Surface evaluation and electrochemical behavior of cerium conversion coating modified with silane on magnesium alloy

A new cerium conversion coating modified with the hydrolysis silane is designed for AZ31 magnesium alloy, which aims at assessing the surface characterizations and electrochemical behaviors between the cerium conversion coating with and without the silane modified. The effect of the silane addictive is studied by scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The adhesion of the coatings is undertaken according to the American Society for Testing and Materials (ASTM) standard D3359‐08 cross tape test. The electrochemical behavior is evacuated by polarization experiment and electrochemical impedance spectroscopy (EIS) in NaCl electrolyte. The results show that the addition of bis‐[triethoxysilylpropyl] tetrasulfide (BTESPT) to loosen and porous cerium conversion coating leads to the formation of a more compact and homogenous film, higher resistance to water uptake and better adhesion to substrate. Electrochemical measurements show that, compared with the non‐modified cerium conversion coating, the coating modified with the silane exhibits better anticorrosion properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface modification on thermoplastic olefins by low‐temperature cascade arc discharge‐air plasmas for enhanced adhesion with primer

Improvement of primer adhesion to thermoplastic olefins (TPOs) by surface modification with a low‐temperature cascade arc discharge‐air plasmas was investigated. Air plasma with a low‐temperature cascade arc plasma torch can be used for improving the primer adhesion to TPOs. Tape‐adhesion tests (ASTM 3359‐92a method) demonstrated this improvement with a rating of “0” for untreated TPOs and “5” for air plasma‐modified TPOs at certain plasma conditions even for aging at 60 °C and 80% relative humidity for 5 days. The adhesion to primer for the soft and flexible kind of TPOs (ETA‐3041c and ETA‐3101) was easily enhanced. The adhesion to primer for the hard and brittle TPOs (ETA‐3183) needs to optimize the plasma conditions to pass the wet‐adhesion test using air plasmas. To relate the surface characteristics of air plasma‐modified TPOs to adhesion performance with primer, the wettability and polarity of TPOs were evaluated by the contact‐angle measurements of primer and deionized water to TPOs. TPO surface morphology was evaluated using scanning electron microscopy. The surface composition was characterized with electron spectroscopy for chemical analysis. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 623–637, 2002; DOI 10.1002/polb.10122     

Methane plasma polymerization by low‐temperature cascade arc discharge for enhanced adhesion of primer to thermoplastic olefins

Improvement of primer adhesion to thermoplastic olefins (TPOs) by methane plasma polymerization with a low‐temperature cascade arc discharge was investigated. Methane plasma with a low‐temperature cascade arc plasma torch can be used for improving the primer adhesion to TPOs. Tape‐adhesion tests (ASTM 3359‐92a method) demonstrated this improvement, with a rating of 0 for untreated TPOs and 5 for methane plasma‐polymerized TPOs at certain plasma conditions even for aging at 60 °C and 80% relative humidity for 5 days. The adhesion to primer for the soft, flexible TPOs (ETA‐3041c and ETA‐3101) was easily enhanced. The adhesion to primer for the hard and brittle TPOs (ETA‐3183) needs to optimize the plasma conditions to pass the dry‐ and wet‐adhesion test with methane plasmas. To relate the surface characteristics of methane plasma‐polymerized TPOs to adhesion performance with primer, the wettability and polarity of TPOs were evaluated by the contact‐angle measurements of primer and deionized water to TPOs. TPO surface morphology was evaluated with scanning electron microscopy. The surface composition was characterized with electron spectroscopy for chemical analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2004–2021, 2003     

Electrically Conductive Polymeric Materials with High Stretchability and Excellent Elasticity by a Surface Coating Method

Electrically conductive polymer films with high stretchability and excellent elasticity were simply fabricated by coating a conductive layer on the surface of an elastomer film. The material used for the conductive layer was a high‐shear processed poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock copolymer (SEBS)/multiwalled carbon nanotubes (MWCNTs) nanocomposite with 20 wt.‐% MWCNTs loading. The nanocomposites were first dissolved in toluene to form a stable solution and then were coated onto the SEBS film by spin coating. The alignment of MWCNTs in the coated layer and the interface between the base film and the coated layer were investigated. It was found that almost all the MWCNTs are aligned parallel to the base film and that there is good adhesion between the two layers. The fabricated films show high electrical conductivity and almost same stretchability and elasticity as the base film. Moreover, the films exhibit extremely high electrical conductive retention after applying high strain.

     

基于二氧化碳共聚物的紫外光固化高分子材料的制备与性能

普通低分子量的二氧化碳共聚物由于预聚体中含有较多的亲水性端羟基, 在紫外光辐照下不能交联而降低材料的耐水性. 为降低亲水性端羟基对材料耐水性的影响, 本文利用锌钴双金属氰化物(Zn-Co DMC)催化剂实现了CO₂与4-乙烯基环氧环己烷、 环氧环己烷的三元无规共聚, 制备出分子量在40000以上, 含C=C双键的脂环族聚碳酸酯; 采用四(3-巯基丙酸)季戊四醇酯为固化剂, 基于紫外光诱导的双键-巯基点击反应制备了紫外光固化高分子材料. 研究发现, 在5.0 mJ/cm²的紫外光辐照剂量下即可制备出高透明硬化涂层, 在可见光(400~750 nm)波段内透光率达到97.5%, 铅笔硬度达到3H, 对马口铁等基体附着力达到0级. 值得指出的是, 该紫外光固化薄膜的玻璃化转变温度超过110 ℃, 与双酚A型环氧树脂相当, 而且不含苯环等结构, 具有更优异的耐紫外光老化性能.     

Electrochemically Tunable Cell Adsorption on a Transparent and Adhesion‐Switchable Superhydrophobic Polythiophene Film

A superhydrophobic polythiophene film (SSPTH) is prepared by double‐layer electrodeposition on an indium tin oxide (ITO) glass electrode. This film shows not only electroresponsive superhydrophobic features, but also high transparency compared with the usual polythiophene film. The water‐droplet adhesion on the SSPTH film can be switched between sliding and pinned states under the applied potential. More intresetingly, the change in water‐droplet adhesion results in a change in cell adsorption on the SSPTH film. The low‐adhesion (dedoped) SSPTH films can prevent Hela cell adhesion, whereas high‐adhesion (doped) SSPTH films can promote Hela cell adsorption. This controllable cell adhesion on a SSPTH film may be developed as a smart biointerface material.

     

Gold Nanoparticle‐Hybridized “Nano‐Sponge” Polymer Coatings to Enhance the Reliability and Sensitivity of Biosensors

We have created a new functional biosensor coating composed of polyelectrolyte multilayers containing gold nanoparticles. This gold‐hybridized polyelectrolyte multilayer film possesses a stable nanoporous structure under physiological conditions. Antibody molecules were successfully conjugated onto the gold nanoparticles within the film. This functional coating successfully extinguished false signals from non‐specific binding of proteins and cells and also provided highly enhanced detection sensitivity. Furthermore, the drastic differences in protein and cellular adhesion properties between a chip coated with the nanoporous PEM film and a bare chip demonstrate that morphological control of biological interactions on chip surfaces is possible.

     

Biocompatibility Studies of Functionalized Regioregular Poly(3‐hexylthiophene) Layers for Sensing Applications

There is a significant medical and biological need for cheap disposable analytical sensing devices, which can be used in clinical settings or medical research. Organic electronics based on polymeric materials, being suitable for large‐area, low‐cost, flexible, and maybe even disposable electronics, could satisfy this need in a very elegant way. Unfortunately, the ensurance of biocompatibility and biofunctionalization of conducting and semiconducting polymers is still often lacking. In the present study, we concentrate on one of the most promising polymeric materials, regioregular poly(3‐hexylthiophene) (P3HT), being both a reasonably conducting and optically active polymer. To overcome biocompatibility problems, protein‐based coatings and oxygen‐plasma treatments are performed to enable growth of adherent living cells on those modified surfaces. For our studies, the polymer material is spun or casted onto glass substrates under an inert nitrogen atmosphere. The toxic solvents are removed by thermal treatment with subsequent application of the coating or functionalizing materials. Cell‐growth studies and adhesion experiments on the modified P3HT thin‐film layers are carried out with mouse fibroblasts. This work demonstrates the biocompatibility and biofunctionalization of an active semiconducting organic polymer, hence opening new possibilities in the realization of biomedical test systems based on organic biosensors in life sciences.

     

Corrosion resistance and durability of superhydrophobic surface formed on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution

The corrosion resistant performance and durability of the superhydrophobic surface on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution were investigated using electrochemical and contact angle measurements. The durability of the superhydrophobic surface in corrosive 5 wt% NaCl aqueous solution was elucidated. The corrosion resistant performance of the superhydrophobic surface formed on magnesium alloy was estimated by electrochemical impedance spectroscopy (EIS) measurements. The EIS measurements and appropriate equivalent circuit models revealed that the superhydrophobic surface considerably improved the corrosion resistant performance of magnesium alloy AZ31. American Society for Testing and Materials (ASTM) standard D 3359-02 cross cut tape test was performed to investigate the adhesion of the superhydrophobic film to the magnesium alloy surface. The corrosion formation mechanism of the superhydrophobic surface formed on the magnesium alloy was also proposed.     

Factors effecting film thickness in glass capillary chromatographic columns coated by the “Mercury Plug” method

Summary The Mercury Plug Dynamic (MPD) method, recently introduced for the coating of glass capillary columns, has several advantages over other methods. However, while general rules governing the film thickness in both the static and the conventional dynamic coating methods have been intensively studied, this in not the case for the MPD method. In this paper, the effect of several parameters determining the film thickness were studied. The volumetric method applied to measure the film thickness was found to be faster and more accurate than the chromatographic methods used by other authors. The effect of viscosity of the coating solution and the velocity of the plug were studied in detail and as a result it was found that the same type of equation as the one describing the film thickness in the dynamic method, was applicable also to the MPD technique. A model is suggested to explain this result.     

Solvent‐Dependent Structure Formation in Drying P3HT:PCBM Films Studied by Molecular Dynamics Simulations

Phase separation in the donor‐acceptor blend poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) during evaporation of a solvent using coarse‐grained molecular dynamics simulations is studied here. To this end, an equilibrated P3HT:PCBM:solvent mixture is placed in an elongated simulation box, after which solvent molecules are removed at regular time intervals from a region above the film. Three often‐used solvents are considered: chloroform (CFM), chlorobenzene (CLB), and orthodichlorobenzene (oDCB). The coarse‐grained solvent–solvent interaction parameters are tuned to reproduce the atmospheric boiling temperatures, while the PCBM–solvent interaction parameters are tuned to reproduce the PCBM solubilities. Other parameters are taken from the literature. During evaporation, the formation of a crust that is depleted of solvent, in which aggregation of P3HT and PCBM occurs, is observed. In agreement with experiment, the top region of the dry film is rich in PCBM for the cases of CLB and oDCB, and rich in P3HT for the case of CFM, while the very top layer of the film is always rich in P3HT. This vertical separation is ascribed to a competition between the tendency of P3HT to move to the surface due to its low surface energy and the different tendencies of PCBM to be dragged along to the surface by the evaporating solvent depending on its solubility. Also in agreement with experiment, the P3HT–PCBM interface area is larger for CLB and oDCB than for CFM. For CLB and oDCB, an indication for a spinodal P3HT–PCBM decomposition starting from the top and bottom surface is found, whereas for CFM the phase separation appears to be initiated in the bulk of the film.

     

Kinetic Effects on Self‐Assembly and Function of Protein–Polymer Bioconjugates in Thin Films Prepared by Flow Coating

The self‐assembly of nanostructured globular protein arrays in thin films is demonstrated using protein–polymer block copolymers based on a model protein mCherry and the polymer poly(oligoethylene glycol acrylate) (POEGA). Conjugates are flow coated into thin films on a poly(ethylene oxide) grafted Si surface, forming self‐assembled cylindrical nanostructures with POEGA domains selectively segregating to the air–film interface. Long‐range order and preferential arrangement of parallel cylinders templated by selective surfaces are demonstrated by controlling relative humidity. Long‐range order increases with coating speed when the film thicknesses are kept constant, due to reduced nucleation per unit area of drying film. Fluorescence emission spectra of mCherry in films prepared at <25% relative humidity shows a small shift suggesting that proteins are more perturbed at low humidity than high humidity or the solution state.

     

Thermal and Photochemical Control of Molecular Orientation of Azo‐Functionalized Polymer Liquid Crystals and Application for Photo‐Rewritable Paper

A photo‐responsive multi‐bilayered film consisting of azobenzene polymer liquid crystals (PA6Az1) and poly(vinyl alcohol) (PVA) has been prepared on a glass substrate by alternate spin coating of the polymer solutions. The reflectivity of the multi‐bilayered film disappears by annealing at 80 °C. The disappearance of the reflection by the annealing is related to the thermal out‐of‐plane molecular orientation of PA6Az1 even in the multi‐bilayered film, which leads to a very small difference in refractive indices between PA6Az1 and PVA. The reflectance of the multi‐bilayered film is increased again by UV irradiation because of the transformation from the out‐of‐plane orientation to an in‐plane random orientation. In this way, on–off switching of the reflection is achieved by combination of the thermally spontaneous out‐of‐plane molecular orientation and following photoisomerization of PA6Az1 comprising the multi‐bilayered film.

     

Tribo-corrosion behavior of Zn-Ni-Cu and Zn-Ni-Cu-TiB2 coated mild steel

In this investigation , Zn-Ni-Cu and Zn-Ni-Cu-TiB₂ were coated on a mild steel specimen using a high velocity oxy fuel thermal spray (HVOF) process. The surface morphology and coated powder distribution of coated specimens were characterized using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and X-ray-Elemental mapping. The pin-on-disc (ASTM G99-17) method was used to examine the wear resistance of the coated and uncoated mild steel specimens. Both coated Zn-Ni-Cu and Zn-Ni-Cu-TiB2 on mild steel saw reduced wear volume loss than uncoated mild steel. The coated samples of Zn-Ni-Cu and Zn-Ni-Cu-TiB2 on Mild Steel were put through a scratch test to determine the adhesion strength of the coating with the substrate. The adhesion strength of coated Zn-Ni-Cu and Zn-Ni-Cu TiB2 mild steel was higher than that of untreated mild steel, indicating a solid link between the coating and substrate and minimal delamination. Using the Vickers hardness test to measure the hardness caused by the coating, it was shown that coated samples of Zn-Ni-Cu and Zn-Ni-Cu-TiB2 coated mild steel had significantly higher hardness than uncoated mild steel. Using ASTM G1-03 and ASTM G-31 standards, a 0.2 M HCl immersion cycle test was conducted for 28 days to test the corrosion resistance of coatings in an acidic media (672Hrs). When compared to Zn-Ni-Cu and Zn-Ni-Cu-TiB2 coated mild steel, the weight loss for the uncoated mild steel was significantly larger. Additionally, XRD examination showed that coated samples had less rust on their surface than uncoated samples. Both Zn-Ni-Cu and Zn-Ni-Cu-TiB2 on Mild Steel were anti-corrosive, as evidenced by increased corrosion potential and reduced corrosion current density when compared to uncoated mild steel, according to electrochemical impedance spectroscopy (EIS)/Tafel study in 0.2 MHCl. The outcomes of each test were very encouraging and demonstrated the durability of these coatings against wear and corrosion.     

Thermoresponsive Poly(N‐isopropylacrylamide)‐Based Block Copolymer Coating for Optimizing Cell Sheet Fabrication

Thermoresponsive surfaces are prepared via a spin‐coating method with a block copolymer consisting of poly(N‐isopropylacrylamide) (PIPAAm) and poly(butyl methacrylate) (PBMA) on polystyrene surfaces. The PBMA block suppresses the removal of deposited PIPAAm‐based polymers from the surface. The polymer coating affects the temperature‐dependent cellular behavior of the surfaces with respect to protein adsorption. By adjusting layer thicknesses, PBMA‐b‐PIPAAm‐coated surfaces are optimized to regulate the adhesion/detachment of cells by temperature changes. Thus, thermoresponsive polymer‐coated surfaces are able to harvest contiguous cell sheets with their basal extracellular matrix proteins.

     

Corrosion processes below organic coatings

The protective mechanisms of paint systems of a 1-pack polyurethane- and an epoxy/2-pack polyurethane-coating system with zinc dust priming coats were investigated on blast-cleaned and on hand-cleaned steel substrates. The coated panels were exposed to the salt spray test and to a cyclic alternating test (VDA 621-415). The protective effect was assessed in determining adhesion, undermining at scratches, water uptake and the corrosion potential. On blast cleaned steel substrates the adhesion of the investigated coating systems was not influenced by water uptake of the coatings. Scratches are especially cathodically protected. On hand-cleaned steel surfaces the rust layer between steel substrate and coating can participate in the corrosion process with rust reduction as cathodic partial reaction. The change of rust morphology is the reason for the loss of adhesion of coating. At scratches rust reduction takes also place at the edge of the defect which is independent from pigments of the base coating.     

Adhesion of Human U937 Monocytes to Nitrogen‐Rich Organic Thin Films: Novel Insights into the Mechanism of Cellular Adhesion

We present a two‐fold study designed to elucidate the adhesion mechanism of human U937 monocytes on novel N‐rich thin films deposited by plasma‐ and VUV photo‐polymerisation, so‐called “PVP:N” materials. It is shown that there exist sharply‐defined (“critical”) surface‐chemical conditions that are necessary to induce cell adhesion. By comparing the film chemistries at the “critical” conditions, we demonstrate the dominant role of primary amines in the cell adhesion mechanism. Quantitative real‐time RT‐PCR experiments using U937 cells that had adhered to PVP:N materials for up to 24 h are presented. The adhesion induces a transient expression of cytokines, markers of macrophage activation, as well as a more sustained expression of PPARγ and ICAM‐I.

     

Surface Hydrophilicities and Enzymatic Hydrolyzability of Biodegradable Polyesters, 2

Control of the surface hydrophilicities and enzymatic hydrolyzability of hydrophobic aliphatic polyesters such as poly(ε‐caprolactone) (PCL) and poly(L ‐lactide) [i.e. poly(L ‐lactic acid) (PLLA)] was attempted by coating with hydrophilic poly(vinyl alcohol) (PVA). The PVA coating was carried out by immersion of the PCL and PLLA films in PVA solutions. The effects of PVA coating on the hydrophilicities were monitored by dynamic contact angle measurements, while the enzymatic hydrolyzability of the PVA‐coated PCL and PLLA films was evaluated by the weight losses after Rhizopus arrhizus lipase‐ and proteinase K‐catalyzed hydrolysis, respectively. It was found that the PVA coating successfully enhanced the hydrophilicities of the aliphatic polyester films and significantly suppressed enzymatic hydrolyzability of the aliphatic polyester films, excluding the PCL film coated at a very low concentration such as 0.01 g · dL^?1 and the crystallized PLLA film coated at 1 g · dL^?1, for which slight enhancement and no significant enhancement, respectively, were observed in the enzymatic hydrolyzability. Moreover, the hydrophilicities and enzymatic hydrolyzability of the aliphatic polyester films were controllable to some extent by varying the PVA solution concentration and the film crystallinity.

Advancing contact angle (θ_a) of PCL, PLLA‐C, and PLLA‐A films before and after the PVA coating by immersion in 1 g · dL^?1 solution.     

Direct Adhesion of Endothelial Cells to Bioinspired Poly(dopamine) Coating Through Endogenous Fibronectin and Integrin α5β1

Mussel‐inspired poly(dopamine) (PDA) coating is proven to be a simple, versatile, and effective strategy to promote cell adhesion onto various substrates. In this study, the initial adhesive behavior of human umbilical vein endothelial cells (HUVECs) is evaluated on a PDA coating under serum‐free conditions. It is found that HUVECs can attach directly to and spread with well‐organized cytoskeleton and fibrillar adhesions on the PDA surface, whereas cells adhere poorly to and barely spread on the control polycaprolactone surface. Endogenous fibronectin and α₅β₁ integrin are found to be involved in the cell adhesion process. These findings will lead to a better understanding of interactions between cells and PDA coating, paving the way for the further development of PDA.

     

Effects of Grafting Density and Film Thickness on the Adhesion of Staphylococcus epidermidis to Poly(2‐hydroxy ethyl methacrylate) and Poly(poly(ethylene glycol)methacrylate) Brushes

Thin polymer films that prevent the adhesion of bacteria are of interest as coatings for the development of infection‐resistant biomaterials. This study investigates the influence of grafting density and film thickness on the adhesion of Staphylococcus epidermidis to poly(poly(ethylene glycol)methacrylate) (PPEGMA) and poly(2‐hydroxyethyl methacrylate) (PHEMA) brushes prepared via surface‐initiated atom transfer radical polymerization (SI‐ATRP). These brushes are compared with poly(ethylene glycol) (PEG) brushes, which are obtained by grafting PEG onto an epoxide‐modified substrate. Except for very low grafting densities (ρ = 1%), crystal violet staining experiments show that the PHEMA and PPEGMA brushes are equally effective as the PEG‐modified surfaces in preventing S. epidermis adhesion and do not reveal any significant variations as a function of film thickness or grafting density. These results indicate that brushes generated by SI‐ATRP are an attractive alternative to grafted‐onto PEG films for the preparation of surface coatings that resist bacterial adhesion.