Simultaneous tailoring of surface topography and chemical structure for controlled wettability

Wettability was controlled in a rational manner by individually and simultaneously manipulating surface topography and surface chemical structure. The first stage of this research involved the adsorption of charged submicrometer polystyrene latex particles to oppositely charged poly(ethylene terephthalate) (PET) film samples to form surfaces with different topographies/roughness; adsorption time, solution pH, solution ionic strength, latex particle size, and substrate charge density are external variables that were controlled. The introduction of discrete functional groups to smooth and rough surfaces through organic transformations was carried out in the second stage. Amine groups (-NH(2)) and alcohol groups (-OH) were introduced onto smooth PET surfaces by amidation with poly(allylamine) and adsorption with poly(vinyl alcohol) (PVOH), respectively. On latex particle adsorbed surfaces, a thin layer of gold was evaporated first to prevent particle redistribution before chemical transformation. Reactions with functionalized thiols and adsorption with PVOH on patterned gold surfaces successfully enhanced surface hydrophobicity and hydrophilicity. Particle size and biomodal particle size distribution affect both hydrophobicity and hydrophilicity. A very hydrophobic surface exhibiting water contact angles of 150 degrees /126 degrees (theta(A)/theta(R)) prepared by adsorption of 1-octadecanethiol and a hydrophilic surface with water contact angles of 18 degrees /8 degrees (theta(A)/theta(R)) prepared by adsorption of PVOH were prepared on gold-coated surfaces containing both 0.35 and 0.1 microm latex particles. The combination of surface topography and surface-chemical functionality permits wettability control over a wide range.     

The tetragonal structure of nanocrystals in rare-earth doped oxyfluoride glass ceramics

Rare-earth doped oxyfluoride glasses and nanocrystalline glass ceramics have been prepared and studied by energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) aiming at investigating the structure and the symmetry of the nanocrystal as well as the site of the rare-earth ion. To solve the problem encountered by previous researchers due to glass host interference, we etched off glass matrix and released the fluoride nanocrystal, which is more convenient for EDS measurement. A tetragonal phase model with the chemical formula as PbREF(5) proved by quantitative EDS and XRD analyses has been proposed in this paper for the first time. Two specific crystalline phases with the same space group have been observed at 460 °C-500 °C and 520 °C-560 °C, respectively. Moreover, a super "pseudo-cubic" cell based on our tetragonal model may give a good explanation to the probable previous cubic-symmetry misunderstanding by researchers. Additionally, the thermodynamic mechanism of phase transition and the thermal stability related to the structure of nanocrystals in glass ceramics have been studied and supported by ab initio calculations and experimental methods. The structure and thermal stability of the nanocrystal and clear environment of the rare-earth ion reported here have far-reaching significance with respect to the optical investigations and further applications of rare-earth doped oxyfluoride glass ceramics.     

Fucoidan: structure and bioactivity

Fucoidan refers to a type of polysaccharide which contains substantial percentages of L-fucose and sulfate ester groups, mainly derived from brown seaweed. For the past decade fucoidan has been extensively studied due to its numerous interesting biological activities. Recently the search for new drugs has raised interest in fucoidans. In the past few years, several fucoidans' structures have been solved, and many aspects of their biological activity have been elucidated. This review summarizes the research progress on the structure and bioactivity of fucoidan and the relationships between structure and bioactivity.     

Characterisation of roof tile coating degradation using nano-indentation test and surface profilometry

Nano-science and nano-technology have been extensively explored to develop functional and smart coating systems. In this context, it is important to investigate novel characterisation methodologies for surface feature measurement and evaluation of diverse coating systems at nano and micrometrical scales which cannot be implemented by conventional tests. In this study, nano-indentation test have been carried out to characterise the environmental degradation of a polymer coating on a building material substrate. Multiple locations were selected for nano-indention for analysis and evaluation. It has shown that the coating weathering led to a reduction in deformation depth and an increase of hardness and modulus. Furthermore, the weathering resulted in surface quality degradation, which was characterised by hugely reduced surface homogeneity in terms of standard deviations in deformation, hardness and modulus. The coating degradations were also characterised by surface roughness measurement by profilometry. There were significant differences in surface roughness at the micrometrical scale for coatings with varying environmental degradations. They were quantified in terms of surface roughness statistics. The micro morphologies of the coating were observed by SEM which showed a good agreement with results from nano-indentation test and surface roughness measurement. This study demonstrates that nano-indentation test and surface roughness measurement are viable methodologies to evaluate specialised polymer coating systems and to characterise their degradations at the nano and micrometrical scales.     

A topography/chemical composition gradient polystyrene surface: toward the investigation of the relationship between surface wettability and surface structure and chemical composition

In this paper, we have prepared of a topography/chemical composition gradient polystyrene (PS) surface, i.e., an orthogonal gradient surface, to investigate the relationship between surface wettability and surface structure and chemical composition. The prepared surface shows a one-dimensional gradient in wettability in the x, y, and diagonal directions, including hydrophobic to hydrophilic, superhydrophobic to hydrophobic, superhydrophobic to superhydrophilic gradients, and so forth. These one-dimensional gradients have different gradient values, gradient range, and contact angle hysteresis, which lie on both the surface roughness and the surface compositions. From the trend of variation of contact angle hysteresis, it can be concluded that the transition from the Cassie's model to the Wenzel's model occurs both by decreasing surface roughness and by increasing surface hydrophilic compositions. Moreover, the transition is more effective via changing surface chemical composition than changing surface roughness herein.     

Characterisation of raw materials for production of ceramics

The aim of this paper is to characterize some raw materials used for ceramics material production. Five samples of clay have been analyzed. It has been carried out a patterned sampling in a quarry in Rosarno (South Italy). Chemical-physical properties on clay samples are determined. Test pieces have been prepared and physical properties after firing are determined by DSC thermal analysis, XRD analysis and X-ray fluorescence. It is important to note the high amount of Fe₂O₃. The mixture principally contains quartz, illite and oligoclase. It has been observed the colour and the shape after firing: predominant colour is red. In this case the clay has been used in mixtures covered with glazes. The colour of internal clay is hidden by opaque of glazes. The analysed raw materials can be used in a slip for single fired red tiles. The A2sp clay produces best ceramics at 1000°C.     

Effect of the topography of silver films on the structure of surface ensembles of 11-mercaptoundecanol

The effect of the topography of the silver surface on the formation of self-assembling monolayers of 11-mercaptoundecanol was examined. The metal surface was modified by nitric acid in the presence of hydrogen peroxide (deep etching (DE)) or aqueous malononitrile (chemical polishing (PE)). The adsorption properties of the monolayers differ significantly for the DE and PE surfaces and are a function of the ratio of functional hydroxyl groups available for reaction with analyte and hydrophobic segments of the hydrocarbon chain of the molecule. A correlation between the amount of adsorption and the analyte acidity was demonstrated. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 2, pp. 98-103, March-April, 2009.     

Influence of the surface topography on the surface transitions in nematics

Abstract

In quasi-homeotropic oriented liquid crystal cells, obtained by oblique SiO deposition on glass and surfactant added to the nematic, a continuous tilt angle versus temperature change followed by an abrupt surface transition was observed. At room temperature, the sign of the tilt angle measured from the normal to the surface depends on the SiO deposition angle. A model for the temperature dependence of the tilt angle is proposed.     

Investigation of surface topography, morphology and structure of amorphous carbon films by AFM and TEM

Morphology and structure of amorphous carbon films deposited with a pulsed arc source (LASER-ARC) have been studied using microscopical methods (SEM, TEM and AFM), electron diffraction and spectroscopical investigation (EELS). The parameters of the arc source and the deposition conditions (substrate temperature) influence morphology and structure of deposited amorphous carbon films. Especially the incorporation and growth of particles, embedded in the film have been investigated. By particle analysis using an optical microscope a majority of particles that is smaller than 500 nm has been determined. The morphology has been also demonstrated similar by AFM and TEM images. Their number and size of particles is strongly influenced by the deposition temperature. The structure of amorphous film is characterized by the EELS-spectra, but the particle structure was not detectable.     

Characterization of the surface structure of gold nanoparticles and nanorods using structure sensitive reactions

The surface structure of gold nanorods has been determined by studying the behavior of electrochemical reactions sensitive to the structure and compared to that obtained by other structure characterization techniques. Lead underpotential deposition (UPD) reveals that the surface of the nanorods is composed by (111) and (110) domains, while (100) domains are practically absent from the surface. In the case of the oxygen reduction reaction, the formation of hydrogen peroxide as a final product of the reaction in the whole potential range also indicates that (100) domains are absent on the surface of the nanoparticles, corroborating the previous result. These results are compared with other surface structure information provided by other techniques.     

Structural study of ternary iron-lead-germanate glass ceramics

Glass ceramics with the composition xFe(2)O(3)·(100-x)[7GeO(2)·3PbO(2)] where 0≤x≤60 mol% were obtained and studied using XRD, FTIR and UV-vis spectroscopy investigations. Heat treatment of glass samples at 400°C for 8 h led to the formation of α, γ-PbGe(4)O(9), Pb(3)Fe(2)Ge(4)O(14) and PbO(1.44) crystalline phases. The content of these crystalline phases depends of Fe(2)O(3) concentration. FTIR spectroscopy data suggest that the lead ions have a pronounced affinity towards [GeO(5)] structural units containing non-bridging oxygens and [FeO(4)] anions producing formation of the Pb(3)Fe(2)Ge(4)O(14) crystalline phase. The introduction of low concentrations of Fe(2)O(3) into the host matrix results in the formation of new absorption UV bands between 320 and 450 nm. These bands arise from to the d-d transitions of the Fe(+3) ions. The light absorption in the range from 250 to 600 nm increases with increasing iron oxide content in matrix network, accompanied with the changes on color from white to brown yellow and darker brown.     

Simulating surface diffusion and surface growth in ceramics

We examine the movement of ion pairs on the surfaces of simple oxides. Using temperature-accelerated dynamics the elementary processes involved are identified and the activation energies of these used as input to kinetic Monte Carlo simulations. Results are presented for the motion of BaO and SrO ion pairs on the (100) surfaces of BaO and SrO, respectively, and the formation of island pairs on these surfaces is studied. The simulations reveal the importance of exchange mechanisms in surface diffusion and growth of oxides. The importance of such reactions has been recognised previously for metallic surfaces but not for ionic systems, where it has been assumed that ionic surface diffusion is surface diffusion via the hopping motion of ion pairs from one surface site to another. Exchange mechanisms can dominate transport processes both on terraces and steps for both homoepitaxial and heteroepitaxial growth. We suggest the unavoidable mixing when an exchange mechanism operates must be considered when attempting to grow sharp interfaces in oxide nanostructures.     

Characterisation of the transparent surface coatings on post-Byzantine icons using microscopic, mass spectrometric and spectroscopic techniques

Icons are frequently covered with superimposed transparent layers of varnish and glaze that often obscure their image and disrupt their study and conservation treatment. Using a combination of microscopic, mass spectrometric and spectroscopic techniques, a micro-analytical methodology was developed for the characterisation of these surface coatings. More specifically, light microscopy (LM), electron ionisation direct temperature resolved mass spectrometry (EI-DTMS), pyrolysis gas chromatography mass spectrometry (Py-GC/MS), imaging Fourier transform infrared spectroscopy (imaging-FTIR) and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) were used to investigate the coatings present on the surface of five Greek post-Byzantine icons. The results showed that the aged layers of varnish and glaze contain various mixtures of materials, including diterpenoid (DTP) and triterpenoid (TTP) resins, linseed oil, lead-containing dryers, egg, and beeswax. This study also elucidated issues regarding the initial application and the later interventions on those coatings, their interaction with each other, as well as some effects observed on the underlying paint layers.     

Enhanced effects of nano-scale topography on the bioactivity and osteoblast behaviors of micron rough ZrO2 coatings

Implant surface topography is one of the most important factors affecting the rate and extent of osseointegration. Randomly micron-roughened surfaces have been documented to support osteoblast adhesion, differentiation, and mineralized phenotype, and thus favoring bone fixation of implants to host tissues. However, few studies have been done yet to investigate whether their effects on osteoblast behaviors can be enhanced by incorporation of nano-scale topographic cues. To validate this hypothesis, zirconia coatings with micron roughness (about 6.6 μm) superimposed by nano-sized grains (<50 nm) were fabricated by plasma spraying. To validate the impact of nano-sized grains, post-treatments of surface polishing (SP) and heat treatment (HT) were performed on the as-sprayed (AS) coatings to change the surface topographies but keep the chemical and phase composition similar. Results of in vitro bioactivity test showed that apatite was formed only on coating surfaces with nano-sized grains (AS coatings), indicating the significance of nano-topographic cues on the in vitro bioactivity. Enhanced osteoblast adhesion and higher cell proliferation rate were observed on coatings with both micron-roughness and nano-sized grains (AS-coatings), compared to coatings with smooth surfaces (SP-coatings) and coatings with only micron-scale roughness (heat-treated coatings), indicating the significant effects of nano-size grains on osteoblast responses. As the micron rough surfaces have been well-documented to enhance bone fixation, results of this work suggest that a combination of surface modifications at both micron and nano-scale is required for enhanced osseointegration of orthopedic implants.     

Adsorption and bioactivity studies of albumin onto hydroxyapatite surface

Bovine serum albumin (BSA) may have an inhibitory or promoter effect on hydroxyapatite (HA) nucleation when apatite is precipitated in a medium containing the protein. In this study we evaluated the influence of BSA on the precipitation of calcium phosphate phases (CP) from simulated body fluid (SBF) when the protein was previously bounded to HA surface. The kinetics of BSA immobilization onto hydroxyapatite surface was performed in different buffers and protein concentrations in order to adjust experimental conditions in which BSA was tightly linked to HA surface for long periods in SBF solution. It was shown that for BSA concentration higher than 0.1mg/mL the adsorption to HA surface followed Langmuir-Freundlich mechanisms, which confirmed the existence of cooperative protein-protein interactions on HA surface. Fourier Transformed Infrared Attenuated Total Reflectance Microscopy (FTIRM-ATR) evidenced changes in BSA conformational state in favor of less-ordered structure. Analyses from high resolution grazing incident X-ray diffraction using synchrotron radiation (GIXRD), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) showed that a poorly crystalline calcium phosphate was precipitated on the surface of HA discs coated with BSA, after the immersion in SBF for 4 days. The new bioactive layer had morphological characteristics similar to the one formed on the HA surface without protein. It was identified as a carbonated apatite with preferential crystal growth along apatite 002 direction. The GIXRD results also revealed that BSA layer bound to the surface inhibited the HA dissolution leading to a reduction on the formation of new calcium phosphate phase.     

Role of the interaction between forming nanocrystals and glass surface on the structure and properties of ZnO-based films

The interaction between glass surface and forming nanocrystals plays the important role in the formation of thin ZnO coatings crystal structure. The comparative study of the crystal structure of thin ZnO-based films and powders having similar chemical compositions was performed with the use of SEM, XRD analysis, optical, and luminescent spectroscopy. The influence of different coatings parameters (chemical composition, thickness) on the spectroscopic and morphological properties of thin films and powders reveals the structural features of the interaction between forming ZnO nanocrystals and glass surface. ZnO–SnO₂ coatings and powders were prepared by liquid polymer-salt technique. This method provides the close contact between the coatings’ precursors with a surface of the glass during both the nucleation and the initial growth stage of forming oxide crystals. The interaction of nanocrystals and substrate surface is responsible for the texture formation in the ZnO films and determines some features of their optical properties.     

Thermal and UV shape shifting of surface topography

The confinement of LCE materials into surface monodomains via micropatterning leads to the formation of reversible, shape-shifting surface patterns. The individual features are liquid crystalline monodomains, and by switching to an isotropic state using light or heat, the features switch between imprinted circular features and anisotropic liquid crystalline features.     

Effect of surface topography on the anodization of titanium

The influence of surface topography and electrolyte composition on the anodization of titanium was investigated. The growth of the anodic oxides layer and the impedance response of the electrode/electrolyte interface were studied by means of ac-voltammetry, and the surface topography before and after anodization was visualized by atomic force microscopy. It was observed that the final topographic features and the instability phenomenon during the anodization of titanium were dependent on the surface finishing and on the nature of the anions in the electrolyte. In particular, it appears that rougher surfaces lead to a more homogeneous anodic film, while polished ones form an irregular morphology. The presence of sulfates is enhancing the breakdown of the film.