Surface investigation of adhesive formulation consisting of UV sensitive triblock poly(styrene–b-butadiene–b-styrene) copolymer

Atomic force microscopy (AFM) analysis in conjunction with macroscopic studies such as peel testing and contact angle measurement have been undertaken to explain the nanomechanical properties of adhesive formulation consisting of triblock poly(styrene–b-butadiene–b-styrene) (SBS) copolymers. The cross-linking of this photosensitive copolymer was investigated by analyzing the mechanical and morphological changes of each phase induced by the UV exposure. Main result is that the adhesive properties are strongly influenced by the cross-linking of the polybutadiene (PB) phase leading to an increase in the surface stiffness without affecting the surface energy. AFM analysis shows that the adhesion force is mostly governed by the contact area between the adhesive and the probe. The surface mobility may explain the increase in adhesion for this pressure sensitive copolymer.     

Computing Particle Surface Areas and Contact Areas from Three‐Dimensional Tomography Data of Particulate Materials

Microtomography is an emerging technique for particle and particulate‐materials characterization. To use this technology effectively, robust and accurate computational algorithms are needed to compute relevant particle properties, including particle surface area and particle‐particle contact area. However, the most accurate algorithms that have been developed for computing the exposed (void/solid) surface area in a microtomography image cannot be used directly for computing surface areas or particle‐particle contact areas for individual particles in a dense packing. This paper presents an algorithm for extracting particle contact areas from a digitized, segmented image of a packed granular material, which in turn can be used to find individual particle surface areas (even if the complete surfaces are not exposed because of contacts in the packing). Results show that small errors in the binary surface‐area computations are magnified in the course of determining particle contact areas; the total error in the computation depends mainly on the size of the contact area in voxel units.     

Interproximal dental caries detection using Photothermal Radiometry (PTR) and Modulated Luminescence (LUM)

Frequency-domain photothermal radiometry (FD-PTR or PTR) has been used to detect mechanical holes and demineralized enamel in the interproximal contact area of extracted human teeth. Thirty four teeth were used in a series of experiments. Preliminary tests to detect mechanical holes created by dental burs and 37% phosphoric acid etching for 20 s on the interproximal contact points showed distinct differences in the signal. Interproximal contact areas were demineralized by using a partially saturated acidic buffer system. Each sample pair was examined with PTR before and after micro-machining or treating at sequential treatment periods spanning 6 hours to 30 days. Dental bitewing radio graphs showed no sign of demineralized lesion even for samples treated for 30 days. μ-CT, TMR and SEM analyses were performed. Although μ-CT and TMR measured mineral losses and lesion depths, only SEM surface images showed visible signs of treatment because of the minimal extent of the demineralization. However, the PTR amplitude increased by more than 300% after 80 hours of treatment. Therefore, PTR has been shown to have sufficient contrast for the detection of very early interproximal demineralized lesions. The technique further exhibited excellent signal reproducibility and consistent signal changes in the presence of interproximal demineralized lesions, attributes which render PTR a reliable probe to detect early interproximal demineralization lesions. Modulated luminescence was also measured simultaneously, but it showed a lower ability to detect these interproximal demineralized lesions than PTR.     

Tunable surface wettability of ZnO nanorods prepared by two-step method

Zinc oxide (ZnO) nanorods were deposited on silicon substrate by two-step method. The crystal structure, surface morphology and water contact angle (WCA) were measured by X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), and water contact angle apparatus. It is demonstrated that the WCA of the as-grown ZnO nanorods varies between 136° and 43° and the contact angle reduction rate of ZnO nanorods changes rapidly with increasing growth time. The variation of contact angle in the as-grown samples and contact angle reduction rate has been attributed to the combined effects of the proportion of nonpolar planes in the outermost surface, the area fraction of vapor on the surface and the increase of surface energy of ZnO nanorods.     

Surface modification of a biomedical polyethylene terephthalate (PET) by air plasma

In this work, low-pressure air plasma has been used to improve polyethylene terephthalate (PET) surface properties for technical applications. Surface free energy values have been estimated using contact angle value for different exposure times and different test liquids. Surface composition and morphology of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Surface topography changes related with the etching mechanism have been followed by weight loss study. The results show a considerable improvement in surface wettability and the surface free energy values even for short exposure times in the different discharge areas (discharge area, afterglow area and remote area), as observed by a remarkable decrease in contact angle values. Change of chemical composition made the polymer surfaces to be highly hydrophilic, which mainly depends on the increase in oxygen-containing groups. In addition to, the surface activation and AFM analyses show obvious changes in surface topography as a consequence of the plasma-etching mechanism.     

Development of a scanning Hall probe microscope for simultaneous magnetic and topographic imaging

A scanning Hall probe microscope that is capable of observing both topographic and magnetic images simultaneously has been developed by constructing a conducting needle, used for the scanning tunneling microscope (STM) measurements, adjacent to the Hall junction of 0.6 μm square. The needle also enables the Hall probe to approach the sample without contact and to scan just above it with close proximity. Morphologies and local magnetic distributions on the surfaces of magnetic recording media, observed by our microscope, indicates that lateral spatial resolution is better than 1 μm for both STM and magnetic measurements.     

Shear thinning and local melting of colloidal crystals

Phenomena such as shear thinning and thickening, occurring when complex materials are exposed to external forces, are generally believed to be closely connected to changes in the microstructure. Here, we establish a direct and quantitative relation between shear thinning in a colloidal crystal and the surface area of the locally melted region by dragging a probe particle through the crystal using optical tweezing. We show that shear thinning originates from the nonlinear dependence of the locally melted surface area on the drag velocity. Our observations provide unprecedented quantitative evidence for the intimate relation between mechanical properties and underlying changes in microscopic structure.     

Analysis of the profile curves of the menisci for the crystal growth by the edge-defined film-fed growth (Stepanov) technique

The behavior of the profile curves of the melt menisci for the growth of sapphire tubes of different diameters by the edge-defined film-fed growth (Stepanov) technique has been investigated. The external and internal circular menisci of the crystal tube are considered. The case of positive contact angle contact between the profile curve and working shaper surface is analyzed.     

Bell clapper impact dynamics and the voicing of a carillon

The periodic re-voicing of the bell clappers of the Australian National Carillon in Canberra provided an opportunity for the study of the acoustic effects of this operation. After prolonged playing, the impact of the pear-shaped clapper on a bell produces a significant flat area on both the clapper and the inside surface of the bell. This deformation significantly decreases the duration of the impact event and has the effect of increasing the relative amplitude of higher modes in the bell sound, making it "brighter" or even "clangy." This effect is studied by comparing the spectral envelope of the sounds of several bells before and after voicing. Theoretical analysis shows that the clapper actually strikes the bell and remains in contact with the bell surface until it is ejected by a displacement pulse that has traveled around the complete circumference of the bell. The contact time, typically about 1 ms, is therefore much longer than the effective impact time, which is only a few tenths of a millisecond. Both the impact time and the contact time are reduced by the presence of a flat on the clapper.     

Experiments on the location of chain ends in monolayer single crystals of polyethylene

The location of vinyl end groups in monolayer polyethylene crystals (specially prepared to have surfaces highly accessible to gaseous reactants) has been investigated by exposing the crystals to ozone and determining the extent of reaction by infrared spectroscopy. It was found that, for the type of crystals used, about nine-tenths of the chain ends reacted very rapidly and it is deduced that these are excluded from the crystal lattice and should lie on the crystal surfaces. The remaining fraction of ends were, by comparison, highly resistant to oxidation.

The consequences of this deduction are discussed; it is suggested that the chain segment ejected together with the chain ends could account for a large part of the amorphous content associated with this type of crystal. In addition, the results imply that the crystal lattice is inaccessible to ozone even when it contains defects such as those caused by end groups, which is of consequence for work on oxidative degradation both for its own sake and in aid of morphological studies.     

Adhesion between an elastic body and a randomly rough hard surface

I have developed a theory of adhesion between an elastic solid and a hard randomly rough substrate. The theory takes into account that partial contact may occur between the solids on all length scales. I present numerical results for the case where the substrate surface is self-affine fractal. When the fractal dimension is close to 2, complete contact typically occurs in the macro-asperity contact areas, while when the fractal dimension is larger than 2.5, the area of (apparent) contact decreases continuously when the magnification is increased. An important result is that even when the surface roughness is so high that no adhesion can be detected in a pull-off experiment, the area of real contact (when adhesion is included) may still be several times larger than when the adhesion is neglected. Since it is the area of real contact which determines the sliding friction force, the adhesion interaction may strongly affect the friction force even when no adhesion can be detected in a pull-off experiment. Received 3 April 2002     

Initial growth process and surface structure of Ag on Si(111) studied by low-energy Ion-Scattering Spectroscopy (ISS) and LEED-AES

The growth process of silver on a Si(111) substrate has been studied in detail by low-energy ion-scattering spectroscopy (ISS) combined with LEED-AES. Neon ions of 500 eV were used as probe ions of ISS. The ISS experiments have revealed that the growth at room temperature and at high temperature are quite different from each other even in the submonolayer coverage range. The following growth models have been proposed for the respective temperatures. At room temperature, the deposited Ag forms a two-dimensional (2D) island at around 2/3 monolayer (ML) coverage, where the Ag atoms are packed commensurately with the Si(111)1 substrate. One third of the substrate Si surface remains uncovered there. Then it starts to develop into Ag crystal, and at a few ML coverage a 3D island of bulk Ag crystal grows directly on the substrate. An intermediate layer, which covers uniformly the whole surface before the growth of Ag crystal, does not exist. At high temperatures (>~200°C), the well-known Si(111)√3-Ag layer is formed as an intermediate layer, which consists of 2/3 ML of Ag atoms and covers the whole surface uniformly. These Ag atoms are embedded in the first double layer of the Si substrate. It is concluded that the formation of the √3 structure needs relatively high activation energy which may originate from the large displacement of Si atoms owing to the embedment of the Ag atoms, and does not proceed below about 200°C. The most stable state of the Ag atoms on the outermost Si layer is in the shape of an island, both for the Si(111) surface and for the Si(111)√3-Ag surface.     

Formation of the composition and topography of surface layers of Cu50Ni50 foils under laser irradiation

The influence of the laser radiation power density on the changes in the composition and mechanical properties of surface layers of Cu₅₀Ni₅₀ foils has been investigated using X-ray photoelectron spectroscopy, scanning probe microscopy, X-ray diffraction, and microhardness measurements. It has been found that, after laser irradiation, the redistribution of elements occurs in the surface layer with a thickness of ～30 nm on the irradiated side of the foil. It has been revealed that there are microdistortions in the crystal lattice of the alloy, microdeformations of grains, and variations in the microhardness of the irradiated surface. The mechanisms explaining the observed changes in the foils after laser irradiation have been proposed.     

Growth of monoatomic layer terraces on a (111) lead crystal face: In situ observations in dark field by UHV-TEM

The growth of (111) lead tabular crystals obtained by vapour deposition onto a cleaved surface of graphite has been observed using an ultra high vacuum transmission electron microscope (UHV-TEM). Monoatomic terraces are observed in dark field where the nucleation site of the terraces seems to be due to dislocations emergent at the surface. The growth of a terrace follows three stages: (i) nucleation and isotropic lateral extension until it reaches one side of the tabular crystal (ii) preferential lateral growth of the terrace along the edge of the crystal, (iii) fill up the hole formed at the end of the previous stage.     

The Effects of Morphological Properties of Henequen Fiber Irradiated by EB on the Mechanical and Thermal Properties of Henequen Fiber/PP Composites

The aim of this study was to investigate the effects of electron beam (EB) irradiation on the morphological properties, crystallinity and surface area of henequen fiber and on the mechanical and thermal properties of henequen fiber reinforced polypropylene (PP) composites. The structure of henequen fiber was characterized by X-ray diffraction, mercury porosimetry and BET surface area analysis. The EB irradiation of 10 kGy led to the increasing of crystalline and surface pore area of henequen fiber, which contributed to the number of interlocking places with PP. From the results of tensile and impact strength tests, the highest value was observed for the composite reinforced with the henequen fiber treated with EB dose of 10 kGy, decreasing overall as EB dose increased. This tendency was also shown by coefficient of thermal expansion (CTE) measurements, but the value of CTE decreased until 50 kGy, meaning that a large total surface area can provide many interlocking places and so improve adhesion between fiber and matrix. Therefore, it can be concluded that the optimum pore surface area by 10 kGy irradiation contributes to successful mechanical interlocking between fiber and matrix and consequently enhances the mechanical and thermal properties of the composites.     

Probing magnetic fields on crystals of the nanomagnet Mn12-acetate by electron paramagnetic resonance

We report on electron paramagnetic resonance (EPR) probing of magnetic fields and magnetic field gradients near the surface of a single crystal of the nanomagnet [Mn12O12(CH3COO)16(H2O)4].2CH3COOH.4H2O (Mn12-Ac). As the EPR probe, we utilized a 0.7 mm x 30 microm x 30 microm fibrous needle of the organic conductor N-methylphenazinium-tetracyanoquinodimethane (NMP-TCNQ), which yields an exceptionally sharp peak, with a 0.2 G (approximately 20 microT) width. In the presence of Mn12-Ac, the probe's peak exhibits splitting on temperature lowering, which depends on the orientation of the Zeeman field relative to the axis of easy magnetization of the employed Mn12-Ac crystal. The shifted peaks yield the magnitude of the magnetic field from Mn12-Ac crystal to which the various fibers of the probe are subjected. In conjunction with electron microscopy, the shifts yield the field gradient at the crystal surface and its change with temperature. For Mn12-Ac at 10 K, the surface magnetic field was measured to be in the mT range and its gradient on the order of 50 T/m.     

Raman analysis of bilayer graphene film prepared on commercial Cu(0.5 at% Ni) foil

This study reports the Raman analysis of bilayer graphene films prepared on commercial dilute Cu(0.5 at% Ni) foils using atmospheric pressure chemical vapor deposition. A bilayer graphene film obtained on Cu foil is known to have small areas of bilayer (islands) with a significant fraction of non‐Bernal stacking, while that obtained on Cu/Ni is known to grow over a large area with Bernal stacking. In the Raman optical microscope images, a wafer‐scale monolayer and large‐area bilayer graphene films were distinguished and confirmed with Raman spectra intensities ratios of 2D to G peaks. The large‐area part of bilayer graphene film obtained was assisted by Ni surface segregation because Ni has higher methane decomposition rate and carbon solubility compared with Cu. The Raman data suggest a Bernal stacking order in the prepared bilayer graphene film. A four‐point probe sheet resistance of graphene films confirmed a bilayer graphene film sheet resistance distinguished from that of monolayer graphene. A relatively higher Ni surface concentration in Cu(0.5 at% Ni) foil was confirmed with time‐of‐flight secondary ion mass spectrometry. The inhomogeneous distribution of Ni in a foil and the diverse crystallographic surface of a foil (confirmed with proton‐induced X‐ray emission and electron backscatter diffraction, respectively) could be a reason for incomplete wafer‐scale bilayer graphene film. The Ni surface segregation in dilute Cu(0.5 at% Ni) foil has a potential to impact on atmospheric pressure chemical vapor deposition growth of large‐area bilayer graphene film. Copyright © 2015 John Wiley & Sons, Ltd.     

Self-poisoning of crystal nuclei in hard-rod liquids

We report a Monte Carlo study of the pathway for crystal nucleation in a fluid of hard, colloidal rods. In the earliest stages of nucleation, a lamellar crystallite forms. Subsequent thickening of this lamella is hampered by the fact that the top and bottom surfaces of this crystallite are preferentially covered by rods that align parallel to the surface. As a consequence, subsequent growth of individual crystals is stunted. Experimental evidence for such stunted crystal growth has recently been reported by Maeda and Maeda in experiments on suspensions of colloidal rods [Phys. Rev. Lett. 90, 018303 (2003)]]. The simulations suggest that, in experiments, the growth of multilayer colloidal crystals can be selectively enhanced by the application of an external aligning field.     

Photoemission studies of the surfactant-aided growth of Ge on Te-terminated Si(100)

The interactions of Ge adatoms with a Si(100) surface terminated by an ordered layer of Te have been studied in detail using XPS, SXPS, STM and LEED. It has been demonstrated that the Te layer has a surfactant action on the growth mode of the Ge in that the two dimensional growth regime is extended to at least 200 Å and the Te is seen to segregate to the growing Ge surface. The surface reconstruction of the Ge layer changes from (1 × 1) in the initial stages to (2 × 2) as growth proceeds and the surface population of Te is reduced. SXPS line shape analysis has indicated that the initial stages of Ge incorporation are characterised by the formation of small islands above those surface Si sites not fully coordinated with Te. Continued growth of such islands is, however, restricted due to their high surface free energy with respect to the surrounding Te-terminated areas. Ge atoms therefore site-exchange with Te atoms in bridge sites, thus becoming incorporated onto the Si lattice and displacing the Te to bridge sites on the growing surface. In this manner islanding is prevented and two-dimensional growth continues beyond the critical thickness. No evidence is seen for any significant incorporation of the Te within the growing Ge layer.