Investigation of phase separation in multiblock copolymers consisting of polysulfone and a liquid crystalline polymer

Multiblock copolymers (MBCPs) consisting of polysulfone (PSU) segments and segments of the liquid crystalline poly(ethyleneterephthalate-co-oxybenzoate) (PET/HBA) form rather complex morphologies. Scanning electron microscopy (SEM), small-angle X-ray scattering (SAXS), and atomic force microscopy (AFM) investigations of two block copolymers with significantly different block molecular weights proved the existence of both macro-and microphase separation. These morphologies, existing on different length scales, were found to be superimposed in the samples. A suitable fractionation procedure was used to suppress macrophase separation. Then, it was found that microphase separation is controlled by the segment molecular weights.     

星形两嵌段共聚高分子薄膜微相分离的耗散粒子动力学模拟

利用耗散粒子动力学模拟研究了两类典型的星形两嵌段共聚高分子薄膜的微相分离行为. 结果表明,(A_x)₄(B_y)₄体系的相图较(A_xB_y)₄体系具有明显的对称性,且前者比后者更易发生相分离,与体相中的情况相近,并可归因于两类星形高分子在结构上的差异;组成相同的星形共聚高分子体系在体相与薄膜中所形成的介观结构之间存在对应关系;减小薄膜厚度与加大A-B组分间排斥强度均有利于增强所形成结构的有序性. 同样是缘于分子结构差异,两类星形高分 子薄膜中的均方回旋半径随体系组分分率的变化规律几乎相反.     

Mapping charge-mosaic surfaces in electrolyte solutions using surface charge microscopy

A significant limitation of electrokinetic measurements is that only an average value of the zeta potential/streaming potential is measured—regardless of whether the surface charge distribution is homogeneous or otherwise. However, in real-world situations, nearly all solids (and liquids) of technological significance exhibit surface heterogeneities. To detect heterogeneities in surface charge, analytical tools which provide accurate and spatially resolved information about material surface potential—particularly at microscopic and sub-microscopic resolutions—are needed.A novel AFM-based technique for mapping surface charge domains on heterogeneous surfaces, which we call Surface Charge Microscopy (SCM), was recently introduced by our research team. It relies on recording colloidal force curves over multiple locations on the substrate surface using small probes. The surface charge characteristics of the heterogeneous substrate are determined from the recorded colloidal force curves, allowing for the surface charge variation to be mapped. In this communication, we briefly review the SCM technique. Examples of results of measurements of the surface interaction forces that were recorded between a silicon nitride AFM cantilever and a multi-phase volcanic rock and heterogeneous surface of bitumen are also given.     

Step dynamics in relaxation of sharp corners on crystal surfaces

The dynamic behavior of steps involved in the relaxation of sharp corners in microfabricated structures on crystalline surfaces have been studied. We find that during the early stages of relaxation of slightly tapered trenches on Si(0 0 1), wide (1 1 0) terraces perpendicular to the substrate are formed near the corners of the trench sidewalls. The evolution of a step profile around the corner region, where step density abruptly changes, is analyzed using one-dimensional step models. It is found that, in case that mass transport occurs through surface diffusion, the preexisting steps on the trench sidewall are accumulated in the corner region, and extensive terraces are formed near the corners.     

Remnant grooves on alumina surfaces

Thermal grooving of grain boundaries in alumina has been studied using a combination of visible-light microscopy (VLM) and atomic-force microscopy (AFM). The partial angles of grooves that develop during heat treatments at 1650 °C were estimated by AFM. The observation of remnant grooves is key to determining the magnitude of the movement of a grain boundary. Imaging using VLM and AFM enabled the smoothing of remnant grooves to be observed through a progression of heat treatments, which enables the anisotropic nature of the surface diffusivity of alumina to be monitored.     

Roughness of pigment coatings and its influence on gloss

A robust method is used for analyzing roughness at a wide range of lateral length scales. The method is based on two-point correlation where both the amplitude and lateral spacing of surface heights are considered when determining the roughness. Atomic force microcopy and confocal optical microscopy images were captured for a set of pigment-coated samples. The effects of sampling interval, image size and filtering on surface roughness were studied. Isotropy and periodicity of roughness were determined by analyzing the angular distribution of the correlation length (T) and the autocorrelation function (ACF). A clear dependence of root mean square (RMS) roughness (σ) on T was established for randomly distributed surfaces. By taking into account the σ-T dependence it was possible to obtain σ for various length scales for each sample and thus attaining the most relevant σ for a certain surface function, which in this study was specular reflection of light (gloss). The roughness analysis showed that a small amount of DPP coating was sufficient to completely cover and change the surface of the substrate, while kaolin coatings gave a different response.     

Scaling properties of fracture surfaces on glass strengthened by ionic exchange

In this work the results of the statistical topometric analysis of fracture surfaces of soda-lime-silica glass with and without ionic exchange treatment are reported. In this case, the mechanism of substitution is K⁺-Na⁺. atomic force microscopy (AFM) was employed to record the topometric data from the fracture surface. The roughness exponent (ζ) and the correlation length (ξ) were calculated by the variable bandwidth method. The analysis for both glasses (subjected and non-subjected to ionic exchange) for ζ shows a value ∼0.8, this value agrees well with that reported in the literature for rapid crack propagation in a variety of materials. The correlation length shows different values for each condition. These results, along with those of microhardness indentations suggest that the self-affine correlation length is influenced by the complex interactions of the stress field of microcracks with that resulting from the collective behavior of the point defects introduced by the strengthening mechanism of ionic exchange.     

Measurements of metal-polymer adhesion properties with dynamic force spectroscopy

We investigate nanoscale interface properties using dynamic mode atomic force microscopy (AFM) operated in the frequency modulation mode in ultrahigh vacuum. The AFM tip was was functionalised by a thin layer of aluminium and the polymer was treated by plasma-etching. In the spectroscopy mode we could measure the adhesion properties between the metal and the polymer surfaces. We found that plasma-etching of the polymer resulted in strongly enhanced force interactions, indicating a chemical activation of the polymer surface. Values for the adhesion force and work of adhesion were measured on the nanometer scale and are compared to conventional macroscopic adhesion failure tests.     

Atomic force microscopy evidence for K domains on freshly cleaved mica

The unit cell height in the c-direction of muscovite mica is well established at 10 Å. However, we have observed steps much lower than this whilst imaging freshly cleaved mica surfaces in an atomic force microscope. The steps, 1.0±0.05 Å high, are unstable and disappear in a period of minutes after cleavage. We propose that they are due to the presence of domains of residual K⁺ ions that form two matching patchworks on the cleaved faces. Upon cleavage, they relax inwards from the bulk equilibrium position 1.6 Å above the oxygen atoms of the tetrahedral silicate. Possible mechanisms for the disappearance of the steps are discussed.     

A comparative study of surface energy data from atomic force microscopy and from contact angle goniometry

Forces of adhesion have been measured for interactions involving self-assembled monolayers or polymer-film structures that had each been deposited onto a gold-coated glass substrate and a probing, gold-coated cantilever. The data have been fitted into mathematical models that allow the calculation of surface energy by considering the work done for the separation of the identically coated contacting surfaces. These values of surface energy are in close agreement with those from corresponding contact angle determinations, highlighting the potential usefulness of the technique for the study of surfaces at a resolution level approaching 1000 atoms. Comparative studies show that the employment of the atomic force microscopy technique may be preferable for the study of samples that are susceptible to penetration by liquids or for investigations under conditions that exceed the useful limits of conventional probing techniques involving liquids.     

Oxidation and adhesion on the quasicrystalline AlPdMn surface studied by nanolithography

We present the novel application of a relatively new technique (nanolithography) to the study of quasicrystalline surface oxidation. The 5-fold surface of an AlPdMn alloy was oxidized using a metallized AFM tip. The electrochemical nature of this process was confirmed by investigating the influence of humidity and polarity of the applied voltage on the quasicrystalline oxide. Oxides of different thickness and adhesive properties were created by altering the applied voltage and the humidity during the lithographic process. The technique can be used in an exhaustive study of properties of the various types of oxides that form on the AlPdMn surface and the preliminary results of one such study are reported.     

Self-inhibition of water dissociation on magnesium oxide surfaces

Hydroxylated MgO surfaces have been prepared by exposure to water vapour of MgO crystals at room temperature. High hydroxyl coverages were achieved on freshly cleaved surfaces. However, upon adsorption–desorption cycles of the hydroxyl adlayer, the ability of the MgO surfaces to dissociate water was seen to be dramatically inhibited. Reduced reactivities have also been observed on both air- and water-exposed MgO surfaces. This reactive behaviour is discussed in relation to the theoretical prediction that the MgO(100) face is not expected to dissociate water molecules.     

Modification in etching characteristics and surface topography of some electron irradiated polymers

Track formation in polymers is a complex phenomenon in which not only primary but also secondary processes, such as formation of radicals and chemical processes, are involved. In the present work, the influence of 2 MeV electrons on the etching properties and the surface topography of polyethylene terephthalate (PET) and polyimide (PI) are studied. The increase in the bulk etch-rate and a decrease in the activation energy of etching were observed for both the polymers. The surface roughness of both polymers was reduced due to electron irradiation.     

Tuning surface interactions to control shape and array behavior of diblock copolymer micelles on a silicon substrate

The micellar shape of liquid crystalline diblock copolymers, PEO_m-b-PMA(Az)_n, consisting of high surface energy components was controlled by tuning surface interactions. On a fluorinated surface, the diblock copolymers formed ordered arrays of spherical micelles consisting of PEO cores surrounded by PMA(Az) coronas. Gold ions could be doped into the PEO cores by immersion in a solution of the gold ion. The Au³⁺-doped micelles were subsequently etched and reduced by VUV radiation to form hexagonally ordered gold nanodots.     

Photo-irradiation effects on the surface morphology of poly(p-phenylene vinylene) films

In this work, we have studied the surface morphology of photo-irradiated poly(p-phenylene vinylene) (PPV) thin films by using atomic force microscopy (AFM). We have analyzed the first-order statistical parameters, the height distribution and the distance between selected peaks. The second-order statistical analysis was introduced calculating the auto-covariance function to determine the correlation length between heights. We have observed that the photo-irradiation process produces a surface topology more homogeneous and isotropic such as a normal surface. In addition, the polymer surface irradiation can be used as a new methodology to obtain materials optically modified.     

Observing the effect of water vapor on post-irradiated surface morphology of SiO2 and Si3N4 insulators by atomic force microscopy

In this work, we investigated the effect of water-vapor treatment on the surface morphology of SiO₂ and Si₃N₄ insulators before and after Co⁶⁰ gamma-ray irradiation by using the atomic force microscopy (AFM) operated under non-contact mode. Before irradiation, no apparent surface morphology change was found in SiO₂ samples even they were water vapor treated. However, bright spots were found on post-irradiated water-vapor-treated SiO₂ sample surfaces but not on those without water-vapor treatment. We attributed the bright spots to the negative charge accumulation in the oxide due to charge balancing between hydroxyl (OH⁻) ions adsorbed on SiO₂ surface and electron-hole pairs (ehps) generated during irradiation since they can be annealed out after low temperature annealing process. On the contrary, no bright spots were observed on post-irradiated Si₃N₄ samples with and without water-vapor treatment. This result confirms that Si₃N₄ is a better water-resist passivation layer than SiO₂ layer.     

Fabrication of rubrene nanowires on vicinal (0 0 0 1) sapphire surfaces

Morphology of high-vacuum deposited rubrene thin films on the annealed (0 0 0 1) vicinal sapphire surfaces was studied by atomic force microscopy in non-contact mode. Atomic force microscopy images of rubrene thin films indicate that a regular array of steps on the sapphire surface acts as a template for the growth of the arrays of rubrene nanosize wires. To further demonstrate that morphological features of a substrate are crucial in determining the morphology of rubrene layers we have grown rubrene on the sapphire surfaces that were characterized by the terrace-and-step morphology with islands. We have found preferential nucleation of rubrene molecules at the intersection between a terrace and a step, as well as around the islands located on terraces.     

Self-assembled structures of alkanethiols on gold-coated cantilever tips and substrates for atomic force microscopy: Molecular organisation and conditions for reproducible deposition

Measurements of surface-liquid interactions (contact-angle goniometry) and tip-surface adhesion forces (atomic force microscopy) combined with infrared spectroscopic studies have been used to investigate surface-preparation and solution-deposition conditions for the reproducible formation of self-assembled molecular structures on gold-coated tips and substrates for atomic force microscopy. Preliminary data show that surface-saturated self-assembled monolayers form reproducibly on prolonged (>20 h) exposure of gold-coated glass substrates to ethanolic solutions of ω-functionalised alkanethiols in the concentration range 80-160 mmol dm⁻³. The data also show that exposure for 16 h to alkanethiol concentrations in the range 160-240 mmol dm⁻³ promote bilayer formation whereas concentrations of 240-320 mmol dm⁻³ result in the deposition of multilayers, the average orientation of which is parallel to that of the first molecular layer; the use of parent 1-undecanethiol solutions at concentrations of 1-80 mmol dm⁻³ results in incomplete monolayer coverage.     

Surface diffusivity of thin polymer films measured by a curvature driven flow and Rouse dynamics

Nanodefects induced by nanoindentation on thin polystyrene (PS) films spin cast on silicon (Si) relax upon annealing at 110 °C. The relaxation process for low molecular weight PS is interpreted in terms of a curvature driven flow which leads to the measurement of a diffusion coefficient. The latter is compared with the expected Rouse predictions using (i) bulk and (ii) surface glass transition temperature data, found in the literature. Deviations from the Rouse predictions are observed when is used for the analysis of the data. On the contrary, excellent agreement with the Rouse model is reported when is used.     

Soft-landing of size-selected W clusters on highly ordered pyrolytic graphite surfaces: Towards the fabrication of thin films of cluster assemblies

Mass-selected W cluster anions in the size range of 20–3500 are deposited on highly ordered pyrolytic graphite (HOPG) surfaces. The structures of resulting thin films are studied using atomic force microscopy. Clusters with more than ∼600 atoms form thin films, in which the clusters are not completely merged but survive as individual species to a certain extent. The new class of materials fabricated here (cluster-assemblies) has a potential for applications in heterogeneous catalysis and in optoelectronic devices. In addition, they are interesting from the perspective of basic research.