Melt processing of cellulose nanocrystals (CNCs) reinforced nanocomposites is still a serious challenge due to the hydrophilic nature of CNCs and their severe agglomeration tendency within the polymer melt. In this study, chemical modification of CNC through grafting poly(glycidyl methacrylate) (PGMA) with various degrees was implemented. Wettability of the modified CNCs (mCNCs) were controlled and their structure was characterized through Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), optical microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The nanocomposites of polybutylene adipate terephthalate (PBAT) with 3 wt% CNC and mCNC were prepared using an internal melt mixer. To differentiate the effects of CNC and PGMA molecules on the final properties of nanocomposites, PBAT/PGMA compounds were separately prepared. To confirm the chain characterization and molecular weight of the synthesized PGMAs, 1H NMR and gel permeation chromatography (GPC) analysis were conducted. Melt rheological analysis, dynamic mechanical analysis (DMA), DSC, and atomic force microscopy (AFM) were used to monitor the mCNC dispersion quality and the effect of PGMA modification in PBAT compounds. The results revealed that grafting CNC with longer PGMA considerably improved the CNCs' dispersion quality within PBAT. Such dispersion enhancement of long-chain mCNCs and interfacial interaction of PGMA and PBAT resulted in a noticeable increase in storage modulus and complex viscosity of the final nanocomposites.

The properties of glasses can change significantly as they evolve toward equilibrium. Mechanical deformation appears to influence this physical aging process in conflicting ways, with experiments and simulations showing both effects associated with rejuvenation away from and overaging toward the equilibrium state. Here we report a significant densification effect in a polymer undergoing shear flow under high pressure. We used the high-aspect ratio geometry of the layer compression test to measure the uniform and homogeneous accumulation of plastic strain during isothermal confined compression of a deeply quenched film of polystyrene glass. Combined scanning transmission x-ray microscopy (STXM) and atomic force microscopy confirmed defect-free deformation leaving up to 1.2% residual densification under conditions of confined uniaxial strain. At higher peak strain, plastic shear flow extruded glass from below the compressing punch under conditions of a high background pressure. A further density increase of 2% was observed by STXM for a highly thinned residual thickness of polymer that nevertheless showed no signs of crystallization or internal strain localization. While the confined uniaxial densification can be accounted for by a simple elastic--plastic constitutive model, the high-pressure extrusion densification cannot.

We performed nanomachining combined with photoluminescence spectroscopy to understand the depth distribution of nitrogen-vacancy (NV) centers formed by low energy nitrogen ion irradiation of the diamond surface. NV- and NV0 fluorescence signals collected from the surface progressively machined by a diamond tip in an atomic force microscope (AFM) initially rise to a maximum at 5 nm depth before returning to background levels at 10 nm. This maximum corresponds to the defect depth distribution predicted by a SRIM simulation using a 2.5 keV implantation energy per nitrogen atom. Full extin-guishing of implantation produced NV- and NV0 zero phonon line peaks occurred beyond 10 nm machining depth, coinciding with the end of easy surface material removal and onset of significant tip wear. The wear ratio of for NV active, ion irradiated diamond compared to the single-crystal diamond tip was surprisingly found to be 22:1. The reported results constitute the first integrated study of in-situ machining and wear characterization via optical properties of the diamond surface containing shallow formed NV centers. We discuss possible metrology applications for diamond tools used in precision manufacturing. (C) 2020 Elsevier Ltd. All rights reserved.

We report simultaneous Force -static deflection of the cantilever-, Force Gradient and Scanning Tunneling topography images of Si(111)(7 x 7) surface using an off-resonance small amplitude non-contact atomic force microscopy technique with improved force sensitivity. The signal-to-noise ratio of the fiber interferometer used to detect the deflections of the cantilever was improved by applying an RF-modulation into the diode laser, which suppresses the noise in the laser. The measured sensitivity of similar to 20 fm/root Hz allows us to obtain atom resolved images of the surface in static deflection of the cantilever, simultaneously with the other imaging channels.

Scanning tunneling microscopy (STM) and atomic force microscopy (AFM) images of graphene reveal either a triangular or honeycomb pattern at the atomic scale depending on the imaging parameters. The triangular patterns at the atomic scale are particularly difficult to interpret, as the maxima in the images could be every other carbon atom in the six-fold hexagonal array or even a hollow site. Carbon sites exhibit an inequivalent electronic structure in HOPG or multilayer graphene due to the presence of a carbon atom or a hollow site underneath. In this work, we report small-amplitude, simultaneous STM/AFM imaging using a metallic (tungsten) tip, of the graphene surface as-grown by chemical vapor deposition (CVD) on Cu foils. Truly simultaneous operation is possible only with the use of small oscillation amplitudes. Under a typical STM imaging regime the force interaction is found to be repulsive. Force-distance spectroscopy revealed a maximum attractive force of about 7 nN between the tip and carbon/hollow sites. We obtained different contrast between force and STM topography images for atomic features. A honeycomb pattern showing all six carbon atoms is revealed in AFM images. In one contrast type, simultaneously acquired STM topography revealed hollow sites to be brighter. In another, a triangular array with maxima located in between the two carbon atoms was acquired in STM topography.

Most of the model lipid membrane studies on gold involve the usage of various surface-modification strategies to rupture liposomes and induce lipid bilayer formation since liposomes with polar surfaces do not interact with bare, hydrophobic gold. In this study, a thiol-modified phospholipid, 1,2-Dipalmitoylsn-Glycero-3-Phosphothioethanol (DPPTE) was incorporated into phosphatidylcholine (PC) based liposomes to form supported lipid bilayer (SLB) on gold surfaces without further modification. The binding kinetics of liposomes with different DPPTE ratio (0.01 to 100% mol/mol) and diameters were monitored by Quartz Crystal Microbalance with Dissipation (QCM-D). The dissipation change per frequency change, i.e. acoustic ratio, which is evaluated as a degree of the viscoelasticity, considerably decreased with the presence of DPPTE (from 162.3 GHz(-1) for flattened PC liposomes to ca. 89.5 GHz(-1) for 100% DPPTE liposomes) when compared to the results of two reference rigid monolayers and two viscoelastic layers. To assess the quality of SLB platform, the interpretation of QCM-D data was also complemented with Surface Plasmon Resonance. The optimum thiolated-lipid ratio (1%, lower thiol ratio and higher rigidity) was then used to determine the dry-lipid mass deposition, the water content and the thickness values of the SLB via viscoelastic modelling. Further surface characterization studies were performed by Atomic Force Microscopy with high spatial resolution. The results suggested that model membrane was almost continuous with minimum defects but showed more dissipative/soft nature compared to an ideal bilayer due to partially fused liposomes/overlapped lipid bilayers/multilayer islands. These local elevations distorted the planarity and led the increase of overall membrane thickness to similar to 7.0 nm. (C) 2017 Elsevier B.V. All rights reserved.

We describe a novel radiation pressure based cantilever excitation method for imaging in dynamic mode atomic force microscopy (AFM) for the first time. Piezo-excitation is the most common method for cantilever excitation, however it may cause spurious resonance peaks. Therefore, the direct excitation of the cantilever plays a crucial role in AFM imaging. A fiber optic interferometer with a 1310 nm laser was used both for the excitation of the cantilever at the resonance and the deflection measurement of the cantilever in a commercial low temperature atomic force microscope/magnetic force microscope (AFM/MFM) from NanoMagnetics Instruments. The laser power was modulated at the cantilever's resonance frequency by a digital Phase Locked Loop (PLL). The laser beam is typically modulated by ∼500 μW, and ∼141.8 nmpp oscillation amplitude is obtained in moderate vacuum levels between 4 and 300 K. We have demonstrated the performance of the radiation pressure excitation in AFM/MFM by imaging atomic steps in graphite, magnetic domains in CoPt multilayers between 4 and 300 K and Abrikosov vortex lattice in BSCCO(2212) single crystal at 4 K for the first time.

To investigate drug–membrane protein interactions, an artificial tethered lipid bilayer system was constructed for the functional integration of membrane proteins with large extra-membrane domains such as multi-drug resistance protein 1 (MDR1). In this study, a modified lipid (i.e., 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino (polyethylene glycol)-2000] (DSPE-PEG)) was utilized as a spacer molecule to elevate lipid membrane from the sensor surface and generate a reservoir underneath. Concentration of DSPE-PEG molecule significantly affected the liposome binding/spreading and lipid bilayer formation, and 0.03mg/mL of DSPE-PEG provided optimum conditions for membrane protein integration. Further, the incorporation of MDR1 increased the local rigidity on the platform. Antibody binding studies showed the functional integration of MDR1 protein into lipid bilayer platform. The platform allowed to follow MDR!-statin-based drug interactions in vitro. Each binding event and lipid bilayer formation was monitored in real-time using Surface Plasmon Resonance and Quartz Crystal Microbalance–Dissipation systems, and Atomic Force Microscopy was used for visualization experiments.

A major challenge for scanned probe microscopy is to identify structures and chemical species on a surface, which have not already been inferred from other analytical techniques. Progress is impeded by the fact that in general the structure and composition of the tip atom is not known. To illustrate some of the issues involved, we report simultaneous scanning tunneling microscopy/atomic force microscopy (STM/AFM) of the TiO2 (110) surface. The use of small amplitudes enabled the simultaneous acquisition of force gradient and barrier height images during standard STM imaging. Surprisingly, we find most STM images exhibit a corrugation contrast inverse to that usually reported in the literature. However, regardless of the contrast in STM, force gradient images always showed greater attraction over O rows. Barrier height images also show this consistency, always being greater over O rows. This supports the theoretical model of the electronic structure of the surface, but shows that the tip structure and interaction cannot be ignored in modeling STM images. We conclude that there is a fine balance between topography and local density of states (LDOS) in STM imaging of this surface; which of them dominates the STM image is determined by the tip. Simultaneous multi-parameter imaging is useful in interpreting images reliably, particularly on multi-component surfaces.

The preparation of a nominal half-monolayer of sulphur on the Ge(001) surface via the adsorption of H2S and subsequent annealing has been monitored by STM. The 'saturated adsorption' surface image of dark-bright pairs is consistent with the dissociative adsorption of H and HS, respectively, on either atom of each Ge dimer. Images obtained at subsequent annealing stages show significant etching of the germanium surface, which is not detectable by electron spectroscopy. These STM images do not show evidence of the bridge-bonded sulphur that ideally results from this recipe.

We report the first results from novel sub-Angstrom oscillation amplitude non-contact atomic force microscopy developed for lateral force gradient measurements. Quantitative lateral force gradients between a tungsten tip and Si(111)–(7×7) surface can be measured using this microscope. Simultaneous lateral force gradient and scanning tunnelling microscope images of single and multi atomic steps are obtained. In our measurement, tunnel current is used as feedback. The lateral stiffness contrast has been observed to be 2.5N/m at single atomic step, in contrast to 13N/m at multi atomic step on Si(111) surface. We also carried out a series of lateral stiffness–distance spectroscopy. We observed lateral stiffness–distance curves exhibit sharp increase in the stiffness as the sample is approached towards the surface. We usually observed positive stiffness and sometimes going into slightly negative region.

In this work, the authors report on a quantitative investigation of lateral-force gradient and lateral force between a tungsten tip and Si(111)-(7×7) surface using combined noncontact lateral-force microscopy and scanning tunneling microscopy. Simultaneous lateral-force gradient and scanning tunneling microscopy images of single and multiatomic step are obtained. In our measurement, tunnel current is used as feedback. The lateral-stiffness contrast has been observed to be 2.5N∕m at a single atomic step, in contrast to 13N∕m at a multiatomic step on Si (111) surface. They also carried out a series of lateral stiffness-distance spectroscopy, which show a sharp increase in tip-surface interaction stiffness as the sample is approached toward the surface.

The authors report simultaneous scanning tunneling and force imaging of Si(111) 7×7 with sub-angstrom oscillation amplitudes. Both constant height and constant current scans with tungsten tips/levers always showed larger attractive stiffness over corner holes than over adatoms, the opposite of theoretical expectations. Constant height scans show that this cannot be explained by interaction of tip motion with long range forces. Silicon levers, however, sometimes exhibited inversions of force contrast following local tip changes. The authors suggest that there may be charge variations between atomic sites on the surface, which produce electrostatic tip forces additional to the covalent forces usually regarded as dominant.

The mechanical patterning of thin films has received recent attention due to significant potential for efficient nanostructure fabrication. For solid films, mechanically thinning wide areas remains particularly challenging. In this work, we introduce a new plastic ratchet mechanism involving small amplitude (< 10 nm), oscillatory shear motion of the forging die. This isothermal mechanism significantly extends mass transport across surfaces, broadening the scope of nanoscale processing for a potentially wide class of solid ductile materials.