In the present work the influence of different modifiers, calculated to B2O3, CeO2, Sb2O3, ZnO, and ZrO2, on their distribution in TiO2 is investigated. The phase composition and phase transformation of prepared rutile-TiO2 is determined by the selective leaching method, ICP-AES, XRD and FT-IR techniques. The addition of Sb2O3 to TiO2 has no influence on the anatase–rutile phase transformation, CeO2 and ZrO2 act as inhibitors of the TiO2 phase transformation and the addition of ZnO or B2O3 to TiO2 accelerates rutile formation. It is observed that boron is located in TiO2 in the form of soluble B2O3, zinc partly reacts with titanium forming co-phase TiZn2O4 and antimony addition to TiO2 presumably causing the formation of a co-phase of Sb with Ti. Cerium forms a separate phase, CeO2, and reacts partly with titanium, probably creating co-phase, CexTi(1-x)O2 (for example Ce0.8Ti0.2O2). Zirconium addition in TiO2 forms separate ZrO2 phase and solid solution of Zr with Ti.

Dielectric polymers with high energy density with low loss at high electric fields are highly desired for many energy storage and regulation applications. A polar-fluoropolymer blend consisting of a high energy density polar-fluoropolymer of poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)) with a low dielectric loss polymer of poly(ethylene-chlorotrifluoroethylene) (ECTFE) was developed and investigated. We show that the two polymers are partially miscible which leads to blends with high energy density and low loss. Moreover, by introducing crosslinking to further tailor the nano-structures of the blends a markedly reduction of losses in the blend films at high field can be achieved. The crosslinked blend films show a dielectric constant of 7 with a dielectric loss of 1% at low field. Furthermore, the blends maintain a high energy density and low loss (∼3%) at high electric fields (> 250 MV/m).

We present the development of highly efficient merocyanine solar cells at the example of the dye MD376. Due to their unique processing flexibility, merocyanines have been applied in solution- as well as vacuum-processed organic photovoltaics. In fully vapor-deposited MD376 single cells, efficiencies up to 5.0% were achieved while maintaining a rather simple device setup with only four organic layers. Moreover, MD376 has been successfully introduced to vacuum-processed tandem cell structures, reporting a high open-circuit voltage of 2.1 V.

Here we introduce a multifunctional copolymer network system with adjustable thermomechanical properties, which is also capable to show a substantial water uptake and in this way should allow the additional alteration of the overall elastic properties besides the variation of the crosslinking density. The swelling capacity in water, the thermal properties as well as the crystallinity of a series of grafted copolymer networks named CLEG composed of water swellable poly(ethylene glycol) (PEG) side chains and crystallizable poly(ε-caprolactone) (PCL) segments acting as covalent crosslinker were explored in an aqueous environment.

The water swelling capability of the CLEG polymer networks was found to increase from 120% to 240% with increasing weight content of PEG. In contrast to the dry state, where two well separated melting temperatures could be observed for all CLEG samples, in aqueous environment only one melting temperature slightly above 40 °C, was obtained, whereby the overall crystallinity after swelling with water was strongly related to the PCL content in the CLEG polymer networks.

The influence of anodic and cathodic pre-treatment on boron doped diamond (BDD) surface for copper (Cu) electrodeposition was studied to assess Cu particle consolidation on BDD electrode. These modified electrodes were applied to study the nitrate electrochemical reduction process. The obtained results showed that the BDD surface cathodically treated presented high Cu particle density as well as even distribution on the electrode surface after the electrodeposition process. For samples anodically treated the electrodeposited Cu was dispersed with lower particle density. This behavior was attributed to a high electrode conductivity imposed by the cathodic pre-treatment leading to an increase in the BDD surface hydrogenation. Therefore, one can conclude that for electrochemical nitrate reduction the anodically treated BDD has a better reproducibility. This response is attributed to the Cu particle consolidation on BDD electrode due to the oxygen surface terminations induced by the anodic pretreatment.

The paper attempts to present a panoramic view of the water cement ratio strength relations adopted by a few national bodies and look at the appropriateness of them while keeping in mind the enormous number of variables that could influence them. These relations are also compared with a couple of databases reported to assess the efficacy of each of these in ensuring a reasonable prediction capability. This in a way will pave the way for an effective use of the cement in concrete leading to significant optimization of the concrete composite.

Semiconductor quantum dots are considered very promising candidates for bio-imaging and diagnosis applications because of their tunable optical properties and good optical stability in aqueous phase. Any practical application of these materials will rely on the viability of their simple and direct synthesis in aqueous phase with no need for toxic and unstable organic media. The optical properties of CdSe quantum dots and CuS nanoparticles are desirable in bio-imaging and cell sorting applications because of their tunable photoluminescence at the visible range. The present work addresses the synthesis of CdSe quantum dots and CuS nanoparticles via an optimized, simple and scalable aqueous processing route at low temperatures. The tunability of the optical properties was achieved by a suitable control of the citrate/Cd mole ratio, temperature of synthesis (20-90°C) and reaction time (0-1 hour). In the case of CuS, the strong plasmonic absorption offers the opportunity to investigate this material as a photothermal coupling agent for photothermal therapy. The intensity of the plasmonic absorption was enhanced by selecting an appropriate sulfide precursor (Na2S, Thioglycolic acid), temperature of synthesis (90-120°C) and reaction time. Nanocrystals were characterized by x-ray diffraction, UV-VIS, photoluminescence (PL) spectroscopy techniques and electron microscopy. The effects of the synthesis conditions on the crystal size and the corresponding functional properties of synthesized quantum dots are presented and discussed.

Effect of non-thermal plasma (NTP) on bio-particles has been studied using Bacillus subtilis (B. subtilis), Escherichia coli (E. coli) and bacteriophages. NTP has been used, and states of different biological components were monitored during the course of the exposure. Analysis of green fluorescent protein (GFP), introduced into E.coli cells proved that NTP causes a prominent protein damages without cutting peptide bonds. We have developed a biological assay which evaluates in vivo DNA damage of the bacteriophages. Different doses of the plasma were applied to wet state of λ phages. From the plasma-exposed λ phages, DNA was purified and subjected to in vitro DNA packaging reactions. The re-packaged phages consist of the DNA from discharged phages and brand-new coat proteins. Survival curves of the re-packaged phages showed extremely large D value (D = 25 s) compared to the previous D value (D = 3 s) from the discharged phages. The results indicate that DNA damage hardly contributed to the inactivation, and the damage in coat proteins is responsible for inactivation of the phages. We also report a single-molecule-based analysis of strand breakages on large DNA molecules induced by the plasma exposure. Single-molecule observation of DNA that involved molecular combing was used to measure the length of individual DNA molecules. The measured DNA length showed that plasma exposure caused a marked change in length of DNA molecules. The rate of plasmainduced strand breakage on large random-coiled DNA molecules was determined using a simple mathematical model. The measured rate shows good relation with the plasma exposure time, and could be used for safety evaluation of the plasma treated water.

The antibacterial activity of nanosilver against Gram negative Escherichia coli bacteria is investigated by immobilizing nanosilver on nanostructured silica particles and closely controlling Ag content and size. These Ag/SiO2 nanoparticles were characterized by S/TEM, EDX spectroscopy, X-ray diffraction. The antibacterical activity of these composite samples was investigated for a constant composite particle concentration. The highest activity was observed for the higher silver content particles.

We investigate through-thickness hardness and modulus of Zr50Cu45Al5 metallic glass melt-spun ribbon. Because of their thinness, the ribbons are challenging to measure, so we employ a novel nanoindentation based-method to remove artifacts caused by ribbon flexing and edge effects. Hardness and modulus vary approximately linearly across the thickness but, unlike bulk ingots, the side of the ribbon that cooled most quickly had the highest hardness and modulus. This “inverse” variation may be caused by the fast-moving solidification front, which might conceivably, for instance, push free volume in advance of it. Annealing near T g causes both hardness and modulus to increase and become more uniform across the thickness.

Photo-excitation of high surface area semiconductor nanorods decorated with surface catalyst particles are investigated. DFT-based simulation is applied to the charge transfer dynamics at the interface of the supported nanocatalyst by modeling dynamics of photo-excitations. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. The energy of photo-excitation is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling as the electron/hole pair relaxes to the conduction / valence band edges. The methodology is applied to TiO2 nanorod modeled as a periodic anatase (100) slab functionalized by minimalistic nano-clusters or doping. Simulations of these models demonstrate the formation of charge transfer state in both time and frequency domain. Computed charge dynamics leads to creation of positively charged areas on the nanorod surface that is an important prerequisite for oxidation catalysis. Our computation identifies optimal composition and morphology of nanocatalyst for such applications as water splitting for hydrogen production or solar cells.

This study aims at gaining a better understanding of the behaviour of montmorillonite in contact with different ground waters; alteration of montmorillonite and possible formation of secondary minerals. Batch experiments were conducted with purified Swy-2 montmorillonite in simulated fresh (I=0.05 M, pH 8) and saline (I=0.1 M, pH 11) waters at 25 and 60ºC in anaerobic (Ar(g)) conditions. The concentrations of Al, Fe; Mg and Si were analysed from ultra-filtered solution samples with HR-ICP-MS (High Resolution Inductively Coupled Plasma Mass Spectrometry). The amount of released Si depended strongly on the experimental conditions. The Si concentrations at 60oC in the saline and fresh waters showed a difference greater than an order of magnitude. The initial purified montmorillonite and the solid materials from experiments were analysed with XRD. The analysis indicated that the nature of smectite did not change, but the experimental conditions, more or less, modified the structure of montmorillonite, e.g., in fresh waters the XRD spectra showed peaks typical of mixed layer minerals, which can refer to the presence of either randomly ordered illite/smectite or randomly ordered collapsed smectite/ hydrated smectite layers. The dissolution of montmorillonite was studied also by modelling with TOUGHREACT. The experimental and modelled results were compared revealing a need to develop the model e.g. in respect of the evolution of pH.

Hierarchically porous materials are of interest in a wide range of applications. If the materials are electronic, or ionic conductors, such materials are of interest as electrodes for use in fuel cells. Using hierarchically porous silica as templates, we have demonstrated the formation of hierarchically porous metal and metal oxide structures. Through the control of the synthesis conditions, we have produced partial replicas ca. 1 cubic centimeter in volume, in which two macroporous networks are separated by a nanoporous membrane. The macroporous network in the silica template is known to be bicontinuous. Our underlying model predicts that the second, induced, macroporous network should be similarly bicontinuous.

Micrometer resolution X-ray tomography of the whole sample confirms that the synthesis produces one bicontinuous macroporous network, and is consistent with the existence of a second set of macropores. Preliminary experiments were carried out using FIB/SEM serial tomography to image the second macropore network, however, the length scale of the structures is such that this approach it is unable to firmly establish that the second macropore network is bicontinuous throughout the entire sample volume.

Bismuth vanadate (BiVO4) thin films are deposited by a low-cost and scalable spray pyrolysis method. Its performance under AM1.5 illumination is mainly limited by slow water oxidation kinetics. We confirm that cobalt phosphate (Co-Pi) is an efficient water oxidation catalyst for BiVO4. The optimum thickness of BiVO4 is 300 nm, resulting in an AM1.5 photocurrent of 1.9 mA/cm2 at 1.23 V vs. RHE when catalyzed with Co-Pi. Once the water oxidation limitation is removed, the performance is limited by low charge separation efficiency. This causes more than 60% of the electron-hole pairs to recombine before reaching the respective interfaces. The slow electron transport is shown to be the main cause of this low efficiency, and future efforts should therefore be focused on addressing this key limitation.

The effects of austenitizing temperature and cooling rate on the microstructures and textures produced by phase transformations in high strength hot rolled Fe-C-Mn steel plates are investigated using orientation imagining microscopy. Samples machined from the plates are austenitized at temperatures between 820-950°C during 30 minutes and quenched in either iced-water, water or oil. Finally, the quenched samples are tempered at 450°C during 30 minutes. Characterization of microstructure and textures produced by these heat treatments was performed by conventional metallography using a reflected light microscope and orientation imaging microscopy using backscattered-electron diffraction patterns in a scanning electron microscope with thermo-ionic electron source.

The results show that the microstructure and texture produced under a given combination of austenitizing temperature and cooling rate are strongly dependent on the mechanism involved in the phase transformation of the austenite (γ). High austenitizing temperatures and cooling rates promote martensitic transformation and development of textures containing significant volume fractions of Br, Cu, transformed-Cu and transformed-Br orientation components. In this case, the austenite and martensite phases are clearly related through the Kurdjumov-Sachs orientation relationship. In contrast, low temperatures and low cooling rates result in a complex mixture of transformation products, such as polygonal ferrite, Widmanstäten ferrite, martensite, bainite and pearlite. The textures formed under these conditions are quite different and contain significant volume fractions of cube, rotated-cube, Goss and rotated-Goss components, following the Bain orientation relationship.

Structural polymers are susceptible to accumulated damage in the form of internal microcracks that propagate through the material, resulting in mechanical failure. Self- healing approaches offer a solution to repair these damages automatically. The first generation self-healing material system includes a microencapsulated healing agent within a catalyst-embedded matrix. Propagating microcracks rupture the microcapsules, releasing the liquid healing agent into the damaged region. Catalyst-triggered polymerization of the released healing agent repairs the damage. Our research focuses on a similar approach for addressing “damage accumulation failure” of poly(methyl methacrylate) (PMMA) bone cement caused by microcrack initiation and propagation. In this study, polyurethane (PU) microcapsules containing a tissue adhesive, 2-octylcyanoacrylate (OCA) were synthesized using in situ interfacial polymerization of toluene-2,4-diisocynate (TDI) and polyethylene glycol 200 (PEG 200) through an oil-in-oil-in-water microemulsion (o/o/w). The process was optimized by studying different combinations of organic solvents, surfactants, temperatures, agitation rates, pH, and reaction times and their effects on microencapsulation were observed. Microcapsule surface morphology, size, shell thickness, encapsulated OCA viability, thermal degradation, and chemical structure of the microcapsule shell were evaluated using a stereoscope, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and fourier transform infrared spectroscopy (FT-IR).

Shape memory effect in pure ultra-high molecular weight polyethylene (UHMWPE) has been studied using dynamic mechanical analysis. Temperature dependencies of properties that define functional characteristics of shape memory polymers (SMP) such as recovery stress, recovery strain and activation temperature of transition were determined for UHMWPE. The recovery stress in UHMWPE deformed by 200% achieved rather high values, up to 7 MPa.

This research work studies the dynamically recrystallized austenitic grain size (D rec) in a new family of low carbon NiCrCuV advanced ultra-high strength steel (A-UHSS) microalloyed with boron under hot deformation conditions. For this purpose, uniaxial hot-compression tests are carried out in a low carbon A-UHSS microalloyed with different amounts of boron (14, 33, 82, 126 and 214 ppm) over a wide range of temperatures (950, 1000, 1050 and 1100°C) and constant true strain rates (10−3, 10−2 and 10−1 s−1). Deformed samples are prepared and chemically etched with a saturated aqueous picric acid solution at 80°C in order to reveal the D rec and examined by light optical (LOM) and scanning electron microscopy (SEM). The D rec is related to the Zener-Hollomon parameter (Z), and thereafter the D rec divided by Burger's vector (b) is related to the steady state stress (σ ss) divided by the shear modulus (µ) (Derby model). Results shown that the D rec in the current steels is fine (≈ 23 μm) and almost equiaxed, and the recrystallized grain size-flow stress relationship observed after of plastic deformation is consistent with the general formulation proposed by Derby. It is corroborated that boron additions to the current A-UHSS do not have meaningful influence on the D rec.

How the molecular structure of proteins in solution correlates with the mechanical properties of the solution at different length scales is not known. Using optical-tweezers based microrheology, we investigate a key physical property, viscoelasticity, of collagen solutions. To do this, we measure short-range thermal fluctuations of probe particles to obtain elastic and viscous moduli of their surrounding medium, and validate our measurement and analysis techniques using the previously studied system of polyethylene oxide. Probing the concentration dependence of viscoelasticity, we find that collagen solutions exhibit elasticity of comparable strength to viscosity when the concentration reaches ∼5 mg/ml. We also find that the presence of telopeptides alters the viscoelasticity of collagen solutions, particularly at high frequencies

Polycrystalline silicon nanowires are synthesized using a classical fabrication method commonly used in microelectronic industry: the sidewall spacer formation technique. Assets of this technological process rest on low cost lithographic tools use, classical silicon planar technology compatibility and the possibility to get by direct patterning numerous parallel nanowires with precise location on the substrate. Grounded and suspended polycrystalline silicon nanowires with a curvature radius as low as 150nm are integrated into resistors and used as gas (ammonia) sensors. Results show potential use of these nanowires for charged chemical species detection with an increase of the sensitivity with the increase of SiNWs exchange surface with the environment.