Increase In Barrier Properties Research Articles

Self-healing epoxy coatings with microencapsulated ionic PDMS oligomers for corrosion protection based on supramolecular acid-base interactions

To obtain a self-healing coating and improve the corrosion resistance of coated low-carbon steel surfaces, a commercial epoxy coating was modified by adding microcapsules composed of a poly(methyl methacrylate) shell and a core of ionic polydimethylsiloxane (PDMS) oligomers. The encapsulation of amino- and carboxylic acid-terminated PDMS was achieved by a solvent evaporation process after the emulsification of core and shell materials, dissolved in CH2Cl2, in a suitable colloidal solution. A high core loading of nearly 50% wt. was successfully obtained by carefully increasing the interfacial tension of oil-in-water emulsion before the solvent evaporation. The microcapsule morphology was evaluated by SEM and optical microscopy analyses, which showed a particle diameter range of 20–70 μm. The presence of ionic PDMS oligomers as core materials was demonstrated by FTIR spectroscopy and thermogravimetric analysis (TGA), which was also employed to determine the core loading. The newly prepared microcapsules were then incorporated into the matrix of a commercial two-component epoxy coating. Corrosion protection abilities were assessed by comparing samples coated with a standard epoxy coating modified with a 20% wt. of microcapsules and the pristine epoxy coating. The corrosion protection performance of the modified coating was evaluated through electrochemical impedance spectroscopy (EIS) tests and potential vs time measurements, which showed that the microcapsules in the coating matrix caused a beneficial increase in barrier properties of a scratched coating. The surface damage triggered the release of functional PDMS oligomers, leading to the formation of a supramolecular ionic network and providing self-healing abilities to the modified coating.

Preparation and evaluation of corrosion resistance of a self-healing alkyd coating based on microcapsules containing Tung oil

A commercial coating was transformed into a self-healing coating by inserting urea-formaldehyde microcapsules (MCs) containing tung oil (TO), to improve coated metal corrosion resistance. The microcapsules were characterized regarding their morphology and chemical composition, and the presence of tung oil as core material was also proven by FTIR analysis. MCs were then incorporated into the matrix of a commercial mono-component alkyd coating, being added in the same proportion as the corrosion inhibitor (zinc phosphate) present in the original commercial coating. Corrosion resistance was evaluated by the comparison between samples coated with an original commercial coating, commercial coating without zinc phosphate and a commercial coating containing MC., employing a corrosive saline medium of NaCl 3.5 % (w/w), where were carried out the electrochemical analysis of open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS). For this, the stimulus-responsive capacity of microcapsules was proven through mechanical disruption. It was observed that the additive coating presented a satisfactory performance for application in 1020 carbon steel specimens, keeping its properties practically unchanged. The self-healing ability of the coating has been proven and the corrosion protection performance of the coating has been assessed through electrochemical techniques, and the results of the OCP and EIS tests showed that the microcapsules in the coating matrix caused a beneficial increase in barrier properties. Additionally, MC additive coating protected the metallic substrate when it suffers a mechanical defect through the release of the oil and its active protection conditioned to the self-healing effect. Thus, when comparing the types of coatings tested, samples containing MCs of tung oil proved to be a more promising additive than the original additive. Also, a self-responsive stimulus mechanism for this smart coating was proposed based on the blistering caused by the presence of corrosion products.

Impact of coated calcium carbonate nanofillers and annealing treatments on the microstructure and gas barrier properties of poly(lactide) based nanocomposite films

ABSTRACTAmorphous poly(lactide) (PLA) and nanocomposite films were prepared from melt‐blending with precipitated calcium carbonate nanofillers (PCC). Nanocomposites based on uncoated PCC (PCC‐UT), stearic acid coated PCC (PCC‐S), and poly(ε‐caprolactone) coated PCC (PCC‐P) were investigated for an inorganic content fixed to 8 wt %. Using coated nanofillers allowed preserving both PLA average molar mass and thermal stability while enhancing the nanofiller dispersion state. Poly(ε‐caprolactone) was identified as the best coating for optimized morphology and thermal properties. Maxwell law accurately described the increase in oxygen barrier properties observed for the nanocomposites based on PCC‐S. A modified Maxwell law was proposed to take account of the additional increase in barrier properties evidenced for the PLA/PCC‐P nanocomposites and assigned to the particularly strong compatibility between PCL and PLA. Different annealing conditions were investigated to respectively study the impact of physical ageing and PLA crystallization on gas permeability. Different extents of physical ageing did not significantly modify the oxygen transport properties. However, a high permeability decrease was observed for the semicrystalline nanocomposites with respect to the amorphous reference PLA film. Finally, the gain in barrier properties was shown to result from both contribution of the nanofillers and the crystalline phase. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 649–658

Barrier Properties and Structural Study of Nanocomposite of HDPE/Montmorillonite Modified with Polyvinylalcohol

In this work was studied the permeation of CO2 in films of high‐density polyethylene (HDPE) and organoclay modified with polyvinylalcohol (MMTHDTMA/PVA) obtained from melt blending. Permeation study showed that the incorporation of the modified organoclay generates a significant effect on the barrier properties of HDPE. When a load of 2 wt% of MMTHDTMA/PVA was incorporated in the polymer matrix, the flow of CO2 decreased 43.7% compared to pure polyethylene. The results of TEM showed that clay layers were dispersed in the polymeric matrix, obtaining an exfoliated‐structure nanocomposite. The thermal stability of nanocomposite was significantly enhanced with respect to the pristine HDPE. DSC results showed that the crystallinity was maintained as the pure polymeric matrix. Consequently, the decrease of permeability was attributable only to the effect of tortuosity generated by the dispersion of MMTHDTMA/PVA. Notably the mechanical properties remain equal to those of pure polyethylene, but with an increase in barrier properties to CO2. This procedure allows obtaining nanocomposites of HDPE with a good barrier property to CO2 which would make it competitive in the use of packaging.

The Effect of Inorganic Nanoadditives on the Thermal, Mechanical and UV Radiation Barrier Properties of Polypropylene Fibres

The objective of this study of modified polypropylene (PP) fibres using nanoadditives (nano-CaCO3 and Cloisite 30B) was to determine the influence of these additives on thermal and mechanical properties, but especially on the barrier properties of the nanocomposite fibres against UV radiation. The DSC data obtained from measurements of PP/CaCO3 or PP/C30B nanocomposite fibres were used for determination of the constants n and K of the Avrami equation and in the estimation of other thermal properties of the fibres, such as their crystallization half-time t1/2, rate of crystallization t1/2, the necessary time for maximum crystallization tmax and free energy per unit area of surface in the lamella perpen-dicular to the axis of a high-molecular chain se. The nano-CaCO3 or Closite 30B fillers (pre-treated separately in three different solvents: glycerine, acetone and water) did not influence the melting temperatures but caused an increase in PP crystallization temperatures in comparison with the pure PP fibres. The pre-treatments of nanoadditives resulted in increase of n, K, t1/2 values and decrease of t1/2, tmax as well as the values of free surface energies per unit area of the modified PP fibres. There was also observed a decrease in the mechanical properties, however, there was an increase of barrier properties against UV radiation of nanocomposite PP fibres in comparison with neat PP fibres, which was one of the main objectives of the study.

Cortisol affects tight junction morphology between pavement cells of rainbow trout gills in single-seeded insert culture

A primary culture system of rainbow trout gill pavement cells grown on permeable support (single-seeded insert, SSI) was used to examine histological and physiological changes induced by the addition of the corticosteroid hormone cortisol. Pavement cell epithelia were cultured under symmetrical conditions (L15 apical/L15 basolateral) and developed a high transepithelial resistance (TER, 6.84±1.99kΩcm(2), mean±SEM) with a low phenol red diffusion rate (PRD, 0.15±0.03μmoll(-1)/day). Addition of cortisol to the basolateral compartment increased TER twofold and reduced PRD threefold over a 5-day period. A similar increase in TER could be seen after 24h apical freshwater (FW) in control cultures. In cortisol-treated cultures FW exposure did not change TER, but PRD increased significantly. Histochemical staining of the cytoskeleton of cells in SSI culture revealed a morphological partitioning into a single mucosal layer of polarized, polygonal cells featuring cortical F-actin rings which were comparable to F-actin rings of epithelial cells on the lamellar and filamental surface, and several unorganized serosal layers of cells with F-actin stress fibers. Addition of cortisol increased cell density by 18% and in the mucosal layer it led to smaller, less polygonal cells with increased height and increased cell contact area. In transmission electron microscopic images two pairs of cytoplasmatic electron-dense structures confining the zonula occludens apically and basally toward the zonula adhaerens were found. Addition of cortisol increased the distance between those paired structures, hence led to deeper tight junctions. The cortisol-induced increase in barrier properties, therefore, involves a structural fortification of the tight junctions which was not generally modified by a short 24-h apical freshwater stress. These results identify cortisol as a regulator of tight junction morphology between pavement cells of euryhaline fish such as the trout.

Pigment epithelium-derived factor inhibits advanced glycation end products-induced retinal vascular permeability

Vascular hyperpermeability associated with retinal vascular leakage is known to occur in patients with diabetes, and contributes to endothelial barrier dysfunction. This study aimed to examine the effect of pigment epithelium-derived factor (PEDF) on advanced glycation end products (AGEs)-induced endothelial cell permeability. Cultured porcine retinal endothelial cell (PREC) was exposed to AGE-modified bovine serum albumin (AGE-BSA) and the endothelial cell permeability was detected by measuring the flux of rhodamine B isothiocyanate (RITC)-dextran across the PREC monolayers. We found that AGE-BSA increased the RITC-dextran flux across a PREC monolayer and PEDF blocked the solute flux induced by AGE-BSA. In order to explore the underlying signaling mechanism of PEDF on the inhibitory effect of AGE-BSA-induced permeability, we demonstrate that PEDF could inhibit the AGE-BSA-induced permeability via phosphatidylinositol 3-kinase (PI3K)/Akt pathway. AGE-BSA also increased the endothelial cell permeability by stimulating the reactive oxygen species (ROS) generation via NADPH oxidase activity and Akt phosphorylation at Ser473. PEDF decreased ROS generation in AGE-BSA-exposed endothelial cells by suppressing the NADPH oxidase activity via down regulating the phosphorylation of p22 PHOx at Thr147. This led to blockade of AGE-induction of PI3K/Akt activation in permeability. Furthermore, PEDF inhibited the AGE-BSA-induced permeability by increased expression of tight junction protein zona occludens-1(ZO-1), co-incident with an increase in barrier properties of endothelial monolayer. Together, our results indicate that PEDF could possibly act as potent anti-permeability molecule by targeting the PI3K/Akt signaling pathway by suppressing if NADPH oxidase mediated ROS generation and ZO-1 tight junction protein and it offers potential targets to inhibit the ocular related diseases such as diabetic retinopathy.

The inhibition of advanced glycation end-products-induced retinal vascular permeability by silver nanoparticles

The increased permeability of the blood–retinal barrier is known to occur in patients with diabetes, and this defect contributes to retinal edema. This study aimed to determine the effects of silver nanoparticles (Ag-NPs) on advanced glycation end-products (AGEs)-induced endothelial cell permeability. Cultured porcine retinal endothelial cells (PRECs) were exposed to AGE-modified bovine serum albumin (AGE-BSA) and the endothelial cell permeability was detected by measuring the flux of RITC-dextran across the PREC monolayers. We found that AGE-BSA increased the dextran flux across a PREC monolayer and Ag-NPs blocked the solute flux induced by AGE-BSA. In order to understand the underlying signaling mechanism of Ag-NPs on the inhibitory effect of AGE-BSA-induced permeability, we demonstrated that Ag-NPs could inhibit the AGE-BSA-induced permeability via Src kinase pathway. AGE-BSA also increased the PREC permeability by stimulating the expression of intracellular adhesion molecule-1 (ICAM-1) and decreased the expression of occludin and ZO-1. Further, Ag-NPs inhibited the AGE-BSA-induced permeability by increased expression of tight junction proteins occludin and ZO-1, co-incident with an increase in barrier properties of endothelial monolayer. Together, our results indicate that Ag-NPs could possibly act as potent anti-permeability molecule by targeting the Src signaling pathway and tight junction proteins and it offers potential targets to inhibit the ocular related diseases.

Barrier and mechanical properties of nanocomposites based on polymer blends and organoclays

AbstractNanoclays (NCs) impart highly effective barrier properties to polymers due to their platelet structure, provided that the NCs are exfoliated and form a parallel array relative to the product surface. High barrier films with enhanced mechanical properties were developed and studied using blends of polyamide (PA) or ethylene vinyl alcohol (EVOH) with polyethylene (PE) and compatibilizing copolymer, and with incorporated NC. Permeability measurements indicated that by increasing the active polymers concentration up to 30%, however, reducing the barrier layer thickness comprising the active polymers (PA or EVOH), resulting in reduction of the oxygen transmission rate (OTR) by more than 7‐ to 8‐folds. When NC was incorporated in the concentrated active polymer layer, the barrier to oxygen was further increased. This resulting in equal or even better barrier properties compared to the case where the active polymers are at 95% concentration. The increase in barrier properties was attributed to the laminar structure of the incompatible active polymer in addition to the orientation of the NC with its additional effects due to nucleation and enhancement of the amorphous phase barrier. The mechanical properties of the concentrated active layer (CAL) films were better or comparable with respect to the high barrier reference films. Furthermore, a nucleation effect, leading to increased crystallinity, was identified in the cases where PA compositions contained NC, whereas selective nucleation was obtained in the case where EVOH compositions contained NC. These observations, on oxygen barrier and mechanical properties, were further supported by the results obtained from thermal analysis (differential scanning calorimetry [DSC]), X‐ray diffraction (XRD) measurements, and transmission electron microscopy (TEM) imaging studies carried out on the hybrid films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Synthesis of polypropylene/clay nanocomposites using bisupported Ziegler-Natta catalyst

In this article, preparation of polypropylene/clay nanocomposites (PPCNC) via in situ polymerization is investigated. MgCl2/montmorillonite bisupported Ziegler-Natta catalyst was used to prepare PPCNC samples. Montmorillonite (MMT) was used as an inert support and reinforcement agent. The nanostructure of the composites was characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy techniques. Obtained results showed that silica layers of the MMT in these PPCNC were intercalated, partially exfoliated, and uniformly dispersed in the polypropylene matrix. Thermogravimetric analysis showed good thermal stability for the prepared PPCNC. Differential scanning calorimetric was used to investigate both melting and crystallization temperatures, as well as the crystallinity of the PPCNC samples. Results of permeability analysis showed significant increase in barrier properties of PPCNC films. Effective parameters on molecular weight and flow ability of produced samples such as Al/Ti molar ratio and H2 concentration were also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

In situ polymerization of polyethylene/clay nanocomposites using a novel clay‐supported Ziegler‐Natta catalyst

AbstractPolyethylene/clay nanocomposites (PECNC) were synthesized via in situ Ziegler‐Natta catalyst polymerization. Activated catalyst for polymerization of ethylene monomer has been prepared at first by supporting of the cocatalyst on the montmorillonite (MMT) smectite type clay and then active complex for polymerization formed by reaction of TiCl4 and aluminum oxide compound on the clay. Acid wash treatment has been used for increasing hydroxyl group and porosity of the clay and subsequently activity of the catalyst. The nanostructure of composites was investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Obtained results show that silica layers of the mineral clay in these polyethylene/nanocomposites were exfoliated, intercalated, and uniformly dispersed in the polyethylene matrix even at very high concentration of the clay. Thermogravimetric analysis (TGA) shows good thermal stability of the PECNCs. Differential scanning calorimeter (DSC) results reveal considerable decrease in the crystalline phase of the PECNC samples. Results of permeability analysis show an increase in barrier properties of PECNC films. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers

Glucocorticoids induce transactivation of tight junction genes occludin and claudin-5 in retinal endothelial cells via a novel cis-element

Tight junctions between vascular endothelial cells help to create the blood–brain and blood–retinal barriers. Breakdown of the retinal tight junction complex is problematic in several disease states including diabetic retinopathy. Glucocorticoids can restore and/or preserve the endothelial barrier to paracellular permeability, although the mechanism remains unclear. We show that glucocorticoid treatment of primary retinal endothelial cells increases content of the tight junction proteins occludin and claudin-5, co-incident with an increase in barrier properties of endothelial monolayers. The glucocorticoid receptor antagonist RU486 reverses both the glucocorticoid-stimulated increase in occludin content and the increase in barrier properties. Transcriptional activity from the human occludin and claudin-5 promoters increases in retinal endothelial cells upon glucocorticoid treatment, and is dependent on the glucocorticoid receptor (GR) as demonstrated by siRNA. Deletion analysis of the occludin promoter reveals a 205 bp sequence responsible for the glucocorticoid response. However, this region does not possess a canonical glucocorticoid response element and does not bind to the GR in a chromatin immunoprecipitation (ChIP) assay. Mutational analysis of this region revealed a novel 40 bp occludin enhancer element (OEE), containing two highly conserved regions of 10 and 13 base pairs, that is both necessary and sufficient for glucocorticoid-induced gene expression in retinal endothelial cells. These data suggest a novel mechanism for glucocorticoid induction of vascular endothelial barrier properties through increased occludin and claudin-5 gene expression.

Three-dimensional growth of endothelial cells in the microgravity-based rotating wall vessel bioreactor.

We characterized bovine aortic endothelial cells (BAEC) continuously cultured in the rotating wall vessel (RWV) bioreactor for up to 30 d. Cultures grew as large tissue-like aggregates (containing 20 or more beads) after 30 d. These cultures appeared to be growing in multilayers around the aggregates, where single beads were covered with confluent BAEC, which displayed the typical endothelial cell (EC) morphology. The 30-d multibead aggregate cultures have a different and smoother surface when viewed under a higher-magnification scanning electron microscope. Transmission electron microscopy of these large BAEC aggregates showed that the cells were viable and formed multilayered sheets that were separated by an extracellular space containing matrix-like material. These three-dimensional cultures also were found to have a basal production of nitric oxide (NO) that was 10-fold higher for the RWV than for the Spinner flask bioreactor (SFB). The BAEC in the RWV showed increased basal NO production, which was dependent on the RWV rotation rate: 73% increase at 8 rpm, 262% increase at 15 rpm, and 500% increase at 20 rpm as compared with control SFB cultures. The addition of l-arginine to the RWV cultures resulted in a fourfold increase in NO production over untreated RWV cultures, which was completely blocked by L-NAME [N(G)-nitro-L-arginine-methylester]. Cells in the SFB responded similarly. The RWV cultures showed an increase in barrier properties with an up-regulation of tight junction protein expression. We believe that this study is the first report of a unique growth pattern for ECs, resulting in enhanced NO production and barrier properties, and it suggests that RWV provides a unique model for investigating EC biology and differentiated function.