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.     

Heavy ion induced damage in MgF 2 crystals

MgF 2 single crystals were irradiated with 22 Ne and 238 U ions in the energy range 31-2642 v MeV. The ion-induced damage was studied by optical spectroscopy, scanning force microscopy, and volume expansion measurements. The efficiency of damage creation depends on the stopping power (d E /d x ) and the fluence of the ions. Out-of-plane swelling and the formation of hillocks on the crystal surface require a critical d E /d x of approximately 3 v keV/nm. The efficiency for creation of simple defects (color centers) and of more complex damage (swelling, hillock formation) in MgF 2 is compared with the corresponding efficiency in LiF.     

Characterization of copper SERS-active substrates prepared by electrochemical deposition

Surface Enhanced Raman Scattering (SERS) on copper substrates of various morphologies, prepared by electrochemical deposition on platinum targets, was investigated. The substrate preparation procedures differed by the coating bath compositions, applied current densities and the duration of individual steps. The surface morphology of the substrates was visualized by means of Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). SERS spectra of selected organic thiols were measured and the relation between SERS spectral intensity and the surface structure of SERS-active substrates was studied. It has been shown that good Raman surface enhancement can be achieved on the copper substrates prepared by electrochemical deposition from ammoniac baths. Copper substrates fabricated from acidic baths did not show efficient Raman surface enhancement. The results of microscopic measurements demonstrated that the average surface roughness value does not play a substantial role, whereas the shape of the surface nanostructures is a key parameter.     

The use of contact angle measurements to estimate the adhesion propensity of calcium carbonate to solid substrates in water

We have studied a series of solids using contact angle measurements; stainless steel, gold, aluminium, titanium nitride and PTFE that are frequently used in domestic water environments. It was found the influence of electron-donor (γ⁻) and electron-acceptor (γ⁺) free energies on material scaling rate was dominated by water wetting angles, providing materials exhibit an average roughness below 100 nm. The γ⁻ component had the greatest influence on theoretical adhesion, while γ^LW, (Lifshitz-van der Waals) γ⁺ and γ^AB (acid-base) had little effect. From the materials analysed, amorphous carbon coatings were least adhesive, while ‘kettle coating’ and highly roughened steel the most adhesive. The size and distribution of asperities also influenced the polar free energies and subsequent adhesion due to fluctuations in the wetting angle. The results obtained indicate works of adhesion can be used as a complementary technique with Lewis acid-base theory to deliver useful information about the propensity of scale to deposit on solids.     

Relationship between triboelectric charge and contact force for two triboelectric layers

A relationship between triboelectric charge and contact force for two triboelectric layers is presented, by combining the theories of insulator contact charging and contact mechanics. Experimental verification has been successfully performed using contact-mode triboelectric nanogenerators (TENGs) in two cases: (a) under varying contact forces while keeping the surface roughness profile constant, and (b) under varying surface roughness profiles while keeping the contact force constant. The theory presented here can serve as an important guide in the design of triboelectric systems, particularly of a contact-mode TENG structure for specific applications and self-powered systems.     

Revisiting the physical processes of vapodeposited thin gold films on chemically modified glass by atomic force and surface plasmon microscopies

The preparation of very thin (at the scale of a few tens of nanometers) gold films by thermal evaporation and deposition on a solid substrate (glass) remains a key step for the elaboration of transparent and sensitive optical biosensors. We study the influence of the glass surface treatment and its thermal conductivity on the structure and composition of evaporated gold films. Using a combination of atomic force microscopy (AFM), high resolution surface plasmon resonance (SPR) imaging, and X-ray photoelectron spectroscopy (XPS), we demonstrate that the grafting of a layer of long chain mercaptant, using 11-mercaptoundecyltrimethoxysilane (S_ξSi), prior to gold deposition produces a drastic modification of gold inner and surface textures. A thorough investigation of AFM image topography by 2D wavelet-based segmentation method reveals the flat conical shape of the gold surface grains and their shape invariance with the glass surface chemical treatment. However, this treatment leads to a drastic decrease of the mean size and polydispersity of these grains by a factor of 2, thereby lowering the gold surface roughness. The rationale is that the combination of surface forces and thermal transfer drives the formation of homogeneous and flatter gold films.     

Measurement of grain–wall contact forces in a granular bed using frequency-scanning interferometry

Micro-mechanical theories have recently been developed to model the propagation of force through a granular material based on single grain interactions. We describe here an experimental technique, developed to validate such theories, that is able to measure the individual contact forces between the grains and the wall of the containing vessel, thereby avoiding the spatial averaging effect of conventional pressure transducers. The method involves measuring interferometrically the deflection of an interface within a triple-layer elastic substrate consisting of epoxy, silicone rubber, and glass. A thin coating of gold between the epoxy and rubber acts as a reflective film, with the reference wave provided by the glass/air interface. Phase shifting is carried out by means of a tunable laser. Phase difference maps are calculated using a 15-frame phase-shifting formula based on a Hanning window. The resulting displacement resolution of order 1 nm allows the wall stiffness to be increased by some two orders of magnitude compared to previously described methods in the literature.     

Heterogeneity of surface potential in contact electrification under ambient conditions: A comparison of pre- and post-contact states

We measured the pattern of charging by contact electrification, following contact between a polydimethylsiloxane (PDMS) stamp and a glass substrate with gold electrodes. We used scanning Kelvin probe microscopy to map the surface potential at the same regions before and after contact, allowing a point-by-point comparison. After contact, the mean surface potential of the glass shifted by 360 mV and micron-scale heterogeneity appeared with a magnitude of ∼100 mV. The gold electrodes showed charge transfer but no discernible heterogeneity. These results show that contact electrification causes heterogeneity of surface potential even on non-polymer surfaces such as glass under ambient conditions.     

Relationship between sliding acceleration of water droplets and dynamic contact angles on hydrophobic surfaces

This study measured sliding acceleration of water droplets on hydrophobic solid surfaces and used expanding and contracting method to compare that value with dynamic contact angles. Sliding action of the droplet was classified into three motion categories: constant accelerated motion, constant velocity and stasis. Differences exist in the dependencies of contact radius and the injection-suction rate in dynamic contact angle hysteresis according to these categories. This method is an effective indicator of water droplets’ sliding acceleration.     

Scratch direction and threshold force in nanoscale scratching using atomic force microscopes

The nanoscaled tip in an AFM (atomic force microscope) has become an effective scratching tool for material removing in nanofabrication. In this article, the characteristics of using a diamond-coated pyramidal tip to scratch Ni-Fe thin film surfaces was experimentally investigated with the focus on the evaluation of the influence of the scratch or scan direction on the final shape of the scratched geometry as well as the applied scratch force. Results indicated that both the scratched profile and the scratch force were greatly affected by the scratch direction. It has been found that, to minimize the formation of protuberances along the groove sides and to have a better control of the scratched geometry, the tip face should be perpendicular to the scratching direction, which is also known as orthogonal cutting condition. To demonstrate the present findings, three groove patterns have been scratched with the tip face perpendicular to the scratching direction and very little amount of protuberances was observed. The threshold scratch force was also predicted based on the Hertz contact theory. Without considering the surface friction and adhesive forces between the tip and substrate, the threshold force predicted was twice smaller than the measurement value. Finally, recommendations for technical improvement and research focuses are provided.     

Single atomic contact adhesion and dissipation in dynamic force microscopy

By combining dynamic force microscopy experiments and first-principles calculations, we have studied the adhesion associated with a single atomic contact between a nanoasperity--the tip apex--and a semiconductor surface--the Ge(111)-c(2 x 8). The nanoasperity's termination has been atomically characterized by extensive comparisons of the measured short-range force at specific sites with the chemical forces calculated using many atomic models that vary in structure, composition, and relative orientation with respect to the surface. This thorough characterization has allowed us to explain the dissipation signal observed in atomic-resolution images and force spectroscopic measurements, as well as to identify a dissipation channel and the associated atomic processes.     

Interphase characterization in polymer composites - monitoring of interphasial behavior in dependence on the mode of loading

Single fiber model composites consisting of epoxy resin matrix and differently sized glass fibers were investigated using pull-out tests, scanning electron microscopy (SEM), scanning force microscopy (SFM) and single fiber dynamic load test (SFDL). The inhomogeneous stress distribution along the embedded fiber length could be visualized by monitoring. SEM images showed either cohesive fracture or adhesive failure on pulled-out fibers with different sizings. The crack initiation and propagation were detected randomly and multiply distributed as the inhomogeneous interphase itself and depending strongly on the fiber-matrix model combination. The meniscus region acts as a material inhomogeneity and its appearence depends on the surface free energies of fiber and matrix and on the curing conditions of the resin. SFM in force modulation mode has visualized different interphase thicknesses and gradients of local stiffness. The SFDL test has been shown as a worthful tool for the comprehensive determination of fiber-matrix interaction.     

Characterization at a local scale of a laser-shock peened aluminum alloy surface

The influence of a laser shock peening mechanical surface treatment on 2050-T8 aluminum alloy has been investigated, mostly using Scanning Kelvin Probe Force Microscopy. Volta potential difference maps around Al(CuFeMn) precipitates were performed before and after laser-shock peening to determine the influence of laser treatment versus galvanic coupling near precipitates, and resulting pit initiations. It has been shown that laser shock peening either preserves or reduces precipitate-matrix Volta potentials gradients, which in this later case, and correlated to recent corrosion electrochemical investigations, could explain corrosion improvement obtained after laser-shock peening treatments of aluminum alloys. The influence of crystal orientation and plastic deformation, and more specifically the effect of laser-induced compressive residual stresses or work-hardening, on the Volta potential values and on the pitting corrosion behavior was also addressed.     

Droplet transient migration and dynamic force balance mechanism on vibration-controlled micro-texture surfaces

In this paper, forced vibration was used to regulate the droplet migration, fully recording the transient migration of droplets on a micro-textured substrate under the resonance frequency by a high-speed camera. The influence of resonance frequency and dynamic migration characteristics of droplets on the solid micro-texture surface under lateral vibration were researched. The experiment demonstrates that the driving force is caused by the difference between the left and right contact angles made the droplet oscillate and migrate, and as time t increases, the left and right contact points are periodically shifted and the amplitude of migration increases. Therefore, based on the droplet migration behavior and its force balance mechanism, a spring vibration model of migration behavior of the vibrating droplet micro unit was set up to predict the complete trajectory of its migration on a solid surface. The calculation results show that the theoretical displacement is less than the experimental displacement, and the longer the time, the larger the difference. Affected by the vibration, part of the droplet permeates through the micro-texture, resulting in the droplet losing height and the contact angle becoming smaller as well. While the other part of droplet overcomes the internal surface tension to migrate.     

Changes in wetting and energetic properties of glass caused by deposition of different lipid layers

An investigation of wetting and energetic properties of different lipid layers deposited on the glass surface was carried out by contact angles measurements and determination of the apparent surface free energy. The topography of the lipid layers was also determined with the help of atomic force microscopy (AFM). Two synthetic phospholipids were chosen for these studies, having the same phosphatidylcholine headgroup bound to the apolar part composed either by two saturated chains (1,2-dipalmitoyl-sn-glycero-3-phospshocholine - DPPC) or two unsaturated chains (1,2-dioleoyl-sn-glycero-3-phosphocholine - DOPC) and one lipid (1,2,3-trihexadecanoyl-sn-glycerol - tripalmitoylglycerol - TPG). The lipid layers, from the 1st to the 5th statistical monolayer, were deposited on the glass surface from chloroform solutions by spreading.The apparent surface free energy of the deposited layers was determined by contact angles measurements (advancing and receding) for three probe liquids (diiodomethane, water, and formamide), and then two concepts of interfacial interactions were applied. In the contact angle hysteresis approach (CAH) the apparent total surface free energy was calculated from the advancing and receding contact angles and surface tension of probe liquids. In the Lifshitz-van der Waals/acid-base approach (LWAB) the total surface free energy was calculated from the determined components of the energy, which were obtained from the advancing contact angles of the probe liquids only. Comparison of the results obtained by two approaches provided more information about the changes in the hydrophobicity/hydrophilicity of the layers depending on the number of monolayers and kind of the lipid deposited on the glass surface.It was found that the most visible changes in the surface free energy took place for the first two statistical monolayers irrespectively of the kind of the lipid used. Additionally, in all cases periodic oscillations from layer-to-layer in the lipid surface free energy were observed. The changes in the surface free energy correlated with those in the topography and roughness of lipid layers.     

Physical and chemical properties of bimetallic surfaces

Recent studies dealing with the structural, electronic, chemical and catalytic properties of well-defined bimetallic surfaces are reviewed. LEED and STM show that two metals interacting on a surface can form compounds with structures not seen in bulk alloys. Many novel phenomena related to the kinetics of growth of metals on metals have been discovered. The knowledge gathered in this area provides a solid basis for the synthesis of new materials with applications in areas of catalysis, electro-chemistry and microelectronics. In many cases, the formation of a surface bimetallic bond induces large changes in the band structure of the metals. For surfaces that contain transition or s,p metals, the strongest metal-metal interactions occur in systems that combine a metal with a valence band almost fully occupied and a metal in which the valence band is almost empty. A very good correlation is found between the electronic perturbations in a bimetallic system and its cohesive energy. Bimetallic bonds that display a large stability usually involve a significant redistribution of charge around the metal centers. The electronic perturbations affect the reactivity of the bonded metals toward small molecules (CO, NO, H₂, O₂, S₂, C₂H₄, CH₃OH, etc.). For supported monolayers of Ni, Pd, Pt and Cu a correlation is observed between the shifts in surface core-level binding energies and changes in the desorption temperature of CO from the metal adlayers. Examples are provided which demonstrate the utility of single-crystal studies for understanding the role of “ensemble” and “ligand” effects in bimetallic catalysts.     

A new laser shadowgraphy method for measurements of dynamic contact angle and simultaneous flow visualization in a sessile drop

A new laser shadowgraphy method is presented to measure the dynamic contact angle of a sessile drop on a nontransparent metal substrate and simultaneously visualize flow motions inside the drop. A collimated laser beam is refracted into the drop, then reflected on the substrate surface and finally refracted out of the drop to form a shadowgraphic image on a screen. The instant diameters of the refracted-shadowgraphic image, cooperated with the corresponding instant contact-diameters of the drop measured from the magnified top view, are used to determine the instant contact angles of the sessile drop. At the same time, flow motions, if any, in the drop can be visualized from the refracted-shadowgraphic image. The new method is demonstrated to be a very simple, accurate, and unique optical technique for simultaneous measuring of the dynamic contact angle of a liquid drop spreading on a nontransparent metal substrate with flow visualization in the drop.     

Surface modification of porous poly(tetrafluoroethylene) film via cold plasma treatment

In this study, cold plasma technology was applied for the surface modification of porous polytetrafluoroethylene (PTFE) film to improve the hydrophilicity. The surface properties of PTFE, modified by air, helium (He) or acrylic acid (AAc), were investigated with scanning electron microscopy (SEM), scanning probe microscope (SPM), in situ X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. The changes of the surface property before and after plasma treatment were discussed. According to SEM and SPM measurements, the surface roughness increased at different levels after plasma treatment. Compared to air and AAc plasma treatment, the He plasma treatment introduced large amounts of oxygen into the surface, as known from XPS results. Contact angle measurements revealed that the hydrophilicity of the PTFE film surface was greatly improved due to the surface roughness and changes of chemical elements on the PTFE surface.     

光栅参数测量技术研究进展

光栅参数测量技术是衡量光栅制作水平的重要标准。本文从直接测量法和间接测量法两个角度对现阶段较成熟的光栅参数测量技术进行了研究。重点介绍了原子力显微镜（AFM）测量法、扫描电子显微镜（SEM）测量法、激光衍射（LD）测量法以及散射测量术的测量原理和研究进展,指出了这些方法各自的优缺点和适用范围。AFM测量法和SEM测量法均可测得光栅的局部形貌信息,可用于检测光栅表面形貌缺陷;LD测量法和散射测量术反映的是激光照射区域的平均结果,其中LD测量法能得到光栅周期参数,而椭偏测量术能得到光栅周期以外的其他形貌参数。这些方法测得的光栅参数结果比较吻合,其中LD测量法不确定度最小,AFM次之,SEM最大。文章最后对未来光栅参数测量技术的发展方向进行了论述。     

Impact of atomic relaxation on the breaks of constant force surfaces in AFM

A calculation model for determination of the shapes of the constant force surfaces and profiles of lateral forces for the case of the AFM tip scanning the closely packed lattice in contact mode is proposed. Atomic relaxation is taken into account in this model. The existence of breaks on constant force surfaces, which was predicted earlier in an approximation of the fixed lattice, is confirmed. It is shown that due to non-zero atomic mobility, breaks appear for smaller scanning forces than assumed earlier. The shapes of the continuous constant force surfaces and profiles of lateral force components are computed. These results may be used for diagnostics of point defects on the surface.