Effect of functionalized multiwalled carbon nanotubes on weather degradation and corrosion of waterborne polyurethane coatings

A series of waterborne polyurethane/functionalized multiwalled carbon nanotube (WBPU/f-MWCNT) nanocomposite dispersions was prepared using three defined concentrations of 0.5, 1.0 and 2.0 wt% carboxyl functionalized multiwalled carbon nanotubes (f-MWCNTs). All dispersions were coated on mild steel and exposed under natural weather condition for a maximum of 365 days. Both exposed and unexposed coatings were characterized by potentiodynamic polarization (PDP) and X-ray photoelectron spectroscopy (XPS) analyses. The pristine WBPU coating showed slight degradation and corrosion protection. Inclusion of a higher content of f-MWCNTs significantly improved both the degradation and corrosion protection efficiencies of the coatings. Maximal degradation and corrosion protection was observed when 2.0 wt% f-MWCNT was mixed with WBPU for all of the coatings.     

Preparation and properties of polydimethylsiloxane (PDMS)/polytetramethyleneadipate glycol (PTAd)-based waterborne polyurethane adhesives: Effect of PDMS molecular weight and content

Waterborne polyurethane (WBPU) dispersions were prepared by pre-polymer process using siloxane polyol, namely polydimethylsiloxane (PDMS), and polyester polyol, namely poly(tetramethyleneadipate glycol) (PTAd), as a soft segment. Three different molecular weights (M_n = 550, 6000, 110,000) of PDMS and one fixed molecular weight of PTAd (M_n = 2000) was used during preparation of WBPU dispersions. This research aims to explore the potential use of PDMS in complementing WBPU by boosting flexibility, water resistance, and adhesive strength. The water swelling (%), tensile strength, and adhesive strength of WBPUs were investigated with respect to PDMS molecular weight and PDMS content (PDMS mol %). The water swelling (%) and tensile strength decreased with increasing PDMS molecular weight at a fixed PDMS content (mol %) in mixed polyol of WBPU films. By contrast, the peel adhesive strength peaked at 6.64 mol % and 4.43 mol % with molecular weight of PDMS at 550 and 6000, respectively, while it only decreased when the molecular weight of PDMS stood at 110,000. The adhesive strength was almost unaffected with optimum content (6.64 mol %) of lower PDMS molecular weight (M_n = 550) in mixed polyol-based WBPU after immersing the adhesive bonded nylon fabrics in water for 48 h among all of the samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Properties of Waterborne Polyurethane Adhesives with Aliphatic and Aromatic Diisocyanates

A series of waterborne polyurethane (WBPU) adhesives were prepared with various ratios of aliphatic/aromatic diisocyanates, namely 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI) as an aliphatic diisocyanate and 4,4′-diphenylmethane diisocyanate (MDI) as an aromatic diisocyanate with poly(tetramethyleneoxideglycol) (PTMG), ethylene diamine (EDA) and dimethylol propionic acid (DMPA). ¹H-NMR spectroscopy was utilized to investigate the side reaction at the dispersion step during synthesis of WBPU dispersions with respect to aliphatic, aromatic and mixed diisocyanates. The tensile strength, Young's modulus, elongation at break (%), storage modulus, glass transition temperature and adhesive strength were measured with respect to aliphatic/aromatic diisocyanate contents. The adhesive strength was maximum using mixed diisocyanates containing 25 mol% MDI in WBPU adhesives.     

Properties of waterborne polyurethane‐fluorinated marine coatings: The effect of different types of diisocyanates and tetrafluorobutanediol chain extender content

Three series of waterborne polyurethane‐ (WBPU) fluorinated coatings were prepared with single aliphatic (4,4′‐dicyclohexylmethane diisocyanate, H₁₂MDI), aromatic (4,4′‐diphenylmethane, MDI) and a mixture of aliphatic and aromatic diisocyanates (1 : 1). Different contents of 2,2,3,3‐tetrafluoro1,4‐butanediol (TFBD) as a chain extender were used in the WBPU coatings. The fluoro‐enriched surface of the WBPU coatings was obtained with a combination of a high TFBD content (8.77 mol %) as well as the aliphatic or mixed diisocyanates. The tensile strength, Young's modulus, elongation at break (%) and adhesive strength were characterized with respect to the TFBD contents. The mechanical strength and adhesive strength increased with increasing TFBD content in the three series. In artificial salt water, the maximum adhesive strength of WBPU was observed for this coating, which was achieved by TFBD bonded H₁₂MDI of mixed diisocyanates with a higher TFBD content (8.77 mol %). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39905.     

Synthesis and characterization of waterborne polyurethane adhesives containing different amount of ionic groups (I)

A series of waterborne polyurethanes (WBPU) containing different amount of 2,2‐bis(hydroxymethyl) propionic acid (DMPA) were synthesized using prepolymer mixing process. Relationships between the DMPA content and physical, mechanical, and thermal properties as well as adhesive behavior at different condition were investigated. Stable aqueous dispersions of WBPU were obtained when the DMPA content was more than 10 mol %. At higher DMPA content, the particle size of the WBPU dispersion was lower but the viscosity of the dispersion was higher. Water swelling and tensile strength of the films increased with increasing of DMPA content. The optimum adhesive strength of WBPU adhesives was found to be depended on the DMPA content, pressing temperature, and pressure on adhesion process. The adhesive strength of WBPU adhesives increased with increasing DMPA content. The optimum pressing temperature decreased with increasing DMPA content. The adhesive strength of WBPU adhesives increased with increasing pressure up to 15 kg f/cm² and then leveled off. The optimum pressing temperature of WBPU adhesives samples containing 24.02, 22.05, and 17.05 mol % DMPA was about 100, 120, and 140°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5684–5691, 2006     

Preparation and properties of microencapsulated octadecane with waterborne polyurethane

A series of microencapsulated blends of waterborne polyurethane (WBPU) as a matrix polymer and phase change material octadecane as a domain material were prepared in the presence of emulsifier. Nylon fabrics were coated with the coating materials formulated from microencapsulated blends, thickener, and hardener. The morphology and thermal behaviors of microencapsulated octadecane and WBPU/octadecane‐coated nylon fabrics were investigated using SEM, DSC, and KES‐F7. The size of octadecane microspheres increased with increasing octadecane contents. However, the size of microcsphere (1–6 μm) decreased with increasing emulsifier contents. ΔH_fusion, ΔH_{crystallization}, and their filling efficiencies of octadecane in film samples were found to increase with increasing microencapsulated blends, thickener, and hardener contents. Especially, thickener and hardener could function in trapping microencapsulated octadecane. Thermal characteristic Q_max (J/cm² s) values of WBPU/octadecane‐coated nylon fabrics are much higher than those of the control nylon fabric and WBPU‐coated nylon fabrics, indicating that the nylon fabrics coated with WBPU/octadecane blends have cooler touch sensation compared with nylon fabrics and WBPU‐coated nylon fabrics. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1596–1604, 2005     

Fabrication of highly monodisperse CeO2@poly(methyl silsesquioxane) microspheres and their application in UV‐shielding films

Highly monodisperse CeO₂@poly(methyl silsesquioxane) (PMSQ) microspheres were successfully prepared by a facile chemical precipitation technique. The structures and properties of CeO₂@PMSQ were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy techniques. We confirmed that the PMSQ microspheres were uniformly coated by CeO₂ nanoparticles, with about an 8 nm crystallite diameter. Then, CeO₂@PMSQ was incorporated into a poly(vinyl alcohol) (PVA) matrix to fabricate PVA/CeO₂@PMSQ composite films by the casting of homogeneous solutions. The thermal and optical properties of the composite films were investigated by thermogravimetric analysis and UV–visible spectroscopy. The results show the high UV‐shielding efficiency of the composites: for a film containing 2.5 wt % CeO₂@PMSQ microspheres, about 80% UV light at wavelengths between 200 and 360 nm was absorbed, whereas the optical transparency in the visible region still remained very high. The addition of CeO2@PMSQ microspheres improved the thermal stability of the PVA films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45065.     

Epoxy coating with self-healing capability based on a 2-mercaptobenzothiazole-loaded CeO2 nanocontainer

In this study, we demonstrated a facile approach for the synthesis of nanocontainers using the encapsulation of a 2-mercaptobenzothiazole (MBT) inhibitor; these nanocontainers were capable of responsively releasing a corrosion inhibitor and of self-healing performances. The anticorrosive performance of the CeO₂ nanocontainers was investigated with electrochemical impedance spectroscopy (EIS) measurement in a saline electrolyte via the incorporation of different weight percentages (0.5, 1, and 2 wt %) of synthesized nanocontainer in epoxy (EP) resin. The EIS results show that the loading of 1 wt % CeO₂ nanocontainer containing MBT inhibitor in the epoxy (EP) coating [EP/NC MBT–CeO₂ (1%)] provided the highest R_coat, the lowest constant phase element of coating, and the optimum release of MBT at different operating pHs. The highest coating resistance R_coat values of this coating (7.81 × 10⁷ Ω cm²) were about 12 and 8573 times greater than those considered for EP–CeO₂ and EP coatings, respectively. Different releases of the MBT inhibitor were detected at various pHs. We found that the coating operating in acidic media exhibited a better self-healing performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47297.     

Preparation and corrosion resistance studies of nanometric sol-gel-based CeO2 film with a chromium-free pretreatment on AZ91D magnesium alloy

Magnesium alloy, although valuable, is reactive and requires protection before it can be applied in many fields. In this study, a novel protective environmental-friendly gradient coating was performed on AZ91D magnesium alloy by non-chromate surface treatments, which consisted of phytic acid chemical conversion coating and the sol-gel-based CeO₂ thin film. The surface morphologies, microstructure and composition of the coatings were investigated by scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and X-ray diffraction (XRD), respectively. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. The effects of the concentration, layers, temperature of heat treatment of CeO₂ sol on the anti-corrosion properties of the gradient coating for magnesium were also investigated. The results showed that the gradient coating was mainly composed of crystalline CeO₂. According to the results of electrochemical tests, the corrosion resistance of AZ91D magnesium alloy was found to be greatly improved by means of this new environmental-friendly surface treatment.     

Organosilane coatings applied on bronze: Influence of UV radiation and thermal cycles on the protectiveness

3-Mercapto-propyl-trimethoxy-silane (PropS-SH) coatings, with or without the addition of three types of oxide particles (CeO₂ (nano-sized), TiO₂ (nano-sized) and La₂O₃ (micro-sized)), were applied on quaternary bronze (Cu-Sn-Zn-Pb) and tested through natural and artificial exposures. In particular, uncoated and coated samples were exposed both in the coastal town of Rimini (Italy) under sheltered/unsheltered conditions and in a climatic chamber where the samples underwent temperature/UV cycles, at constant humidity. The sample surfaces were periodically characterized by SEM, EDS, micro-Raman, FTIR and XRD techniques. Moreover, during natural exposures, runoff rainwater was collected monthly, in order to evaluate the release of the alloying metals from bronze by atomic absorption spectrometry (AAS). The results showed that micro-scale cracking and spalling phenomena took place during natural exposure, partly limiting the protective efficiency of the organosilane coating. In fact, UV radiation has a strong influence on coating performance, inducing structural modifications of the polymer. Oxide particle- and especially TiO₂-charged coatings proved to be more resistant to UV degradation.     

High glass transition temperature polyester coatings for the protection of stones

Copolymers of lactic acid with mandelic or salicylic acid were synthetized through ring‐opening polymerization (ROP) and tested as protective coatings for stones. Most notably, glass transition temperature (T_g), hydrophobicity, and UV barrier properties were increased, making these materials more suitable as protective coating for outdoor stones than poly(lactic acid). A T_g of 76°C was obtained for the alternating copolymer lactic acid/mandelic acid and it was considerably higher than the one of poly(lactic acid) with similar molecular weight (50–55°C). Furthermore, the introduction of a perfluorinated moiety as chain‐end group, using a perfluoro alcohol as initiator of the ROP process, allowed to increase the hydrophobicity and stability of the new coatings. These polymers showed a good protective efficiency when applied on marble stones and preliminary stability tests under solar light showed low degradation, good stability to photo‐oxidative conditions, and negligible color changes after an aging time of 1000 h. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42323.     

Preparation of a hydrophobic cerium oxide nanoparticle coating with polymer binder via a facile solution route

In this work, cerium oxide (CeO₂) nanoparticles (NPs) were synthesized using a facile, low temperature solution process and coated using spin coating and spray coating approaches, for the fabrication of a hydrophobic surface coating. Silicon wafer (Si) substrates coated with CeO₂ NPs exhibited excellent hydrophobic behavior, but poor adhesion of the NPs to the substrate was observed - likely due to the low surface polarity of CeO₂ NPs. Polyacrylic acid (PAA) was introduced as an adhesion promoter to improve NP surface characteristics and obtain an adherent and cohesive coating. Slight polarity tuning and binder inclusion significantly enhanced the binding capability of the NPs as determined by peel-off measurements. The superior mechanical properties of NP coatings were attributed to the incorporation of PAA in the polymeric network. It improves inter-particle and particle-substrate secondary interactions, ultimately aiding NP cohesion and adhesion when deposited onto the Si substrate. The adhesive and hydrophobic properties of CeO₂ NP coatings were maintained upon exposure to high temperatures, and the coatings are transparent as well, making them suitable for various applications, such as cookware, glass coating and technology components.     

Preparation and properties of waterborne polyurethane‐urea/sodium alginate blends for high water vapor permeable coating materials

To improve the water vapor permeability of coating materials, aqueous sodium alginate (SA) solution was blended with waterborne polyurethane‐urea (WBPU) dispersions synthesized by prepolymer mixing process. The content of SA for stable WBPU/SA dispersions was found to be below 30 wt %. As the SA content increased, the number and density of total micropores (tunnel‐like micropores/isolated micropores) formed after dissolution of SA in water increased, and the water vapor permeability of coated Nylon fabric also increased remarkably. These results clearly demonstrate that utilizing WBPU/water soluble polymer SA blends as coating materials and then dissolving SA in water surely facilitate obtaining prominent breathable fabrics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

High Performance Organic Coatings of Polypyrrole Embedded with Manganese Iron Oxide Nanoparticles for Corrosion Protection of Conductive Copper Surface

Herein, we report the formation of organic composite coating consists of epoxy (EP) reinforced para toluene sulphonic acid (PTSA) doped polypyrrole (PPy)–manganese iron oxide (MnFe₂O₂) as an efficient corrosion inhibitor for copper substrates. The PTSA doped PPy:MnFe₂O₂ nanocomposite was synthesized via in situ polymerization of PPy in the presence of MnFe₂O₂ nanoparticles. Structural features of the prepared samples were characterized through scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), UV–visible spectroscopy and thermogravimetric analysis (TGA). The PTSA doped PPy:MnFe₂O₂ nanocomposite shows excellent conductivity and improved dielectric performance in comparison to pure PPy. The anti-corrosion performance of this organic composite coating was analyzed through Tafel polarization curves, open circuit potential (OCP), corrosion resistance, impedance spectroscopy and oxygen permeability barrier tests. The nanocomposite coating on copper substrate shows superior corrosion protection efficiency (99%) in comparison to pure epoxy (22%). Adhesion strength of the nanocomposite coating shows significant enhancement due to strong dispersions of MnFe₂O₂ nanoparticles in the host matrix. Owing to its improved conductivity, excellent anti-corrosion performance along with superior mechanical properties, the organic nanocomposite coating reported in this work can potentially be used to protect the conductive copper surfaces from harsh corrosive environments.

     

Characteristics of waterborne polyurethane/poly(N‐vinylpyrrolidone) composite films for wound‐healing dressings

For ideal wound‐healing dressings, a series of waterborne polyurethane (WBPU)/poly(N‐vinylpyrrolidone) (PVP) composite films (transparent film dressings) were prepared by in situ polymerization in an aqueous medium. Stable WBPU/PVP composites, which had a high remaining weight greater than 98.4%, were obtained. The maximum content of PVP for stable WBPU/PVP dispersions was found to be about 15 wt %. The water absorption (%) and equilibrium water content (%) of the WBPU/PVP composite films remarkably increased in proportion to the PVP content and the time of water immersion. The maximum water absorption and equilibrium water content of the WBPU/PVP composite films were in the range of 21–158 and 22–56%, respectively. The water vapor transmission rate of the WBPU/PVP composite films was in the range of 1816–2728 g/m²/day. These results suggest that WBPU/PVP composite films may have high potential as new wound‐dressing materials that provide and maintain the moist environment needed to prevent scab formation and dehydration of the wound bed. By a wound‐healing evaluation using a full‐thickness rat model experiment, it was found that a wound covered with a typical WBPU/PVP composite film (15 wt % PVP) was completely filled with new epithelium without any significant adverse reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

复合薄膜用水性聚氨酯胶粘剂的研究

以聚已二酸1,4-丁二醇酯(PBA)、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)等为主要原料合成了水性聚氨酯复膜胶,讨论了亲水性扩链剂DMPA用量对水性聚氨酯复膜胶的稳定性、耐水性、粘接强度等的影响;使用差示扫描量热仪(DSC)和原子力显微镜(AFM)观察了分子结构中的软、硬段微相结构分布。结果表明,当DMPA质量分数占预聚体总质量的2.67%～5.34%时能够制得稳定乳液;水性复膜胶乳液的粘度以及胶膜的吸水率随着亲水性扩链剂DMPA用量的增加而增加,而乳液的粒径随着亲水性扩链剂DMPA用量的增加而减小;硬段含量的增加会降低软段结晶,增加水性聚氨酯复膜胶高分子链的极性和粘接强度,当硬段质量分数为22.79%时,胶膜具有较好的T型剥离强度;提高复合压力能够显著提高T型剥离强度;该复膜胶对聚对苯二甲酸乙二醇酯(PET)膜有着比聚丙烯(OPP)膜更好的粘接效果。     

The preparation,characterization and photocatalytic activity of radical-shaped CeO2/ZnO microstructures

This paper uses a wet-chemical precipitation route to prepare radical-shaped ZnO microprisms and to deposit Cerium oxide (CeO₂) on the surface of ZnO, to form CeO₂/ZnO microstructures. The samples are characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and UV–vis diffuse reflectance spectroscopy. Their catalytic activity is also evaluated using methylene blue (MB) as a detection reagent. CeO₂/ZnO systems exhibit higher UV absorption and transparency in the visible region. The experimental results show that the deposition of CeO₂ nanospecies is successful and that the radical-shaped microstructures of ZnO are well maintained. The CeO₂/ZnO microstructures exhibit a much greater intensity of UV-light absorptivity and much higher photocatalytic activity than those of radical-shaped ZnO microprisms.     

Properties of Waterborne Polyurethane/Clay Nanocomposite Adhesives with Various Countercations of Carboxyl Acid Salt Group

Four series of waterborne polyurethane (WBPU)/clay nanocomposite adhesives were prepared using three different countercations, namely triethylamine (TEA), lithium hydroxide (LiOH) and copper hydroxide (Cu(OH)₂ ) as well as one mixed countercation of TEA and Cu(OH)₂ (1:0.5). The interaction of carboxyl acid salt group using different countercations with clay platelet was characterized by SEM and TEM, and the interaction effects on properties such as water swelling (%), thermal stability, tensile strength, glass transition temperature ( T _g ), and adhesive strength were investigated. The tensile strength, water resistance and adhesive strength increased with increasing clay content up to an optimal value at which point the maximum tensile strength, water resistance and adhesive strength were recorded for each series. However, the optimal clay contents were 1.00 and 0.50 wt% for TEA/LiOH mixed countercation series and (Cu(OH)₂ ) series, respectively. Among all of the samples the maximum tensile strength, water resistance and adhesive strength were found using mixed countercation (TEA and Cu(OH)₂ = 1:0.5) with 1 wt% clay content.     

Synthesis of heterostructured Bi2O3–CeO2–ZnO photocatalyst with enhanced sunlight photocatalytic activity

The development of heterostructured semiconductor photocatalysts makes a noteworthy advancement in environmental purification technology. In this work, a novel heterostructured Bi₂O₃−CeO₂−ZnO, fabricated by a combination of microwave-assisted hydrothermal and thermal decomposition methods, showed an enhanced photocatalytic activity for Rhodamine B (RhB) degradation under sunlight, as compared to pristine ZnO, Bi₂O₃, CeO₂, and commercial Degussa TiO₂-P25. The obtained products were thoroughly characterized by various techniques including X- ray powder diffraction (PXRD), field emission scanning electron microscopy (FE-SEM), elemental color mapping, energy-dispersive X-ray spectroscopy (EDAX), Raman spectrometry, Fourier transform infrared (FT-IR) spectroscopy, UV–visible diffuse reflectance spectroscopy (UV–vis DRS), and photoluminescence (PL) spectroscopy. PXRD analysis reveals that the heterostructure has the monoclinic lattice phase of α-Bi₂O₃, the cubic phase of CeO₂ and the hexagonal wurtzite phase of ZnO. FE-SEM images show that Bi₂O₃−CeO₂−ZnO has an ordered mixture of nanorod and nanochain structures. EDAX, elemental color mapping, Raman and FT-IR analyses confirm the successful formation of the heterostructured Bi₂O₃−CeO₂−ZnO. The UV–Vis DRS results demonstrate that Bi₂O₃−CeO₂−ZnO exhibits wide visible-light photoabsorption in 400–780 nm range. Moreover, the reduction in PL intensity of the heterostructured Bi₂O₃−CeO₂−ZnO, when compared to the pristine Bi₂O₃, CeO₂, and ZnO, indicates enhanced charge separation. The study on the mechanism displayed that the improved photocatalytic activity of Bi₂O₃−CeO₂−ZnO could be attributed to (1) the efficient separation of photoinduced electrons and holes of the photocatalysts, caused by the vectorial transfer of electrons and holes among ZnO, CeO₂ and Bi₂O₃, and (2) the wide visible-light photoabsorption range. This study introduces a new class of promising sunlight-driven photocatalysts.     

Comparison of Two Preparation Methods in the Redox Properties of Pd/CeO<Subscript>2</Subscript>/Ta/Si Model Catalysts: Spin Coating Versus Sputter Deposition

Pd/CeO₂/Ta/Si model catalysts were prepared by spin coating and sputter deposition method, and characterized by means of AFM, SEM and in situ XPS, especially focusing on the redox properties of Ce and Pd elements. Compared with thin CeO₂ films (about 2.2nm), the thicker ones (about 22nm) maintained Ce⁴⁺ oxidation state even after treatment with H₂ up to 500°C while the presence of Pd facilitated the reduction of ceria. The reduction of ceria brought about following that of PdO, which was explained by the spillover of hydride in Pd to CeO₂ originating from hydrogen adsorption on the Pd surface. Compared with the sputter deposition method, spin coating produced the smaller size of Pd particles, thus leading to formation of the stable PdO species against hydrogen. Based on these results, a schematic model of Pd/CeO₂/Ta/Si was suggested and it might be assumed that spin coating method provided with an environment similar to the conventional impregnation.