Electrochemical, atomic force microscopy and infrared reflection absorption spectroscopy studies of pre-formed mussel adhesive protein films on carbon steel for corrosion protection

Electrochemical measurements, in situ and ex situ atomic force microscopy (AFM) experiments and infrared reflection absorption spectroscopy (IRAS) analysis were performed to investigate the formation and stability as well as corrosion protection properties of mussel adhesive protein (Mefp-1) films on carbon steel, and the influence of cross-linking by NaIO₄ oxidation. The in situ AFM measurements show flake-like adsorbed protein aggregates in the film formed at pH 9. The ex situ AFM images indicate multilayer-like films and that the film becomes more compact and stable in NaCl solution after the cross-linking. The IRAS results reveal the absorption bands of Mefp-1 on carbon steel before and after NaIO₄ induced oxidation of the pre-adsorbed protein. Within a short exposure time, a certain corrosion protection effect was noted for the pre-formed Mefp-1 film in 0.1 M NaCl solution. Cross-linking the pre-adsorbed film by NaIO₄ oxidation significantly enhanced the protection efficiency by up to 80%.     

Extreme Reconfigurable Nanoelectronics at the CaZrO3/SrTiO3 Interface

Complex oxide heterostructures have fascinating emergent properties that originate from the properties of the bulk constituents as well as from dimensional confinement. The conductive behavior of the polar/nonpolar LaAlO₃/SrTiO₃ interface can be reversibly switched using conductive atomic force microscopy (c‐AFM) lithography, enabling a wide range of devices and physics to be explored. Here, extreme nanoscale control over the CaZrO₃/SrTiO₃ (CZO/STO) interface, which is formed from two materials that are both nonpolar, is reported. Nanowires with measured widths as narrow as 1.2 nm are realized at the CZO/STO interface at room temperature by c‐AFM lithography. These ultrathin nanostructures have spatial dimensions at room temperature that are comparable to single‐walled carbon nanotubes, and hold great promise for alternative oxide‐based nanoelectronics, as well as offer new opportunities to investigate the electronic structure of the complex oxide interfaces. The cryogenic properties of devices constructed from quasi‐1D channels, tunnel barriers, and planar gates exhibit gate‐tunable superconductivity, quantum oscillations, electron pairing outside of the superconducting regime, and quasi‐ballistic transport. This newly demonstrated ability to control the metal–insulator transition at nonpolar oxide interface greatly expands the class of materials whose behavior can be patterned and reconfigured at extreme nanoscale dimensions.     

Effect of Mn on the Surface Morphological Properties of (Bi, Pb)2 Sr2Ca2Cu3?x Mn x O10+δ (Bi-2223) Superconductor

Samples of (Bi, Pb)₂Sr₂Ca₂Cu_3?x Mn _x O_10+?? (Bi-2223, x=0.0 to 0.30) were synthesized by a solid-state reaction route. The surface morphology investigated through scanning electron microscopy and atomic force microscopy (SEM and AFM) as a result shows that voids and grain sizes increase as the Mn concentration increases, and besides, nanosphere-like structures occur on the surface of the Mn-doped Bi-2223 sample. For x=0, compact granular structures of variously shaped thin grains and larger pores are observed in some local region. In the three-dimensional (3D) AFM view of the same surface the formation of the humps and roughness in some places can also be clearly seen, which is due to the formation of an oxide layer with different thicknesses, depending on the chemical composition of the phases. Besides the said features, two types of inhomogeneity have been observed in our investigations such as, first type, planar nanogranules of various sizes and, second type, closely packed planar rounded nanogranules.     

Micro/nanoscale mechanical characterization and in situ observation of cracking of laminated Si3N4/BN composites

Micro/nanoscale mechanical characterization of laminated Si₃N₄/BN composites was carried out by nanoindentation techniques. A custom-designed micro mechanical tester was integrated with an optical microscope and an atomic force microscope to perform in situ three-point bending tests on notched Si₃N₄/BN composite bend specimens where the crack initiation and propagation were imaged simultaneously with the optical microscope and atomic force microscope during bending loading. The whole fracture process was in situ captured. It was found that crack deflection was initiated/induced by the pre-existing microvoids and microcracks in BN interfacial layers. New fracture mechanisms were proposed to provide guidelines for the design of biomimetic nacre-like composites.     

Preparation and characterization of EP/SiO<Subscript>2</Subscript> hybrid materials containing PEG flexible chain

EP/SiO₂ hybrid materials, which contained flexible chain, were prepared by epoxy resin (EP) and polyethylene glycol (PEG)-grafted polysilicic acid (PSA), which was obtained by endcapping polyethylene glycol-1000 with toluene 2,4-diisocyanate (TDI), followed by a reaction with polysilicic acid. The formation of hybrid materials was confirmed by a wide-angle X-ray diffraction (WAXD) and atomic force microscopy (AFM) analysis. Results showed that the EP/SiO₂ hybrid particles were nanosized and the average size was about 20–50 nm. The mechanical properties, dynamic mechanical properties, and thermal properties were evaluated and compared with the corresponding matrix. The improvement in impact properties in hybrid materials was explained in terms of the impact fracture surface analysis by scanning electron microscope (SEM).     

Local chemical fluctuation mediated ductility in body-centered-cubic high-entropy alloys

High-entropy alloys (HEAs) open up a new horizon for discovering un-explored mechanical properties and deformation mechanisms. Local chemical fluctuations (LCFs) in HEAs were found to have significant influences on their mechanical performance, however, the underlying origins remain unclear. In this work, direct dynamic observation of the interaction between LCFs and dislocations was captured by in situ transmission electron microscopy in a ductile body-centered-cubic (BCC) HfNbTiZr HEA under loading. The observed dislocation pinning induced by LCFs contributes to the increment not only in the strength but also in the ductility due to strongly promoted dislocation interaction. The observed local double cross-slips caused by the LCFs distribute dislocations onto various atomic planes homogenously, which is also beneficial for ductilization in HfNbTiZr. Our findings not only shed light on the understanding of deformation mechanisms of HEAs, but also provide a new perspective to design ductile BCC HEAs.     

Microstructure-hardened silver nanowires

To exploit the novel size-dependent mechanical properties of nanowires, it is necessary for one to develop strategies to control the strength and toughness of these materials. Here, we report on the mechanical properties of silver nanowires with a unique fivefold twin structure using a lateral force atomic force microscopy (AFM) method in which wires are held in a double-clamped beam configuration. Force-displacement curves exhibit super elastic behavior followed by unexpected brittle failure without significant plastic deformation. Thermal annealing resulted in a gradual transition to weaker, more ductile materials associated with the elimination of the twinned boundary structure. These results point to the critical roles of microstructure and confinement in engineering the mechanical properties of nanoscale materials.     

Impact of monoolein on aquaporin1-based supported lipid bilayer membranes

Aquaporin (AQP) based biomimetic membranes have attracted considerable attention for their potential water purification applications. In this paper, AQP1 incorporated biomimetic membranes were prepared and characterized. The morphology and structure of the biomimetic membranes were characterized by in situ atomic force microscopy (AFM), infrared absorption spectroscopy, fluorescence microscopy, and contact angle measurements. The nanofiltration performance of the AQP1 incorporated membranes was investigated at 4 bar by using 2 g l⁻¹ NaCl as feed solution. Lipid mobility plays an important role in the performance of the AQP1 incorporated supported lipid bilayer (SLB) membranes. We demonstrated that the lipid mobility is successfully tuned by the addition of monoolein (MO). Through in situ AFM and fluorescence recovery after photo-bleaching (FRAP) measurements, the membrane morphology and the molecular mobility were studied. The lipid mobility increased in the sequence DPPC < DPPC/MO (R_MO = 5/5) < DOPC/MO (R_MO = 5/5) < DOPC, which is consistent with the flux increment and salt rejection. This study may provide some useful insights for improving the water purification performance of biomimetic membranes.     

Revealing the atomistic deformation mechanisms of face-centered cubic nanocrystalline metals with atomic-scale mechanical microscopy: A review

Nanocrystalline metals have many functional and structural applications due to their excellent mechanical properties compared to their coarse-grained counterparts. The atomic-scale understanding of the deformation mechanisms of nanocrystalline metals is important for designing new materials, novel structures and applications. The review presents recent developments in the methods and techniques for in situ deformation mechanism investigations on face-centered-cubic nanocrystalline metals. In the first part, we will briefly introduce some important techniques that have been used for investigating the deformation behaviors of nanomaterials. Then, the size effects and the plasticity behaviors in nanocrystalline metals are discussed as a basis for comparison with the plasticity in bulk materials. In the last part, we show the atomic-scale and time-resolved dynamic deformation processes of nanocrystalline metals using our in-lab developed deformation device.     

Emerging X-ray imaging technologies for energy materials

With the growing need for sustainable energy technologies, advanced characterization methods become more and more critical for optimizing energy materials and understanding their operation mechanisms. In this review, we focus on the synchrotron-based X-ray imaging technologies and the associated applications in gaining fundamental insights into the physical/chemical properties and reaction mechanisms of energy materials. We will discuss a few major X-ray imaging technologies, including X-ray projection imaging, transmission X-ray microscopy, scanning transmission X-ray microscopy, tender and soft X-ray imaging, and coherent diffraction imaging. Researchers can choose from various X-ray imaging techniques with different working principles based on research goals and sample specifications. With the X-ray imaging techniques, we can obtain the morphology, phase, lattice and strain information of energy materials in both 2D and 3D in an intuitive way. In addition, with the high-penetration X-rays and the high-brilliance synchrotron sources, operando/in-situ experiments can be designed to track the qualitative and quantitative changes of the samples during operation. We expect this review can broaden readers’ view on X-ray imaging techniques and inspire new ideas and possibilities in energy materials research.     

Room temperature single electron transistor with two-dimensional array of Au–SiO2 core–shell nanoparticles

The composite nanoparticles of gold core coated with SiO₂ shell have been fabricated into 2-dimensional array on a silicon surface by a simple self-assembly method combined with the technique of AFM (atomic force microscopy) nanolithography. The double-barrier-tunneling junction with AFM tip was also fabricated for the room-temperature single-electron tunneling study, by which the AFM tip was orientated on the surface of the SiO₂ coated gold composite nanoparticles. The 2D array shows well-pronounced Coulomb staircases with a period of 200 mV at room temperature, demonstrating single electron transistor behavior.     

Photoinitiator grafted styrene–butadiene–styrene triblock copolymer

Grafting of photoinitiator-4-maleimidobenzophenone (4-MBP) onto styrene–butadiene–styrene (SBS) triblock copolymer was carried out by free radical polymerization. The grafting ratio was evaluated by varying initiator concentrations, and the structure of grafted copolymer (SBS-g-MBP) was characterized by attenuated total reflectance infrared Fourier transform spectroscopy (ATR-FTIR), proton nuclear magnetic resonance (¹H NMR) and X-ray photoelectron spectroscopy (XPS). The results confirmed that 4-MBP was successfully grafted onto the SBS backbone. Thermal gravimetric analyzer (TGA), dynamic mechanical thermal analysis (DMTA), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to study the thermal properties and morphology of the SBS-g-MBP. From the data of TGA, the SBS-g-MBP had better thermal stability compared with that of SBS. DMTA testing indicated that the glass transition temperature (T_g) of SBS-g-MBP was higher than that of SBS. With the aid of SEM and AFM, the structure of micro-phase separation can be observed obviously. What is more, the aggregates become smaller compared with those of pure SBS. The experiment of UV-crosslinked SBS-g-MBP revealed that the gel fraction could be facilely controlled by adjusting grafting ratio and exposure time. The results suggested that this novel grafted copolymer could be attractive for its application in biomedical materials such as medical pressure-sensitive adhesive.     

Hybrid Nanoscopy of Hybrid Nanomaterials

The combination of complementary techniques to characterize materials at the nanoscale is crucial to gain a more complete picture of their structure, a key step to design and fabricate new materials with improved properties and diverse functions. Here it is shown that correlative atomic force microscopy (AFM) and localization‐based super‐resolution microscopy is a useful tool that provides insight into the structure and emissive properties of fluorescent β‐lactoglobulin (βLG) amyloid‐like fibrils. These hybrid materials are made by functionalization of βLG with organic fluorophores and quantum dots, the latter being relevant for the production of 1D inorganic nanostructures templated by self‐assembling peptides. Simultaneous functionalization of βLG fibers by QD655 and QD525 allows for correlative AFM and two‐color super‐resolution fluorescence imaging of these hybrid materials. These experiments allow the combination of information about the topography and number of filaments that compose a fibril, as well as the emissive properties and nanoscale spatial distribution of the attached fluorophores. This study represents an important step forward in the characterization of multifunctionalized hybrid materials, a key challenge in nanoscience.     

Morphology of CaF2 nanocrystals and elastic properties in transparent oxyfluoride crystallized glasses

An oxyfluoride glass with the composition of 25CaF₂-5CaO-20Al₂O₃-50SiO₂ (mol%) and crystallized glasses containing CaF₂ nanocrystals (10-70 nm) are fabricated. The size and morphology of CaF₂ nanocrystals is examined using transmission electron microscopy and atomic force microscopy (AFM), and elastic properties of crystallized glasses are evaluated using a cube resonance method. The large increase in the glass transition temperature in crystallized glasses suggests that the Al₂O₃-SiO₂ based glass network having a high thermal stability is created due to the formation of CaF₂ nanocrystals. It is suggested from AFM observations that the chemical bonding between CaF₂ nanocrystals and oxide glass matrix is weak. Young’s modulus (E) increases with increasing heat treatment temperature, i.e., E = 88.4 GPa for the glass and E = 93.3 GPa for the sample heat-treated at 700 °C for 1 h. The present study demonstrates that oxyfluoride crystallized glasses containing CaF₂ nanocrystals have good elastic (mechanical) properties, being available in practical device applications even from the mechanical point of view.     

Microhardness,chemical etching,SEM, AFM and SHG studies of novel nonlinear optical crystal – l-threonine formate

The crystal l-threonine formate, an organic NLO crystal was synthesized from aqueous solution by slow evaporation technique. The grown crystal surface has been analyzed by scanning electron microscopy (SEM), chemical etching and atomic force microscopy (AFM). SEM analysis reveals pyramidal shaped minute crystallites on the growth surface. The etching study indicates the occurrence of etch pit patterns like striations and step like pattern. The mechanical properties of LTF crystals were evaluated by mechanical testing which reveals certain mechanical characteristics like elastic stiffness constant (C₁₁) and young's modulus (E). The Vickers and Knoop microhardness studies have been carried out on LTF crystals over a range of 10–50 g. Hardness anisotropy has been observed in accordance with the orientation of the crystal. AFM image shows major hillock on growth surface. The second harmonic generation (SHG) efficiency has been tested by the Kurtz powder technique using Nd:YAG laser and found to be about 1.21 times in comparison with standard potassium dihydrogen phosphate (KDP) crystals.     

Single cell profiling of surface carbohydrates on Bacillus cereus

Cell surface carbohydrates are important to various bacterial activities and functions. It is well known that different types of Bacillus display heterogeneity of surface carbohydrate compositions, but detection of their presence, quantitation and estimation of variation at the single cell level have not been previously solved. Here, using atomic force microscopy (AFM)-based recognition force mapping coupled with lectin probes, the specific carbohydrate distributions of N-acetylglucosamine and mannose/glucose were detected, mapped and quantified on single B. cereus surfaces at the nanoscale across the entire cell. Further, the changes of the surface carbohydrate compositions from the vegetative cell to spore were shown. These results demonstrate AFM-based ‘recognition force mapping’ as a versatile platform to quantitatively detect and spatially map key bacterial surface biomarkers (such as carbohydrate compositions), and monitor in situ changes in surface biochemical properties during intracellular activities at the single cell level.     

Atomic layer deposition of ZnS via in situ production of H2S

Atomic layer deposition (ALD) of ZnS films utilizing diethylzinc and in situ generated H₂S was performed over a temperature range of 60 °C-400 °C. This method for generating H₂S in situ was developed to eliminate the need to store high pressure H₂S gas. The H₂S precursor was generated by heating thioacetamide to 150 °C in an inert atmosphere, producing acetonitrile and H₂S as confirmed with mass spectroscopy. ALD behavior was confirmed by investigation of growth behavior and saturation curves. The properties of the films were studied with X-ray diffraction, transmission electron microscopy, ellipsometry, atomic force microscopy, scanning electron microscopy, ultraviolet-visible spectroscopy, and X-ray photoelectron spectroscopy. The results show a growth rate that monotonically decreases with temperature, and films that are stoichiometric in Zn and S. The root mean square roughness of the films increases with temperature above 100 °C. A change in crystal phase begins at ∼ 300 °C. The band gap is dependent on the crystal phase and is estimated to be 3.6-4 eV.     

Nanostructural and chemical characterization of supported metal oxide catalysts by aberration corrected analytical electron microscopy

The performance of catalyst materials are usually governed by the precise atomic structure and composition of very specific catalytically active sites. Therefore, structural and chemical characterization at the atomic scale becomes a vital requirement in order to identify any structure-performance relationships existing in heterogeneous catalyst systems. Aberration-corrected scanning transmission electron microscopy (STEM) represents an ideal means to probe the atomic scale structural and chemical information via a combination of various imaging and spectroscopy techniques. In particular, high-angle annular dark-field (HAADF) imaging provides directly interpretable atomic number (Z) contrast information; while X-ray energy dispersive spectroscopy (XEDS) and electron energy-loss spectroscopy (EELS) spectrum imaging can be used to identify the chemical composition and oxidation state. Here we review some applications of aberration-corrected STEM to catalyst research, firstly in the context of supported metal catalysts, which serve as ideal material systems to illustrate the power of these techniques. Then we focus our attention on more recent progress relating to the characterization of supported metal oxide catalysts using aberration-corrected STEM. We demonstrate that it is now possible to directly image supported surface oxide species, study oxide wetting characteristics, identify the catalytic active sites and develop new insights into the structure-activity relationships for complex double supported oxide catalysts. Future possibilities for in situ and gentle low voltage electron microscopy studies of oxide-on-oxide materials are also discussed.     

Nanostructure and morphology of poly(vinylidene fluoride)/polymethyl (methacrylate)/clay nanocomposites: correlation to micromechanical properties

Nanocomposites based on poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) with untreated clay were prepared in one step by reactive melt extrusion. Chemical reactions took place between the polymer matrices, the inorganic clay particles, and three reactive agents, leading to the PVDF/PMMA/clay nanocomposites. The microstructure characterizations were carried out by differential scanning calorimetry and wide-angle X-ray scattering (WAXS). The mechanical behavior was investigated by tensile experiments, impact tests, and microhardness measurements. The morphological characterization was carried out by optical and atomic force microscopy (AFM). The decrease of the melting and crystallization temperatures of the PVDF with the increasing PMMA content is attributed to the interactions between the oxygen of the PMMA carbonyl group and the PVDF’s hydrogen atom. WAXS analysis shows that there is neither an intercalation step nor total exfoliation in any composition. As the PMMA content increases, WAXS diagrams show either the PVDF α-crystallographic form, both, α- and β-forms, or only the β-form. For PMMA contents higher than 40 wt%, the materials became amorphous. The microhardness of the samples decrease for a PMMA content up to 20 wt%. The study by optical microscopy and AFM illustrates the significant effect in the presence of clay on the film’s surface morphology.     

Study of GaAs and GaN based heterostructure surfaces and interfaces using ion beams and other complementary techniques

GaAs and GaN semiconductors and their heterostructures have been of interest for a few years now, because of their promising applications. Ion beams and other complimentary techniques are used for characterization of the surface and interfaces, to understand the novel properties of these materials. In this work we have reported the use of complimentary techniques like high-resolution X-ray diffraction (HRXRD), Rutherford backscattering/channelling (RBS/C), atomic force microscopy (AFM), and transmission electron microscopy (TEM) for characterization of these materials. We have studied InGaAs/GaAs heterostructures of various thicknesses by RBS/C, HRXRD, AFM, and TEM before and after irradiation. Bulk epitaxial layers of GaN grown on sapphire with and without AlN cap layer were characterized by HRXRD and AFM while the AlGaN/GaN heterostructures were characterized by RBS/C. The results are analyzed by taking account of the information extracted from these complementary techniques.