Variable Temperature Spectroscopic Ellipsometry as a Tool for Insight into the Optical Order in the P3HT:PC70BM and PC70BM Layers.

Two combined ellipsometric techniques-variable angle spectroscopic ellipsometry (VASE) and variable temperature spectroscopic ellipsometry (VTSE)-were used as tools to study the surface order and dielectric properties of thin films of a poly(3-hexylthiophene-2,5-diyl) (P3HT) mixture with a fullerene derivative (6,6-phenyl-C71-butyric acid methyl ester) (PC70BM). Under the influence of annealing, a layer of the ordered PC70BM phase was formed on the surface of the blend films. The dielectric function of the ordered PC70BM was determined for the first time and used in the ellipsometric modeling of the physical properties of the P3HT:PC70BM blend films, such as their dielectric function and thickness. The applied ellipsometric optical model of the polymer-fullerene blend treats the components of the blend as a mixture of optically ordered and disordered phases, using the effective medium approximation for this purpose. The results obtained using the constructed model showed that a layer of the ordered PC70BM phase was formed on the surface of the layer of the polymer and fullerene mixture. Namely, as a result of thermal annealing, the thickness of the layer of the ordered fullerene phase increased, while the thickness of the underlying material layer decreased.

Hybrid Mesoporous TiO2/ZnO Electron Transport Layer for Efficient Perovskite Solar Cell.

In recent years, perovskite solar cells (PSCs) have gained major attention as potentially useful photovoltaic technology due to their ever-increasing power-conversion efficiency (PCE). The efficiency of PSCs depends strongly on the type of materials selected as the electron transport layer (ETL). TiO2 is the most widely used electron transport material for the n-i-p structure of PSCs. Nevertheless, ZnO is a promising candidate owing to its high transparency, suitable energy band structure, and high electron mobility. In this investigation, hybrid mesoporous TiO2/ZnO ETL was fabricated for a perovskite solar cell composed of FTO-coated glass/compact TiO2/mesoporous ETL/FAPbI3/2D perovskite/Spiro-OMeTAD/Au. The influence of ZnO nanostructures with different percentage weight contents on the photovoltaic performance was investigated. It was found that the addition of ZnO had no significant effect on the surface topography, structure, and optical properties of the hybrid mesoporous electron-transport layer but strongly affected the electrical properties of PSCs. The best efficiency rate of 18.24% has been obtained for PSCs with 2 wt.% ZnO.

Phase behavior of π-conjugated polymer and non-fullerene acceptor (PTB7-Th:ITIC) solutions and blends.

Phase diagrams of ternary π-bonded polymer (PTB7-Th) solutions were constructed as a function of molecular weight, temperature, and electron acceptor species (ITIC, PC61BM and PC71BM). For this purpose, the Flory-Huggins lattice theory was employed with a constant χ interaction parameter, describing a binodal, spinodal, tie line, and critical point. Then, the morphologies of the blends composed of highly disordered PTB7-Th and crystallizable ITIC were investigated by atomic force microscopy. Subsequently, the surface polarities of the PTB7-Th:ITIC thin films were examined by water contact-angle goniometer, exhibiting a transition at the composition of ~ 60 ± 10 wt.% ITIC. Furthermore, X-ray diffraction indicated the presence of ITIC's crystallites at ≥ 70 wt.% ITIC. Hence, the PTB7-Th:ITIC system was observed to undergo a phase transition at ~ 60-70 wt.% ITIC.

An Investigation of the Thermal Transitions and Physical Properties of Semiconducting PDPP4T:PDBPyBT Blend Films.

This work focuses on the study of thermal and physical properties of thin polymer films based on mixtures of semiconductor polymers. The materials selected for research were poly [2,5-bis(2-octyldodecyl)-pyrrolo [3,4-c]pyrrole-1,4(2H,5H)-dione-3,6-diyl)-alt-(2,2';5',2″;5″,2'''-quater-thiophen-5,5'''-diyl)]-PDPP4T, a p-type semiconducting polymer, and poly(2,5-bis(2-octyldodecyl)-3,6-di(pyridin-2-yl)-pyrrolo [3,4-c]pyrrole-1,4(2H,5H)-dione-alt-2,2'-bithiophene)-PDBPyBT, a high-mobility n-type polymer. The article describes the influence of the mutual participation of materials on the structure, physical properties and thermal transitions of PDPP4T:PDBPyBT blends. Here, for the first time, we demonstrate the phase diagram for PDPP4T:PDBPyBT blend films, constructed on the basis of variable-temperature spectroscopic ellipsometry and differential scanning calorimetry. Both techniques are complementary to each other, and the obtained results overlap to a large extent. Our research shows that these polymers can be mixed in various proportions to form single-phase mixtures with several thermal transitions, three of which with the lowest characteristic temperatures can be identified as glass transitions. In addition, the RMS roughness value of the PDPP4T:PDBPyBT blended films was lower than that of the pure materials.

Investigation of Ti/Al2O3 + TiO2 and Ti + TiO2/Al2O3 + TiO2 hybrid coatings as protection of ultra-light Mg-(Li)-Al-RE alloys against corrosion.

Low corrosion resistance is a significant problem of magnesium alloys, particularly ultra-light magnesium-lithium alloys. Surface treatment is one way to improve their corrosion resistance. The paper presents the results of tests of Ti/Al2O3 + TiO2 and Ti + TiO2/Al2O3 + TiO2 coatings obtained in a hybrid process combining PVD and ALD methods and ALD coating of Al2O3 + TiO2 type obtained on AE42 (Mg-4Li-2RE) and LAE442 (Mg-4Li-4Al-2RE). Structural studies were performed using scanning and transmission electron microscopy (SEM and TEM), atomic force microscopy and EDS and XPS spectroscopic methods. Potentiodynamic tests and electrochemical impedance spectroscopy EIS in 0.05 M NaCl solution were performed to determine the electrochemical properties of the tested materials. Moreover, tests of surface wettability and tribological properties using the ball-on-disc method were performed. Based on the analysis of anodic polarisation curves and Tafel analysis, it was found that the Ti + TiO2/Al2O3 + TiO2 coating showed the best potentiodynamic properties on both substrates. In particular, on the magnesium-lithium substrate, the value of the polarisation resistance of this hybrid coating is Rpol = 14 × 103 Ω × cm2, and the value of the corrosion current is jcorr = 0.4 µA/cm2. For the uncoated LAE442 substrate, the polarisation resistance is Rpol = 1.05 × 103 Ω × cm2, and the corrosion current value is jcorr = 5.49 µA/cm2. This improvement is due to the synergistic effect of the combined PVD and ALD technologies. The study confirmed the impact of hybrid coatings on improving the anti-corrosion and tribological properties of ultra-light magnesium alloys.

Hydrophilic ZnO thin films doped with ytterbium and europium oxide.

Hydrophilic photocatalytically active ZnO and ZnO thin films doped with Yb2O3 and Eu2O3 (rare earth metal oxide, REM) with optical transmittance exceeding 76% in the visible light range (λ = 550 nm) were prepared by a combination of sol-gel technique, spin-coating and high temperature thermal treatment at 500 and 600 °C. The thin films were tested using advanced research methods, i.e.: morphology and topography and fractures along with approximate thickness values were investigated on scanning electron microscope (SEM), chemical composition was determined using X-ray Energy Dispersive Spectroscopy (X-ray Energy Spectroscopy), topography and roughness were measured on atomic force microscope (AFM), water contact angle values were determined by sitting water droplet method, optical properties of the fabricated materials were investigated using UV/Vis spectrophotometer. The decolorization efficiency of rhodamine B in aqueous solution was analyzed over a period of 190 min, obtaining degradation rates of: 54.7% and 43.1%, for ZnO and ZnO coatings doped with ytterbium oxide and europium oxide, respectively. The roughness of thin hybrid coatings did not exceed 50 nm, ensuring effective absorption of electromagnetic radiation by the layers. The methodology presented by the authors for the fabrication of thin hybrid films characterized by the key properties of self-cleaning coatings can be successfully applied to coatings of photovoltaic panels and architectural glass structures.

Microstructural and Mechanical Properties of Novel Co-Free Maraging Steel M789 Prepared by Additive Manufacturing.

This research aims to characterize and examine the microstructure and mechanical properties of the newly developed M789 steel, applied in additive manufacturing. The data presented herein will bring about a broader understanding of the processing−microstructure−property−performance relationships in this material based on its chemical composition and heat treatment. Samples were printed using the laser powder bed fusion (LPBF) process and then the solution was annealed at 1000 °C for 1 h, followed by aging at 500 °C for soaking times of 3, 6 and 9 h. The AM components showed a relative density of 99.1%, which arose from processing with the following parameters: laser power of 200 W, laser speed of 340 mm/s, and hatch distance of 120 µm. Optical and electron microscopy observations revealed microstructural defects, typical for LPBF processes, like voids appearing between the melted pools of different sizes with round or creviced geometries, nonmelted powder particle formation inside such cavities, and small spherical porosity that was preferentially located between the molten pools. In addition, in heat-treated conditions, AM maraging steel has combined oxide inclusions of Ti and Al (TiO2:Al2O3) that reside along the grain boundaries and secondary porosities; these may act as preferential zones for crack initiation and may increase the brittleness of the AM steel under aged conditions. Consequently, the elongation of the AM alloy was low (<3%) for both annealed and aged solution conditions. The tensile strength of AM M789 increased from 968 MPa (solution annealed) to 1500−1600 MPa after the aging process due to precipitation within the intermetallic η-phase. A tensile strength and yield point of 1607 ± 26 and 1617 ± 45 MPa were obtained, respectively, after a full heat treatment at 500 °C/6 h. The results show that 3 h aging of solution annealed AM M789 steel achieves satisfactory material properties in industrial practice. Extending the aging time of printed parts to 6 h yields slightly improved properties but may not be worth the effort, while long-term aging (9 h) was shown to even reduce quality.

A Short Review on Various Engineering Applications of Electrospun One-Dimensional Metal Oxides.

The growing scientific interest in one-dimensional (1D) nanostructures based on metal-oxide semiconductors (MOS) resulted in the analysis of their structure, properties and fabrication methods being the subject of many research projects and publications all over the world, including in Poland. The application of the method of electrospinning with subsequent calcination for the production of these materials is currently very popular, which results from its simplicity and the possibility to control the properties of the obtained materials. The growing trend of industrial application of electrospun 1D MOS and the progress in modern technologies of nanomaterials properties investigations indicate the necessity to maintain the high level of research and development activities related to the structure and properties analysis of low-dimensional nanomaterials. Therefore, this review perfectly fits both the global trends and is a summary of many years of research work in the field of electrospinning carried out in many research units, especially in the Department of Engineering Materials and Biomaterials of the Faculty of Mechanical Engineering and Technology of Silesian University of Technology, as well as an announcement of further activities in this field.

Impact of TiO2 Nanostructures on Dye-Sensitized Solar Cells Performance.

The effect of TiO2 nanostructures such as nanoparticles, nanowires, nanotubes on photoanode properties, and dye-sensitized solar cells photovoltaic parameters were studied. The series of dye-sensitized solar cells based on two dyes, that is, commercially N719 and synthesized 3,7'-bis(2-cyano-1-acrylic acid)-10-ethyl-phenothiazine were tested. Additionally, the devices containing a mixture of this sensitizer and chenodeoxycholic acid as co-adsorbent were fabricated. The amount of adsorbed dye molecules to TiO2 was evaluated. The prepared photoanodes with different TiO2 nanostructures were investigated using UV-Vis spectroscopy, optical, atomic force, and scanning electron microscopes. Photovoltaic response of constructed devices was examined based on current-voltage characteristics and electrochemical impedance spectroscopy measurements. It was found that the highest UV-Vis absorption exhibited the photoanode with nanotubes addition. This indicates the highest number of sensitizer molecules anchored to the titanium dioxide photoanode, which was subsequently confirmed by dye-loading tests. The highest power conversion efficiency was (6.97%) for solar cell containing nanotubes and a mixture of the dyes with a co-adsorbent.

Effect of polyaniline content and protonating dopants on electroconductive composites.

Elastic constructive elements prepared by electrospinning using polyacrylonitrile/polyaniline (PAN/PANI) electroconductive composites were prepared and investigated in terms of their thermal and mechanical properties. This study was focused on the impact of the type of counterion of polyaniline and the PANI content in composites on the thermal, conductive and morphological properties of electrospun fibers. In this study, composites obtained from PANI doped with sulfuric acid showed the highest conductivity, and composites obtained from PANI doped with hydrochloric acid showed the highest thermal stability. All obtained composites exhibited good thermal stability, with T5 values in the range of 230-268 °C that increased with increasing PANI content. The prepared composites exhibited comparable PAN Tg values, which indicates their suitability for processing. Instrumental analysis of polymers and composites was carried out using UV-visible spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical thermal analysis and scanning electron microscopy.

Ultrasound Effect on the Microstructure and Hardness of AlMg3 Alloy under Upsetting.

To date, numerous investigations have shown the beneficial effect of ultrasonic vibration-assisted forming technology due to its influence on the forming load, flow stress, friction condition reduction and the increase of the metal forming limit. Although the immediate occurring force and mean stress reduction are known phenomena, the underlying effects of ultrasonic-based material softening remain an object of current research. Therefore, in this article, we investigate the effect of upsetting with and without the ultrasonic vibrations (USV) on the evolution of the microstructure, stress relaxation and hardness of the AlMg3 aluminum alloy. To understand the process physics, after the UAC (ultrasonic assisted compression), the microstructures of the samples were analyzed by light and electron microscopy, including the orientation imaging via electron backscatter diffraction. According to the test result, it is found that ultrasonic vibration can reduce flow stress during the ultrasonic-assisted compression (UAC) process for the investigated aluminum-magnesium alloy due to the acoustic softening effect. By comparing the microstructures of samples compressed with and without simultaneous application of ultrasonic vibrations, the enhanced shear banding and grain rotation were found to be responsible for grain refinement enhancement. The coupled action of the ultrasonic vibrations and plastic deformation decreased the grains of AlMg3 alloy from ~270 µm to ~1.52 µm, which has resulted in a hardness enhancement of UAC processed sample to about 117 HV.

Synthesis of hybrid amorphous/crystalline SnO2 1D nanostructures: investigation of morphology, structure and optical properties.

The aim of the study was to prepare SnO2 nanowires via a combination of electrospinning and the sol-gel method from a polyvinylpyrrolidone (PVP)/dimetylformamide (DMF)/ethanol(EtOH)/tin(IV) chloride pentahydrate (SnCl4·5H2O) solution. The morphology, structure and chemical composition of the obtained PVP/SnO2 nanofibers and SnO2 nanowires were examined using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) as well as a scanning electron microscope (SEM) with an energy dispersive spectrometer (EDX). The optical property analysis was performed on the basis of UV-Vis spectra of absorbance as a function of the wavelength, based on which the rated values of band gaps of the fabricated 1D nanostructures were determined. The morphology analysis showed that the obtained amorphous SnO2 nanowires with crystalline protuberances were characterized by a diameter of 50 to 120 nm. Results demonstrated that nanowires with a ratio of 1:1 precursor to polymer in the spinning solution were characterized by the smallest diameter after calcination and the smallest energy gap of 3.3 eV among all investigated samples. The rest of the studied materials were characterized by a larger energy gap (3.8 and 3.9 eV).

Phase Behavior of Amorphous/Semicrystalline Conjugated Polymer Blends.

We report the phase behavior of amorphous/semicrystalline conjugated polymer blends composed of low bandgap poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b']dithiophene) -alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) and poly{(N,N'-bis(2-octyldodecyl)naphthalene -1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)). As usual in polymer blends, these two polymers are immiscible because ΔSm ≈ 0 and ΔHm > 0, leading to ΔGm > 0, in which ΔSm, ΔHm, and ΔGm are the entropy, enthalpy, and Gibbs free energy of mixing, respectively. Specifically, the Flory-Huggins interaction parameter (χ) for the PCPDTBT /P(NDI2OD-T2) blend was estimated to be 1.26 at 298.15 K, indicating that the blend was immiscible. When thermally analyzed, the melting and crystallization point depression was observed with increasing PCPDTBT amounts in the blends. In the same vein, the X-ray diffraction (XRD) patterns showed that the π-π interactions in P(NDI2OD-T2) lamellae were diminished if PCPDTBT was incorporated into the blends. Finally, the correlation of the solid-liquid phase transition and structural information for the blend system may provide insight for understanding other amorphous/semicrystalline conjugated polymers used as active layers in all-polymer solar cells, although the specific morphology of a film is largely affected by nonequilibrium kinetics.

Strengthening of AA5754 Aluminum Alloy by DRECE Process Followed by Annealing Response Investigation.

In this study, a dual rolls equal channel extrusion (DRECE) process has been applied for improving the mechanical properties of the 5754 alloy. Supplementary experiments involving metallography, electron backscattered diffraction (EBSD), and XRD tests were carried out to evaluate the effect of the DRECE process. XRD analysis showed that the maximum dislocation density was achieved after six DRECE passes, which were accompanied by the formation that is typical for low-strain structures. The increasing dislocation density, as well as grain refinement throughout DRECE deformation, resulted in an increase in the mechanical properties. Annealing of the as-deformed sample resulted in grain growth and strength reduction.

Complex Corrosion Properties of AISI 316L Steel Prepared by 3D Printing Technology for Possible Implant Applications.

This paper deals with the investigation of complex corrosion properties of 3D printed AISI 316L steel and the influence of additional heat treatment on the resulting corrosion and mechanical parameters. There was an isotonic solution used for the simulation of the human body and a diluted sulfuric acid solution for the study of intergranular corrosion damage of the tested samples. There were significant microstructural changes found for each type of heat treatment at 650 and 1050 °C, which resulted in different corrosion properties of the tested samples. There were changes of corrosion potential, corrosion rate and polarization resistance found by the potentiodynamic polarization method. With regard to these results, the most appropriate heat treatment can be applied to applications with intended use in medicine.

Fabrication of electrospun poly(lactic acid) nanoporous membrane loaded with niobium pentoxide nanoparticles as a potential scaffold for biomaterial applications.

Tissue engineering aims to regenerate and restore damaged human organs and tissues using scaffolds that can mimic the native tissues. The requirement for modern and efficient biomaterials that are capable of accelerating the healing process has been considerably increased. In this work, a novel electrospun poly(lactic acid) (PLA) nanoporous membrane incorporated with niobium pentoxide nanoparticles (Nb2 O5 ) for biomaterial applications was developed. Nb2 O5 nanoparticles were obtained by microwave-assisted hydrothermal synthesis, and different concentrations (0, 1, 3, and 5% wt/wt) were tested. Chemical, morphological, mechanical, and biological properties of membranes were evaluated. Cell viability results demonstrated that the membranes presented nontoxic effects. The incorporation of Nb2 O5 improved cell proliferation without impairing the wettability, porosity, and mechanical properties of membranes. Membranes containing Nb2 O5 nanoparticles presented biocompatible properties with suitable porosity, which facilitated cell attachment and proliferation while allowing diffusion of oxygen and nutrients. This study has demonstrated that Nb2 O5 nanoparticle-loaded electrospun PLA nanoporous membranes are potential candidates for drug delivery and wound dressing applications.

Erratum: Phase Diagrams of n-Type Low Bandgap Naphthalenediimide-Bithiophene Copolymer Solutions and Blends. Polymers 2019, 11, 1474.

The authors wish to make a change to the published paper [...].

Phase Diagrams of n-Type Low Bandgap Naphthalenediimide-Bithiophene Copolymer Solutions and Blends.

Phase diagrams of n-type low bandgap poly{(N,N'-bis(2-octyldodecyl)naphthalene -1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-5,5',-(2,2'-bithiophene)} (P(NDI2OD-T2)) solutions and blends were constructed. To this end, we employed the Flory-Huggins (FH) lattice theory for qualitatively understanding the phase behavior of P(NDI2OD-T2) solutions as a function of solvent, chlorobenzene, chloroform, and p-xylene. Herein, the polymer-solvent interaction parameter (χ) was obtained from a water contact angle measurement, leading to the solubility parameter. The phase behavior of these P(NDI2OD-T2) solutions showed both liquid-liquid (L-L) and liquid-solid (L-S) phase transitions. However, depending on the solvent, the relative position of the liquid-liquid phase equilibria (LLE) and solid-liquid phase equilibria (SLE) (i.e., two-phase co-existence curves) could be changed drastically, i.e., LLE > SLE, LLE ≈ SLE, and SLE > LLE. Finally, we studied the phase behavior of the polymer-polymer mixture composed of P(NDI2OD-T2) and regioregular poly(3-hexylthiophene-2,5-dyil) (r-reg P3HT), in which the melting transition curve was compared with the theory of melting point depression combined with the FH model. The FH theory describes excellently the melting temperature of the r-reg P3HT/P(NDI2OD-T2) mixture when the entropic contribution to the polymer-polymer interaction parameter (χ = 116.8 K/T -0.185, dimensionless) was properly accounted for, indicating an increase of entropy by forming a new contact between two different polymer segments. Understanding the phase behavior of the polymer solutions and blends affecting morphologies plays an integral role towards developing polymer optoelectronic devices.

Synthesis of the Novel Type of Bimodal Ceramic Nanowires from Polymer and Composite Fibrous Mats.

The purpose of this paper was to produce SiO2 and TiO2 nanowires via the electrospinning process from a polyvinylpyrrolidone (PVP)/Tetraethyl orthosilicate (TEOS)/Titanium (IV) butoxide (TNBT)/dimethylformamide (DMF) and ethanol (EtOH) solution. The as-obtained nanofibers were calcined at temperatures ranging from 400 °C to 600 °C in order to remove the organic phase. The one-dimensional ceramic nanostructures were studied using a scanning electron microscope (SEM) and a transmission electron microscope (TEM) to analyze the influence of the used temperature on the morphology and structures of the obtained ceramic nanomaterials. In order to examine the chemical structure of the nanowires, energy dispersive spectrometry (EDX) and Fourier-Transform Infrared spectroscopy (FTIR) were used. The optical property analysis was performed on the basis of UV-Vis spectra of absorbance as a function of the wavelength. Using the modified Swanepoel method, which the authors proposed and the recorded absorbance spectra allowed to determine the banded refractive index n, real n' and imaginary k part of the refractive index as a function of the wavelength, complex dielectric permeability ε, and real and imaginary part εr and εi of the dielectric permeability as a function of the radiation energy of the produced ceramic nanowires.

Manufacturing and investigation of physical properties of polyacrylonitrile nanofibre composites with SiO2, TiO2 and Bi2O3 nanoparticles.

The aim of this study was to produce nanocomposite polymer fibres, consisting of a matrix of polyacrylonitrile (PAN) and a reinforcing phase in the form of SiO2/TiO2/Bi2O3 nanoparticles, by electrospinning the solution. The effect of the nanoparticles and the electrospinning process parameters on the morphology and physical properties of the obtained composite nanofibres was then examined. The morphology of the fibres and the dispersion of nanoparticles in their volume were examined using scanning electron microscopy (SEM). All of the physical properties, which included the band gap width, dielectric constant and refractive index, were tested and plotted against the concentration by weight of the used reinforcing phase, which was as follows: 0%, 4%, 8% and 12% for each type of nanoparticles. The width of the band gap was determined on the basis of the absorption spectra of radiation (UV-vis) and ellipsometry methods. Spectroscopic ellipsometry has been used in order to determine the dielectric constant, refractive index and the thickness of the obtained fibrous mats.