Mechanical Reinforcement of Electrospun Poly(Vinyl Alcohol) by a-FeOOH Nanowires

Anna Sutka, Martin Jarvekulg, Andris Sutka, Ivo Heinmaa, Uno Maeorg, Krisjanis Smits, Martin Timusk

We report the mechanical performance of α-FeOOH nanowire reinforced poly(vinyl alcohol) (PVA) composite nanofiber mat, fabricated using straightforward aqueous processing methods. Goethite (α-FeOOH) nanocrystals have a high elastic modulus and –OH rich surface, ensuring strong interactions with hydrophilic polymers and effective reinforcement. Needle-less electrospinning resulted in alignment of the nanowires along fibre axis, as confirmed by transmittance electron microscopy studies. Produced composite PVA nanofibers containing 10 wt% goethite nanoparticles exhibited an outstanding fivefold increase in Young’s modulus and 2.5-fold improvement of tensile strength compared to mats of neat PVA. The addition of α-FeOOH had a significant influence on glass transition temperature indicating formation of interphase regions around nanowire inclusions. Observed properties are explained by nanowire grafting in the precursor solution, extensive interactions between the adsorbed PVA chains and the matrix and percolation of interphase regions at 10 wt% α-FeOOH.

Published in Polymer Composites, John Wiley and Sons Ltd.

DOI: 10.1002/pc.24231

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Unexpected Epitaxial Growth of a Few WS2 Layers on 1100 Facets of ZnO Nanowires

Boris Polyakov, Alexei Kuzmin, Krisjanis Smits, Janis Zideluns, Edgars Butanovs,
Jelena Butikova, Sergei Vlassov, Sergei Piskunov, and Yuri F. Zhukovskii


Core-shell nanowires is an interesting and perspective class of radially heterostructured nanomaterials where epitaxial growth of the shell can be realized even at signi ficant core-shell lattice mismatch. In this study epitaxial hexagonally-shaped shell consisting of WS2 nanolayers was grown on f1100g facets of prismatic wurtzite-structured
[0001]-oriented ZnO nanowires for the first time. A synthesis was performed by annealing in a sulfur atmosphere of ZnO/WO3 core-shell structures, produced by reactive
DC magnetron sputtering of amorphous a-WO3 layer on top of ZnO nanowire array.
The morphology and phase composition of synthesized ZnO/WS2 core-shell nanowires were con firmed by scanning and transmission electron microscopy (SEM and TEM),micro-Raman and photoluminescence spectroscopy. Epitaxial growth of WS2(0001) layer(s) on f1100g facets of ZnO nanowire is unexpected due to incompatibility of their symmetry and structure parameters. To relax the interfacial incoherence, we propose a model of ZnO/WS2 interface containing WS2 bridging groups inside and use first-principles simulations to support its feasibility.

J. Phys. Chem. C

DOI: 10.1021/acs.jpcc.6b06139

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Luminescent PEO Coatings on Aluminum

Aleksejs Zolotarjovs, Krisjanis Smits, Anete Krumina, DonatsMillers, and Larisa Grigorjeva

Results show the possibilities of pore filling approach to modify alumina coatings with various materialspeo-raksta-bilde in order to enhance coating optical (or other) properties and develop new functional materials; as well as demonstrate novel alumina phase transition detection approach. Luminescent PEO coatings were
produced on aluminum surface using pore-filling method. Three stage process was developed to modify alumina coating in order to enhance its luminescent properties. Eu3+ recharging to Eu2+ followed by significant (up to 10 times) total luminescence intensity increase was observed, Eu ion presence evaluated in final coating by measuring fast decay kinetics. Structure of obtained coatings was analyzed using XRD and FTIR spectroscopy indicating presence of η-alumina phase.

ECS Journal of Solid State Science and Technology, 5 (9) R150-R153 (2016)

DOI: 10.1149/2.0401609jss

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Complex tribomechanical characterization of ZnO nanowires: nanomanipulations supported by FEM simulations

Sergei Vlassov, Boris Polyakov, Sven Oras, Mikk Vahtrus,
Mikk Antsov, Andris Šutka Krisjanis Smits, Leonid M Dorogin and
Rünno Lõhmus

In the present work, we demonstrate a novel approach to nanotribological measurements based
on the bending manipulation of hexagonal ZnO nanowires (NWs) in an adjustable halfsuspended
configuration inside a scanning electron microscope. A pick-and-place manipulation
technique was used to control the length of the adhered part of each suspended NW. Static and
kinetic friction were found by a ‘self-sensing’ approach based on the strain profile of the
elastically bent NW during manipulation and its Young’s modulus, which was separately
measured in a three-point bending test with an atomic force microscope. The calculation of static
friction from the most bent state was completely reconsidered and a novel more realistic crackbased
model was proposed. It was demonstrated that, in contrast to assumptions made in
previously published models, interfacial stresses in statically bent NW are highly localized and
interfacial strength is comparable to the bending strength of NW measured in respective bending

Nanotechnology 27 (2016) 335701 (10pp)


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Europium(III)-doped A2Hf2O7 (A ¼ Y, Gd, Lu) nanoparticles: Influence of annealing temperature, europium(III) concentration and host cation on the luminescent properties

Jelena Papan , Dragana J. Jovanovic , Katarina Vukovic , Krisjanis Smits ,
Vesna ÐorCevic , Miroslav Dramicanin 

The detailed analyses of structure and luminescence of europium(III)-doped A2Hf2O7 (A ¼ Y, Gd, Lu)
nanoparticles is presented. Samples were prepared by time and cost effective combustion method that
utilize polyethylene glycol both as a chelating agent and as a fuel, with different europium(III) concentrations
(from 1 to 12 at.%), annealed at temperatures ranging from 800 to 1400 C, and with alternating
A3þ cation in the A2Hf2O7 host. Then, structural variations between materials were analysed by Xray
diffraction and structural refinement, while the changes in the luminescence were assessed from the
Judd-Ofelt analyses of emission spectra. Nanoparticles prepared at the lowest temperature (800 C) had
the smallest particle size of ~6 nm and showed the highest quantum efficiency when doped with 1 and
2 at.% of europium(III). Radiative transition rate and quantum efficiency of emission showed
Lu2Hf2O7 > Gd2Hf2O7 > Y2Hf2O7 trend.

Optical Materials xxx (2016) 1e9


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Effect of Point Defects on Luminescence Characteristics of ZnO Ceramics

P. A. Rodnyi, K. A. Chernenko, A. Zolotarjovs, L. Grigorjeva,
E. I. Gorokhova, and I. D. Venevtsev

Abstract—Photo- and thermally stimulated luminescence of ZnO ceramics are produced by uniaxial hot pressing. The luminescence spectra of ceramics contain a wide band with a maximum at 500 nm, for which oxygen vacancies VO are responsible, and a narrow band with a maximum at 385 nm, which is of exciton nature. It follows from luminescence excitation spectra that the exciton energy is transferred to luminescence centers in ZnO. An analysis of the thermally stimulated luminescence curves allowed detection of a set of discrete levels of point defects with activation energies of 25, 45, 510, 590 meV, and defects with continuous energy distributions in the range of 50–100 meV. The parameters of some of the detected defects are characteristic of a lithium impurity and hydrogen centers. The photoluminescence kinetics are studied in a wide temperature range.
DOI: 10.1134/S1063783416100309

ISSN 1063-7834,

Physics of the Solid State, 2016, Vol. 58, No. 10, pp. 2055–2061.

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Ag sensitized TiO2 and NiFe2O4 three-component nanoheterostructures: synthesis, electronic structure and strongly enhanced visible light photocatalytic activity

A. Šutka, T.
Käämbre, R. Pärna, N. Doebelin, M. Vanags, K. Smits and V. Kisand

This study reports on the synthesis and characterisation of two- and three-component visible light active photocatalytic
nanoparticle heterostructures, based on TiO2 and NiFe2O4 and sensitized with Ag. We observe that Ag content as small as
1 at.% in the TiO2/NiFe2O4 heterostructure increases by more than an order of magnitude the rate constant for the visible
light photocatalytic process. We rationalise this in terms of the measured structure and electronic structure data of the
binary and ternary combinations of the component materials and focus on details, which show that an optimised
deposition sequence is vital for attaining the high values of photocatalytic efficiency, because the charge transfer across
the interfaces appears to be sensitive to where the Ag is loaded in the heterostructure. The overall higher visible light
photocatalytic activity of the TiO2/Ag/NiFe2O4 heterostructure was observed and is attributed to enhanced charge carrier
separation efficiency and migration via vectorial electron transfer.

RSC Advances., 2016,

DOI: 10.1039/C6RA00728G

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Rare earth doped glass–ceramics containing NaLaF4 nanocrystals

E. Elsts , G. Krieke, U. Rogulis, K. Smits, A. Zolotarjovs, J. Jansons, A. Sarakovskis, K. Kundzins

Oxyfluoride glasses 16Na2O–9NaF–5LaF3–7Al2O3–63SiO2 (mol%) activated with 3% terbium, dysprosium,
praseodymium and neodymium fluorides have been prepared and studied by differential thermal analysis,
cathodoluminescence, X-ray induced luminescence, X-ray diffraction, scanning electron microscopy
and energy dispersive X-ray spectroscopy. We found out that the presence of crystalline phase enhances
the X-ray induced luminescence intensity. X-ray induced luminescence is the most intense for the sample
activated with terbium and treated at 700 C, whereas the praseodymium and neodymium activated
samples have the fastest decay times.

Optical Materials xxx (2016) xxx–xxx

doi: 10.1016/j.optmat.2016.01.005

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