Effect of nano-ZnO addition on the silicone-modified alkyd-based waterborne coatings on its mechanical and heat-resistance properties

A silicone-modified alkyd-based waterborne coating was developed using hexamethylmethoxymelamine (HMMM) as crosslinking agent and para-toluene sulphonic acid (p-TSA) as catalyst. The crosslinking ratio for resin and HMMM was fixed to 70:30, based on FTIR and DSC studies. Nano-ZnO particles were added to this system in different concentrations. The coatings with nano-ZnO particles were characterized using FTIR and DSC. The nano-composite coatings were applied on mild steel panels and were cured at 130 °C for 30 min. The coatings were evaluated for their mechanical and heat-resistance properties. They were exposed to 350 °C for 10 min followed by water quenching. The process was repeated for 10 cycles. Heat-resistance property of the coatings was examined by TGA. Also, surface morphological changes were assessed using SEM and optical microscopy. It was found that the heat-resistance and mechanical properties of the coatings improved significantly as a function of nano-ZnO addition.     

Effect of nano-Al2O3 particles on the corrosion behavior of alkyd based waterborne coatings

A modification in the alkyd based waterborne coatings was studied with the addition of 0.05%, 0.1%, 0.2%, and 0.3% nano-Al₂O₃. Corrosion performance of the nano-composite coatings were evaluated by applying these nanocomposites on mild steel substrate and exposing them to salt spray, humidity, and accelerated weathering. Mechanical properties were studied by subjecting the coating to scratch and abrasion test. The results showed that, with an increase in the concentration of nano-Al₂O₃ there was an improvement in the corrosion resistance, UV resistance, and mechanical properties of the coatings indicating the positive effect of addition of nano-Al₂O₃ particles in the coatings. Further, the transparency of the coating was not altered, maintaining the optical clarity of the coating.     

Effect of nano-ZnO particles on the corrosion resistance of polyurethane-based waterborne coatings immersed in sodium chloride solution via EIS technique

Nano-composite coatings were formed by incorporating 3 wt% nano-ZnO in a polyurethane-based waterborne coating. The nano-ZnO based composite coatings were applied on standard phosphated steel panels by cathodic electrodeposition. The electrodeposited nano-composite coatings were then baked for 20 min at 165 °C. To investigate the corrosion resistance of the coatings, the coated panels were immersed in 3.5 wt% NaCl solutions for 2880 h (120 days). The improvement in corrosion performance of the composite coatings was evaluated using electrochemical impedance spectroscopy technique. It was found that the films containing nano-sized ZnO particles show a corrosion resistance of 2 orders of magnitude higher than that of the neat films.     

Inhibitor properties of “green” pigments for paints

Zinc chromate is one of the anticorrosive pigments most frequently used in the formulation of primers. However, its environmental aggressiveness and toxicity severely restrict its use, and different green alternatives have been proposed in order to replace zinc chromate. In the last decade, the behaviour of zinc phosphate as anticorrosive pigment has been intensively researched. During this time, various modifications have been made to this family of pigments to improve its properties, and a “second generation” of phosphate pigments, incorporating elements such as molybdenum, aluminium, or iron, has been produced. In this paper, the inhibitive properties of zinc phosphate and three second-generation phosphates have been investigated, using zinc chromate pigment as a reference. Pigment extract solutions, at different values of pH, have been used as corrosive media. Carbon steel samples were immersed in such solutions and their corrosion rates were measured using electrochemical techniques. The data obtained suggest that zinc chromate provides the highest percentage of inhibition in neutral and basic solutions, but phosphate-based pigments showed better results in acid solutions. Given this performance advantage, together with their less harmful environmental impact, these phosphate-based pigments can be proposed as realistic alternatives to chromates in the formulation of protective paints for use in acidic conditions.     

Water resistance of the membranes for UV curable waterborne polyurethane dispersions

The water absorption of the membranes made from UV curable waterborne polyurethane dispersions (UV-PUDs) was investigated systematically and correlated with the nature of the polymer and its gel content after curing. It was found that the water absorption of the membranes was reduced significantly by using polyester polyols, reducing the COOH content and increasing the gel content through a higher CC level. In particular, the membranes made from polyurethanes having hydroxyl-terminated polybutadiene (HTPB) or modified with dihydroxybutyl-terminated polydimethylsiloxane (PDMS) presented a superior water resistance. The results showed a linear relationship between the water absorption and the surface tension of the membrane.     

The role of pore structure in the catalytic behavior of “unaged” and “aged” silica-alumina catalysts

This is a review of research concerning the role played by the porous structure of silica-alumina catalysts on the evolution of organic catalytic processes. A strong effect of the geometrical shape of the pores on catalytic activity and selectivity has been evidenced. The experimental results have also been interpreted by means of a simplified mathematical model, able to relate selectivity for a reaction of the type A → B → C to the geometrical features of macro-microporous catalyst pellets, or granules. The theoretical results are in qualitatively satisfactory agreement with the experimental data.     

Effect of average functionality on properties of UV-curable waterborne polyurethane-acrylate

A series of ultraviolet (UV) curable waterborne polyurethane-acrylate (WPUA) with different average functionalities were synthesized in new methods. The chemical structures of WPUA were confirmed by Fourier-transform infrared spectroscopy (FT-IR) and the effect of average functionality on properties of WPUA was systemically investigated. It was found that the average functionality had a positive effect on the water resistance and tensile strength of WPUA, to make optimal formation of WPUA molecule chains available, whereas the increasing of average functionality decreased the viscosity and extension of WPUA samples. Besides, through the investigation on the UV curing kinetics, it was found that the average functionality too high or too low was unfavorable for the increase of unsaturation conversion. The morphology and microstructure of WPUA films were also comprehensively discussed with WAXD patterns and fractured surface observed from SEM images.     

Value addition to waterborne polyurethane resin by silicone modification for developing high performance coating on aluminum alloy

Silicone–polyurethane waterborne coatings were synthesized using sol–gel technique for protecting aluminum and its alloys. These are derived using polyurethane (PU), hexamethoxymethylmelamine (HMMM) and silicones such as methyltrimethoxysilane (MTMS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) as precursors. Structural and morphological features of coatings were assessed using Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Performance of the coatings was evaluated using potentiodynamic polarization studies, contact angle measurement, DSC/TGA, UV–vis spectrophotometer, and mechanical tests such as flexibility, pencil hardness test and impact resistance.     

Antioxidative Effect of “Herbalox” on Edible Oils

Antioxidative effect of BHA (Butylated hydroxyanisole) and rosemary extract (Herbalox Type 0) in soybean and sunflower seed oil were investigated. Stability to oxidation was determined by measurement of induction time with the Rancimat 679 at 100°C. Changes in control (no antioxidant added) and experimental oil samples were monitored. The addition of antioxidants reduce oxidation thus increasing product stability. Presence of synthetic antioxidant BHA in sunflower seed oil at the concentration of 0.02% (w/w) increases induction time from 6.0 to 8.09 hours. The results obtained indicated higher synthetic antioxidant efficacy compared with natural Herbalox Type 0 antioxidant, as the induction time for the later one, used at the same concentration, increased from originally 6.0 to 6.67 hours.     

改性纳米氧化锌对丙烯酸聚氨酯涂层防腐性能的影响

为了改善纳米ZnO在涂料中的分散性,以钛酸酯偶联剂对其进行改性。研究了丙烯酸聚氨酯清漆、含未改性纳米氧化锌的丙烯酸聚氨酯涂层和添加钛酸酯偶联剂改性后的纳米氧化锌的丙烯酸聚氨酯涂层的防腐蚀性能。结果表明,经过钛酸酯偶联剂改性的纳米ZnO其团聚现象明显消失,与涂料表现出良好的相容性,所得的复合涂层的抗渗透能力明显比清漆和含未改性纳米ZnO复合涂层强。改性纳米ZnO显著提高了丙烯酸聚氨酯涂料的防腐性能。     

Effect of the hard segment on the properties of UV curable waterborne blocked polyurethanes

Two types of UV curable waterborne blocked polyurethanes (PUs) were obtained from 2,4-tolylene diisocyanate(TDI) and isophorone diisocyanate (IPDI), which had the same soft segments and different hard segments. The PUs contained both the UV curable C=C bond and the blocked NCO groups which could be de-blocked when heated. Effect of the hard segment on the properties of the two types of PUs was investigated. The FTIR spectra method was employed to confirm the structure of the PUs. The photo-DSC was used to study the photo-polymerization rate of the PUs under UV irradiation in the presence of a photo-initiator and the C=C conversion behaviors. Heating-up IR analysis was used to track the de-blocking process and the heat curing process. The thermal degradation analysis (TGA) was employed to investigate the thermal stability of the UV cured films before and after heat curing process. Dynamic mechanical properties of the UV and heat cured films were investigated by the dynamic mechanical thermal analysis (DMTA).     

环氧／纳米ZnO复合涂层对镁锂合金耐腐蚀性的影响

以聚丙烯酰胺凝胶法制备了纳米ZnO,并对其进行改性,得到了环氧/纳米ZnO复合涂层.采用XRD和SEM对环氧/纳米ZnO复合涂层进行了表征.通过极化曲线和交流阻抗研究了裸基、复合涂层以及经锡酸盐转化处理后涂覆环氧/纳米ZnO的复合涂层的耐蚀性能.结果表明:复合涂层呈明显的两相结构,纳米ZnO分布均匀;复合涂层和锡酸盐转化协同,提高了镁锂合金的耐腐蚀性能.涂层中纳米ZnO质量分数不同,对镁锂合金耐蚀性能有不同的影响,纳米ZnO质量分数为2%时,复合涂层对镁锂合金的保护作用最强.     

聚苯胺颗粒对水性环氧树脂涂层防腐性能的影响

以盐酸为掺杂剂、过硫酸铵为氧化剂、咪唑类离子液体为稳定剂,采用化学氧化聚合法合成了导电聚苯胺(PANI)颗粒,将其分散到水性环氧树脂(ER)中制成聚苯胺水性环氧防腐涂层,研究了聚苯胺颗粒对涂层防腐性能和机械性能的影响。结果表明,添加聚苯胺显著提高了水性环氧涂层的阻隔性能,信号频率f=0.01 Hz时,PANI/ER涂层的阻抗(|Z|f=0.01Hz)均高于纯ER涂层。添加5.0wt% PANI时ER涂层阻隔性能最好,浸泡0~168 h时|Z|f=0.01Hz稳定在约8.0×108 Ω?cm2,浸泡168 h后|Z|f=0.01Hz=7.5×108 Ω?cm2,远高于ER和其它PANI/ER体系。中性盐雾实验结果表明,聚苯胺赋予了涂层钝化腐蚀的能力,显著提高了涂层的防腐性能,且其添加量越高,防腐性能越好。弯曲和冲击实验结果表明,涂层的机械性能随聚苯胺含量增加先上升后降低,当聚苯胺添加量不超过5.0wt%时,涂层的机械性能优异,附着力和韧性均较好;PANI添加量增至7.0wt%时,ER涂层的脆性明显变大,机械性能下降。聚苯胺在水性环氧体系中的最宜添加量为5.0wt%,此时涂层的机械性能良好,综合防腐性能最优。     

Theory of “Cohesive” vs “Adhesive” Separation in an Adhering System

It is shown that there is limited validitity to the doctrine that true interfacial separation, in an adhering system, is highly improbable. An analysis employing the Griffith-Irwin crack theory yields these results: The important parameters are, difference in elastic moduli, ΔE; differences in g, the energy dissipation per unit crack extension; thickness, Δ₁ or δ₂, of the region where dissipation occurs; and the presence or absence of strong interfacial bonds. If the forces across the interface are appreciably weaker than the cohesive forces in either phase, there is a strong minimum in g at the interface. For flaws of equal size, an interfacial flaw will be the site of initiation of failure. If strong interfacial bonds are present, then if Δg and ΔE have the same sign, failure is most probable, deep within one phase. If Δg and ΔE have opposite signs, failure may be initiated, and may propagate, at a distance δ from the interface, in the phase with lower g. This may be mistaken for weak-boundary layer failure.     

Studying the effects of micro and nano sized ZnO particles on the corrosion resistance and deterioration behavior of an epoxy-polyamide coating on hot-dip galvanized steel

The effects of micro and nano sized ZnO particles on the corrosion resistance and hydrolytic degradation of an epoxy coating were studied. Different analytical techniques including scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), dynamic thermal mechanical analysis (DMTA) and nano-indentation were utilized to evaluate the hydrolytic degradation as well as the corrosion resistance of the coatings in exposure to 3.5 wt% NaCl solution. It was found that the epoxy coating resistance against corrosive electrolyte was significantly improved using nano and micro sized ZnO particles. The corrosion resistance of the nanocomposite was considerably greater than the one reinforced with the micro-ZnO particles. Moreover, the resistance of the coating reinforced with the nano sized particles against hydrolytic degradation in exposure to the corrosive electrolyte was considerably greater than the one reinforced with the micro sized particles. Decrease in both nano hardness and cross-linking density of the epoxy coating reinforced with nanoparticles after exposure to the corrosive electrolyte were considerably lower than the blank sample and the sample reinforced with the micro sized ZnO particles. Using nano sized particles the coating adhesion loss decreased.