粒（silver nanoparticles, Ag NPs），研究Ag NPs添加量（0.04wt%-0.2wt%）对鱼鳞明胶-琼脂复合膜的理化性能和抗菌性能的影响。通过透射电子显微镜和X射线粉末衍射对合成的Ag NPs进行表征，结果表明制得Ag NPs为球形形貌，平均粒径为9.3 ?1.8 nm。随着Ag NPs添加量的增加，鱼鳞明胶-琼脂复合膜的色泽变黄渐深，透明度下降，对紫外和可见光的吸收增强，同时，复合膜的断裂延展性、水蒸气阻隔性能和耐水性能显著增强，而厚度和抗拉强度却无明显变化。FTIR和热重分析结果表明，Ag NPs与膜基质间存在化学相互作用，并在一定程度上改善了复合膜的热稳定性。抑菌环实验结果显示，复合膜可以在0.04wt%-0.2wt%较低的银浓度下实现良好的抗菌效果。研究结果将为鱼鳞明胶可降解抗菌包装材料的开发提供新思路。     

Microwave-assisted synthesis of hybrid colloids for design of conducting films

We report synthesis of colloids with polymer core and inorganic shell consisting of silver nanoparticles (AgNPs) which can be used as building blocks for the preparation of conducting composite films. Polymer colloids based on copolymer of styrene and butyl acrylate with variable film formation temperature and functional surface have been prepared by surfactant-free emulsion polymerization. Polymer particles with average size between 140 nm and 220 nm and narrow size distribution were used as templates for deposition of AgNPs by microwave-assisted reduction of silver precursors in aqueous medium. The loading of the AgNPs on the polymer particle surface has been increased up to 60 wt.-%. Obtained hybrid colloids were used for preparation of composite films. The electrical conductivity of the composite films starts to increase if the AgNPs loading on the polymer particle surface is above 20 wt.-%.     

Anticorrosive polyurethane paints with nano- and microsized phosphates

Two types of phosphate fillers (nanosized aluminum phosphate and microsized aluminum–zinc phosphate) were tested as anticorrosive fillers in 2 K solvent-borne polyurethane paints based on commercial acrylic resin with OH groups and an isophorone diisocyanate-type hardener. Three coating compositions containing commercial fillers (mica/quartz, TiO₂, wollastonite, talc) and also mentioned nanosized aluminum phosphate or microsized aluminum–zinc phosphate were prepared using a pearl-mill as well as a laboratory dissolver, applied onto a steel substrate and cured at room temperature for 14 days. An influence of the type and content of a phosphate filler on properties of polyurethane paints and coatings has been investigated. Incorporation of nanosized aluminum phosphate into coating compositions increases their viscosity while cured paints exhibit reduced adhesion to steel substrates. The results of corrosion tests in a salts spray chamber as well as immersion in an aqueous NaCl solution indicated that the paint system with 9.8 wt.% of applied nanofiller had similar protective properties to a polyurethane coat containing a higher dose (i.e. 15.6 wt.%) of commercial microsized aluminum–zinc phosphate.     

Simple preparation of long-persistent luminescent paint with superhydrophobic anticorrosion efficiency from cellulose nanocrystals and an acrylic emulsion

Novel photoluminescent paint was prepared for safety marking purposes using an emulsion system composed of an acrylic polymer, cellulose nanocrystals and lanthanide-doped strontium aluminate (LdSA) nanopaticles. The effect of LdSA concentration in the paint formula was investigated. Cellulose nanocrystals (CNCs) have been an attractive reinforcement material that can be incorporated into protective coatings due to their distinctive properties, such as biocompatibility, biodegradability, and renewability. The produced acrylic/cellulose nanocrystals/lanthanide-doped strontium aluminate paints were applied onto different surfaces of asphalt concrete and tinplate panels. LdSA was developed in the nano-scale form as described by transmission electron microscope (TEM) to allow a better dispersion in the paint formula. The applied paints were studied by energy-dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), scan electron microscopy (SEM), and infrared spectra (FTIR). Both transparency and coloration measurements of the applied paints were investigated by luminescence spectra and CIE Lab. The resistance to scratching, hydrophobic and corrosion resistivity were investigated. CNCs were monitored to be a key component for the anti-corrosion activity. The best long-lived luminescence was monitored for more that 60 min in the dark for LdSA concentration of 12% w/w. The paints containing cellulose nanocrystals and sodium hexametaphosphate demonstrated satisfactory results upon mixing with acrylic emulsion.     

Progress of fluoropolymers on coating applications: Development of mineral spirit soluble polymer and aqueous dispersion

Fluoro-olefine vinyl ether copolymer (FEVE) has been well known as highly durable polymer for paints industry. FEVE has been widely used for ambient temperature curable solvent-borne paints. In this report, recent developments of FEVE copolymer are reported for mild-solvent paint system and water-borne paint system. Firstly, mineral spirit soluble FEVE copolymers are mentioned for both 1-component and crosslinkable 2-component mild-solvent paint systems. Secondly, FEVE aqueous dispersion polymers are mentioned for non-crosslinkable 1-component latex paint system, crosslinkable 2-component emulsion paint system with isocyanate as containing high OH value and for 1-component crosslinkable emulsion paint system containing carboxyl functionality reactive with hydrazide.     

Preparation of highly dispersed gold microparticles and their electrocatalytic activity for the oxidation of formaldehyde

The electrochemical preparation of highly dispersed Au microparticles on the surfaces of glassy carbon (GC) electrodes and their electrocatalytic activities for the oxidation of formaldehyde were studied. It was found that the reduction of Au3+ to Au is controlled by diffusion and the formation mechanism of Au microparticles on the GC surfaces corresponds to an instantaneous nucleation and diffusion-controlled three dimensional growth process. The particle size is about 80–90 nm in diameter after the electrochemical ageing treatment. These highly dispersed Au microparticles have high surface areas and exhibit better electrocatalytic activity than that of bulk-form Au toward the electrochemical oxidation of formaldehyde in alkaline media.     

Anticorrosive properties of the epoxy–cardanol resin based paints

An epoxy–cardanol resin was developed using epichlorohydrin, bisphenol-A and cardanol. On evaluation it was found that epoxy–cardanol resin exhibits better properties as compared to epoxy resin in terms of increase in tensile strength, elongation, bond with steel and lowering of water vapour transmission of the film. The improvement in these properties indicated that the paints based on modified resin would be more durable than the epoxy based paints. Accordingly, paints were formulated using the developed resin and their performance were compared with their counterparts made with unmodified epoxy resin. Zinc powder, zinc phosphate, micaceous iron oxide and synthetic iron oxide were used as pigments along with fillers, additives and an aromatic polyamine adduct hardener. For both types of paints similar doses of pigments and additives were used. Physico-mechanical properties, chemical resistance and corrosion protection efficiency of the formulated paints were determined. It was found that the anticorrosive properties of epoxy–cardanol resin based paints are superior to that of the paints formulated with the unmodified epoxy resin. Micaceous iron oxide based paints in epoxy–cardanol resin showed the best performance followed by zinc phosphate based paints. It is concluded that the developed resin is a better binder media for the formulation of paints.     

Antimicrobial PLA/TPS/gelatin sheets with enzymatically crosslinked surface containing silver nanoparticles

In the present work, poly (lactic acid)/thermoplastic starch/gelatin sheets were produced by calendering–extrusion process and silver nanoparticles (AgNPs, synthesized by chemical reduction with d ‐glucose), were incorporated at sheet surfaces to promote antimicrobial activity. A gelatin solution containing AgNPs was enzymatically crosslinked as a layer at sheets surface using transglutaminase. AgNPs presented 63 nm (z average size) and spherical shape (scanning electron microscopy, SEM) while morphology analysis showed that sheets presented internal porosity. Mechanical properties (Young modulus, elongation at break, and tensile strength) and water vapor permeability presented significant difference in function of gelatin amount added to sheets formulation due to increased internal porosity. Antimicrobial activity was demonstrated against Bacillus cereus, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa for the AGNPs solution as well as for the surface treated films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43039.     

Evaluation of Mesua ferrea L. seed oil modified polyurethane paints

Two types of stoving paints have been prepared from Mesua ferrea L. seed oil (MFLSO) modified poly(urethane ester) (PUE) binder systems. One stoving paint system was prepared from partially butylated melamine formaldehyde (MF) resin modified MFLSO-based PUE (70:30 weight ratio) and other one comprised of bisphenol-A-based epoxy resin modified with MFLSO-based PUE (50:50 weight ratio). Paints made with these two resin systems as binders were evaluated against the standard paint system. The physical properties of the paint systems viz. non-volatile content, specific gravity, viscosity, drying time, flexibility, adhesion, scratch hardness, gloss, etc. and chemical properties such as corrosion resistance, salt spray resistance, UV resistance, etc. were measured as per the standard methods and were compared. Thermal stability and surface morphology of the paints were also studied by using thermogravimetric analysis (TGA) and scanning electron microscopy (SEM), respectively. The performance characteristics of both the test paints were found to be comparable with the corresponding industrial standard paints. Out of the two test paints, the epoxy modified PUE-based stoving paint has been found to be preferred.     

Waterborne epoxy protective coatings for metal

Recent enhancements in waterborne resin system polymers as well as the way they are formulated have produced paints with a set of barrier properties that are superior to their standard solventborne analogs. New generation waterborne epoxy and curing agent dispersions, and the paints formulated from them, have been introduced with changes from older generation waterbornes. These changes include (1) totally nonionically dispersed paints in place of the older ionically dispersed types, (2) quicker coalescing, mutually soluble epoxy/amine vehicle resins rather than the former slow coalescing, highly branched epoxy/amine systems, and (3) utilization of stable, water compatible additives and fillers that complement the nonionic epoxy/amine resin vehicles. In this paper, the success of these implemented technology changes is demonstrated by comparing the performance properties of the new generation with an industry standard epoxy/polyamide solventborne paint. This paper presents novel two-component waterborne epoxy resin and amine curing agent technology for ambient cure metal coatings. Presented at the 79th Annual Meeting of the Federation of Societies for Coatings Technology, on November 4–7, 2001, in Atlanta, GA. P. O. Box 1380, Houston, TX 77251.     

一种石墨烯水性除醛木器漆制备研究

创新性的将公司独自研发的甲醛分解技术应用于环保家具漆领域,制备了一种石墨烯水性除醛木器漆,初步探索了漆膜主要性能、甲醛净化效果并且同市场上类似产品的优势。研究表明,在石墨烯除醛助剂用量2%时,综合性能最好,进过测定其甲醛净化效率高达93.7%,远高于国家标准要求的Ⅱ类产品85%,除此之外其性能均符合甚至高于国家标准GB/T 23999-2009 《装饰装修用水性木器漆涂料》指标要求。     

Storage stability and solubility of poly(urea‐formaldehyde) microcapsules containing A‐olefin drag reducing polymer

Microcapsules containing α‐olefin drag reducing polymer were prepared by in situ and interfacial polymerization with urea, formaldehyde, and styrene as shell materials, respectively. IR spectrums of prepared shells indicated the formations of poly(urea‐formaldehyde) and polystyrene in the microencapsulating process. The morphologies of uncoated particles and microcapsules were observed by scanning electron microscopy (SEM) which proved that the α‐olefin drag reducing polymer particles were effectively coated. For the purpose of determining the stability of microcapsules in transportation and storage, the static pressure experiment was carried out and lasted for 6 months. In this process, microcapsules with polystyrene as shell material stuck together after 3 months; however, those with poly(urea‐formaldehyde) kept the state of particles. The thermal characteristics of uncoated particles (core), poly(urea‐formaldehyde) (shell), and microcapsules with that as shell material were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) which proved that thermal stable temperature of microcapsules containing α‐olefin drag reducing polymer with poly(urea‐formaldehyde) as shell material was below 225°C, and the mean heat absorbed by microcapsules in the temperature increasing process was 1.5–2.0 W/g higher than that by cores. The evaluation of drag reducing rate of microcapsules showed that the microencapsulating process had no influence on the drag reduction of α‐olefin drag reducing polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011