Search

Biobased and biodegradable polyhydroxyalkanoates (PHAs) are currently gaining momentum. Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) polymer has a useful processing window for extrusion and injection molding of packaging, agricultural and fishery applications with required flexibility. Processing PHBHHx into fibers using electrospinning or centrifugal fiber spinning (CFS) can further broaden the application area, although CFS remains rather unexplored. In this study, PHBHHx fibers are centrifugally spun from 4-12 wt.% polymer/chloroform solutions. Beads and beads-on-a-string (BOAS) fibrous structures with an average diameter (ϕav) between 0.5 and 1.6 µm form at 4-8 wt.% polymer concentrations, while more continuous fibers (ϕav = 3.6-4.6 µm) with few beads form at 10-12 wt.% polymer concentrations. This change is correlated with increased solution viscosity and enhanced mechanical properties of the fiber mats (strength, stiffness and elongation values range between 1.2-9.4 MPa, 11-93 MPa, and 102-188%, respectively), though the crystallinity degree of the fibers remains constant (33.0-34.3%). In addition, PHBHHx fibers are shown to anneal at 160 °C in a hot press into 10-20 µm compact top-layers on PHBHHx film substrates. We conclude that CFS is a promising novel processing technique for the production of PHBHHx fibers with tunable morphology and properties. Subsequent thermal post-processing as a barrier or active substrate top-layer offers new application potential. This research was funded by the Special Research Fund (BOF) of Hasselt University, grant number BOF20DOC06. The authors acknowledge Prof, Wouter Marchal (Analytical&Circular Chemistry, IMO-IMOMEC,UHasselt) for providing access to the DSC and rheometer equipment and Prof Louis Pitet (Advanced Polymer Functionalization, IMO-IMOMEC, UHasselt) for access to the hot-press. Jorgo Merchiers is acknowledged for the initial work on centrifugal fiber spinning, equipment development, polymer solution preparation, fiber fabrication and characterization. Lieze Schruers is acknowledged for the preliminary work on testing polymer concentrations for PHBHHx fibers using CFS.

Because of their intriguing properties for optoelectronic applications, research on organic semiconducting polymers has steadily progressed over the past decades, yielding increasingly fine-tuned (hetero)aromatic polymer backbones. In this work, the push-pull copolymer PDTPQx is synthesized, both via Stille poly-condensation and direct arylation polymerization (DArP), permitting comparison of the two procedures. Near-infrared organic photodetectors (OPDs) are constructed based on these different polymer batches in combination with PC 61 BM, and their performance was investigated. From the current-voltage characteristics, it is clear that the DArP polymer-based devices outperform those prepared from the Stille polymers, both in terms of dark current density and external quantum efficiency (EQE), and therefore in terms of specific detectivity as well. The relatively high highest occupied molecular orbital energy level of PDTPQx, in combination with the clear charge-transfer absorption band observed for the DArP-based device, is beneficial for application in organic resonant cavity photodetectors. Such OPDs are prepared for the DArP PDTPQx:PC 61 BM (1:4) blends with 180 and 210 nm thick bulk heterojunction active layers. EQEs of 2.5% at 1016 nm and 1% at 1140 nm are achieved, with full-width-at-half-maximum peak responses of 44 and 45 nm, respectively, and detectivities of 2.24 × 10 10 and 1.06 × 10 10 Jones. The authors thank Huguette Penxten for CV analysis, Christel Willems for the TEM sample preparation, and Brent Fripont for the graphical abstract artwork. We also thank the Research Foundation – Flanders (FWO Vlaanderen) for continuing financial support (projects G0D0118 N, G0B2718 N, 1S50820 N, 11D2618 N), as well as the European Research Council (ERC, grant agreement 864625). Dr. Q. Liu acknowledges financial support from the European Union’s Horizon 2020 research and innovation program under the Marie-Curie grant agreement no. 88279.

Driven by expanding interest in battery storage solutions and the success story of lithium-ion batteries, the research for the discovery and optimization of new battery materials and concepts is at peak. The generation of experimental (dis)charge data using coin cells is fast and feasible and proves to be a favorite practice in the battery research labs. The quantitative interpretation of the data, however, is not trivial and decelerates the process of screening and optimization of electrode materials and recipes. Here, we introduce the concept of polarographic map and demonstrate how it can be leveraged to quantify the contribution of different non-equilibrium phenomena to the performance limitation and total polarization of a lithium-ion cell. We showcase the accuracy and diagnostic power of this approach by preparing and analyzing the electrochemical performance of 54 sets of LiNixMnyCo1-x-yO2 electrodes with different formulations and designs discharged in a range of 0.2C to 5C.

Seed endophyte inoculation can enhance the plant tolerance to pollutants, which allows plant cultivation on trace element (TE) polluted soils. Methylobacterium sp. CP3 and Kineococcus en-dophyticus CP19 were tested in vitro for their tolerance to Zn and Cd and their plant growth promotion traits. The in vivo effects of bioaugmentation with individual strains or both strains were tested using two poplar cultivars, Populus deltoides x (P. trichocarpa x P. maximowiczii) ‘Dender’ and ‘Marke’, grown in TE polluted soil for six weeks. Methylobacterium sp. was found to grow on media enriched with 0.4 and 0.8 mM Cd, and both endophytes tolerated 0.6 and 1 mM Zn, due to the presence of genes involved in Zn and Cd tolerance and transport. Methylobacterium sp. showed an extracellular ion sequestration mechanism. Production of indole-3-acetic acid by Methylobacterium sp. and K. en-dophyticus, as well as phosphorus solubilization by Methylobacterium sp. were observed. Bioaugmen-tation with both endophytes increased the shoot length of Populus ‘Marke’ and enhanced the Mg uptake in both cultivars. Inoculation with Methylobacterium sp. reduced the bioaccumulation of Zn in ‘Marke’, conferring it an excluder strategy. Methylobacterium sp. and K. endophyticus seemed to improve the plant nutritional status, which can alleviate abiotic stress. Fil: Vannucchi, Francesca. Scuola Superiore Sant’Anna; Italia Fil: Imperato, Valeria. Hasselt University; Bélgica Fil: Saran, Anabel. Hasselt University; Bélgica. Instituto Nacional de Tecnología Agropecuaria. Centro Regional La Pampa-San Luis. Estación Experimental Agropecuaria Anguil; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis; Argentina Fil: Staykov, Svetoslav. Hasselt University; Bélgica Fil: D'Haen, Jan. Hasselt University; Bélgica Fil: Sebastiani, Luca. Scuola Superiore Sant’Anna; Italia Fil: Vangronsveld, Jaco. Hasselt University; Bélgica. Maria Curie-Skłodowska University; Polonia Fil: Thijs, Sofie. Hasselt University; Bélgica

Ni-rich layered lithium transition metal oxides (LiNi x Mn y Co z O 2) have gained significant attention as high-capacity positive electrode materials for lithium-ion batteries. However, their poor cyclability, capacity retention, and rate capability at higher working potentials limit their applications in commercial batteries. Here, we demonstrate a cost-effective chemical solution deposition route of a thin TiO x shell on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC-622) particles and the effect of surface modification on the electrochemical properties. The crystallinity and morphology of the NMC-622 particles are unaffected by the deposition step and verified by powder X-ray diffraction and electron microscopy. High-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) analysis showed that the TiO x surface layer is amorphous and prone to enhance the electronic conductivity of the cathode material. The TiO x-coated material has an improved rate performance and experiences a lower charge-transfer resistance compared to the pristine material. The effect of the surface modification on the electrochemical performance of NMC-622 was investigated further by the assembly of NMC-622/Li 4 Ti 5 O 12 (LTO) full cells. The beneficial impact of the TiO x coating on the electrochemical performance of NMC-622 positive electrodes in lithium-ion battery applications was showcased by the higher initial Coulombic efficiency and lower aging rates during 150 cycles at 1C in NMC-622/LTO cells.

Modern lighting is expected to be light weight, flexible, efficient, non-expensive and environmentally friendly fabricated. Organic light emitting diodes (OLEDs) meet all these requirements and can be manufactured using inexpensive and roll-to-roll compatible printing techniques. They, however, often use low work function, highly reactive metals, such as barium and calcium to facilitate electron injection, deposited using expensive and non-continuous vacuum techniques. Efficient and stable alternatives can be found in the aliphatic amines, polyethylenimine (PEI) and polyethylenimine(ethoxylated) (PEIE), that shift the work function of aluminum favorably for electron injection. This work demonstrates ultrasonic spray coating of PEI(E) as electron injection and transport layer for OLEDs, reducing the work function of the aluminum cathode by 0.355 eV allowing a luminous efficacy comparable to that of the OLEDs using calcium/aluminum electrodes. Slightly higher luminous results are noted for the OLEDs with spin coated PEI(E), indicating that the surface morphology and thickness of the PEI(E) layer are crucial factors: ultrasonic spray coated PEI(E) layers have an increased overall thickness and surface roughness. This study shows the potential of ultrasonic spray coating and the suitability of PEI(E) as excellent electron injection and transport layer for OLEDs and paves the way towards fully spray coated OLEDs. K E Y W O R D S electron injection and transport layer, organic light emitting diodes, printing techniques, ultrasonic spray coating This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

npj Materials degradation 5(1), 29 (2021). doi:10.1038/s41529-021-00169-2, Detrimental corrosion is an ever-concerning challenge for metals and alloys. One possible remedy is to apply organic corrosion inhibitors. Despite progress in molecular assembly and inhibitor research, better mechanistic insight on the molecular level is needed. Here we report on the behavior of well-defined artificial molecular interfaces created by micro-contact printing of thiol-inhibitor molecules and subsequent backfilling. The obtained heterogeneity and defects trigger localized dealloying-corrosion of well-defined Cu3Au surfaces. The stability of applied inhibitor molecules depends on alloy surface morphology and on intermolecular forces of the molecular layers. On extended terraces, dealloying preferentially starts at the boundary between areas composed of the two different chain-length inhibitor molecules. Inside of the areas hardly any nucleation of initial pits is visible. Step density strongly influences the morphology of the dealloying attack, while film heterogeneity avoids cracking and controls molecular-scale corrosion attack. The presented surface-science approach, moreover, will ultimately allow to verify the acting mechanisms of inhibitor-cocktails to develop recipes to stabilize metallic alloy surfaces., Published by Macmillan Publishers Limited, part of Springer Nature, [London]

The gradual loss of capacity and increase in the cell impedance are the mainstream of aging patterns for the lithium-ion batteries and mainly result from the depletion of cell’s cyclable-lithium reservoir. The irreversible drain from this reservoir is well understood and originates from the phenomena such as electrolyte oxidation and reduction at the electrode/electrolyte interfaces. There is, however, limited knowledge about the circumstances leading to the recuperation of misplaced lithium, gain in cell’s energy, and impedance drop. Here, we showcase that the intragranular fracture induces a peculiar aging behavior in the LiNi0.6Mn0.2Co0.2O2 electrodes. Fracture enables an alternative path for the (de)insertion of lithium from the hard-to-reach center of the secondary particles by lithium pore-wall flux instead of solid-state diffusion. The possible consequences are the energy recovery and decrease of the charge-transfer resistance in the electronically well wired electrodes.

Two novel high gap donor polymers – PBDTTSi-TzBI and PBDTTS-TzBI, based on imide-fused benzotriazole (TzBI) with asymmetric side chains and alkylsilyl (Si) or alkylthio (S) substituted 4,8-di(thien-2-yl)benzo-[1,2-b:4,5-b′]dithiophene (BDTT) – are successfully synthesized. The effect of the side chain variation on the photophysical, morphological and photovoltaic properties of blends of these polymers with fullerene and non-fullerene acceptors is investigated. The PBDTTSi-TzBI polymer shows a deeper highest occupied molecular orbital energy level, which results in higher open-circuit voltages. Nevertheless, the polymer solar cells fabricated using PBDTTS-TzBI in combination with PC71BM afford a higher power conversion efficiency of 7.3% (vs 4.0% for PBDTTSi-TzBI:PC71BM). By using the non-fullerene acceptor ITIC, the absorption of the blends extends to 850 nm and better device efficiencies are achieved, 6.9% and 9.6% for PBDTTSi-TzBI:ITIC and BDTTS-TzBI:ITIC, respectively. The better performance of the PBDTTS-TzBI:ITIC-based devices is attributed to the strong and broad absorption and balanced charge transport, and is among the best performances reported for non-fullerene solar cells based on TzBI-containing polymer donors.

Lead (Pb) and cadmium (Cd) are major environmental pollutants, and the accumulation of these elements in soils and plants is of great concern in agricultural production due to their toxic effects on crop growth. Also, these elements can enter into the food chain and severely affect human and animal health. Bioaugmentation with plant growth-promoting bacteria (PGPB) can contribute to an environmentally friendly and effective remediation approach by improving plant survival and promoting element phytostabilization or extraction under such harsh conditions. We isolated and characterised Pb and Cd-tolerant root-associated bacteria from Helianthus petiolaris growing on a Pb/Cd polluted soil in order to compose inoculants that can promote plant growth and also ameliorate the phytostabilization or phytoextraction efficiency. One hundred and five trace element-tolerant rhizospheric and endophytic bacterial strains belonging to eight different genera were isolated from the aromatic plant species Helianthus petiolaris. Most of the strains showed multiple PGP-capabilities, ability to immobilise trace elements on their cell wall, and promotion of seed germination. Bacillus paramycoides ST9, Bacillus wiedmannii ST29, Bacillus proteolyticus ST89, Brevibacterium frigoritolerans ST30, Cellulosimicrobium cellulans ST54 and Methylobacterium sp. ST85 were selected to perform bioaugmentation assays in greenhouse microcosms. After 2 months, seedlings of sunflower (H. annuus) grown on polluted soil and inoculated with B. proteolyticus ST89 produced 40% more biomass compared to the non-inoculated control plants and accumulated 20 % less Pb and 40% less Cd in the aboveground plant parts. In contrast, B. paramycoides ST9 increased the bioaccumulation factor (BAF) of Pb three times and of Cd six times without inhibiting plant growth. Our results indicate that, depending on the strain, bioaugmentation with specific beneficial bacteria can improve plant growth and either reduce trace element mobility or enhance plant trace element uptake. This research was funded by the UHasselt-Methusalem project 08M03VGRJ, as got an UHasselt BOF-BILA grant in the frame of collaboration between Hasselt University, Belgium and the University of Buenos Aires, and Ibero-American Development Bank under FONTAGRO project ATN/RF-16110-RG. Thijs, S (reprint author), Hasselt Univ, Ctr Environm Sci, Environm Biol, Agoralaan Bldg D, B-3590 Diepenbeek, Belgium. saran.anabel@inta.gob.ar; valeria.imperato@uhasselt.be; fernandez.lucia@inta.gob.ar; panos.gkorezis@uhasselt.be; jan.d'haen@uhasselt.be; merini.luciano@inta.gob.ar; jaco.vangronsveld@uhasselt.be; sofie.thijs@uhasselt.be

This paper presents the formulation, inkjet printing, and vacuum forming of a conductive and stretchable polymer, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), ink on a stretchable and transparent thermoplastic polyurethane (TPU) substrate. The formulation of the conductive and stretchable ink is achieved by combining PEDOT:PSS with additional solvents, to achieve the right inkjet properties for drop-on-demand (DoD) inkjet printing. A conductive pattern can be printed from the 21 &micro, m orifice on a flexible and stretchable TPU substrate, with a linewidth down to 44 &micro, m. The properties of the printed pattern, in terms of sheet resistance, morphology, transparency, impact of weather conditions, and stretching are investigated and show sheet resistances up to 45 Ohm/sq and transparencies as high as 95%, which is comparable to indium tin oxide (ITO). Moreover, in contrast to ITO, one-time stretching up to 40% can be achieved, increasing the sheet resistance up to 214 Ohm/sq only, showing the great potential of this ink for one-time stretching. Finally, as a proof of this one-time stretching, the printed samples are vacuum formed around a 3D object, still showing sufficient conductivity to be applied as a capacitive touch sensor.

Integrating photovoltaic applications within urban environments creates the need for more compact and efficient power electronics that can guarantee long lifetimes. The upcoming wide-bandgap semiconductor devices show great promise in providing the first two properties, but their packaging requires further testing in order to optimize their reliability. This paper demonstrates one iteration of the design for reliability methodology used in order to compare the generated thermo-mechanical stress in the die attach and the bond wires of a GaN and SiC MOSFET. An electro-thermal model of a photovoltaic string inverter is used in order to translate a cloudy and a clear one-hour mission profile from Arizona into a junction losses profile. Subsequently, the finite element method models of both devices are constructed through reverse engineering in order to analyze the plastic energy. The results show that the plastic energy in the die attach caused by a cloudy mission-profile is much higher than that caused by a clear mission-profile. The GaN MOSFET, in spite of its reduced losses, endures around 5 times more plastic energy dissipation density in its die attach than the SiC MOSFET while the reverse is true for the bond wires. Potential design adaptations for both devices have been suggested to initiate a new iteration in the design for reliability methodology, which will ultimately lead to a more reliable design.

Two push-pull type conjugated polymers - PIDTT−BTz and PIDTT−DTBTz, based on the ladder-type donor unit indacenodithieno[3,2-b]thiophene (IDTT) and bithiazole (BTz) as acceptor component - are designed and synthesized for photovoltaic applications. The polymers exhibit relatively high optical gaps of ~2.0 eV with strong absorption in the range of 400–600 nm, rendering them of particular interest for the harvesting of indoor light and/or multijunction devices. Electrochemical investigations indicate a lower highest occupied molecular orbital energy level (−5.44 eV) for PIDTT−BTz as compared to PIDTT−DTBTz (−5.36 eV), enabling to achieve a higher open-circuit voltage. Under solar illumination, the best power conversion efficiency (5.1%) is achieved for the combination PIDTT−DTBTz:PC71BM (compared to 4.6% for PIDTT−BTz:PC71BM).

In-Ga-Zn-oxide (IGZO), in its amorphous state, is known to have a high electron mobility and low off-state current inside transistor devices, which may even be further improved by crystallization. Thin films of the IGZO superlattice structure require an optimal layer homogeneity in addition to precise control of the stoichiometry, which can be achieved by using a solution-based process. In this work, an aqueous precursor system is developed, starting from the respective metal (hydr) oxides. A stable multimetal precursor is obtained, which is ideally suited for solution-deposition via spin-coating. Through an optimized multi-step thermal treatment, crystalline thin films of IGZO are obtained that show a preferential c-axis orientation after rapid-thermal annealing at 1000 °C in inert conditions. The resulting film shows a good optical transparency (>70%) and an improved carrier mobility (27.2 cm²/Vs) compared to typical solution-processed amorphous IGZO films, and is therefore promising for further application. This research is financially supported by the Research Foundation-Flanders (FWO Vlaanderen, project nr.(G054312N). The authors would like to thank Bart Ruttens for performing the rocking curve measurements.

The highest efficiency in perovskite solar cells is currently achieved with mixed-cation hybrid perovskites. The ratio in which the cations are present in the perovskite structure has an important effect on the optical properties and the stability of these materials. At present, the formamidinium cation is an integral part of many of the highest efficiency perovskite systems. In this work, we introduce a nuclear magnetic resonance (NMR) spectroscopy protocol for the identification and differentiation of mixed perovskite phases and of a secondary phase due to formamidinium degradation. The influence of the cooling rate used in a precipitation method on the FA/MA ratio in formamidinium–methylammonium lead iodide perovskites (FAxMA1–xPbI3) was investigated and compared to the FA/MA ratio in thin films. In order to obtain the FA/MA ratio from fast and accessible liquid-state 1H NMR spectra, the influence of the acidity of the solution on the line width of the resonances was elucidated. The ratio of the organic cations incorporated into the perovskite structure could be reliably quantified in the presence of the secondary phase through a combination of liquid-state 1H NMR and solid-state 13C NMR spectroscopic analysis. W.T.M.V.G. is an SB Ph.D. fellow at FWO (project number 1S17516N), and the FWO is acknowledged for the funding of the research. R.H. is a special research fund (BOF) Doctoral (Ph.D.) student at UHasselt/IMO. This work has been carried out in the context of the Solliance network (www.solliance.eu), from which the UHasselt is a full member. Research Foundation Flanders (FWO) and the EU funded network MERA.NET are acknowledged for the funding of the PROMISES project.

Sodium-ion batteries (SIBs) are potential cost-effective solutions for stationary energy storage applications. Unavailability of suitable anode materials, however, is one of the important barriers to the maturity of SIBs. Here, we report a Na2+xTi4O9/C composite as a promising anode candidate for SIBs with high capacity and cycling stability. This anode is characterized by a capacity of 124 mAh g(-1) (plus 11 mAh g(-1) contributed by carbon black), an average discharge potential of 0.9 V vs Na/Na+, a good rate capability and a high stability (89% capacity retention after 250 cycles at a rate of 1 degrees C). The mechanisms of sodium insertion/deinsertion and of the formation of Na2+xTi4O9/C are investigated with the aid of various ex/in situ characterization techniques. The in situ formed carbon is necessary for the formation of the reduced sodium titanate. This synthesis method may enable the convenient synthesis of other composites of crystalline phases with amorphous carbon.

Research into 2D layered hybrid perovskites is on the rise due to the enhanced stability of these materials compared to 3D hybrid perovskites. Recently, interest towards the use of functional organic cations for these materials is increasing. However, a vast amount of the parameter space remains unexplored in multi-layered (n > 1) hybrid perovskites for solar cell applications. Here, we incorporate carbazole derivatives as a proof of concept towards the use of tailored functional molecules in multi-layered perovskites. Films of low-n carbazole containing perovskites show high photoconductivity half-lifetimes. Higher-n (〈n〉 = 40) multi-layered perovskite films possess charge carrier diffusion lengths comparable to MAPI thin films. Solar cells containing these materials have comparable efficiencies to our MAPI and phenethylammonium (PEA)-containing multi-layered perovskite reference devices. Moisture stability tests were performed both at the material and device levels. In comparison to MAPI and PEA-based materials and solar cells, the addition of a small percentage of the carbazole derivative to the perovskite material significantly enhances the moisture stability.

Advanced applications in optics, for example, Faraday isolators, demand forcomplex magneto-plasmonic nanostructures which exhibit large Faradayrotation. These structures is fabricated by a Layer-by-Layer approach, albeitthis being a slow technique. Here, the ultrasonic spray coating as apromising alternative method toward the formation of hybrid magneto-plasmonic structures is pioneered by the authors. Ultrasonic spray coating isa stable, fast, and tunable mass production method applied in this work todeposit gold and iron oxide nanoparticles. Altering multiple depositionparameters give the spray coating technique a large amount of control overthe coverage. Optical and magneto-optical properties, layer formation andsurface coverage of single and hybrid layers with increasing thickness andnumber of layers are studied and compared to samples synthesized by Layer-by-Layer deposition. Ultrasonic spray coating paves the way to the wide-spread application of innovative and versatile hybrid magnetic-plasmonicnanocomposites

The particle surface of LiNi0.5Mn1.5O4-δ (LNMO), a Li-ion battery cathode material, has been modified by Ti cation doping through a hydrolysis-condensation reaction followed by an anneal in oxygen. The effect of different annealing temperatures (500-850oC) on the Ti distribution and electrochemical performance of the surface modified LNMO was investigated. Ti cations diffuse from the preformed amorphous ‘TiOx’ layer into the LNMO surface during annealing at 500oC. This results in a 2-4 nm thick Ti-rich spinel surface having lower Mn and Ni content compared to the core of the LNMO particles, which was observed with scanning transmission electron microscopy coupled with compositional EDX mapping. An increase in the annealing temperature promotes the formation of Ti bulk doped LiNi(0.5-w)Mn(1.5+w)-tTitO4 phase and Ti-rich LiNi0.5Mn1.5-yTiyO4 segregates above 750°C. Fourier-transform infrared spectrometry indicates an increasing Ni-Mn ordering withannealing temperature, for both bare and surface modified LNMO. Ti surface modified LNMO annealed at 500oC shows a superior cyclic stability, Coulombic efficiency and rate performance compared to bare LNMO annealed at 500oC when cycled at 3.4-4.9 V vs. Li/Li+. The improvements are probably due to suppressed Ni and Mn dissolution with Ti surface doping. This research is supported by the Research Foundation Flanders (FWO Vlaanderen, grant number G040116N). This project receives the support of the European Union, the European Regional Development Fund ERDF, Flanders Innovation & Entrepreneurship and the Province of Limburg (project 936). Greet Cuyvers and Gilles Bonneux (UHasselt) are acknowledged for the ICP-AES sample preparation and measurements. Vera Meynen and Karen Leyssens (Antwerp University, Belgium) are acknowledged for the BET measurements. Special thanks to Bart Ruttens (UHasselt) for XRD measurements and discussions on the refinements.

Push-pull-type conjugated polymers applied in organic electronics do not always contain a perfect alternation of donor and acceptor building blocks. Misscouplings can occur, which have a noticeable effect on the device performance. In this work, the influence of homocoupling on the optoelectronic properties and photovoltaic performance of PDTSQx(ff) polymers is investigated, with a specific focus on the quinoxaline acceptor moieties. A homocoupled biquinoxaline segment is intentionally inserted in specific ratios during the polymerization. These homocoupled units cause a gradually blue-shifted absorption, while the highest occupied molecular orbital energy levels decrease only significantly upon the presence of 75-100% of homocouplings. Density functional theory calculations show that the homocoupled acceptor unit generates a twist in the polymer backbone, which leads to a decreased conjugation length and a reduced aggregation tendency. The virtually defect-free PDTSQx(ff) affords a solar cell efficiency of 5.4%, which only decreases substantially upon incorporating a homocoupling degree over 50%. The calculations were performed on the computers of the Consortium des Equipements de Calcul Intensif (CECI, ), including those of the Technological Platform of High-Performance Computing, for which the authors gratefully acknowledge the financial support of the FNRS-FRFC (Conventions No. 2.4.617.07.F and 2.5020.11) and the University of Namur. The UHasselt co-authors thank Hasselt University and the Research Foundation - Flanders (FWO Vlaanderen) for the continuous financial support and postdoctoral fellowships for J.K. and P.V.

One of the major challenges for the nuclear industry is the safe and sustainable immobilisation of radioactive wastes (RAW). Currently, the most commonly used immobilisation matrices for low and intermediate level wastes are based on ordinary Portland cement. For the more difficult to immobilise nuclides, such as caesium (Cs+) and strontium (Sr2+), researchers have been studying alternative immobilisation matrices, of which alkali-activated materials (AAM) are a very promising option. However, the differences in precursor compositions and the use of different types of activating solutions make it difficult to fully understand the effects of precursor composition on the immobilisation of introduced nuclides. Therefore, six different compositions of laboratory-synthesised Ca-Si-Al slags were developed to serve as precursors for low-alkaline AAMs to study their immobilisation behaviour. Immobilisation capacities up to 97.6% Cs+ and 99.9% Sr2+ were achieved with 1 wt% and 0.1 wt% waste loading, respectively, when leaching for 7 days at 20 °C in Milli Q water. Cs+ immobilisation is higher at lower Si/Al and Ca/(Si + Al) ratios. Immobilisation of Sr2+ is higher at a lower Ca/(Si + Al) ratio and independent of Si/Al ratio. The results of this study offer a deeper understanding of the immobilisation behaviour of AAMs and can encourage further research and application of AAMs for RAW immobilisation.

Thin films of amorphous and crystalline perovskite Li3xLa(2/3)−xTiO3 (LLT) (x = 0.117) are prepared by means of aqueous chemical solution deposition onto rutile TiO2 thin films as an anode, yielding an electrochemical half-cell. The Li-ion conductivity of the pin-hole free, amorphous LLT thin film (90 nm thick) is 3.8 × 10−8 S cm−1 on Pt and 1.3 × 10−8 S cm−1 on rutile TiO2, while measuring perpendicular to the thin film direction with impedance spectroscopy. Grazing angle attenuated total reflectance-Fourier transform infrared spectroscopy shows that all organic precursor molecules have been decomposed at 500 °C. In addition, in situ (heating) X-ray diffraction analysis shows that phase pure crystalline perovskite LLT (x = 0.117) is formed on top of the rutile TiO2 anode at 700 °C. Furthermore, thickness control is possible by varying the precursor solution concentration and the number of deposition cycles. The current study presents a promising synthesis route to develop all-solid-state battery devices based on multi-metal oxide materials using aqueous precursor chemistry.

To reduce the high surface roughness of additive manufactured (AM) products, typically a post-treatment is required. Subtractive post-treatments are often performed by hand and are therefore expensive and time consuming, whereas conventional additive post-treatments, such as pneumatic spray coating, require large quantities of coating material. Ultrasonic spray coating, in contrast, is an additive post-treatment technology capable of applying coatings in an efficient way, resulting in less material usage. In this paper, we investigate the application of the ultrasonic spray coating process and the final properties of the coated AM part by applying a thin coating to reduce surface roughness of the AM substrate and to impart hydrophobic functionality. The hydrophobic coating is applied onto flat selective laser sintered (SLS) surfaces prepared from polyamide 12 (PA12) having a surface roughness of Ra = 20 µm. The hydrophobic coating consists of 5 wt % polyvinylidene fluoride (PVDF) in acetone. The coated substrates are analyzed for roughness using a profilometer, a contact angle using a goniometer, and a coating uniformity and thickness using light and scanning electron microscopes. The layer formation applying the ultrasonic spray coating is studied and compared with layer formation using pneumatic spray coating. It is found that a roughness reduction down to 5 µm was achieved via an ultrasonic spray coating with 30 layers of PVDF solution. It is shown in cross-section electron microscopy pictures that, due to the nature of the ultrasonically generated droplets, the rough and porous surface of the SLS surface is filled with the PVDF material after which the roughness is reduced by adding a thin layer on top. In comparison to a standard industry-applied pneumatic spray coating process, the results obtained from ultrasonic spray coating show less material usage, a reduced roughness, and a better filling of the pores, obviously resulting in optimized adhesion. The authors would like to thank the support of Flanders Make vzw for partial funding of the ultrasonic spray coating installation.

Several aqueous solution-gel precursors for the Li ion battery cathode material LiFePO4, were synthesized. These differ in their composition, both regarding their Fe source, as well as in the complexing agent present. Fe(II) lactate hydrate is for the first time used as Fe2+ source. The ability to use an Fe3+ source (Fe(III) nitrate nonahydrate) for the synthesis of LiFePO4 is also investigated. Our results show that it is possible to reduce the Fe3+ to Fe2+, necessary to enable LiFePO4 phase formation, during annealing under specific conditions. The decomposition behavior for these precursors in dry air, as well as in an inert atmosphere, is shown. Raman spectroscopy is used to evaluate the structure of the carbon phases present after annealing of the precursor powders. Thomas Vranken is a Ph.D. fellow of the Research Foundation—Flanders (FWO).

The microwave assisted reaction between P25 titanium dioxide (TiO2) and phenylphosphonic acid (PPA) is explored thoroughly and the influence of the reaction conditions on the grafting mechanism and formed products is presented. While the surface grafting is observed at low temperatures and water free conditions, the formation of titaniumphosphonate is favored in water and high reaction temperatures. For the first time the correlation between the amorphous TiO2 phase and the formation of titani-umphenylphosphonate is reported. Materials are fully characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), solid-state P-31 Nuclear Magnetic Resonance (P-31 NMR) spectroscopy, energy dispersive X-ray (EDX) spectroscopy and transmission electron microscopy (TEM). (C) 2016 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved. This work is financially supported by the Fund for Scientific Research of Flanders (FWO-Vlaanderen) via the project G. O127.12N. We further acknowledge the financial support from the Interuniversity Attraction Poles Programme (P7/05) initiated by the Belgian Science Policy Office (BELSPO).

Solid-state Dye-Sensitized Solar Cells (ss-DSSCs) are promising candidates for future low cost photovoltaic energy generation and are based on polymer/metal oxide donor/acceptor heterojunctions. However, a crucial drawback of hybrid solar cells is the use of environmental unfriendly solvents, such as toluene, chloroform, chlorobenzene, etc. in the phase of preparation. In this work towards eco-friendly processing, we use water as a solvent in the preparation of the photo-active layer for hybrid solar cells. We demonstrate eco-friendly hybrid polymer/titania solar cells consisting of water soluble polythiophene as light-absorber, donor and Hole Transporting Layer (HTL), above a TiO 2 layer that acts as an acceptor and electron conductor. The water soluble conjugated polymer materials are studied in terms of their opto-electrical and morphological properties, leading to a better understanding of the resulting photovoltaic performance. An alternative new processing method in device preparation is introduced; yielding prototype solar cells with an efficiency of 0.7%. This promising solar cell device performance can be considered as a proof-of-principle for future eco-friendly solar cells.

Within the field of organic bulk heterojunction solar cells, the morphology of the active layer has a key role in obtaining high power conversion efficiencies. P3HT nanofibers, obtained in highly concentrated solutions, are able to give controlled morphologies directly upon deposition. Since the solar cell efficiency of fiber solar cells depends on the fiber content of the casting solution, it is important to control this parameter. Here, we demonstrate an easy way to control the fiber content in the casting solution, i.e. changing the solution temperature. By using solution heating, the overall molecular weight of the polymer in the blend is kept constant, fiber isolation is not needed and the use of solvent mixtures is avoided. The obtained optimal power conversion efficiency is shown to be linked to the morphology of the active layer, which is studied with Transmission Electron Microscopy (TEM).

Mimicking the selectivity and sensitivity of biological systems for sensor devices is of increasing interest in biomedical, environmental and chemical analysis. Synthetic materials with imprinted nanocavities, acting as highly selective artificial receptors, are a tailor-made solution in obtaining such a sensor. Incorporation of such molecularly imprinted polymers (MIPs) in a platform suitable for electrochemical measurements, can offer high sensitivity together with device miniaturization and an electronic read-out. As a proof of principle, a MIP-based sensor for l -nicotine has been developed. To this end, the molecular structure of l -nicotine was imprinted in a polymer matrix of polymethacrylic acid (PMAA). Subsequently, microparticles of the imprinted polymer were immobilized on thin films of the conjugated polymer OC1C10-PPV. These films were incorporated in an impedimetric sensing device. Using electrochemical impedance spectroscopy, the real part of the impedance was monitored for various concentrations. This setup allows for the detection of l -nicotine from 1 to 10 nM and is insensitive for the resembling molecule l -cotinine.

The disclosure of the nanomorphology of thin films in organic solar cells, prepared from blends of conjugated polymers and pcbm, is of key importance for a better understanding of the occurring photovoltaic (pv) mechanisms. Hereto solid-state nmr relaxometry has been evaluated as a complementary technique to traditional microscopic techniques like atomic force microscopy and transmission electron microscopy. It is demonstrated that proton wide-line solid-state nmr relaxometry is a useful and innovative tool to study the phase morphology of blends used in semi-conducting polymer based pv devices. Attention is focused on the influence of the blend composition and casting conditions on the resulting phase morphology. Two different casting techniques, i.e. Spincoating and doctor blading, were compared. To demonstrate the applicability of nmr relaxometry in this field, mdmo-ppv/pcbm blends where used, since these are known for their significant phase separation behavior in combination with toluene as solvent. In films prepared from blends in toluene with a pcbm content =70 wt %, a fraction of the pcbm is phase separated into crystalline domains, whereas the remaining part remains homogeneously mixed with the mdmo-ppv.

A superior field electron emission (FEE) source made from a hierarchical heterostructure, where two-dimensional hexagonal boron nitride (hBN) nanowalls were coated on one-dimensional diamond nanorods (DNRs), is fabricated using a simple and scalable method. FEE characteristics of hBN-DNR display a low turn-on field of 6.0 V mu m(-1), a high field enhancement factor of 5870 and a high life-time stability of 435 min. Such an enhancement in the FEE properties of hBN-DNR derives from the distinctive material combination, i.e., high aspect ratio of the heterostructure, good electron transport from the DNR to the hBN nanowalls and efficient field emission of electrons from the hBN nanowalls. The prospective application of these heterostructures is further evidenced by enhanced microplasma devices using hBN-DNR as a cathode, in which the threshold voltage was lowered to 350 V, affirming the role of hBN-DNR in the improvement of electron emission. The authors like to thank the financial support of the Research Foundation Flanders (FWO) via Research Projects G.0456.12 and G.0044.13N, the Methusalem "NANO" network. KJ Sankaran, and P Pobedinskas are Postdoctoral Fellows of the Research Foundation-Flanders (FWO).

The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT) or thiazolo[5,4-d]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs' lifetime. This work has been supported by the Villum Foundation's Young Investigator Program (second round; project: Materials for Energy Production). The work was partly done during an external research stay of Ilona Heckler at Hasselt University in the group of Wouter Maes. The Hasselt University co-authors acknowledge the support by the IAP (Interuniversity Attraction Poles) 7/05 project FS2 (Functional Supramolecular Systems), granted by the Science Policy Office of the Belgian Federal Government (BELSPO), and the Research Foundation-Flanders (Fonds voor Wetenschappelijk Onderzoek-Vlaanderen) (Projects G.0415.14N, G.0B67.15N and M.ERA-NET Project RADESOL).

In this study we demonstrate and explain the direct relationship between precursor chemistry and phase formation of LiMn2O4 powders and thin films from aqueous chemical solution deposition (CSD). The processing conditions applied to transform the precursor into the LiMn2O4 phase are investigated with a focus on the heating atmosphere and temperature. We found that the Mn2+ ions, used as a starting product, already partially oxidize into Mn3+/Mn4+ in the precursor solution. The Mn3+ ions present in the gel or the dried film are extremely sensitive to O-2, leading to fast oxidation towards Mn4+. Here, we suggest that the oxygen, introduced in the precursor solution by the citrate complexing agent, suffices to oxidize the Mn2+ into Mn3+/Mn4+ which is crucial in the formation of phase pure spinet and stoichiometric LiMn2O4. Any additional oxygen, available as O-2 during the final processing, should be avoided as it leads to further oxidation of the remaining Mn3+ into Mn4+ and to the formation of the gamma-Mn2O3 and lambda-MnO2 secondary phases. Based on these insights, the preparation of phase pure, spinet and stoichiometric LiMn2O4 in a N-2 ambient was achieved both in powders and films. Moreover, the study of the precursor chemistry and final annealing leads to the possibility of reducing the final temperature to 450 degrees C, enabling the use of temperature and oxidation sensitive current collectors such as TiN. This inert ambient and low temperature processing of LiMn2O4 provides the opportunity to have large flexibility and compatibility with process conditions for other materials in the thin film battery stack, without undesired oxidations. The authors acknowledge financial support by the IWT Flanders (SBO project SOSLion). Special thanks to K. Elen and B. Ruttens for XRD analysis, Thomas Vranken for TEM, Wouter Marchal for thermal analysis, Christopher De Dobbelaere and Dries De Sloovere for FT-IR and GATR and Elsy Thijssen for ICP-AES.

© 2015, Springer Science+Business Media New York. This paper reports a thorough microstructural investigation of bismuth ferrite (BFO) thin films subjected to various processing conditions and discusses their influence on the stability of the BiFeO3 perovskite phase. The formation of secondary phases in BFO thin films is studied as a function of annealing temperature and time, film thickness, Bi excess, and Ti substitution. While films annealed at 600 °C consist of the desired BiFeO3 phase, higher temperatures induce the decomposition leading to a significant amount of secondary phases, particularly the iron-rich Bi2Fe4O9 phase. A longer annealing time at 700 °C further enhances the decomposition of BiFeO3. Qualitative microstructural analysis of the films is performed by electron backscattered diffraction which provides phase analysis of individual grains. The morphology of the single-crystalline Bi2Fe4O9 grains that are embedded in the BiFeO3 matrix drastically changes as a function of the film thickness. Nucleation of these Bi2Fe4O9 grains probably occurs at the film/substrate interface, after which grain growth continues toward the surface of the film through the depletion of the BFO phase. Addition of Bi excess or the substitution of Fe with Ti in the precursor solutions significantly reduces the formation of an iron-rich secondary phase. Influence of the secondary phases as well as Ti substitution on magnetic properties of BFO films was investigated. ispartof: Journal of Materials Science vol:50 issue:13 pages:4463-4476 status: published

Lead phthalocyanine (PbPc) thin films of 5 and 50 nm have been deposited on hydrogen and oxygen terminated single crystal diamond (SCD) using organic molecular beam deposition. Atomic force microscopy and X-ray diffraction (XRD) studies showed that PbPc grown on the hydrogen terminated SCD forms layers with a high degree of crystallinity, dominated by the monoclinic (320) orientation parallel to the diamond surface. The oxygen terminated diamond led to a randomly oriented PbPc film. Absorption and photocurrent measurements indicated the presence of both polymorphs of PbPc, however, the ratio differed depending on the termination of the SCD. Finally, polarized Raman spectroscopy was used to determine the orientation of the molecules of the thin film. The results confirmed the random orientation on the O-terminated diamond. On SCD:H, the PbPc molecules are lying down in accordance with the XRD results.

Printed chalcopyrite thin films have attracted considerable attention in recent years due to their potential in the high-throughput production of photovoltaic devices. To improve the homogeneity of printed CuInSe2 (CISe) layers, chemical additives such as binder can be added to the precursor ink. In this contribution, we investigate the influence of the dicyandiamide (DCDA) content, used as a binder in the precursor ink, on the physical and electrical properties of printed CISe solar cells. It is shown that the use of the binder leads to a dense absorber, composed of large CISe grains close to the surface, while the bulk of the layer consists of CISe crystallites embedded in a CuxS particle based matrix, resulting from the limited sintering of the precursor in this region. The expected additional carbon contamination of the CISe layer due to the addition of the binder appears to be limited, and the optical properties of the CISe layer are similar to the reference sample without additive. The electrical characterization of the corresponding CISe/CdS solar cells shows a degradation of the efficiency of the devices, due to a modification in the predominant recombination mechanisms and a limitation of the space charge region width when using the binder; both effects could be explained by the inhomogeneity of the bulk of the CISe absorber and high defect density at the CISe/CuxS-based matrix interface.

Al-doped ZnO nanoparticles are synthesized by means of a heating up solution based thermal decomposition method. The synthesis involves a reaction of zinc acetylacetonate hydrate, aluminium acetylacetonate and 1,2-hexadecanediol in the presence of oleic acid and oleyl amine. A proposed reaction mechanism from reagents to monomers is corroborated by analysis of the evolving gases using headspace GC-MS analysis. The Al-doped ZnO nanoparticles synthesized are dynamically stabilized by adsorbed oleate ions, after deprotonation of oleic acid by oleyl amine, as was found by NOESY proton NMR and complementary FTIR spectroscopy. Precession electron diffraction shows a simultaneous increase in lattice parameters with Al concentration. This, together with HAADF-STEM and EDX maps, indicates the incorporation of Al into the ZnO nanoparticles. By the combination of complementary characterization methods during all stages of the synthesis, it is concluded that Al is incorporated into the ZnO wurtzite lattice as a dopant.

Tailoring the properties of superparamagnetic nanoparticles (MNPs) is essential for various nano-based biological applications. Having control over the properties of the MNPs permits a maximum flexibility. Starting from monodisperse iron oxide MNPs produced by thermal decomposition, we report on the optimization and characterization of a first and second seed mediated growth step by varying the surfactant amount and by optimizing the heating steps. We demonstrate the ability to gradually increase the size of crystalline MNPs from 6 over 9 to 12 nm with an improving monodispersity as demonstrated by Transmission Electron Microscopy, Dynamic Light Scattering and X-ray diffraction. The magnetic properties of the MNPs, studied by Vibrating Sample Magnetometry, were in concert with their size increase. We also show the functionalization of these particles with polyethylene glycolated silanes, to render the MNPs stable in water. Different characterization techniques, namely Transmission Electron Microscopy, Dynamic Light Scattering, Fourier-transform InfraRed, Thermo gravimetric analysis and X-ray Photoelectron Spectroscopy, confirmed the successful engraftment of the silanes on the MNP's surface. In conclusion, the proposed route of step-wise synthesis in combination with silane functionalization allows fine tuning the physical properties of iron oxide MNPs for applications in an aqueous environment ispartof: IEEE Transactions on Magnetics vol:49 issue:1 pages:219-226 ispartof: location:MN, Minneapolis status: published