Small additions of nanofiber materials make it possible to change the properties of polymers. However, the uniformity of the additive distribution and the strength of its bond with the polymer matrix ...are determined by the surface of the nanofibers. Silanes, in particular, allow you to customize the surface for better interaction with the matrix. The aim of our work is to study an approach to silanization of nanofibers of aluminum oxide to obtain a perfect interface between the additive and the matrix. The presence of target silanes on the surface of nanofibers was shown by XPS methods. The presence of functional groups on the surface of nanofibers was also shown by the methods of simultaneous thermal analysis, and the stoichiometry of functional groups with respect to the initial hydroxyl groups was studied. The number of functional groups precipitated from silanes is close to the number of the initial hydroxyl groups, which indicates a high uniformity of the coating in the proposed method of silanization. The presented technology for silanizing alumina nanofibers is an important approach to the subsequent use of this additive in various polymer matrices.
Copper-doped titanium oxynitride (TiN x O y ) thin films were grown by atomic layer deposition (ALD) using the TiCl4 precursor, NH3, and O2 at 420 °C. Forming gas was used to reduce the background ...oxygen concentration and to transfer the copper atoms in an ALD chamber prior to the growth initiation of Cu-doped TiN x O y . Such forming gas-mediated Cu-doping of TiN x O y films had a pronounced effect on their resistivity, which dropped from 484 ± 8 to 202 ± 4 μΩ cm, and also on the resistance temperature coefficient (TCR), which decreased from 1000 to 150 ppm °C–1. We explored physical mechanisms causing this reduction by performing comparative analysis of atomic force microscopy, X-ray photoemission spectroscopy, X-ray diffraction, optical spectra, low-temperature transport, and Hall measurement data for the samples grown with and without forming gas doping. The difference in the oxygen concentration between the films did not exceed 6%. Copper segregated to the TiN x O y surface where its concentration reached 0.72%, but its penetration depth was less than 10 nm. Pronounced effects of the copper doping by forming gas included the TiN x O y film crystallite average size decrease from 57–59 to 32–34 nm, considerably finer surface granularity, electron concentration increase from 2.2(3) × 1022 to 3.5(1) × 1022 cm–3, and the electron mobility improvement from 0.56(4) to 0.92(2) cm2 V–1 s–1. The DC resistivity versus temperature R(T) measurements from 4.2 to 300 K showed a Cu-induced phase transition from a disordered to semimetallic state. The resistivity of Cu-doped TiN x O y films decreased with the temperature increase at low temperatures and reached the minimum near T = 50 K revealing signatures of the quantum interference effects similar to 2D Cu thin films, and then, semimetallic behavior was observed at higher temperatures. In TiN x O y films grown without forming gas, the resistivity decreased with the temperature increase as R(T) = – 1.88T 0.6 + 604 μΩ cm with no semimetallic behavior observed. The medium range resistivity and low TCR of Cu-doped TiN x O y make this material an attractive choice for improved matching resistors in RF analog circuits and Si complementary metal–oxide–semiconductor integrated circuits.
•Uncoated and capped Ag NPs of about 3–5nm and 10–12nm in diameter were studied.•Resistive switching was found in the tunneling spectra at smaller uncapped NPs.•Anodic oxidation of uncapped NPs to ...Ag2O and AgO nontrivially depends on their size.•Capping of Ag NPs impedes the anodic oxidation.
Many applications and environmental impact of silver-bearing nanomaterials critically depend upon their specific reactivity, which is still poorly understood. Here, silver nanoparticles (Ag NPs) of about 3–5nm and 10–12nm in diameter, uncapped and capped with l-glucose or citrate, were prepared, characterized using UV–vis absorption spectroscopy, SAXS, TEM, and their (electro)chemical oxidation was examined in comparison with each other and bulk metal applying scanning tunneling microscopy and spectroscopy, cyclic voltammetry, and XPS. A resistive switching effect was found in the tunneling spectra measured in air at the smaller uncapped Ag NPs deposited on HOPG and was interpreted in terms of Ag transfer between the particle and the probe. The anodic oxidation of these Ag NPs in 1M NaOH yielded 3D Ag2O, while only a layer of “primary” Ag(I) oxide emerged on larger uncapped nanoparticles during the potential sweep. The formation of AgO at higher potentials proceeded readily at the “primary” oxide but was retarded at the smaller NPs. The citrate- and glucose-capping substantially impeded the formation both of Ag2O and AgO. The findings highlighted, particularly, a non-trivial effect of particle size and transient mobilization of Ag species on the reactions of silver nanoparticles.
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•Surface analysis of citrate-stabilized AgNPs immobilized from a dense sol was performed.•Capping species are largely products of citrate decomposition.•Species adsorbed on AgNPs ...having various sizes are different.•Ligands bound to surface Ag via one or two carboxylate and alcohol groups.•No surface ketone group was found.
Citrate is an important stabilizing, reducing, and complexing reagent in the wet chemical synthesis of nanoparticles of silver and other metals, however, the exact nature of adsorbates, and its mechanism of action are still uncertain. Here, we applied X-ray photoelectron spectroscopy, soft X-ray absorption near-edge spectroscopy, and other techniques in order to determine the surface composition and to specify the citrate-related species at Ag nanoparticles immobilized from the dense hydrosol prepared using room-temperature reduction of aqueous Ag+ ions with ferrous ions and citrate as stabilizer (Carey Lea method). It was found that, contrary to the common view, the species adsorbed on the Ag nanoparticles are, in large part, products of citrate decomposition comprising an alcohol group and one or two carboxylate bound to the surface Ag, and minor unbound carboxylate group; these may also be mixtures of citrate with lower molecular weight anions. No ketone groups were specified, and very minor surface Ag(I) and Fe (mainly, ferric oxyhydroxides) species were detected. Moreover, the adsorbates were different at AgNPs having various size and shape. The relation between the capping and the particle growth, colloidal stability of the high-concentration sol and properties of AgNPs is briefly considered.
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