A beam of variable-energy positrons, whose back-diffusion probability is measured as a function of positron implantation energy, is applied to studies of depth distribution of sputtering damage in aluminum. The defects are produced by argon ion bombardment of an Al(110) surface in ultra-high vacuum. We have varied the Ar⁺ energy, incident angle and dose, as well as sputtering and annealing temperatures. The extracted defect profiles have typically a narrow peak at the surface with a width of 10-20 A and a broader tail extending down to 50-100 Å. The shape of the defect profile varies only slightly with the sputtering energy and angle. Defect production at less than 1 keV Ar⁺ energies is typically 1-5 vacancies per incident ion. The defect profiles become fluence-independent at about 2 × 10¹⁶ Ar⁺ cm^-2. The defect density at the outer atomic layers saturates at high argon fluences to a few at%, depending on sputtering conditions. The sputtering temperature (below or above the vacancy migration stage at 250 K) has little effect on vacancy profiles. Defects anneal out gradually between 100 °C and 400 °C. Sputtering damage was also evaluated with the molecular dynamics technique. The shape and depth scale of the simulated collision cascades are in agreement with the experimentally extracted quantities.

This review article highlights and summarizes the recent developments in the field of surface modification methods for aramid fibers. Special focus is on methods that create a multifunctional fiber surface by incorporating nanostructures and enabling mechanical interlocking. To give a complete picture of adhesion promotion with aramids, the specific questions related to the challenges in aramid-matrix bonding are also shortly presented. The main discussion of the surface modification approaches is divided into sections according to how material is added to the fiber surface; (1) coating, (2) grafting and (3) growing. To provide a comprehensive view of the most recent developments in the field, other methods with similar outcomes, are also shortly reviewed. To conclude, future trends and insights are discussed.

Noncovalent binding of azobenzenes to polymers allows harnessing light-induced molecular-level motions (photoisomerization) for inducing macroscopic effects, including photocontrol over molecular alignment and self-assembly of block copolymer nanostructures, and photoinduced surface patterning of polymeric thin films. In the last 10 years, a growing body of literature has proven the utility of supramolecular materials design for establishing structure-property-function guidelines for photoresponsive azobenzene-based polymeric materials. In general, the bond type and strength, engineered by the choice of the polymer and the azobenzene, influence the photophysical properties and the optical response of the material system. Herein, we review this progress, and critically assess the advantages and disadvantages of the three most commonly used supramolecular design strategies: hydrogen, halogen and ionic bonding. The ease and versatility of the design of these photoresponsive materials makes a compelling case for a paradigm shift from covalently-functionalized side-chain polymers to supramolecular polymer-azobenzene complexes.

This feature article focuses on the highlights in the development of photonic polymer coatings that can change their volume or surface topology in a reversible, dynamic fashion when exposed to an external stimulus. Topographic response is established using hydrogels or liquid crystal polymer networks. By changing the surface corrugation in response to light various functional coating properties can be modulated, for instance wettability and/or mechanical friction. The same volume changes in photonic coatings caused by different stimuli lead to changes in light reflection.

Our study focuses on understanding the damage tolerance and performance reliability of WC-CoCr coatings. In this paper, the formation of HVOF-sprayed tungsten carbide-based cermet coatings is studied through an integrated strategy: First-order process maps are created by using online-diagnostics to assess particle states in relation to process conditions. Coating properties such as hardness, wear resistance, elastic modulus, residual stress, and fracture toughness are discussed with a goal to establish a linkage between properties and particle characteristics via second-order process maps. A strong influence of particle state on the mechanical properties, wear resistance, and residual stress stage of the coating was observed. Within the used processing window (particle temperature ranged from 1687 to 1831 °C and particle velocity from 577 to 621 m/s), the coating hardness varied from 1021 to 1507 HV and modulus from 257 to 322 GPa. The variation in coating mechanical state is suggested to relate to the microstructural changes arising from carbide dissolution, which affects the properties of the matrix and, on the other hand, cohesive properties of the lamella. The complete tracking of the coating particle state and its linking to mechanical properties and residual stresses enables coating design with desired properties.

Protective coatings are needed for metallic interconnects used in solid oxide fuel cell (SOFC) stacks to prevent excessive high-temperature oxidation and evaporation of chromium species. These phenomena affect the lifetime of the stacks by increasing the area-specific resistance (ASR) and poisoning of the cathode. Protective MnCo₂O₄ and MnCo_1.8Fe _0.2O₄ coatings were applied on ferritic steel interconnect material (Crofer 22 APU) by high velocity oxy fuel spraying. The substrate-coating systems were tested in long-term exposure tests to investigate their high-temperature oxidation behavior. Additionally, the ASRs were measured at 700 C for 1000 h. Finally, a real coated interconnect was used in a SOFC single-cell stack for 6000 h. Post-mortem analysis was carried out with scanning electron microscopy. The deposited coatings reduced significantly the oxidation of the metal, exhibited low and stable ASR and reduced effectively the migration of chromium.

Heat exchanger surfaces of waste to energy and biomass power plant boilers experience often severe corrosion due to very aggressive components in the used fuels. High velocity oxy-fuel (HVOF) coatings offer excellent protection for boiler tubes against high temperature corrosion due to their high density and good adherence to the substrate material. Several thermal spray coatings with high chromium content were sprayed with HVOF technique. Their mechanical properties and high temperature corrosion resistance were tested and analyzed. The coating materials included NiCr, IN625, Ni-21Cr-10W-9Mo-4Cu, and iron-based partly amorphous alloy SHS9172 (Fe-25Cr-15W-12Nb-6Mo). High temperature corrosion testing was performed in NaCl-KCl-Na₂SO₄ salt with controlled H₂O atmosphere at 575 and 625 C. The corrosion test results of the coatings were compared to corrosion resistance of tube materials (X20, Alloy 263 and Sanicro 25).

Lubricated icephobic coatings were fabricated by flame spraying with hybrid feedstock injection. In this one-step process, composite coatings were produced by spraying a matrix material from a combustion flame spray gun and a lubricating additive from an injector, externally to the flame. External injection avoided possible thermal degradation of the heat sensitive additive during spraying. Inexpensive and widely available feedstock materials were used, polyethylene as the matrix and solid cottonseed oil as the lubricating additive. The coating properties were investigated by thermal and chemical analyses, surface roughness and wettability measurements at room temperature and in cold conditions. The icephobic behaviour was evaluated by accreting ice from supercooled water droplets in the icing wind tunnel. Ice adhesion was measured by the centrifugal ice adhesion test. The results showed that lubricant addition improved the icephobic performance of the coatings. Moreover, cooling the flame temperature with compressed air addition reduced thermal degradation of polymers. This was beneficial for the icephobic behaviour, thus lowering the shear ice adhesion strength down to 23 kPa ± 6 kPa. In conclusion, lubricated icephobic coatings were successfully produced by combining the hybrid feedstock injection and the thorough optimization of process parameters. This approach provides a potential surface engineering solution for the industrial sectors facing icing problems.

An initial friction peak typically occurs in a dry self-mated quenched and tempered steel fretting contact in gross sliding conditions. The peak is related to adhesive friction and wear, which causes non-Coulomb friction. An early surface degradation including cracks may occur. To avoid such a peak, different media were studied using a flat-on-flat fretting test device with a large annular contact. All the media decreased the initial friction peak in comparison to the dry reference case, and in one series the peak was completely removed. The peak could often be delayed by lubrication. The steady-state coefficient of friction values mostly remained at similar levels to those of the dry contact, but decreased when oil was applied. Nevertheless, some surface damage occurred in every test, with varying amounts of wear.

Novel NaYF₄:Yb³⁺, Er³⁺ nanocrystals containing phosphate glass with composition 83.25NaPO₃–9.25NaF-5ZnO-2.5Ag₂O (in mol%) was prepared by adding the NaYF₄:Yb³⁺, Er³⁺ nanocrystals in the glass using the direct doping method. The optical and luminescence properties of this new glass are presented and discussed. The newly developed glass exhibits visible emission under 980 nm pumping with high intensity confirming the presence of the NaYF₄:Yb³⁺, Er³⁺ nanocrystals in the glass. From the absorption spectrum of the as-prepared glass, it is showed that the as-prepared glasses contains already Ag nanoparticles which are thought to precipitate due to the decomposition of some of the NaYF₄:Yb³⁺, Er³⁺ nanocrystals occurring during the glass preparation. A heat treatment of the glass was found to lead to the migration of Ag species at the surface of the glass as evidenced using SEM and to a decrease of the intensity of the upconversion mostly due to an increase of the inter defects in the NaYF₄:Yb³⁺, Er³⁺ nanocrystals due to the heat treatment.

This study encompasses a comprehensive account of the abrasive wear properties of carbide-free, ultrahigh-strength bainitic steels processed through ausforming at three different temperatures well below the recrystallization stop temperature followed by bainitic transformation at temperatures close to the M_s temperature. Five medium-carbon, high-silicon compositions were designed for the study by suitably varying the alloying levels of carbon, vanadium, niobium, molybdenum, and aluminum. While ausforming at lower temperatures enabled a large number of nucleation sites leading to significant refinement of bainitic laths, the decomposition of austenite at relatively low transformation temperatures was accelerated due to the presence of a high dislocation density, thus enabling completion of bainitic transformation in a reasonable length of time. The steels were characterized in respect of microstructural features and mechanical properties, besides evaluation of wear resistance through a high-stress abrasive wear testing method with natural granite abrasives. The microstructures comprised different fractions of bainitic ferrite and/or granular bainite (56–68%), martensite (0–25%), besides a significant fraction of retained austenite (20–34%) manifesting as pools and also interlath films, depending on the ausforming conditions and subsequent cooling paths. A tensile strength of 1900 MPa level was achieved with hardness exceeding 500 HV for the medium-temperature ausformed steel containing a high carbon content that also showed lowest mass loss in the wear test. The hardness-to-mass loss ratio appeared highly promising with some of the carbide-free bainitic steels on par with or better than the reference martensitic steel. The high work-hardening capability as a consequence of the strain-induced austenite to martensite transformation was considered as the main factor for the superior abrasive wear resistance of the carbide-free bainitic steels.

Prior austenite grain size has a marked effect on the hardenability, strength, and impact toughness properties of steels. This study was conducted in order to understand the effect of prior austenite grain size and morphology on the mechanical properties and abrasive wear performance of an ultra-high strength steel. A commercial quenched 500 HB grade wear-resistant steel was selected for the study: the steel was austenitized at two different temperatures and compared to the original, as-received quenched condition. The resulting mean prior austenite grain size was ranging from 14 μm to 34 μm. The decrease in grain size improved the low-temperature impact toughness properties. A high stress abrasive wear testing method with natural granite abrasives was utilized for the evaluation of abrasive wear resistance. The results suggest that decreasing the prior austenite grain size improves the abrasive wear resistance with similar hardness level martensitic steels. In addition, high-resolution electron backscatter diffraction measurements revealed formation of ultra-fine grain structures in the severely deformed regions of the wear surfaces.

In this paper, additive layer-by-layer fabrication of a fully screen printed monolithic supercapacitor exhibiting performance comparable with supercapacitors prepared using lamination is reported. A novel separator material improves the performance of the monolithic supercapacitor, is easily applicable using scalable processes such as screen and stencil printing, and is based on sustainable biomaterials. The additive monolithic manufacturing offers advantages for system integration and avoids the need of an additional alignment step as needed in the fabrication of laminated supercapacitors. Previously, the monolithically fabricated supercapacitors showed higher equivalent series resistance (ESR) and leakage current than the laminated ones. By using microfibrillated cellulose (MFC) and chitosan as separator materials ESR and leakage current were decreased. These disposable and non-toxic aqueous electrolyte supercapacitors are optimized for autonomous sensor systems, for example in Internet-of-Things (IoT) applications, with capacitance of 200–300 mF and ESR of about 10 Ω. The new composite separator material consisting of MFC and chitosan has good adhesion on the electrodes and the substrate, is easy to apply using printing and coating processes, and does not diffuse into the porous electrode. Graphic Abstract: [Figure not available: see fulltext.].

Membrane proteins travel along cellular membranes and reorient themselves to form functional oligomers and protein-lipid complexes. Following the Saffman-Delbrück model, protein radius sets the rate of this diffusive motion. However, it is unclear how this model, derived for ideal and dilute membranes, performs under crowded conditions of cellular membranes. Here, we study the rotational motion of membrane proteins using molecular dynamics simulations of coarse-grained membranes and 2-dimensional Lennard-Jones fluids with varying levels of crowding. We find that the Saffman-Delbrück model captures the size-dependency of rotational diffusion under dilute conditions where protein-protein interactions are negligible, whereas stronger scaling laws arise under crowding. Together with our recent work on lateral diffusion, our results reshape the description of protein dynamics in native membrane environments: The translational and rotational motions of proteins with small transmembrane domains are rapid, whereas larger proteins or protein complexes display substantially slower dynamics.

Material and spray process selection are the key factors in the tailoring of thermal sprayed coatings for demanding industrial applications. In this study, four commercial Cr₃C₂-based feedstock materials were sprayed with gas-fuelled high-velocity oxygen-fuel (HVOF) and modern high-velocity air-fuel (HVAF) spray processes. Two materials with standard Cr₃C₂–25NiCr composition (porous and dense), a Cr₃C₂–50NiCrMoNb and Cr₃C₂–37WC–18NiCoCr materials were sprayed in addition to the reference WC-10Co4Cr material. The Cr₃C₂–50NiCrMoNb had a higher content of the Ni-based metal matrix compared to standard Cr₃C₂–25NiCr composition for added corrosion resistance, while the Cr₃C₂–37WC–18NiCoCr material contained additional tungsten carbide (WC) particles to improve the wear resistance. In abrasion and dry particle erosion, the Cr₃C₂–50NiCrMoNb coatings showed a higher degree of plastic deformation and increased material loss, whereas the Cr₃C₂–37WC–18NiCoCr coating had wear resistance between the standard Cr₃C₂–25NiCr and reference WC-10Co4Cr coatings. In cavitation erosion, the lower carbide content of Cr₃C₂–50NiCrMoNb coatings turned out to improve the resistance against fatigue wear due to higher fracture toughness. Overall, the HVAF sprayed coatings had higher elastic modulus, higher fracture toughness, equal or higher abrasion and erosion resistance, and higher cavitation erosion resistance compared to the HVOF sprayed counterparts.

Borosilicate bioactive glasses are promising for bone tissue engineering. The objective was to assess the impact of magnesium and/or strontium, when substituted for calcium on the glasses' thermal and dissolution properties. Both Mg and Sr substitution appeared to enhance the hot forming domain, i.e. the ability to hot process (sinter, draw fibres) without adverse crystallization. Structural analysis indicated that substitution of MgO and/or SrO for CaO results in changes in the BO₃/BO₄ ratio as well as in the ratio between bridging and non-bridging oxygen atoms in the silicate structure. Additionally, a de-shielding effect was noticed when Ca, Mg and Sr are present together in the glass network, possibly owing to PO₄ ³⁻ charge-balanced preferentially by Na⁺. The Mg and/or Sr substitution resulted in a lower ion release in simulated body fluid and delayed formation of hydroxyapatite. However, once this layer formed it consisted of a Mg/Sr-substituted apatite. This work highlights the effect of combined ionic substitutions on bioactive glass structure and properties.

The straightforward synthesis of structurally unique DPP-BODIPY hybrids has been developed using unsymmetrical, imidazopyridine substituted DPPs. These hybrids exhibit a superb combination of photophysical properties including high photostability, good fluorescence quantum yield as well as markedly bathochromically shifted absorption and emission compared to conventional diketopyrrolopyrroles. Increasing the size of the imidazopyridine substituent and/or the electron donating power of the other aryl substituent can further redshift both absorption and emission to reach ∼650 nm for the free-base and ca. 700 nm for boron-chelates. A strong intramolecular hydrogen bond is responsible for the small change in geometry between the ground and excited states and hence relatively small differences in photophysical properties upon formation of boron-chelates are observed. The solvent dependence of the photophysical properties for the free base and DPP-BF2 complexes were investigated and show strong fluorescence with long lifetimes in both non-polar and polar aprotic environments.

Yb³⁺ doped oxyfluorophosphate glasses with the composition (98.75) [90NaPO₃-(10-x) Na₂O-xNaF] - 1.25Yb₂O₃ (in mol%) with x = 0, 2.5, 5, 7.5 and 10 were prepared using a standard melting process. The progressive replacement of Na₂O by NaF leads to an increase in the number of Q² units at the expense of the Q¹ units. This increase in the polymerization of the glass network leads to a shift of the optical band gap to lower wavelength, to a slight increase in the intensity of the emission at 1000 nm and more importantly to a change in the glass crystallization process. Indeed, both surface and bulk crystallization were observed in the glass with x = 0 while surface crystallization only occurs when NaF is added in the phosphate network. The heat treatment leads to the precipitation of at least three crystalline phases: as x increases, the NaPO₃ phase grows at the expense of Na₅P₃O₁₀. All glasses precipitate the Yb containing crystal, NaYbP₂O₇ which leads to an increase in the intensity of the emission at 1000 nm compared to the emission at 975 nm. We show for the first time to the best of our knowledge that transparent Yb³⁺ doped phosphate glass-ceramics can be obtained within this glass system when free of NaF.

Cold gas spraying was used to make a coating from an equiatomic CrFeNiMn high-entropy alloy. This four-component alloy was chosen because it is Co-free, thus allowing application in nuclear industries as a possible replacement of currently used stainless steel coatings. The feedstock material was gas atomized powder with a particle size distribution from 20 to 45 μm. A number of parameters were tested, such as the powder feed rate and gas feed pressure, in order to obtain as dense a coating as possible with nitrogen as the process gas. Spraying was performed using a gas preheating temperature of 1000 °C, gas feed pressure ranging from 50 to 60 bar, and two powder feeding rates. The coating thicknesses ranging from 230 to 490 m and porosities ranging from 3% to 10% were obtained depending on the powder feed rate and gas feed pressure. The hardness of the cross-section of the coating was usually lower than that of the surface. The highest coating hardness obtained was above 300 HV_0.3 for both the surface and the cross-section. The as-atomized powder consisted of a face-centered cubic (FCC) phase with a minute amount of body-centered cubic (BCC) phase, which was no longer detectable in the coatings. The microstructure of the coating was highly stressed due to the high degree of deformation occurring in cold gas spraying. The deformation leads to strain hardening and induces a pronounced texture in the coating. The 111 planes tend to align along the coating surface, with deformation and texturing concentrating mainly on particle boundaries. A high-entropy alloy (HEA) coating was successfully sprayed for the first time using nitrogen as a process gas. The coating has the potential to replace stainless steel coatings in nuclear industry applications.

Mechanical recycling of multilayer plastic films from food packages was investigated. The multilayer films were manually separated from municipal solid waste, washed, grinded, and finally compounded at 0–100 wt% concentrations with virgin low-density polyethylene (PE-LD). Polyethylene grafted with maleic anhydride (PE-g-MA) compatibilizer was used in two of the compounds to replace 2 and 5 wt% of the PE-LD to study its effect as well. PE-g-MA is expected to improve the mechanical properties of the compounds by promoting the adhesion between incompatible polymer phases. The composition of the compounds was characterized with Fourier-transform infrared spectroscopy and differential scanning calorimetry and their properties were studied with tensile testing and rotational rheometer measurements. All tested compounds had relatively good mechanical properties and processability. This indicates that recycled multilayer films could replace at least part of the virgin PE-LD in applications where high-thermal stability or good visual appearance is not required. The PE-g-MA compatibilizer did not have a significant effect on the mechanical properties of the compounds.

We investigate electronic transport properties of as-grown and annealed n-type modulation-doped Al_0.15Ga_0.85As/GaAs_1-xBi_x (x = 0 and 0.04) quantum well (QW) structures using magnetotransport measurements in the temperature range 4.2 K and 60 K and at magnetic fields up to 18 T. Thermal annealing process was applied at two different temperatures, 700 °C and 350 °C during 60 s and 180 s, respectively. We find that electron effective mass and 2D electron density in as-grown Bi-containing sample are slightly lower than that in Bi-free one. Furthermore, quantum electron mobility and quantum scattering time are observed to be decreased in Bi-containing samples. The annealing process at 700 °C causes a slight increase in electron effective mass and 2D electron density. A negligible decrease in electron effective mass and an increase in 2D electron density are determined following annealing at 350 °C. The observed change in electron effective mass following thermal annealing process is attributed to changing 2D electron density in the samples. No improvement on quantum electron mobility and quantum scattering time are observed following thermal annealing at both process temperatures. We determine that one electron subband (e1) for as-grown and annealed (at 700 °C for 60 s) Bi-containing QWs and two electron subbands (e1 and e2) for the annealed (at 350 °C for 180 s) GaAsBi QW sample and the Bi-free QW sample contribute to electronic transport. Our results reveal that there is no significant direct effect of Bi on effective electron mass, but an indirect effect, in which Bi can provoke changes in 2D electron density and hence causes not to observe actual band-edge electron mass but a deviation from its band-edge value. Therefore, it can be concluded that dispersion curve of conduction band does not change as an effect of Bi incorporation in GaAs.

This paper presents a systematic study of the effect of various WC-CoCr powders on the residual stresses of the high pressure HVOF sprayed coating. As the residual stresses are recognized to play a significant role in the mechanical and fatigue resistance of the coating, it is understandable that their management is important for damage tolerant coating design. Several studies have recently shown that processes, which produce high particle kinetic energy and lower particle temperature, such as Warm spray, HVAF and high-pressure HVOF processes, generate higher peening stresses and therefore final residual stresses is more compressive compared to lower kinetic energy HVOF systems. In addition to the spraying process, powder properties are known to be one of the most important variables in thermal spraying. Nevertheless, only few studies can be found on the effect of powder properties on residual stresses. The aim of this study was to understand the effect of different powder properties on the formation of residual stress. In situ monitoring was utilized to record curvature and temperature during spraying and to calculate coating residual stresses. This approach is a useful tool for understanding of residual stresses during the thermal spraying process enabling their manipulation. It was found that the powders, with only minor differences in density and particle size, produced a significant difference of about 350 MPa in the stress states of the coatings. The combined effect of spray powder properties and spray parameters on residual stress was almost 560 MPa.

The ultrafast photochemistry of the [Cr(NCS)₆]^3- complex upon excitation to the ⁴T₂ ligand-field (LF) state was studied in dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in a wide temporal range (100 fs to 9 ms) by a combination of femtosecond and nanosecond transient absorption spectroscopy techniques and supported by quantum-chemical DFT/TD-DFT calculations. The initially excited ⁴T₂ state undergoes intersystem crossing to the vibrationally hot ²E state with time constants of 1.1 ± 0.2 and 1.8 ± 0.1 ps in DMSO and DMF, respectively. Vibrational relaxation occurs in the same time scale and takes 1-5 ps. A major part of the [Cr(NCS)₆]^3- complex in the ²E state undergoes intersystem crossing to the ground state with time constants of 65 ± 5 and 85 ± 5 ns in DMSO and DMF, respectively. A minor part of electronically excited [Cr(NCS)₆]^3- undergoes irreversible photochemical decomposition. In DMSO, the photolysis of the [Cr(NCS)₆]^3- complex results in single or double isothiocyanate ion release followed by the coordination of the solvent molecules with a time constant of 1 ± 0.2 ms.

Process optimization and quality control are important issues in cold spraying and coating development. Because the cold spray processing is based on high kinetic energy by high particle velocities, online spray monitoring of particle inflight properties can be used as an assisting process tool. Particle velocities, their positions in the spray jet, and particle size measurements give valuable information about spraying conditions. This, in turn, improves reproducibility and reliability of coating production. This study focuses on cold spraying of Al6061 material and the connections between particle inflight properties and coating characteristics such as structures and mechanical properties. Furthermore, novel 2D velocity scan maps done with theHWCS2 online spray monitoring system are presented as an advantageous powder and spray condition controlling tool. Cold spray processing conditions were similar using different process parameters, confirmed with the online spray monitoring prior to coating production. Higher particle velocities led to higher particle deformation and thus, higher coating quality, denser structures, and improved adhesions. Also, deposition efficiency increased significantly by using higher particle velocities.

Persistent luminescent amorphous borosilicate scaffolds were successfully prepared, for the first time, with a porosity of >70% using the burn-off technique. The persistent luminescence was obtained by adding the SrAl₂O₄:Eu²⁺,Dy³⁺ microparticles: i) in the glass melt or ii) in the glass crushed into powder prior to the sintering. The scaffolds prepared by adding the microparticles in the glass melt exhibits lower persistent luminescence and a slower reaction rate in simulated body fluid than the scaffolds prepared by adding the microparticles in the glass powder due to the release of strontium from the microparticles into the glass during the glass melting.

Thermal spray processes have been developing toward lower particle temperature and higher velocity. Latest generation high-velocity oxygen-fuel (HVOF) and high-velocity air-fuel (HVAF) can produce very dense coating structures due to the higher kinetic energy typical for these thermal spray processes. Thermally sprayed coatings usually contain residual stresses, which are formed by a superposition of thermal mismatch, quenching and, in case of high kinetic energy technologies, peening stresses. These stresses may have a significant role on the mechanical response and fatigue behavior of the coating. Understanding these effects is mandatory for damage tolerant coating design and wear performance. For instance, wear-resistant WC-CoCr coatings having high compressive stresses show improved cavitation erosion performance. In this study, comparison of residual stresses in coatings sprayed by various thermal spray systems HVOF (Thermico CJS and Oerlikon Metco DJ Hybrid) and HVAF (Kermetico AcuKote) was made. Residual stresses were determined through thickness by utilizing Tsui and Clyne analytical model. The real temperature and deposition stress data were collected in the coating process by in situ technique. That data were used for the model to represent realistic residual stress state of the coating. The cavitation erosion and abrasion wear resistance of the coatings were tested, and relationships between residual stresses and wear resistance were discussed.

Global warming and environmental awareness in general have increased the research into thermal energy storage fields. Phase-change materials (PCMs) are efficient in storing thermal energy because of their high latent heat during the phase change. As the phase change is often based on the melting of the PCM, they need to be encapsulated, for example, by dispersing the PCM to a polymer matrix. In this study, the feasibility of the use of paraffin-natural rubber composites in applications requiring both the good ability to store heat energy and good vibration-damping properties is studied. This includes studies on PCM concentration and the microencapsulation of the PCM. It was found that the heat storage capacity increases with increasing PCM content, although the theoretical maximum capacity is not achieved because the PCM is released during vulcanization and the paraffin blooms. In addition, the loss factor was found to be increased at elevated temperatures, indicating improved damping properties. The encapsulation of PCM is found to have a positive influence on the heat storage capacity and the mechanical and damping properties of the rubber compound.

Phase change materials are utilized in heat storage applications, as they have high latent heat during the phase transition. In addition, high thermal conductivity is required from the heat storage materials to achieve high energy efficiency. In this study, the effect of carbon nanotubes (CNTs) and nanodiamonds (NDs) on the thermal conductivity and the heat storage capacity of the paraffin–natural rubber composites was studied. It was found that the CNTs work better than NDs in such composites. They increase thermal conductivity significantly and thus improve the heat transfer rate of the composite. They were also found to prevent the migration of paraffin out of the rubber during the vulcanization process, which increases the lifetime of the composite.

In this study, the local electrochemical activity of untreated and passivated (natural or chemical passivation) zinc specimens was observed during immersion in a 0.1-M NaCl solution. The localized anodic activity during the exposure, measured with the scanning vibrating electrode technique, was linked to zinc dissolution by the pitting corrosion mechanism. It was correlated to specific corrosion products characterized by Fourier transmission infrared (FTIR) microscopy. FTIR molecule maps were produced from individual pitting corrosion sites (100–200 µm in width). With argon ion beam milling and latest energy-dispersive X-ray spectroscopy (EDS) technology, element maps with a high spatial resolution (≪100 nm) were recorded from abrasion- and beam-sensitive corrosion products, showing a residual layer structure. This study demonstrates the capability of FTIR mapping, cross-section polishing, and state-of-the-art scanning electron microscopy imaging, and EDS element mapping to produce high-resolution elemental, molecular, and visual information about pitting corrosion mechanisms on a hot-dip galvanized steel sample.

Magnesium aluminate, MgAl₂O₄, spinel powders for thermal spraying, were synthesized from secondary raw materials by spray drying and subsequent reaction sintering. Talc ore mining tailings and aluminium hydroxide precipitate from aluminium anodizing process were studied. A stoichiometric MgAl₂O₄ spinel coating was prepared as a reference using pure raw materials. Atmospheric plasma spraying resulted in the formation of ceramic coatings. Microstructural investigations revealed that the reference coatings exhibited crystalline lamellar microstructure of MgAl₂O₄ but secondary coatings contained amorphous areas between the crystalline MgAl₂O₄ clusters. Abrasive wear test results revealed considerably lower wear rate for secondary coatings. It is suggested that the different structure of coatings, particularly the high degree of amorphous phase between the isolated crystalline MgAl₂O₄ clusters caused the higher abrasive wear resistance by changing the wear mechanism. The dielectric breakdown strength of the secondary coatings were at the same level, 24 V/μm, as compared to reference coating, 23 V/μm.

We present a colour tunable system obtained by combining a humidity-responsive cholesteric liquid crystal network and hydrogel coatings, in a diligently designed cell-geometry. The design enables sensitive colour tuning via temperature-induced changes in humidity inside the cell. Uniquely, the system exhibits a bifacial response, causing either a blue- or red-shift in the reflected color when heated from opposite sides.

Natural rubber (NR) is a versatile material possessing outstanding mechanical properties, which can be used in multiple applications including the rapidly developing dielectric elastomer generators (DEGs). One of the drawbacks of the existing DEGs is their low efficiency, which can be improved by lowering the dielectric and mechanical losses originating from the material. Therefore, the present research was focusing on assessing the ways to minimize the dielectric and mechanical losses of NR films rather than developing a DEG. In this article, the effect of natural proteins and the rubber stabilizers on energy dissipation of NR films was evaluated. Moreover, the effect of sample posttreatment (with water and acetone), curing and time after cure was discussed. As a result, deproteinized NR stabilized by ammonium caseinate outperformed unmodified NR due to reduced dielectric losses, mechanical hysteresis and stress relaxation. Moreover, the posttreatment methods were found to moderately reduce the material-relates losses.

We report on the power loss mechanisms of hot electrons in as-grown and annealed n-type modulation-doped Al0.15Ga0.85As/GaAs1-xBix (x = 0 and 0.04) quantum well structures considering acoustic phonon interactions via the deformation potential (non-polar) and piezoelectric (polar) scatterings. The two-dimensional (2D) electron gas is heated by applying various electric fields under a steady-state magnetic field, and the effect of the applied electric field on the Shubnikov de Haas (SdH) oscillations is analyzed to investigate the power loss mechanism. The temperature of hot electrons (T e) has been obtained by comparing the lattice temperature and applied electric field dependencies of the SdH oscillation amplitude. The hot electron temperature is almost the same for both Bi-free and Bi-containing samples except for the sample annealed at a higher temperature (700 °C) than the growth temperature of GaAsBi. The electron temperature dependence of power loss is analyzed using current theoretical analytic models derived for 2D semiconductors. We find that energy relaxation occurs in the intermediate temperature regime, including mixing of piezoelectric and deformation potential scattering. The power loss of hot electrons is found to be proportional to (Teγ-TLγ) with γ in the range from 2.4 to 4.2, which indicates that the hot electron relaxation is due to acoustic phonon scatterings via unscreened deformation potential and piezoelectric scattering. It is found that deformation potential scattering is dominant over piezoelectric scattering in the Bi-free sample, while the incorporation of Bi into the GaAs lattice makes these processes comparable. After thermal annealing at lower than growth temperature (350 °C), the scattering mechanism switches from deformation potential to piezoelectric scattering. After thermal annealing at higher than growth temperature (700 °C), the theoretical model does not fit to the experimental results due to degradation of the sample.

Tempering is an essential part in the fabrication of ultra-high strength steels and it is also widely applied in the processing of wear-resistant steels. In this paper, the effects of different tempering temperatures on the impact-abrasive and abrasive wear properties of martensitic ultra-high strength steels were studied. A novel press-hardening steel with carbon content of 0.4 wt% was received in hot-rolled condition and further austenitized, water-quenched and tempered for 2 h at different temperatures (150–400 °C). Tensile strength values up to 2200MPa and hardness exceeding 650HV were measured. Wear testing was done with impact-abrasive impeller-tumbler and abrasive dry-pot application-oriented test methods simulating mining and mineral handling environments. A laboratory rolled 600HB steel and a commercial 500HB grade wear-resistant steel were included for comparison. The wear surfaces and cross-sections of the samples were thoroughly characterized. Both testing methods produced highly deformed surface layers and strong work-hardening. Wear performance was mainly controlled by the initial hardness of the steels, but differences were found in the highly work-hardened surfaces of the steels.

Using the spectroscopic limited maximum efficiency, and Shockley and Queisser predictor models, we compute the solar efficiency of the chalcopyrites AgMX ₂ (M = In, Al; X = S, Se, Te). The results presented are based on the estimation of the electronic and optical properties obtained from first principles density functional theory as well as the many-body perturbation theory calculations. The results from this report were consistent with the experimental data.The optical bandgap was accurately estimated from the absorption spectra, obtained by solving the Bethe and Salpeter equation. Fitting the Tauc's plot on the absorption spectra, we also predicted that the materials studied have a direct allowed optical transition. The theoretical estimations of the solar cell performance showed that the efficiencies from the Shockley and Queisser model are higher than those from the spectroscopic limited maximum efficiency model. This improvement is attributed to the absorption, the recombination processes and the optical transition accounted in the calculation of the efficiency.

In the last decade, several studies have shown that polybutylene succinate (PBSu)has a high potential as a biomaterial enabling cell adhesion and growth. In this study, porous PBSu films have been prepared by the breath figure method (BF)and by particulate leaching (PL), and characterized in terms of thickness, surface properties, diffusion capacity and in vitro stability. Because porous films are of high interest for tissue engineering of retinal pigment epithelium (RPE), the initial viability and adhesion of human embryonic stem cell-derived RPE onto the PBSu films was then evaluated. To the best of our knowledge, this is the first study on the adhesion behavior of hESC-RPE onto porous and biodegradable polymer surfaces. The results clearly demonstrated that the two manufacturing methods produced materials with very distinct properties. Films produced by BF expressively demonstrated the highest roughness and surface area, and the lowest water contact angle. These features likely contributed to increase the biocompatibility of the surface, particularly when coated with laminin and collagen IV, as observed by the improved cell viability, cell morphology, adhesion and production of extracellular matrix proteins. Altogether, our results showed not only that PBSu holds high potential in retinal tissue engineering, but also that the physical properties and biocompatibility of the material are highly dependent on the adopted casting method.

The antibacterial features of natural pine/spruce rosin are well established, yet the functionality in various thermoplastics has not been surveyed. This work focuses on the processing of industrial grade purified rosin mixed with polyethylene (PE), polypropylene (PP), polylactic acid (PLA), polyamide (PA)and corn starch based biopolymer (CS). Homopolymer masterbatches were extrusion-compounded and melt-spun to form fibres for a wide range of products, such as filters, reinforcements, clothing and medical textiles. Due to the versatile chemical structure of rosin, it was observed compatible with all the selected polymers. In general, the rosin-blended systems were shear-thinning in a molten condition. The doped fibres spun of PE and PP indicated adequate melt-spinning capability and proper mechanical properties in terms of ultimate strength and Young's modulus. The antibacterial response was found dependent on the selected polymer. Especially PE with a 10 wt% rosin content showed significant antibacterial effects against Escherichia coli DH5α and Staphylococcus aureus ATCC 12598 when analysed in the Ringer's solution for 24 h.

Two different analytical approaches—collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) and chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (CI-APi-TOF)—were applied to detect and identify the online gaseous KOH and HCl formed in the addressed high-temperature reactions. Samples of pure KCl, KCl+Cr, KCl+Fe, and KCl+316 L were studied at 550°C under dry and humid conditions with varying oxygen concentrations. The goal was to shed more light on the gas-phase chemistry during KCl-induced corrosion under conditions relevant to biomass combustion. CI-APi-TOF proved to be a valuable tool for high-temperature corrosion studies: HCl was identified to have formed during the reactions under humid conditions. On the contrary, despite the known sensitivity of CPFAAS, the formation of KOH could not be verified in any of the performed measurements.

The fatigue life of thermally sprayed Al₂O₃- and Cr₂O₃-based coatings has been studied under low-energy (0.7–5 mJ) impact conditions. A threshold impact energy and amount of repetitions the coatings can endure with said energy before catastrophic failure was obtained. The catastrophic failure was determined to occur when the fracture mode of the coating switched from brittle cone cracking to quasi-plastic radial cracking. The results are examined relative to the microstructural features along with other properties of the coatings - hardness and cavitation resistance. The experiment provided a new approach for a straightforward comparison of the micro-scale impact fatigue life of thermally sprayed coatings unachievable with previous methods.

Er ³⁺ doped phosphate glasses with the composition 75NaPO _3- 25CaF ₂ (mol%)were prepared at different melting temperatures to demonstrate the importance to quantify the fluorine content when preparing oxyfluoride glasses. Indeed, increasing the melting temperature from 900 to 1000 °C leads to a small reduction in the fluorine content from 9.4 at % to 8.8 at % as quantified using EPMA. Whereas this loss of fluorine can be suspected from small changes in the thermal properties of the glass, it increases significantly the glass crystallization tendency in this glass system. This means that a heat treatment of the as-prepared glass should be performed when evaporation of fluorine during the glass melting is suspected. Sample preparation for the characterization of the spectroscopic properties of the glasses is discussed here as well; bulk glasses should be used when measuring the spectroscopic properties of oxyfluoride glasses, which are known to be hygroscopic. It is shown, in this work, that a heat treatment of the glass within the investigated glass system leads to transparent glass-ceramics with volume precipitation of Er ³⁺ doped CaF ₂ crystals with strong upconversion.

The use of practical high temperature superconductors (HTS), REBCO tapes especially, in magnet applications has become possible thanks to the increasing interest of manufacturers. One difficulty has been the nonlinear material properties that are challenging to measure and model. To advance in such, demo systems are needed and they must be thoroughly analyzed. Recently, one of the first HTS dipole magnets was built to study the usability of REBCO Roebel cables in particle accelerator magnets. The prototype magnet Feather-M2 was designed, constructed and tested within EUCARD2 collaboration project at CERN in 2017. In the measurements, the magnet behaved in an unexpected way: the magnet was able to be operated at operation currents above the maximum current that was predicted based on short-sample measurements. Additionally, unexpectedly gradual dependency between magnet's resistive voltage and operation current was observed. In this work, a thermodynamical model is formulated in order to study the behavior of Feather-M2. The model was parametrized and the parameters were solved via inverse problem by finding the best match to experimental results. Thereby insight was gained on the prospects of the utilized thermodynamical model and also on the behavior and operation conditions of the magnet via the inverse problem solutions. To summarize, this paper presents a new methodology for analyzing magnets in operation and applies it to a state-of-the-art magnet.

Thermally sprayed hardmetal coatings are widely used to protect components and surfaces against wear in various applications. Hard and wear resistant coatings increase the component lifetime and can generate significant savings promoting ecological manufacturing. This study focuses on the performance of tungsten carbide (WC-10Co4Cr)and chromium carbide (Cr ₃ C ₂ -25NiCr)based hardmetal coatings sprayed with gaseous and liquid fuelled high-velocity oxygen-fuel (HVOF)spray processes and a modern high-velocity air-fuel (HVAF)spray process. The coating characterisation revealed reduced carbide dissolution with decreasing process temperature and denser feedstock powder particles. Smaller carbide size in the Cr ₃ C ₂ -25NiCr material significantly reduced the carbide rebounding leading to higher carbide content in the sprayed coating and improved erosion wear resistance. Most significant improvements were observed in cavitation erosion for HVAF sprayed WC-10Co4Cr coatings (0.4 μm/h)compared to the HVOF sprayed coatings (1.5–3.7 μm/h). The cavitation erosion resistance of the HVAF sprayed coatings was almost at the level of the WC-10Co sintered bulk (0.2 μm/h).

A new biomimetic stimuli-responsive adaptive elastomeric material, whose mechanical properties are altered by a water treatment is reported in this paper. This material is a calcium sulphate (CaSO₄) filled composite with an epoxidized natural rubber (ENR) matrix. By exploiting various phase transformation processes that arise when CaSO₄ is hydrated, several different crystal structures of CaSO₄·xH₂O can be developed in the cross-linked ENR matrix. Significant improvements in the mechanical and thermal properties are then observed in the water-treated composites. When compared with the untreated sample, there is approximately 100% increase in the dynamic modulus. The thermal stability of the composites is also improved by increasing the maximum degradation rate temperature by about 20 °C. This change in behavior results from an in situ development of hydrated crystal structures of the nanosized CaSO₄ particles in the ENR matrix, which has been verified using Raman spectroscopy, transmission electron microscopy, atomic force microscopy, and X-ray scattering. This work provides a promising and relatively simple pathway for the development of next generation of mechanically adaptive elastomeric materials by an eco-friendly route, which may eventually also be developed into an innovative biodegradable and biocompatible smart polymeric material.

GaSbBi alloys have recently emerged as attractive materials for mid-infrared optoelectronics owing to strong band gap reduction enabled by Bi incorporation into the GaSb matrix. The fundamental understanding of the epitaxial process required to demonstrate high quality crystals is in an early-developmental phase. From this perspective, we report on the key role played by the Sb/Ga flux ratio in controlling the structural quality and incorporation of high Bi content GaSbBi (up to 14.5%-Bi), revealing three distinct epitaxial phases. The first phase (below stoichiometric Sb/Ga) exhibits Ga-Bi compound droplets, low crystal quality, and reduced Bi content. At the second phase (above stoichiometric Sb/Ga), the crystal exhibits smooth surfaces and excellent crystallinity with efficient Bi incorporation. The last phase corresponds to exceeding a Sb/Ga threshold that leads to reduced Bi incorporation, Bi droplets and degraded crystallinity. This threshold value that defines the optimal growth window is controlled by the temperature as well as the Bi/Ga ratio. Increasing temperature increases the threshold, albeit simultaneously reducing Bi incorporation. Conversely, increasing the Bi/Ga flux ratio increases Bi incorporation, while narrowing down and ultimately closing the window. This study provides a general framework enabling development of high quality GaSbBi heterostructures for emerging mid-infrared optoelectronics.

Two new low alloyed steels were developed with different fracture toughness values but at similar level of hardness with same composition and microstructural phase. The steels were subjected to impact-abrasion wear test. This work examines specifically the additional role of toughness during impact-abrasion wear, using a newly developed high toughness steel. Microstructural characterisation of the damaged samples revealed that better toughness helps resist both impact and abrasion damage.

The demanding environments typically encountered by the wear resistant steels create challenges for the materials selection, because the hardness grades of the steels alone do not reveal the true nature of their wear behavior. In this study, five commercial wear resistant steels were tested using three application oriented test methods with five different test variables for abrasion, impact-abrasion, and slurry erosion. All the used test methods produced high-stress conditions that crushed the used mineral abrasive, plastically deformed the sample surfaces, and led to the formation of adiabatic shear bands. When the results produced by the chosen methods were compared, the normalization of the wear losses by the wear area and test time revealed well the differences between the methods. The test methods ranked the steels similarly, but there were clear differences in the wear rates and wear mechanisms between the tests. In addition, the abrasive methods produced surface adiabatic shear bands, while subsurface shear bands were initiated by the more impacting methods. In the studied conditions, the work hardening ability of the steel had a clear influence on its wear resistance, which largely explains the marked differences in the wear rates of the studied commercial 500HB grade steels.

The control of Bi incorporation and material properties in III-V-Bi alloys has proved challenging due to their high sensitivity to the epitaxial growth parameters. Here, we present a methodology for determining the variation in the Ga, As, and Bi fluxes and the temperature across a stationary substrate in molecular beam epitaxy. By correlating the flux distributions with material properties, we identify distinct regimes for epitaxy of GaAsBi. In particular, we devise a detailed image of the interplay between Bi incorporation and structural properties of a bulk GaAs _0.96 Bi _0.04 layer grown on GaAs(1 0 0) with respect to the As/Ga ratio. The influence of As/Ga is analyzed with high resolution over the important stoichiometric range (i.e. As/Ga = 0.6–1.6). Growth outside the near-stoichiometric As/Ga regime leads to decreased Bi incorporation, decreased structural quality and the formation of Ga, Ga/Bi or Bi droplets. On the other hand, growth at As/Ga = 1.00–1.17 leads to maximized material quality. For this regime, the surface roughness is further optimized by fine-tuning the As/Ga ratio to suppress surface mounding to a value of 0.5 nm. The results reveal the extreme sensitivity of GaAsBi growth to small variations in the As/Ga ratio, and demonstrate the applicability of stationary growth in studying these effects.

The ability to release active agents from a porous scaffold structure in situ enables the simultaneous structural support for the cells proliferating and differentiating towards tissue as well as the stimulation of tissue regeneration. Due to the great potentiality of such approach, drug-releasing scaffolds were fabricated from hydrolytically degradable polymers. Three copolymers of poly(ethylene glycol), ɛ-caprolactone, L- and D,L-lactide were synthesized and blended with bone-growth inducing active agents, dexamethasone (DM) and 2-phospho-L-ascorbic acid trisodium salt (AS). Porous scaffolds were prepared by means of super-critical carbon dioxide foaming. In the final scaffold structures, the particle size, location and the water solubility of the drug affected the release kinetics. As the large and water soluble AS particles were more exposed to the buffer solution compared to small DM particles, the AS release was burst-like whereas DM showed a long-term release. The material structure had a significant effect on the release kinetics as the porous scaffolds released active agents faster compared to the solid cylinders. Furthermore, this study showed the strong effect of polymer degradation and wettability on the release, which were more determinative than the pore architecture.

This paper presents studies on the utilization of aluminosilicate-based mining tailings as raw materials for mullite-based ceramics. Based on the 3:2 stoichiometric composition, mullite was synthesised by reactive sintering with a series of powder mixtures with alumina additions. X-ray diffractometry and scanning electron microscopy analyses revealed that, at the specific mineralogical composition, mullite structure formed surrounded by an amorphous glass phase in reaction-sintered powder mixtures. Results demonstrated that the chemical and mineralogical composition of mining tailings do have an effect on mullite formation possibilities and, only with the particular mineralogical composition, the mullite formation is possible regardless of the correct Al:Si ratio in tailings. Physical and mechanical properties of the formed ceramics were defined, showing comparable values to 3:2 mullite reference. Mullite structure formation enables a better thermal resistance up to above 1450 °C of the formed tailings-based ceramics compared to other aluminosilicates, reflecting their utilization potential for refractory ceramic applications.

Cellulose nanofiber films (CNFF) were treated via a welding process using ionic liquids (ILs). Acid-base-conjugated ILs derived from 1,5-diazabicyclo[4.3.0]non-5-ene [DBN] and 1-ethyl-3-methylimidazolium acetate ([emim][OAc]) were utilized. The removal efficiency of ILs from welded CNFF was assessed using liquid-state nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared spectroscopy (FTIR). The mechanical and physical properties of CNFF indicated surface plasticization of CNFF, which improved transparency. Upon treatment, the average CNFF toughness increased by 27%, and the films reached a Young's modulus of ∼5.8 GPa. These first attempts for IL "welding" show promise to tune the surfaces of biobased films, expanding the scope of properties for the production of new biobased materials in a green chemistry context. The results of this work are highly relevant to the fabrication of CNFFs using ionic liquids and related solvents.

Thermal spraying using liquid feedstock can produce coatings with very fine microstructures either by utilizing submicron particles in the form of a suspension or through in situ synthesis leading, for example, to improved tribological properties. The focus of this work was to obtain a bimodal microstructure by using simultaneous hybrid powder-precursor HVOF spraying, where nanoscale features from liquid feedstock could be combined with the robustness and efficiency of spraying with powder feedstock. The nanostructure was achieved from YSZ and ZrO₂ solution-precursors, and a conventional Al₂O₃ spray powder was responsible for the structural features in the micron scale. The microstructures of the coatings revealed some clusters of unmelted nanosized YSZ/ZrO₂ embedded in a lamellar matrix of Al₂O₃. The phase compositions consisted of γ- and α-Al₂O₃ and cubic, tetragonal and monoclinic ZrO₂. Additionally, some alloying of the constituents was found. The mechanical strength of the coatings was not optimal due to the excessive amount of the nanostructured YSZ/ZrO₂ addition. An amount of 10 vol.% or 7 wt.% 8YSZ was estimated to result in a more desired mixing of constituents that would lead to an optimized coating architecture.

We report the formation of a new class of solvent-intercalated two-dimensional (SI-2D) formamidinium lead halide perovskites. They can be mixed with three-dimensional (3D) stoichiometric perovskites by controlling the ratio of the precursor solutions. The composite leads to greatly improved photoluminescence quantum yield (PLQY) over the 3D compound. The enhanced PLQY is attributed to a type-I band alignment between the 3D and SI-2D, as revealed by first-principles calculations, which results in confined excitons with enhanced radiative recombination. The films exhibited excellent thermal and air stability retaining PLQY > 20% over 2 months in ambient conditions. Assemblies of halide perovskites with mixed dimensionality offer a pathway to enhance optoelectronic performance and device lifetimes.

The aim of this study was to fabricate a bioactive optical fiber able to monitor “in situ” its reaction with the body through changes in its optical properties. Core and cladding preforms were prepared with the composition (97.25*(0.50P₂O₅-0.40SrO-0.10Na₂O)-2.5ZnO-0.25Er₂O₃) and (98.25*(0.50P₂O₅-0.40SrO-0.10Na₂O)-1.75ZnO) (in mol%), respectively, and successfully drawn into a multimode core/clad optical fiber. Optical and near-Infrared images assessed the proper light guiding properties of the fiber. The fibers favor the precipitation of a Ca-P reactive layer at its surface concomitant with a reduction in the fiber diameter, when immersed in SBF, often assigned as a sign of bioactivity. It is clearly shown here that the bio-response of the fiber upon immersion in SBF can be tracked from the decrease in the intensity of the Er³⁺ ions emission at 1.5 µm. This confirms that the newly developed optical fiber, which combines good optical properties with a suitable bioactive behavior, is a promising platform for the development of novel biomedical devices for biophotonic and photomedical applications. Finally, the successful splicing of the newly developed fiber with commercial optical fibers was an evidence of the possibility to integrate the newly developed phosphate fiber within existing components used in the field of biomedicine.

Optically-pumped vertical external cavity surface emitting lasers (VECSELs) based on flip-chip gain mirrors emitting at the 1.55-μm wavelength range are reported. The gain mirrors employ wafer-fused InAlGaAs/InP quantum well heterostructures and GaAs/AlAs distributed Bragg reflectors fixed on a diamond heat-sink substrate in a flip-chip geometry, incorporated in a V-cavity configuration. A maximum output power of 3.65 W was achieved for a heat sink temperature of 11°C and employing a 2.2% output coupler. The laser exhibited circular beam profiles for the full emission power range. This demonstration represents more than 5-fold increase of the output power compared to state-of-the-art flip-chip VECSELs previously reported at the 1.55 μm wavelength range. It opens new perspectives for developing practical VECSEL-based laser systems operating at a wavelength range widely used in many applications.

The decrease of stress at constant strain, that is, the stress relaxation process as a function of temperature, is a central mechanical characteristics of elastomer nanocomposites for their potential applications. However, in the conventional stress relaxation test, the relaxation behavior is usually determined as a function of time at constant temperature. The present work reports the temperature scanning stress relaxation (TSSR) characteristics of a new kind of mechanically adaptive elastomer nanocomposite by monitoring the nonisothermal relaxation behavior as a function of temperature. This kind of adaptive elastomer nanocomposite was prepared by introducing calcium sulfate (CaSO₄), as the water-responsive phase into the hydrophilic elastomer matrix. The influence of water-induced structural changes on TSSR behavior was investigated. Water treatment had a strong effect on the shape of the relaxation spectrum of the nanocomposite. It was revealed that the in situ development of hydrated nano-rod crystal structures of CaSO₄ in the elastomer matrix was responsible for the changes in the mechanical relaxation behavior of the composites. Atomic force microscopy was used to verify this nano-rod crystal morphology in the elastomer matrix. The mechanism of water-induced mechanical reinforcement of the composite was explored from dynamic mechanical analysis of the material and correlated with its stress relaxation behavior.

Combining multiple stimuli-responsive functionalities into the polymer design is an attractive approach to improve nucleic acid delivery. However, more in-depth fundamental understanding how the multiple functionalities in the polymer structures are influencing polyplex formation and stability is essential for the rational development of such delivery systems. Therefore, in this study the structure and dynamics of thermosensitive polyplexes were investigated by tracking the behavior of labeled plasmid DNA (pDNA) and polymer with time-resolved fluorescence spectroscopy using fluorescence resonance energy transfer (FRET). The successful synthesis of a heterofunctional poly(ethylene glycol) (PEG) macroinitiator containing both an atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) initiator is reported. The use of this novel PEG macroinitiator allows for the controlled polymerization of cationic and thermosensitive linear triblock copolymers and labeling of the chain-end with a fluorescent dye by maleimide-thiol chemistry. The polymers consisted of a thermosensitive poly(N-isopropylacrylamide) (PNIPAM, N), hydrophilic PEG (P), and cationic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA, D) block, further referred to as NPD. Polymer block D chain-ends were labeled with Cy3, while pDNA was labeled with FITC. The thermosensitive NPD polymers were used to prepare pDNA polyplexes, and the effect of the N/P charge ratio, temperature, and composition of the triblock copolymer on the polyplex properties were investigated, taking nonthermosensitive PD polymers as the control. FRET was observed both at 4 and 37 °C, indicating that the introduction of the thermosensitive PNIPAM block did not compromise the polyplex structure even above the polymer's cloud point. Furthermore, FRET results showed that the NPD- and PD-based polyplexes have a less dense core compared to polyplexes based on cationic homopolymers (such as PEI) as reported before. The polyplexes showed to have a dynamic character meaning that the polymer chains can exchange between the polyplex core and shell. Mobility of the polymers allow their uniform redistribution within the polyplex and this feature has been reported to be favorable in the context of pDNA release and subsequent improved transfection efficiency, compared to nondynamic formulations.

Chromium oxide (Cr₂O₃) is commonly used as an atmospheric plasma-sprayed (APS) coating from powder feedstock in applications requiring resistance to sliding wear and corrosion, as well as amenability to texturing, e.g., in anilox rolls. Recently, high-velocity oxy-fuel spray methods involving suspension feedstock have been considered an extremely promising alternative to produce denser and more homogeneous chromium oxide coatings with lower as-sprayed surface roughness, higher hardness and potentially superior wear performance compared to conventional APS-sprayed coatings. In this study, the impact of process parameters namely auxiliary air cleaning nozzles and a transverse air curtain on suspension high-velocity oxy-fuel-sprayed Cr₂O₃ suspensions is presented. The produced coatings are characterized for their microstructure, mechanical properties and wear resistance by cavitation erosion. The results reveal the importance of optimized air nozzles and air curtain to achieve a vastly improved coating structure and performance.

Since the discovery of 45S5 Bioglass^® by Larry Hench, bioactive glasses have been widely studied as bone substitute materials and, in more recent years, have also shown great promise for producing three-dimensional scaffolds. The development of additive manufacturing techniques and their application in bone tissue engineering allows the design and fabrication of complex structures with controlled porosity. However, achieving strong and mechanically-reliable bioactive glass scaffolds is still a great challenge. Furthermore, there is a relative paucity of studies reporting an exhaustive assessment of other mechanical properties than compressive strength of glass-derived scaffolds. This research work aimed at determining key mechanical properties of silicate SiO₂-Na₂O-K₂OMgO-CaO-P₂O₅ glass scaffolds fabricated by robocasting and exhibiting a porosity gradient. When tested in compression, these scaffolds had a strength of 6 MPa, a Young's modulus around 340 MPa, a fracture energy of 93 kJ/m³ and a Weibull modulus of 3, which provides a quantification of the scaffold reliability and reproducibility. Robocasting was a suitable manufacturing method to obtain structures with favorable porosity and mechanical properties comparable to those of the human cancellous bone, which is fundamental regarding osteointegration of bone implants.

Fragmentation of molecular clusters inside mass spectrometers is a significant source of uncertainty in a wide range of chemical applications. We have measured the fragmentation of sulfuric acid clusters driving atmospheric new-particle formation, and developed a novel model, based on first principles calculations, capable of quantitatively predicting the extent of fragmentation.

In this work, the electronic bandstructure of GaAs_1-xBi_x/GaAs single quantum well (QW) samples grown by molecular beam epitaxy is investigated by photomodulated reflectance (PR) measurements as a function of Bi content (0.0065 ≤ x ≤ 0.0215) and substrate orientation. The Bi composition is determined via simulation of high-resolution x-ray diffraction measurement and is found to be maximized in the 2.15%Bi and 2.1%Bi samples grown on (100) and (311)B GaAs substrates. However, the simulations indicate that the Bi composition is not only limited in the GaAsBi QW layer but extends out of the GaAsBi QW towards the GaAs barrier and forms a GaAsBi epilayer. PR spectra are fitted with the third derivative function form (TDFF) to identify the optical transition energies. We analyze the TDFF results by considering strain-induced modification on the conduction band (CB) and splitting of the valence band (VB) due to its interaction with the localized Bi level and VB interaction. The PR measurements confirm the existence of a GaAsBi epilayer via observed optical transitions that belong to GaAsBi layers with various Bi compositions. It is found that both Bi composition and substrate orientation have strong effects on the PR signal. Comparison between TDFF and calculated optical transition energies provides a bandgap reduction of 92 meV/%Bi and 36 meV/%Bi and an interaction strength of the isolated Bi atoms with host GaAs valence band (C _BiM ) of 1.7 eV and 0.9 eV for (100) and (311)B GaAs substrates, respectively.

Here we are reporting solvothermal synthesis derived diluted magnetic and plasmonic Co-Ga co-doped ZnO nanocrystals with high magnetization values (from 1.02 to 4.88 emu/g) at room temperature. Co-Ga co-doped ZnO nanocrystals show up to 2 fold increase in saturation magnetization compared to Co doped ZnO nanocrystals at the same Co concentration, with the observed room temperature magnetization higher than previously reported values for multifunctional magnetic and plasmonic nanocrystals, and the effect of Ga suggesting some role of the correspondingly introduced itinerant charge. While at the lowest Ga content the nanoparticles appear homogeneously doped, we note that already a moderate Ga content of several percent triggers a fraction of Co to segregate in metallic form in the bulk of the nanoparticles. However, the amount of segregated Co is not sufficient to account for the total effect, whereas a dominating contribution to the observed magnetism has to be related to itinerant charge mediated exchange interactions.