Resonance Raman and surface-enhanced resonance Raman studies of polymer-modified electrodes which mimic heme enzymes

Iron-5,10,15,20-tetraphenylporphyrin (FeTPP) has been incorporated into films of a coordinating hydrogel polymer support medium, poly(gamma-ethyl-L-glutamate) (PEG) functionalised with imidazole pendant arms (PEG-Im), and studied in situ on silver electrodes using a combination of both resonance Raman (RR) and surface-enhanced resonance Raman (SERR) spectroscopy. The SERR spectra give information on the portion of the film close to the electrode surface while RR spectra probe the

Synthesis of spherical ultra-high-surface-area monodisperse amphipathic polymer sponges in the low-micrometer size range

Spherical, ultra-high specific surface area monodisperse polymer particles with diameters in the low micrometer size range are disclosed for the first time. The polymer particles are able to sorb significant levels of both hydrocarbon solvents and water, acting in effect as amphipathic micro-sponges. Exciting possibilities for exploitation of the particles in chromatography, diagnostics, sensors, delivery vehicles and catalysis are suggested.

Strengthening timber beams with near surface mounted carbon fiber reinforced polymer rods

Many timber structures may require strengthening due to either decay and aging or an increase of load. This paper presents an experimental study in which eleven timber beams were tested, including three unstrengthened reference beams and eight beams strengthened with NSM CFRP bars. The test parameters include the position of NSM (tensile face or the bottom of the sides), the number of CFRP bars (1 or 2), and additional anchorage of NSM CFRP bars (steel wire U anchors or CFRP U strips). The test results show that the ultimate flexural strength of the timber beams were increased by 14%∼85% with an average of 47% due to NSM CFRP bar strengthening. Their deflection corresponding to the peak load was increased by 33% in average.

Surface patterns induced by laser irradiation on thin polymer bilayer films

We report on the preparation of wavelike surface patterns with characteristic wavelengths on thin bilayers of poly(methyl methacrylate) on azobenzene liquid crystalline polymer films (LCP/PMMA) by irradiation of a single polarized pulsed laser beam. The formation of such patterns was influenced by the thickness of the upper layer and the laser fluence. We were also able to guide the wavelike pattern to have a specific orientation by placing an elastic polydimethylsiloxane (PDMS) mold on the surface of bilayer film prior to laser irradiation. Moreover, the property of the laser irradiation, that is, the selectivity through mask-projection systems, allowed us fabricating complicated micropattems for novel microdevices. (c) 2007 Elsevier B.V. All rights reserved.

Objective surface evaluation of fiber reinforced polymer composites

The mechanical properties of advanced composites are essential for their structural performance, but the surface finish on exterior composite panels is of critical importance for customer satisfaction. This paper describes the application of wavelet texture analysis (WTA) to the task of automatically classifying the surface finish properties of two fiber reinforced polymer (FRP) composite construction types (clear resin and gel-coat) into three quality grades. Samples were imaged and wavelet multi-scale decomposition was used to create a visual texture representation of the sample, capturing image features at different scales and orientations. Principal components analysis was used to reduce the dimensionality of the texture feature vector, permitting successful classification of the samples using only the first principal component. This work extends and further validates the feasibility of this approach as the basis for automated non-contact classification of composite surface finish using image analysis.

Water-soluble complexes of hydrophobically modified polymer and surface active imidazolium-based ionic liquids for enhancing oil recovery

The current study introduces the water-soluble complexes containing hydrophobically associating copolymer and a series of surface activity imidazolium-based ionic liquids (CnmimBr, n=6, 8, 10, 12, 14 and 16). The polymer, denoted as PAAD, was prepared with acrylamide (AM), acrylic acid (AA) and N,N-diallyl-2-dodecylbenzenesulfonamide (DBDAP). And the hydrophobic associative behavior of PAAD was studied by a combination of the pyrene fluorescence probe and viscosimetry. Incorporation of CnmimBr (n=10, 12, 14 and 16) in PAAD leaded to the white thick gel, while the pellucid solutions were obtained in complexes of PAAD and CnmimBr (n=6 and 8); addition of C6mimBr around critical micelle concentration resulted in a large decrease in viscosity of solution. Therefore, we particularly investigated the performance of PAAD/C8mimBr complex. The interfacial tension of PAAD/C8mimBr complex solution and crude oil under different conditions was examined. Moreover, PAAD/C8mimBr complex exhibited superior temperature resistance and shear reversible performance for enhancing oil recovery (EOR) by rheological test. The promising EOR of 21.65% can be obtained by PAAD/C8mimBr complex showing high potential to utilize this kind of new complex in EOR processes.

Surface characterization of absorbing polymer films deposited on transparent glasses

PANI films were deposited on glass substrates by in-situ polymerization and characterized by UV-VIS spectroscopy and atomic force microscopy. A method is developed to accurately analyze ellipsometric data obtained for transparent glass substrates before and after modification with absorbing polymer films. Surface modification was made with an overlayer such as polyaniline ( PANI), which exhibits different optical properties by varying its oxidation state. First, the issue of using transparent substrates for ellipsometry studies was examined and then, spectroscopic ellipsometry was used to characterize absorbing overlayers on transparent glasses. The same methodologies of data analysis can be also applied to other absorbing films on transparent substrates, and deposited by different techniques.

Antimicrobial activity and surface properties of an acrylic resin containing a biocide polymer

Objective: To evaluate the antimicrobial activity and surface properties of an acrylic resin containing the biocide polymer poly (2-tert-butylaminoethyl) methacrylate (PTBAEMA). Background: Several approaches have been proposed to prevent oral infections, including the incorporation of antimicrobial agents to acrylic resins. Materials and methods: Specimens of an acrylic resin (Lucitone 550) were divided into two groups: 0% (control) and 10% PTBAEMA. Antimicrobial activity was assessed by adherence assay of one of the microorganisms, Staphylococcus aureus, Streptococcus mutans and Candida albicans. Surface topography was characterised by atomic force microscopy and wettability properties determined by contact angle measurements. Results: Data of viable cells (log (CFU + 1)/ml) for S. aureus (control: 7.9 ± 0.8; 10%: 3.8 ± 3.3) and S. mutans (control: 7.5 ± 0.7; 10%: 5.1 ± 2.7) showed a significant decrease with 10% of PTBAEMA (Mann-Whitney, p < 0.05). For C. albicans (control: 6.6 ± 0.2; 10%: 6.6 ± 0.4), there was no significant difference between control and 10% of PTBAEMA (Kruskal-Wallis, p > 0.05). Incorporating 10% PTBAEMA increased surface roughness and decreased contact angles. Conclusion: Incorporating 10% PTBAEMA into acrylic resins increases wettability and roughness of acrylic resin surface; and decreases the adhesion of S. mutans and S. aureus on acrylic surface, but did not exhibit antimicrobial effect against C. albicans. © 2012 The Gerodontology Society and John Wiley & Sons A/S.

Surface properties and color stability of an acrylic resin combined with an antimicrobial polymer

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Enhanced Polymer Grafting from Multiwalled Carbon Nanotubes through Living Anionic Surface-Initiated Polymerization

Anionic surface-initiated polymerization of ethylene oxide and styrene has been performed using multiwalled carbon nanotubes (MWNTs) functionalized with anionic initiators. The surface of MWNTs was modified via covalent attachment of precursor anions such as 4-hydroxyethyl benzocyclobutene (BCBEO) and 1-benzocyclobutene-1′-phenylethylene (BCB-PE) through Diels-Alder cycloaddition at 235 °C. Surface-functionalized MWNTs-g-(BCB-EO) n and MWNTs-g-(BCB-PE) n with 23 and 54 wt % precursor initiators, respectively, were used for the polymerizations. Alkoxide anion on the surface of MWNTs-g-(BCB-EO) n was generated through reaction with potassium triphenylmethane for the polymerization of ethylene oxide in tetrahydrofuran and phenyl substituted alkyllithium was generated from the surface of MWNTs-g-(BCB-PE) n using sec-butyllithium for the polymerization of styrene in benzene. In both cases, the initiation was found to be very slow because of the heterogeneous reaction medium. However, the MWNTs gradually dispersed in the reaction medium during the polymerization. A pale green color was noticed in the case of ethylene oxide polymerization and the color of initiator as well as the propagating anions was not discernible visually in styrene polymerization. Polymer grafted nanocomposites, MWNTs-g-(BCB-PEO) n and MWNTs-g-(BCB-PS) n containing a very high percentage of hairy polymer with a small fraction of MWNTs (<1 wt %) were obtained. The conversion of ethylene oxide and the weight percent of PEO on the surface of the MWNTs increased with increasing reaction time indicating a controlled polymerization. The polymer-grafted MWNTs were characterized using FTIR, 1H NMR, Raman spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy (TEM). Size exclusion chromatography of the polymer grafted MWNTs revealed broad molecular weight distributions (1.3 < Mw/Mn < 1.8) indicating the presence of different sizes of polymer nanocomposites. The TEM images showed the presence of thick layers of polymer up to 30 nm around the MWNTs. The living nature of the growing polystyryllithium was used to produce diblock copolymer grafts using sequential polymerization of isoprene on the surface of MWNTs.

Surface layer formation in polymer melts and in solutions

In this work the surface layer formation in polymer melts and in polymer solutions have been investigated with the atomic force microscope (AFM). In polymer melts, the formation of an immobile surface layer results in a steric repulsion, which can be measured by the AFM. From former work it is know, that polydimethyl siloxane (PDMS) forms a stable surface layer for molecular weights above 12 kDa. In the present thesis, polyisoprene (PI) was investigated apart from PDMS, by a)measuring the steric surface interactions and b)measuring the surface slip in hydrodynamic experiments. If a polymer flows over a surface, the flow velocity at the surface is larger then zero. If case of a surface layer formation the flow plane changes to the top of the adsorbed layer and the surface slip is reduced to zero. By measuring the surface slip in hydrodynamic experiments, it is therefore possible to determine the presence of a stable surface layer. The results show no stable repulsion for PI and only a small decrease of the surface slip. This indicates that PI does not form a stable surface layer, but is only adsorbed weakly to the surface. Furthermore for 8 kDa PDMS the timescale of the formation of a surface layer was investigated by changing themaximal force the tip applied to the surface. With a repulsive force present, applying a higher force than 15 nN resulted in a destruction of the surface layer, indicated by attractive forces. Reducing the applied force below 15 nN then resulted in an increase of the repulsion to the former state during one minute, thus indicating that a surface layer can be formed within one minute even under the influence of continuous measurements. As a next step, mixtures of two PDMS homopolymers with different chain lengths have been investigated. The aim was to verify theoretical predictions that shorter chains should predominate at the surface due to their smaller loss in conformational entropy. The measurements where done in dependence of the volume fractions of short and long chain PMDS. The results confirmed the short chain dominance for all mixtures with less then 90 vol.% long chain PDMS. Surface layer formation in solution was investigated for superplasticizers which are industrially used as an additive to cement. They change the surface interaction between the cement grains from attractive to repulsive and the freshlymixed cement paste therefore becomes liquid. The aimin this part of the thesis was, to investigate cement particle interactions in a close to real environment. Therefore calcium silicate hydrate phases have been precipitated onto an AFM tip and onto a calcite crystal and the interaction between these surfaces have beenmeasured with and without addition of superplasticizers. The measurements confirmed the change from attraction to repulsion upon addition of superplasticizers. The repulsive steric interaction increased with the length of the sidechain of the superplasticizer, and the dependence of the range of the steric interactions on the sidechain length indicated that the sidechains are in a coiled conformation.

The role of the interplay between polymer architecture and bacterial surface properties on the microbial adhesion to polyoxazoline-based ultrathin films

Surface platforms were engineered from poly(L-lysine)-graft-poly(2-methyl-2-oxazoline) (PLL-g-PMOXA) copolymers to study the mechanisms involved in the non-specific adhesion of Escherichia coli (E. coli) bacteria. Copolymers with three different grafting densities (PMOXA chains/Lysine residue of 0.09, 0.33 and 0.56) were synthesized and assembled on niobia (Nb O ) surfaces. PLL-modified and bare niobia surfaces served as controls. To evaluate the impact of fimbriae expression on the bacterial adhesion, the surfaces were exposed to genetically engineered E. coli strains either lacking, or constitutively expressing type 1 fimbriae. The bacterial adhesion was strongly influenced by the presence of bacterial fimbriae. Non-fimbriated bacteria behaved like hard, charged particles whose adhesion was dependent on surface charge and ionic strength of the media. In contrast, bacteria expressing type 1 fimbriae adhered to the substrates independent of surface charge and ionic strength, and adhesion was mediated by non-specific van der Waals and hydrophobic interactions of the proteins at the fimbrial tip. Adsorbed polymer mass, average surface density of the PMOXA chains, and thickness of the copolymer films were quantified by optical waveguide lightmode spectroscopy (OWLS) and variable-angle spectroscopic ellipsometry (VASE), whereas the lateral homogeneity was probed by time-of-flight secondary ion mass spectrometry (ToF-SIMS). Streaming current measurements provided information on the charge formation of the polymer-coated and the bare niobia surfaces. The adhesion of both bacterial strains could be efficiently inhibited by the copolymer film only with a grafting density of 0.33 characterized by the highest PMOXA chain surface density and a surface potential close to zero.

Analytical Parametric Model Used to Study the Influence of Electrostatic Force on Surface Coverage During Electrospinning of Polymer Fibers

Electrospinning (ES) can readily produce polymer fibers with cross-sectional dimensions ranging from tens of nanometers to tens of microns. Qualitative estimates of surface area coverage are rather intuitive. However, quantitative analytical and numerical methods for predicting surface coverage during ES have not been covered in sufficient depth to be applied in the design of novel materials, surfaces, and devices from ES fibers. This article presents a modeling approach to ES surface coverage where an analytical model is derived for use in quantitative prediction of surface coverage of ES fibers. The analytical model is used to predict the diameter of circular deposition areas of constant field strength and constant electrostatic force. Experimental results of polyvinyl alcohol fibers are reported and compared to numerical models to supplement the analytical model derived. The analytical model provides scientists and engineers a method for estimating surface area coverage. Both applied voltage and capillary-to-collection-plate separation are treated as independent variables for the analysis. The electric field produced by the ES process was modeled using COMSOL Multiphysics software to determine a correlation between the applied field strength and the size of the deposition area of the ES fibers. MATLAB scripts were utilized to combine the numerical COMSOL results with derived analytical equations. Experimental results reinforce the parametric trends produced via modeling and lend credibility to the use of modeling techniques for the qualitative prediction of surface area coverage from ES. (Copyright: 2014 American Vacuum Society.)