Scanning Transmission X-ray Research Articles

The effect of Cr content on intragranular κ-carbide precipitation in Fe-Mn-Al-(Cr)-C low-density steels: A multiscale investigation

The effect of Cr content on intragranular κ-carbide precipitation behaviors in Fe-Mn-Al-Cr-C low-density steels was investigated by X-ray diffraction (XRD), scanning (SEM) and (high-resolution) scanning transmission electron microscopy ((HR)STEM), atom probe tomography (APT), thermodynamic and first-principles calculations. We found that the volume fraction of κ-carbides in near-rapidly solidified samples was decreased with increasing Cr content. The increased Cr content also significantly slowed down the growth rate of κ-carbides during isothermal aging treatment (600 °C/9 h). Thermodynamic calculations showed that the increased Cr content decreased the precipitation temperature of κ-carbides and narrowed the temperature range of κ-carbide formation. The impurity of Cr atoms in κ-carbide structure increased its interfacial energy and elastic strain energy for nucleation, thereby significantly increasing the critical energy for the κ-carbide formation in γ-austenite. Simultaneously, the results of APT and first-principles calculation indicated that the impurity of Cr atoms in the κ-carbide structure preferred to occupy the Al sites, which increased the formation energy of κ-carbides making the κ-carbide formation difficult. In addition, the increased interfacial energy between the κ-carbides and γ-austenite, the improved solubility of Al and C in the γ-austenite and the decreased diffusion coefficient of C in γ-austenite caused by increasing Cr content resulted in a slower growth rate of the κ-carbides. • Effect of Cr addition on intragranular κ-carbides is investigated at multiscale. • Cr addition suppresses formation and reduces growth of κ-carbides. • Cr impurity prefers to substitute Al site increasing formation energy of κ-carbides. • Interfacial and strain energies between κ-carbides/γ-austenite are increased by Cr. • Cr addition affects solubility and diffusion rates of Al and C in γ-austenite.

Ferroelectric and piezoelectric properties of 100 nm-thick CeO2-HfO2 epitaxial films

Scaling up the film thickness of HfO2-based ferroelectrics is an important factor leading to their potential application in piezoelectric devices. In this paper, we report the ferroelectric and piezoelectric properties of 100 nm-thick 0.1CeO2-0.9HfO2 films, epitaxially grown on (001) indium-tin-oxide//(001)yttria-stabilized zirconia substrates. The crystal structure was investigated using x-ray diffraction and scanning transmission electron microscopy (STEM). These analyses revealed that the polar orthorhombic phase was stabilized, even at a thickness of 100 nm, whereas the formation of a nonpolar monoclinic phase was suppressed. In addition, the elemental mappings obtained by STEM–energy dispersive x-ray spectroscopy revealed that the film was compositionally uniform across its thickness. The chemical state of Ce in the polar orthorhombic domain was investigated using STEM–electron energy loss spectroscopy, which revealed the coexistence of Ce4+ and Ce3+. In addition, pinched polarization-electric field loops were observed, and their shapes were found to remain unaltered even after 109 electric field cycles. The strain-electric field curves originating from ferroelectricity were observed before and after the electric field cycling, and the high-field observed strain, Smax/Emax, was found to be approximately 7.2 pm/V. These results demonstrate that thicker CeO2-HfO2 ferroelectric films are promising candidates for use as piezoelectric materials.

Self-Assembly Ultrathin Fe-Terephthalic Acid as Synergistic Catalytic Platforms for Selective Hydrogenation

Self-Assembly Ultrathin Fe-Terephthalic Acid as Synergistic Catalytic Platforms for Selective Hydrogenation

Human Neocortex Layer Features Evaluated by PIXE, STIM, and STXM Techniques.

The human neocortex has a cytoarchitecture composed of six layers with an intrinsic organization that relates to afferent and efferent pathways for a high functional specialization. Various histological, neurochemical, and connectional techniques have been used to study these cortical layers. Here, we explore the additional possibilities of swift ion beam and synchrotron radiation techniques to distinguish cellular layers based on the elemental distributions and areal density pattern in the human neocortex. Temporal cortex samples were obtained from two neurologically normal adult men (postmortem interval: 6-12h). A cortical area of 500 × 500 μm2 was scanned by a 3MeV proton beam for elemental composition and areal density measurements using particle induced x-ray emission (PIXE) and scanning transmission ion microscopy (STIM), respectively. Zinc showed higher values in cortical layers II and V, which needs a critical discussion. Furthermore, the areal density decreased in regions with a higher density of pyramidal neurons in layers III and V. Scanning transmission X-ray microscopy (STXM) revealed the cellular density with higher lateral resolution than STIM, but not enough to distinguish each cortical lamination border. Our data describe the practical results of these approaches employing both X-ray and ion-beam based techniques for the human cerebral cortex and its heterogeneous layers. These results add to the potential approaches and knowledge of the human neocortical gray matter in normal tissue to develop improvements and address further studies on pathological conditions.

Epitaxial (110)-oriented La0.7Sr0.3MnO3 film directly on flexible mica substrate

Manufacture and characterizations of perovskite-mica van der Waals epitaxy heterostructures are a critical step to realize the application of flexible devices. However, the fabrication and investigation of the van der Waals epitaxy architectures grown on mica substrates are mainly limited to (111)-oriented perovskite functional oxide thin films up to now and buffer layers are highly needed. In this work, we directly grew La0.7Sr0.3MnO3 (LSMO) thin films on mica substrates without using any buffer layer. By the characterizations of x-ray diffractometer and scanning transmission electron microscopy, we demonstrate the epitaxial growth of the (110)-oriented LSMO thin film on the mica substrate. The LSMO thin film grown on the mica substrate via van der Waals epitaxy adopts domain matching epitaxy instead of conventional lattice matching epitaxy. Two kinds of domain matching relationships between the LSMO thin film and mica substrate are sketched by Visualization for Electronic and STructural Analysis software and discussed. A decent ferromagnetism retains in the (110)-oriented LSMO thin film. Our work demonstrates a new pathway to fabricate (110)-oriented functional oxide thin films on flexible mica substrates directly.

Strongly Coupled Tin(IV) Sulfide–MultiWalled Carbon Nanotube Hybrid Composites and Their Enhanced Thermoelectric Properties

Herein, tin(IV) sulfide (SnS2) and multiwalled carbon nanotube (MWCNT) composites are fabricated via a simple solution-mixing method in a hydrothermal reactor. SnS2 is closely coupled to the MWCNT surface, thus forming a coaxial nanostructure. Examination by X-ray photoelectron spectroscopy and scanning transmission electron microscopy indicates that the strong interface between SnS2 and the MWCNTs in the composite material is due to the formation of Sn-O and Sn-S bonds. In addition, an examination of the temperature-dependent thermoelectric (TE) properties demonstrates that the SnS2-MWCNT hybrid composite with 3 wt % MWCNTs exhibits the maximum power factor of ∼91.34 μW/(m·K2) at 500 K, which is ∼50 times larger than that of the pristine SnS2. These results highlight the fabrication and enhanced TE properties of hybrid composites via the coupling of SnS2 and MWCNTs.

Structural and Chemical State Analyses on Nitrided GaOOH as a Visible Light Response Photocatalyst

To prepare photocatalysts promoting water splitting under visible light irradiation, GaOOH was nitrided by the calcination at a temperature ranging from 773 to 1273 K under a NH3 flow to produce nitrogen doped Ga2O3. X-ray diffraction measurements suggested that even under NH3 atmosphere dehydration of GaOOH to α-Ga2O3 occurred by calcining below 873 K. In the samples nitrided above 973 K, gallium nitride (GaN) phase started to appear and the crystallinity became better with increasing the nitriding temperature. In diffuse reflectance ultraviolet-visible measurements, absorption bands appeared in the visible light region after the nitrization, and the shift of the absorption edge with nitriding temperature suggested the formation of a new phase like gallium oxy-nitride. X-ray photoelectron spectroscopy and scanning transmission electron microscopy-electron energy-loss spectroscopy analyses revealed that oxygen atoms were distributed homogeneously and mixed with nitrogen atoms in the sample nitrided at 1173 K [referred as S(1173 K)] while oxygen atoms were mainly distributed at the surface of the sample nitrided at 1273 K [S(1273 K)]. The differences in the composition and chemical state near the sample surface closely related to the activity and stability during water splitting reaction under visible light irradiation between S(1173 K) and S(1273 K), i.e., the former sample provided stable H2 and O2 evolution while the latter sample was inactive and unstable.

Impact of Si on the high-temperature oxidation of AlCr(Si)N coatings

• AlCr(Si)N coatings with an Al/Cr ratio of 70/30 and 0, 2.5 and 5 at.% Si were deposited • The oxidation behaviour up to 1460 °C was studied • Coatings were analysed by advanced cross-sectional X-ray nanodiffraction • The onset of oxidation was increased by the addition of Si from 1100 °C to 1260 °C • Complex elemental and micro-structural variations after oxidation were characterized The resistance of wear protective coatings against oxidation is crucial for their use at high temperatures. Here, three nanocomposite AlCr(Si)N coatings with a fixed Al/Cr atomic ratio of 70/30 and a varying Si-content of 0 at.%, 2.5 at.% and 5 at.% were analyzed by differential scanning calorimetry, thermogravimetric analysis and X-ray in order to understand the oxidation behavior depending on their Si-content. Additionally, a partially oxidized AlCrSiN coating with 5 at.% Si on a sapphire substrate was studied across the coating thickness by depth-resolved cross-sectional X-ray nanodiffraction and scanning trans-mission electron microscopy to investigate the elemental composition, morphology, phases and residual stress evolution of the oxide scale and the non-oxidized coating underneath. The results reveal enhanced oxidation properties of the AlCr(Si)N coatings with increasing Si-content, as demonstrated by a retarded onset of oxidation to higher temperatures from 1100 °C for AlCrN to 1260 °C for the Si-containing coatings and a simultaneous deceleration of the oxidation process. After annealing of the AlCrSiN sample with 5 at.% Si at an extraordinary high temperature of 1400 °C for 60 min in ambient air, three zones developed throughout the coating strongly differing in their composition and structure: (i) a dense oxide layer comprising an Al-rich and a Cr-rich zone formed at the very top, followed by (ii) a fine-grained transition zone with incomplete oxidation and (iii) a non-oxidized zone with a porous structure. The varying elemental composition of these zones is furthermore accompanied by micro-structural variations and a complex residual stress development revealed by cross-sectional X-ray nanodiffraction. The results provide a deeper understanding of the oxidation behavior of AlCr(Si)N coatings depending on their Si-content and the associated elemental, microstructural and residual stress evolution during high-temperature oxidation.

Polarization in pseudocubic epitaxial relaxed PMN-PT thin films

Understanding the relationship between structural characteristics and functional properties of complex relaxor ferroelectric thin films is of high interest for designing materials with high performances. In this work, the structure of epitaxial relaxed pulsed-laser-deposited Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-xPT; x = 25, 33, and 40) thin films on LaNiO3/SrTiO3 substrates is analyzed using a variety of diffraction and spectroscopic techniques. While based on the data obtained from high-resolution x-ray diffraction and scanning transmission electron microscopy analysis, the average structure of the PMN-xPT films is metrically cubic, micro-Raman polarimetry measurements indicate the tetragonal-like ferroelectric phase with marked preference for the polarization perpendicular to the film for all three compositions. The results of the Raman scattering analysis are supported by electromechanical properties of the samples, which clearly show that the films have a locally non-centrosymmetric structure. Furthermore, only a gradual enhancement of the electrical properties from PMN-25PT to PMN-40PT is observed, which is attributed to small tetragonal distortions that are highly similar for all three compositions.

Mechanisms of orthophosphate removal from water by lanthanum carbonate and other lanthanum-containing materials

Removing phosphorus (P) from water and wastewater is essential for preventing eutrophication and protecting environmental quality. Lanthanum [La(III)]-containing materials can effectively and selectively remove orthophosphate (PO4) from aqueous systems, but there remains a need to better understand the underlying mechanism of PO4 removal. Our objectives were to 1) identify the mechanism of PO4 removal by La-containing materials and 2) evaluate the ability of a new material, La2(CO3)3(s), to remove PO4 from different aqueous matrices, including municipal wastewater. We determined the dominant mechanism of PO4 removal by comparing geochemical simulations with equilibrium data from batch experiments and analyzing reaction products by X-ray diffraction and scanning transmission electron microscopy with energy dispersive spectroscopy. Geochemical simulations of aqueous systems containing PO4 and La-containing materials predicted that PO4 removal occurs via precipitation of poorly soluble LaPO4(s). Results from batch experiments agreed with those obtained from geochemical simulations, and mineralogical characterization of the reaction products were consistent with PO4 removal occurring primarily by precipitation of LaPO4(s). Between pH 1.5 and 12.9, La2(CO3)3(s) selectively removed PO4 over other anions from different aqueous matrices, including treated wastewater. However, the rate of PO4 removal decreased with increasing solution pH. In comparison to other solids, such as La(OH)3(s), La2(CO3)3(s) exhibits a relatively low solubility, particularly under slightly acidic conditions. Consequently, release of La3+ into the environment can be minimized when La2(CO3)3(s) is deployed for PO4 sequestration.

Metal coordination in C2N-like materials towards dual atom catalysts for oxygen reduction.

Single-atom catalysts, in particular the Fe–N–C family of materials, have emerged as a promising alternative to platinum group metals in fuel cells as catalysts for the oxygen reduction reaction. Numerous theoretical studies have suggested that dual atom catalysts can appreciably accelerate catalytic reactions; nevertheless, the synthesis of these materials is highly challenging owing to metal atom clustering and aggregation into nanoparticles during high temperature synthesis treatment. In this work, dual metal atom catalysts are prepared by controlled post synthetic metal-coordination in a C2N-like material. The configuration of the active sites was confirmed by means of X-ray adsorption spectroscopy and scanning transmission electron microscopy. During oxygen reduction, the catalyst exhibited an activity of 2.4 ± 0.3 A gcarbon−1 at 0.8 V versus a reversible hydrogen electrode in acidic media, comparable to the most active in the literature. This work provides a novel approach for the targeted synthesis of catalysts containing dual metal sites in electrocatalysis.

NiO nanoparticles via calcination of a Schiff base complex: Photocatalytic and microbicidal activity

Calcination method has been used to create NiO nanoparticles with a diameter of 19 to 30 nm from [NiL] [L: 2,2'-((1E,1'E)-(1,2-phenylenebis(azanylylidene))bis(methanylylidene))bis(4-bromophenolate)]. Formation and purity of the NiO nanoparticles produced under mild conditions without any special needs are evidenced by fourier-transformed infrared (FT-IR) spectroscopy, ultraviolet visible (UV-Vis) spectroscopy, X-ray powder diffraction (XRD), energy-dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM). According to the spectral methods, transformation of the synthesized nickel-Schiff base complex into the nanoparticles has been achieved with high purity, high crystallinity and low agglomeration by thermal decomposition which is an efficient and simple approach. The nanoparticles are employed as a catalyst for the decomposition of methylene blue, an industrial synthetic dye, and the nanoparticles exhibit mild photocatalytic activity. Furthermore, biological activity of nanoparticles has been investigated on five bacterial strains and two fungi, with promising results.

The delicate balance of phase speciation in bimetallic nickel cobalt nanoparticles.

Bimetallic nickel-cobalt nanoparticles are highly sought for their potential as catalytic and magnetic nanoparticles. These are typically prepared in organic solvents in the presence of strong stabilizing ligands such as tri-n-octylphosphine (TOP). Due to the variety of cobalt crystallographic phases and to the strong interaction of the ligands with the metallic surfaces, forming fcc nanoparticles rather than a phase mixture is a challenging endeavor. Here, using a two-step synthesis strategy that aims at a core-shell nickel-cobalt morphology, we demonstrated that many parameters have to be adjusted: concentration of the metal precursors, stoichiometry of TOP, and heating program from room temperature to 180 °C. We found optimized conditions to form size-controlled fcc NiCo nanoparticles from preformed Ni nanoparticles, and the phase attribution was confirmed with a combination of X-Ray diffraction on powder and X-Ray absorption spectroscopy at the Co K edge. We then investigated the early stages of Co nucleation on the nickel using a lower stoichiometry of Co, down to 0.05 equiv. vs. Ni. Using X-ray photoelectron spectroscopy and scanning transmission electron microscopy coupled to energy-dispersive X-Ray spectroscopy and electron energy loss spectroscopy, we showed that cobalt reacts first on the nickel nanoparticles but easily forms cobalt-rich larger aggregates in the further steps of the reaction.

Flexible translucent persistent luminescent films based on Sr2MgSi2O7:Eu2+,Dy3+ cellulose ether composites.

Persistent luminescent materials are present in several recent studies on new applications and novel properties. In this work, we demonstrate, for the first time, the production of translucent flexible persistent composites based on Sr2MgSi2O7:Eu2+,Dy3+ (SMSO) into cellulose ether matrix film. The composite was successfully prepared through a new optimized route of co-precipitation and microwave-assisted annealing followed by (3-aminopropyl)triethoxysilane (APTES) coating and dispersion in hydroxypropyl methylcellulose (HPMC). The SMSO@APTES/HPMC films show persistent luminescence emission at 475 nm (blue) and high transmittance in the visible range. To understand the fine distribution of the nanoparticles in the matrix, we have investigated their structure and dispersion by using Synchrotron Radiation X-ray fluorescence mapping and Scanning Transmission X-ray Microscopy. This innovative composite could bring new perspectives for the class of persistent luminescence materials, enhancing technologies in progress throwing light on new applications never perceived.

Investigation on the properties of vanadium doping WO3 nanostructures by hydrothermal method

To make tungsten trioxide nanostructures, hydrothermal methods were used. A temperature of 200 °C was used to prepare the samples. 48-hour reactions were used to examine how reaction time affected the characteristics of tungsten trioxide nanostructures. For one hour, the samples were calcined at 500 °C. After using ammonium metavanadate to dope vanadium, the same method for making WO3 was used. Many different characterization techniques have been performed on the calcined and prepared samples. X-ray diffraction (XRD) and scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) were used to examine the samples' structural and morphological characteristics (SEM). EDAX has verified that vanadium has been doped. Fourier transformed infrared spectroscopy was used to do the vibrational analysis (FTIR).

Electronic and transport properties in Ruddlesden-Popper neodymium nickelates Ndn+1NinO3n+1 ( n=1–5 )

A series of Ruddlesden-Popper nickelates, Nd$_{n+1}$Ni$_{n}$O$_{3n+1}$ (${n}$ = 1-5), have been stabilized in thin film form using reactive molecular-beam epitaxy. High crystalline quality has been verified by X-ray diffraction and scanning transmission electron microscopy. X-ray photoelectron spectroscopy indicates the ${n}$-dependent valence states of nickel in these compounds. Metal-insulator transitions show clear ${n}$ dependence for intermediate members (${n}$ = 3-5), and the low-temperature resistivities of which show logarithmic dependence, resembling the Kondo-scattering as observed in the parent compounds of superconducting infinite-layer nickelates.

Microstructure and residual stress evolution in nanocrystalline Cu-Zr thin films

Grazing incidence X-ray diffraction (GIXRD) and scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) were employed to study the microstructure evolution and stress development in the nanocrystalline Cu100−X-ZrX (2.5 at% ≤ x ≤ 5.5 at%) alloy thin films. Small Zr additions to Cu led to significant lattice parameter anisotropy in the as-deposited Cu-Zr thin films both due to macroscopic lattice strain and stacking faults in the Cu matrix. Strain free lattice parameters obtained after the XRD stress analysis of Cu-Zr thin films confirmed formation of a supersaturated substitutional Cu-Zr solid solution. For the first time, the study of film microstructure by XRD line profile analysis (XLPA) confirmed progressive generation of dislocations and planar faults with increasing Zr composition in Cu-Zr alloy films. These microstructural changes led to the generation of tensile stresses in the thin films along with considerable stress gradients across the films thicknesses which are quantified by the traditional dψhkl−Sin2ψ and GIXRD stress measurement methods. The origin of tensile stresses and stress gradients in the Cu-Zr film are discussed on the basis of film growth and heterogeneous microstructure with changing Zr composition.

Structural and Valence State Modification of Cobalt in CoPt Nanocatalysts in Redox Conditions.

Platinum is the primary catalyst for many chemical reactions in the field of heterogeneous catalysis. However, platinum is both expensive and rare. Therefore, it is advantageous to combine Pt with another metal to reduce cost while also enhancing stability. To that end, Pt is often combined with Co to form Co-Pt nanocrystals. However, dynamical restructuring effects that occur during reaction in Co-Pt ensembles can impact catalytic properties. In this study, model Co2Pt3 nanoparticles supported on carbon were characterized during a redox cycle with two in situ approaches, namely, X-ray absorption spectroscopy (XAS) and scanning transmission electron microscopy (STEM) using a multimodal microreactor. The sample was exposed to temperatures up to 500 °C under H2, and then to O2 at 300 °C. Irreversible segregation of Co in the Co2Pt3 particles was seen during redox cycling, and substantial changes of the oxidation state of Co were observed. After H2 treatment, a fraction of Co could not be fully reduced and incorporated into a mixed Co-Pt phase. Reoxidation of the sample increased Co segregation, and the segregated material had a different valence state than in the fresh, oxidized sample. This in situ study describes dynamical restructuring effects in CoPt nanocatalysts at the atomic scale that are crucial to understand in order to improve the design of catalysts used in major chemical processes.

Anaerobic Microscopic Analysis of Ferrous Saponite and Its Sensitivity to Oxidation by Earth’s Air: Lessons Learned for Analysis of Returned Samples from Mars and Carbonaceous Asteroids

Ferrous saponite is a secondary mineral that can be used to reveal the redox state of past aqueous environments on Mars. In mineralogical analyses for ferrous saponite formed in laboratory simulations or contained in future returned samples from Mars, its oxidation by the Earth’s air could be problematic due to the high redox sensitivity. Here, we performed micro X-ray diffraction and scanning transmission X-ray microscopy analyses for a single particle of synthesized ferrous saponite without any exposure to air. The sample was reanalyzed after air exposure for 10–18 h to assess the adequacy of our anoxic preparation/measurement methods and the impacts of air on the sample. We found that the crystal structures agreed with ferrous saponite, both before and after air exposure; however, ferrous iron in saponite was partially oxidized, at least until 0.1–1 μm from the surface, after air exposure at the submicron scale, forming micro-vein-like Fe(III)-rich features. Together with our results of infrared spectroscopy of ferrous saponite, we showed that oxidation of octahedral iron occurred rapidly and heterogeneously, even in a short time of air exposure without any structural rearrangement. Since ferrous saponite is expected to exist on carbonaceous asteroids and icy dwarf planets, our methodology is also applicable to mineralogical studies of samples returned from these bodies.

Microstructures of magnetron sputtered Fe–Au thin films

Abstract Freestanding films of highly pure iron and gold multilayers were fabricated and characterized for their intended use as biodegradable implant materials. These samples were deposited using magnetron sputtering on unheated substrates. This technology allows the combination of various non-compounding materials. After annealing for 2 h at 685 °C and 850 °C, respectively to homogenize the multilayer, the microstructures were investigated using X-ray diffraction, energy dispersive X-ray spectroscopy and scanning transmission electron microscopy. Due to the annealing, the multilayered microstructure converts into a new multiphase system consisting of an iron matrix and two different kinds of gold morphologies: segregations along grain boundaries and nanosized core–shell like precipitates.