Improving corrosion resistance of epoxy coatings modified with silane monomers on AZ31D magnesium alloy

Abstract

In recent years, there has been growing interest in developing high performance silane containing epoxy coatings. In this work, two silane monomers (3-glycidoxypropyltrimethoxysilane and vinyltrimethoxy silane) were incorporated in epoxy coatings. The results demonstrated that the incorporation of 5 wt-% 3-glycidoxypropyltrimethoxysilane in coating formulation improved the anticorrosive performance of the epoxy coating on AZ31D magnesium alloy. The improving effect of 3-glycidoxypropyltrimethoxysilane was much better than that of vinyltrimethoxy silane, which can be ascribed to the compatibility of the former with epoxy vehicle. The adhesion between epoxy coatings and substrate was also strengthened by addition of the two silane monomers.

Ces dernières années, on note un intérêt grandissant dans le développement de revêtements à haute performance de résine époxy contenant du silane. Dans ce travail, on a incorporé deux monomères de silane (3-glycidoxypropyltriméthoxysilane et vinyltriméthoxy silane) dans des revêtements de résine époxy. Les résultats ont démontré que l’incorporation de 5% en poids de 3-glycidoxypropyltriméthoxysilane dans la formule du revêtement améliorait le rendement anti-corrosif du revêtement de résine époxy sur l’alliage au magnésium AZ31D. L’amélioration du 3-glycidoxypropyltriméthoxysilane était bien meilleure que celle du vinyltriméthoxy silane, ce que l’on peut attribuer à la compatibilité du premier avec le véhicule de la résine époxy. L’adhésion entre les revêtements de résine époxy et le substrat était également renforcée par l’addition des deux monomères de silane.     

Effect of rapid curing process on the properties of carbon fiber/epoxy composite fabricated using vacuum assisted resin infusion molding

Long processing cycle makes vacuum assisted resin infusion molding (VARIM) only suitable for low and medium volumes of production, and shortening of curing time is critical to improving the processing efficiency of automotive composite parts. In this paper, unidirectional carbon fiber reinforced composite laminates were fabricated by VARIM. Three different processes (namely quick, quick-post and preheating) were employed, in which a kind of rapid curing epoxy resin is used. The preheating of mold and fiber was conducted to shorten the filling time compared with that of quick process. Quick-post process with a post cure stage was investigated to verify the composite properties fabricated by quick process. The cycle time was 16 min for preheating process, about 30% shorter than that of quick process, simultaneously, flexural strength and interlaminar shear strength (ILSS) were respectively improved by 29% and 7% compared with those of quick process. The non-uniformity of mechanical properties at different positions along resin flow direction under preheating process was found, but the processing quality of composite was good. The preheating process is confirmed to be suitable for the improvement of processing efficiency of VARIM with good mechanical properties. In addition, the composite fabricated by quick-post process has better mechanical properties, which is attributed to the alleviation of residual stress during post curing process.     

非异氰酸酯聚氨酯的制备与性能研究

采用双酚F型环氧树脂NPEF-170与聚乙二醇400二缩水甘油醚为原料制备了双官能度的环碳酸酯，再与聚醚胺T403反应合成了非异氰酸酯聚氨酯（NIPU），并且利用FT-IR时产物的结构进行了表征。同时探讨了反应条件对环氧树脂转化率的影响。研究了不同质量比的原料对非异氰酸酯聚氨酯力学性能的影响，研究表明，当原料的质量比为3：7时所制备的NIPU材料的力学性能最好。最大拉伸强度为7．58MPa，扯断伸长率为347％。     

Ring Opening of Epoxidized Soybean Oil with Compounds Containing Two Different Functional Groups

Epoxidized vegetable oils are desirable chemicals due to their eco‐friendly characteristics and their being a major source of many green products. Ring opening is one of the ways to convert these epoxidized oils to some new intermediates. The use of mono‐functional amines, alcohols, acid anhydrides and thioethers for epoxy ring opening has been reported in the literature. In this study, thioglycolic acid (TGA) bearing thiol and carboxylic acid as two different functional groups and methyl ester of thioglycolic acid (TGAME) were used. Currently, there is no reported literature describing epoxy ring opening using chemicals bearing two different functional groups simultaneously. In this way, two new polyols were synthesized, one with TGA (polyol 1) and one with TGAME (polyol 2). FTIR and ¹H‐ and ¹³C‐NMR spectroscopy confirmed that the ring was opened by the carboxylic acid group of TGA, and the thiol group was not involved in the ring opening whereas the ring was opened by the thiol group in the case of TGAME.     

Identification of the Elastic–Plastic Behavior of Adhesively Bonded Structures Under Multi-Axial Loadings: Comparison of a Modified Arcan Test and a Tension/Compression–Torsion Test

Structural bonding is nowadays widespread in the industry. However, characterisation methods and 3D modelling of the adhesives need to be improved. The characterisation requires an experimental procedure to obtain a large experimental database under various loading cases, which represents a significant amount of data. The 3D modelling requires advanced models with several parameters to identify and generally uses inverse identification procedures, which can be time expensive. For a good accuracy, the constitutive models need to take into account the dependency on the hydrostatic stress and be written under the non-associated formalism. In this study, the experimental database is obtained via a modified Arcan test that can cover a wide range of loadings between tension, shear, mixed tension–shear, and mixed compression–shear. A second experimental campaign is realized with a tension/compression–torsion (TCT) test that can cover a greater range of loadings: from tension to compression and mixed tension/compression–shear, with an infinite possibility of mixed loadings. The modified Arcan database is used to identify a 3D elastic–plastic Mahnken–Schlimmer type model, according to an inverse identification procedure developed in a previous study. This model identification is validated on the experimental database coming from the TCT test: a numerical/experimental comparison is realized. This allows the validation of the model and emphasizes the benefits of the TCT test. Indeed, it proves that this test is well suited to characterize adhesive joints and presents several capacities that will be really useful for further studies, like an infinite range of non-proportional loadings available.     

Effect of Nanoclay on the Mechanical,Thermal, and Water Absorption Properties of an UP-toughened Epoxy Network

Unsaturated polyester (UP)-toughened epoxy nanocomposites were prepared, and their effective mechanical and thermal properties were studied. Two types of organo-modified montmorillonite (OMMT) clays were used to prepare the nanocomposites. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis showed the formation of exfoliated silicate layers in the UP-toughened epoxy matrix. Mechanical tests revealed that nanocomposites (containing 1 wt% OMMT clay) showed an increase in tensile strength to 13.8%, flexural strength to 10%, and impact strength to 4% compared with an UP-toughened epoxy blend. The effect of different heating rates on the curing behavior of UP-toughened epoxy nanocomposites was investigated using non-isothermal differential scanning calorimetry. The data were interpreted using the Kissinger and Flynn–Wall–Ozawa models to find the curing reaction parameter. The water uptake behavior for nanocomposites increased with the addition of OMMTs. Scanning electron microscopy micrographs indicated morphological changes in the impact fractured samples of UP-toughened epoxy nanocomposites.     

Formation of Furan Fatty Alkyl Esters from their Bis‐Epoxide Fatty Esters

Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2‐ethylhexanol, benzyl alcohol, in the presence of Brønsted acid catalyst, were investigated. Products, not reported in prior studies of similar reactions, were found. These were furan fatty acid alkyl esters (FFE, mixture of alkyl 8‐(5‐hexyl‐2‐furyl) octanoate and alkyl 9‐(5‐pentyl‐2‐furyl)nonanoate) which were unambiguously identified by means of GC–MS and two‐dimensional NMR. Evidence suggests that the FFE are formed by an acid‐catalyzed rearrangement of the epoxidized linoleates. The FFE were formed in presence of all four alcohols tested and in the presence of either sulfuric acid or Amberlyst 15 catalyst. Yields of up to 13 %, as quantified by GC and NMR spectroscopies, were observed.     

Morphological and mechanical study of nanostructured epoxy systems modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide)triblock copolymer

Thermosetting systems based on DGEBA epoxy resin and poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) triblock copolymer were prepared and investigated. Different mixtures were obtained by using different contents of EPE block copolymer in order to study the influence of the modifier on the properties of the final materials. All thermosetting systems were prepared without using any solvent and were cured at ambient temperature, taking into account the lower critical solution temperature (LCST) behavior of the block copolymer. DSC results indicated that the addition of block copolymer affected to the curing reaction time and to the glass transition temperature of the mixtures and also the miscibility of EPE triblock copolymer in the epoxy resin was proved. The morphologies studied by AFM and TEM showed clear nanostructuration up to 25 wt % EPE content. The addition of 5 and 15 wt % of EPE block copolymer led to a considerable improvement in the toughness of the materials. When EPE block copolymer was added to the epoxy resin, the surface became more hydrophilic and the UV–vis transmittance decreased slightly maintaining a high level of transparency.     

Thermo-oxidative aging of epoxy coating systems

The thermo-oxidative behavior of unformulated (unfilled) samples of epoxy coatings has been studied at five temperatures ranging from 70 °C to 150 °C. Two epoxy networks based on diglycidyl ether of bisphenol A (DGEBA), respectively, cured by jeffamine (POPA) or polyamidoamine (PAA) were compared. Infrared spectrophotometry (IR), differential scanning (DSC) and sol–gel analysis (SGA) were used to monitor structural changes.     

Expression of the transportation of corrosive media into epoxy coating using nano-indentation

Nano-hardness (H_nano) and nano-elastic modulus (E_nano) of corroded coating surface layer were investigated using nano-indentation after epoxy coated specimens were immersed in 5% NaCl solution. The penetration depths (d) of corrosive media into epoxy coating were calculated fitting the curves of (H/E)_nano vs. indentation depth (h). EIS spectra of epoxy coated specimens immersed in 5% NaCl solution for different time were measured. Finally the relationship of capacitance (C_f,T) of corroded epoxy coating with the penetration depth of corrosive media was studied. The experimental results showed that the transportation process of corrosive media into epoxy coating was studied through the profiles of (H/E)_nano with indentation depth. The penetration depth of corrosive media into the epoxy coating increases rapidly with immersed time firstly, and then increases slowly. The capacitance of corroded epoxy coating has a linear function relationship with the penetration depth of corrosive media into epoxy coating. Nano-indentation can be used to study the transportation process of corrosive media into organic coating.