Time‐lapse lab‐based x‐ray nano‐CT study of corrosion damage

An experimental protocol (workflow) has been developed for time‐lapse x‐ray nanotomography (nano‐CT) imaging of environmentally driven morphological changes to materials. Two case studies are presented. First, the leaching of nanoparticle corrosion inhibitor pigment from a polymer coating was followed over 14 days, while in the second case the corrosion damage to an AA2099 aluminium alloy was imaged over 12 hours. The protocol includes several novel aspects relevant to nano‐CT with the use of a combination of x‐ray absorption and phase contrast data to provide enhanced morphological and composition information, and hence reveal the best information to provide new insights into the changes of different phases over time. For the pigmented polymer coating containing nominally strontium aluminium polyphosphate, the strontium‐rich components within the materials are observed to leach extensively whereas the aluminium‐rich components are more resistant to dissolution. In the case of AA2099 it is found that the initial grain boundary corrosion is driven by the presence of copper‐rich phases and is then followed by the corrosion of grains of specific orientation.     

Application of nano electrolyte in the electrochemical discharge machining process

As a nontraditional machining process, electrochemical discharge machining (ECDM) can apply to hard and brittle materials such as glass and ceramic. Improvement of process efficiency is an important topic that has been addressed in many investigations using various techniques such as magnetic field and ultrasonic vibrations.Nano particles are new and advanced materials that can be dispersed in a fluid to obtain a nano fluid with desirable specifications. This method can be implemented in the ECDM process by the application of the nano electrolyte. Nano electrolyte can present enhanced properties, in particular enhanced electrical and thermal conductivities which lead to more powerful discharges and greater material removal.In order to study the variation of discharge physics, consequent captures from discharges were taken. Besides using current signal diagrams, larger numbers of discharges were found using nano electrolytes. Results of hole depth showed that both Cu and Al₂O₃ nano electrolytes improved the hole depth as 21.1% and 18.7%, respectively. An undesirable effect of nano electrolyte was observed on the entrance overcut, which raised 8.3% and 10.7% using Cu and Al₂O₃ nano electrolytes, respectively, in comparison to the simple electrolyte. This drawback is negligible compared to the significant improvement of hole depth. SEM images of tool wear showed larger molten materials on the tool main edges by the application of nano electrolyte.     

Effect of the molecular weight on deformation states of the polystyrene film by AFM single scanning

Nanobundles patterns can be formed on the surface of most thermoplastic polymers when the atomic force microscope (AFM)‐based nanomechanical machining method is employed to scratch their surfaces. Such patterns are reviewed as three‐dimensional sine‐wave structures. In the present study, the single‐line scratch test is used firstly to study different removal states of the polystyrene (PS) polymer with different molecular weights (MWs). Effects of the scratching direction and the scratching velocity on deformation of the PS film and the state of the removed materials are also investigated. Single‐wear box test is then employed to study the possibility of forming bundle structures on PS films with different MWs. The experimental results show that the state between the tip and the sample plays a key role in the nano machining process. If the contact radius between the AFM tip and the polymer surface is larger than the chain end‐to‐end distance, it is designated as the “cutting” state that means the area of both side ridges is less than the area of the groove and materials are removed. If the contact radius is less than the chain end‐to‐end distance, it is designated as the “plowing” state that means the area of both side ridges is larger than the area of the groove and no materials are removed at all. For the perfect bundles formation on the PS film, the plowing state is ideal condition for the larger MW polymers because of the chains’ entanglement. SCANNING 35:308‐315, 2013. © 2012 Wiley Periodicals, Inc.     

Tuning the mechanical properties of self‐assembled mixed‐peptide tubes

In this study, nano‐ and microscale fibrillar and tubular structures formed by mixing two aromatic peptides known to self‐assemble separately, (diphenylalanine and di‐D‐2‐napthylalanine) have been investigated. The morphology, mechanical strength and thermal stability of the tubular structures formed have been studied. The tubes are shown to consist of both peptides with some degree of nanoscale phase separation. The ability of the mixed peptides to form structures, which display variable mechanical properties dependent on the percentage composition of the peptides is presented. Such materials with tuneable properties will be required for a range of applications in nanotechnology and biotechnology.     

添加纳米磁性微粒的润滑油摩擦学行为研究

用化学方法制备纳米MnZnFe2O4磁性微粒,在四球摩擦磨损试验机和立式万能摩擦磨损试验机上考察了MnZnFe2O4纳米磁性微粒作为润滑油添加剂的抗磨减摩性能及对磨损表面的修复作用,并用扫描电子显微镜观察分析了磨斑表面形貌。实验表明,MnZnFe2O4纳米微粒添加剂可以显著提高基础油的承载能力,减小磨斑直径;磁性颗粒有利于加强吸附在摩擦副表面上形成物理吸附膜,并在摩擦表面形成自修复膜,对磨损表面具有一定的修复作用。     

Surface forces, surface chemistry and tribology

Scanning probe methods have been applied to the investigation of tribological phenomena on the nanometre and nanonewton scale. The systems studied have included parallel investigation of identical tribosystems on the macro and nano scales, where the inherent differences in the AFM/LFM and flat-on-disk experiments have been compared; oxide-covered surfaces in contact under electrolytes, where the adhesion hysteresis and frictional behaviour was shown to be strongly dependent on the solution pH; and polymer surfaces, where advantage can be taken of variations in the interactions between the scanning tip and different polymers, to perform chemically sensitive, high-resolution surface imaging of polymer blends.     

Mechanical properties of tribologically modified nano‐layers

Wear in modern mechanical systems is characterised by ultra‐low wear rates in the range of a few nanometres per hour. Both the surfaces of the materials involved and their volumes undergo modification as regards morphology, crystalline arrangement, and chemical composition. The depth of tribological interactions for given conditions is in the order of a micrometre or less. Synchrotron‐based X‐ray diffraction and nano‐indentation were used to probe these thin modified zones. The specimens were taken from tribometric experiments employing the radionuclide technique as the ultimate tool to measure ultra‐low wear rates. To obtain different degrees of tribological interaction various loads and sliding velocities were applied. The specimens were classified according to the total power dissipated during the tribometric experiment.     

Near-field optical microscope observation of dye-containing nano-domains

A novel method for forming dye‐containing nano‐domains in thin films using a polymer alloy system has been developed. The polymer alloy system (PS‐b‐PMMA), which consists of polystyrene (PS) and polymethyl methacrylate (PMMA), forms microphase separation in thin films. The film was treated using a previously reported technique under vacuum conditions, and an organic dye was selectively dispersed into the PS. Selective association of the dye (diarylethene; cis‐1, 2‐dicyano‐1, 2‐bis (2,4,5‐trimethyl‐3‐thienyl) ethene) with the PS nano‐domains was then observed, with both transmission electron microscopy and scanning near‐field optical microscopy with an absorption spectrum.     

Polysaccharide properties probed with atomic force microscopy

In recent years, polysaccharides have been extensively studied using atomic force microscopy (AFM). Owing to its high lateral and vertical resolutions and ability to measure interaction forces in liquids at pico‐ or nano‐Newton level, the AFM is an excellent tool for characterizing biopolymers. The first imaging studies showed the morphology of polysaccharides, but gradually more quantitative image analysis techniques were developed as the AFM grew easier to use in aqueous liquids and in non‐contact modes. Recently, AFM has been used to stretch polysaccharides and characterize their physicochemical properties by application of appropriate polymer stretching models, using a technique called single‐molecule force spectroscopy. From application of such models as the wormlike chain, freely jointed chain, extensible‐freely jointed chain, etc., properties such as the contour length, persistence length and segment elasticity or spring constant can be calculated for polysaccharides. The adhesion between polysaccharides and surfaces has been quantified with AFM, and this application is particularly useful for studying polysaccharides on microbial and other types of cells, because their adhesion is controlled by biopolymer characteristics. This review presents a synthesis of the theory and techniques currently in use to probe the physicochemical properties of polysaccharides with AFM.     

The influence of oxidation on the tribological performance of diester lubricant

The oxidative degradation test of di‐2‐ethylhexyl sebacate (DEHS) was carried out by a sealed stainless steel reactor. Fourier transform infrared spectroscopy and gas chromatography–mass spectrometry (GC–MS) were utilised to characterise the chemical composition and molecular structure of the oxidation products. The results revealed that 2‐ethyl‐1‐hexanol and mono(2‐ethylhexyl)sebacate were major degradation products in the liquid phase. Tribological behaviour was measured using a four‐ball tester. Scanning electron microscopy was employed to investigate the morphologies of the worn surface. Tribological results showed that anti‐wear and friction‐reducing performances of DEHS were highly dependent on the chemical composition of the oxidation products generated during the test. The hydroperoxides formed during the initial oxidation process could deteriorate lubrication properties of DEHS. However, certain amount of highly polar degradation products (acids and alcohols) generated could significantly improve the friction‐reducing performance of DEHS by the formation of boundary adsorption films on the rubbing surfaces. Copyright © 2013 John Wiley & Sons, Ltd.     

Imaging and studying human topoisomerase I on mica surfaces in air and in liquid by atomic force microscopy

In this study, the topography of human topoisomerase I (TOPO I) on mica surfaces in air and in liquid has been studied by atomic force microscopy (AFM). The average height of TOPO I on mica surface in air measured by AFM was 2.59±0.32 nm. After adsorption of the 0.3 U/µl TOPO I on mica surfaces for 2 h, and then imaged in liquid by AFM, well‐separated single TOPO I was observed. The average height of TOPO I on mica surfaces in liquid measured by AFM was 2.93±0.42 nm. After adsorption of the 4 U/µl TOPO I on mica surfaces for 1.5 h, TOPO I monolayer can be formed. The produced TOPO I monolayer on mica was flat and exhibited good stability. SCANNING 31: 160–166, 2009. © 2009 Wiley Periodicals, Inc.     

Tribological Characteristics and Tribochemical Reactions of Various Ceramics Lubricated with HFC-134a Gas

The role of tribochemical products in the friction and wear reduction of ceramics with different fractional ionic character in CF₃CH₂F (HFC-134a) gas was investigated using a ball-on-disk type tribometer. Without exposure to air, the wear tracks on the disks were characterized with the aid of a micro-spot X-ray Photoelectron Spectroscope (XPS) whose analytical chamber was connected to the friction chamber of the tribometer. Further, the adsorption and desorption behaviors of HFC-134a molecules on the nascent surfaces of the ceramics were studied using an adsorption test apparatus in high vacuum. It was found that the lubricating effect of HFC-134a gas was closely related to the fractional ionic or covalent characters of the ceramics. HFC-134a gas was more effective in lubricating ionic ceramics than the covalent ceramics. XPS analysis revealed that metal fluorides were mainly formed on the frictional surfaces of the ionic ceramics, whereas the composition of the tribochemical products on the frictional surfaces of the other ceramics was complicated. The adsorption tests proved that HFC-134a was decomposed to an olefin CF₂=CHF on the nascent surfaces of the ionic ceramic Al₂O₃ and the covalent ceramics. However, the formation of organic fluorine-containing compounds was not detected on the frictional surfaces of the ionic ceramics by XPS. This result implies that the mechanism of tribochemical reactions is strongly dependent on the bond type of ceramics. It is concluded that the low friction and wear of the ionic ceramics in HFC-134a gas result from the metal fluorides formed with high surface concentration on the sliding surfaces.     

Morphology and protein adsorption characteristics of block copolymer surfaces

Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because novel, structurally diverse polymers can be synthesized from biocompatible blocks. Block copolymer nanostructure and surface morphology is easily tunable with synthetic techniques and the diverse nanostructures can be used to affect cell and tissue behaviour. In this paper, we present atomic force microscopy studies on the morphology and corresponding protein adsorption behaviour of a novel class of methyl methacrylate and acrylic acid diblock and triblock copolymers. The topography, phase angle and adhesion maps were obtained to study the morphology. Atomic force microscopy imaging reveals that the diblock and triblock copolymers present distinct nanomorphologies, although their chemical composition is the same. This has implications on the role of nanomorphology in cell-polymer interactions independent of chemical composition. Protein adsorption on a biomaterial surface is critical to understanding its biocompatibility and bovine serum albumin was used to model that behaviour on the block copolymer surfaces. An increase in the adhesive force of the surface was observed to correlate with the adsorption of bovine serum albumin on the block copolymer surfaces investigated.     

Application of atomic force microscopy methods for testing the surface parameters of coatings of medical implants

Atomic force microscopy methods are used to study calcium phosphate coatings that are formed on surfaces of various materials, which are used in medicine, by radio-frequency magnetron sputtering of a hydroxyapatite target. The roughness parameters and values of the surface potentials of metal, polymer, and hybrid substrates are determined in a semicontact regime. Calcium phosphate coatings increase the roughness of surfaces of polymer and metal materials, thus presenting a stimulating factor for the attachment and proliferation of osteogenic cells. Using the Kelvin method, it is shown that calcium phosphate coatings change the surface potential of substrates.     

Experimental Characterization of Micro-Friction on a Mica Surface Using the Lateral Motion and Force Measurement Capability of an Instrumented Indenter

An experimental characterization of friction forces between asymmetric surfaces in the micro-regime is presented. The lateral motion and force-measurement capability of an instrumented indenter (triboindenter) is characterized and explored for determining friction properties at low velocities. Friction experiments are performed using the triboindenter with high repeatability. It is observed that real-time depth measurements closely follow the Hertzian prediction. Friction spikes with magnitudes depending on the drive velocity input are observed with peak friction force increasing with the dwell time. Anisotropy is observed between surfaces of different materials with stick-slip occurring only at specific relative orientations. Directions for expanding the current range of the triboindenter to obtain data from the nano to the macro scale are also presented.     

Biomineralization induced by chitosan and collagen-based materials with fluoride for dentin coverage: Chemical and morphological analysis

The prevention and treatment of erosive tooth wear are becoming increasingly important due to its increasing prevalence. The use of natural solutions to modify dental surfaces has become an area of research. Organic materials such as chitosan and hydrolyzed collagen may be a promising option to treat dentin. This in vitro study aimed to evaluate the influence of chitosan or hydrolyzed collagen, alone or combined with acidulated phosphate fluoride (APF) gel, on the composition and morphology of dentin after erosion. Bovine dentin samples were prepared (n = 84) and treated with artificial saliva (AS, negative control); APF gel (F, positive control); chitosan solution (Chi); hydrolyzed collagen solution (Col); fluoride/chitosan composition (F_Chi); and fluoride/hydrolyzed collagen composition (F_Col). Erosive cycles (six cycles of immersion in orange juice for 1 min, followed by immersion in AS for 1 hr) were performed. The materials were characterized by their morphology, composition, and particle size distribution. Micro-energy dispersive X-ray fluorescence spectroscopy and scanning electron were used to evaluate the dentin's inorganic chemical composition and morphology. The F_Col and F groups had a reduction in calcium loss by 17 and 26%, respectively (p < .001). Both of these groups still had a covering layer of agglomerates at the dentin surface after the erosive cycles. The fluoridated chitosan or collagen solutions improved the dentin resistance to erosion as a novel hybrid-fluoride-based material approach to provide surface protection from erosion.     

The Influence of Surface Roughness on the Lubrication Properties of Adsorbing and Non-Adsorbing Biopolymers

The lubrication properties of a glycoprotein (pig gastric mucin or PGM) and a high-molecular-weight hydrosoluble polymer (guar gum) have been studied. Friction has been measured over a wide range of entrainment speeds and Stribeck curves have been obtained spanning the boundary, mixed and hydrodynamic lubrication regimes. The adsorption properties of the polymers have also been assessed using evanescent wave spectroscopy. The results show that the polymer that adsorbs on solid surfaces is able to reduce friction in the boundary lubrication regime (PGM). Guar, which does not adsorb on surfaces, shows high friction in boundary lubrication but still promotes the onset of mixed lubrication; thus friction starts to fall from its boundary values at low speeds. These results can be explained in classical terms of entrainment of polymer solution into the thin film conjunction and associated shear thinning in the contact inlet. With roughened surfaces, a shift of the Stribeck curves towards high speed is observed.     

Friction and wear effects on a micro/nano‐scale

In this paper are described tribological effects which can be found in micro‐tribological systems, and in those macro‐systems which can be analysed by micro‐methods, e.g., by atomic force microscopy (AFM) or related methods. Micro‐tribology systems have friction contacts with loads in the micro/nano‐newton range and/or dimensions in the micro/nanometre range. Experiments on the micro/nano‐scale should be easier to explain by theoretical modelling due to their simpler system structure. An example is discussed of adhesion and friction measurements between AFM tips and clean, flat, solid surfaces in ultra‐high vacuum, which shows some of the special aspects of micro/nano‐tribology. Surprising friction characteristics on surfaces with an artificial micro‐structure can be explained by skilled and careful topographical analysis of the friction path with an AFM. In micro‐sensor contacts, ‘single wear events’ can be detected using AFM analysis of the contact region. For ceramic compounds, different friction levels for the components of the material can be found. The problems, difficulties, and dangers of misinterpretation are also discussed.     

Modelling and experimental investigations of thin filmsof Mg phosphorus‐doped tungsten bronzes obtainedby ultrasonic spray pyrolysis

In this study, the synthesis of thin films of Mg phosphorus doped tungsten bronzes (MgPTB; MgHPW₁₂O₄₀·29H₂O) by the self‐assembly of nano‐structured particles of MgPTB obtained using the ultrasonic spray pyrolysis method was investigated. As the precursor, MgPTB, prepared by the ionic exchange method, was used. Nano‐structured particles of MgPTB were obtained using the ultrasonic spray pyrolysis method. The nano‐structure of the particles used as the building blocks in the MgPTB thin film were investigated experimentally and theoretically, applying the model given in this article. The obtained data for the mean particle size and their size distribution show a high degree of agreement. These previously tailored particles used for the preparation of thin films during the next synthesis step, by their self‐assembly over slow deposition on a silica glass substrate, show how it is possible to create thin MgPTB films under advance projected conditions of the applied physical fields with a fully determined nanostructure of their building block particles, with a relatively small roughness and unique physical properties.     

Friction reduction in rolling bearing by using polymer additives

The friction torque on the outer ring of a tapered roller bearing has been experimentally measured for a mineral oil (base oil), as well as for samples of the base oil additived with low‐density polyethylene. The data show an important reduction of friction by introducing the polymer into the base oil due to the film formed by the adsorption of macromolecular coils on the solid surface. The effectiveness of macromolecular additive contribution to friction behaviour is described in terms of polymer efficiency, which shows maximum values at low polymer concentrations. Copyright © 2009 John Wiley & Sons, Ltd.