Phase Composition Structure Research Articles

Determination of rare earth elements in synthetic calcium phosphates by high-resolution continuum source electrothermal atomic absorption spectrometry

Ceramic, cement and composite biomaterials have been developed based on hydroxyapatites (HA) and tricalcium phosphates (TCP), which are analogous in phase and chemical composition to the mineral component of bone tissue. The crystal structures of HA and TCP are arranged in isomorphic substitutions. Recently, research has focused on the modification of HA and TCP structures with ions of various metals, including rare earth ions (REEs), with the aim of creating materials with a range of beneficial properties for medical applications. REEs are known to have a number of useful properties, including antibacterial, antitumour, catalytic, magnetic and luminescent properties. The replacement of some of the Ca ions in the structures of HA and TCP with REE ions therefore makes it possible to obtain a material with biocompatibility and biological activity, giving it the required properties depending on the REE used and its concentration. In order to achieve the specified properties, it is necessary to control not only the structure (phase composition, lattice parameters of the powders) and the presence of characteristic functional groups, but also the chemical elemental composition. Modifications of hydroxyapatites and tricalcium phosphates containing from one to several different alloying elements are currently being developed. Various analytical methods are used for this purpose, including X-ray, atomic emission and a number of others. This article is devoted to the study of the analytical capabilities of the method of atomic absorption spectrometry with electrothermal atomization and a continuous spectrum source in relation to the determination of Eu and Yb in hydroxyapatites and tricalcium phosphates. The article considers the optimal conditions and modes of analysis, including temperature-time programs, the use of modifiers, the construction of calibration curves, and other factors that can be adjusted for more precise results. The results demonstrated the possibility of simultaneous determination of both Eu and Yb in the concentration range of 0.09 to 2 wt.%, with a relative standard deviation of less than 6 rel.%.

Identification of diffusion interlayers of dissimilar welds under static tension by acoustic emission method

The paper studies the possibility of carbide and decarburized ferrite interlayers detection formed during the production and operation of dissimilar welded joints of austenitic to pearlitic steels. Diffusion interlayers may be interpreted as welded joint microstructure defects, since their formation can cause premature failure of the product under high-temperature operation conditions. In addition, with a certain chemical and structural-phase composition of the welded metals, brittle interlayers formation and development of cracks in the weld zone may be occurred. To identify diffusion interlayers, the acoustic emission (AE) method is used in this research. Specimens cut from welded joints were tested by tension until rupture with simultaneous recording of AE signals. Based on the research results, particular AE data signatures corresponding to the specimens with diffusion interlayers were identified. The main feature indicating the presence of diffusion interlayers is an increase in the amplitudes of AE impulses and AE activity at a stress value of 300 MPa, corresponding to the ultimate strength of the ferrite phase.

Simulation of the Evolution of Phase Composition and Austenite Grain Size upon Multi-Pass Hot Deformationof Low-Alloy Steels

The paper presents a model for predicting the structural characteristics and phase composition of low-alloy steels upon hot rolling in the multi-pass deformation mode. The model considers recovery, dynamic, primary, dynamic and static recrystallization of grains, and the normal grain growth, as well as nucleation (including accelerated nucleation during deformation), growth or dissolution, and coarsening of carbonitride particles. The comparison between the calculated results and the experimental data available in the publications shows a satisfactory agreement.

Increasing the Wear and Corrosion Resistance of a CP-Ti Surface by Plasma Electrolytic Borocarburizing and Polishing

The paper examines the possibility of increasing the wear and corrosion resistance of a CP-Ti surface by duplex plasma electrolytic treatment (borocarburizing and polishing). The structure and composition of diffusion layers, their microhardness, surface morphology and roughness, wear resistance during dry friction and corrosion resistance in Ringer’s solution were studied. The formation of a surface-hardened layer up to 200 μm thick with a microhardness of up to 950 HV, including carbides and a solid solution of boron and carbon, is shown. Subsequent polishing makes it possible to reduce surface roughness and remove weak areas of the porous oxide layer, which are formed during high-temperature oxidation in aqueous electrolyte vapor during borocarburizing. Changing the morphology and structural-phase composition of the CP-Ti surface helps reduce weight wear by a factor of three (the mode of frictional interaction changes from microcutting to oxidative wear) and corrosion current density by a factor of four after borocarburizing in a solution of boric acid, glycerin and ammonium chloride at 950 °C for 5 min and subsequent polishing in an ammonium fluoride solution at a voltage of 250 V for 3 min.

Investigation of the Influence of the Oxygen Flow Rate on the Mechanical, Structural and Operational Properties of 86WC-10Co-4Cr Coatings, as Determined Using the High-Velocity Oxyfuel Spraying Method

The structural-phase composition and tribological and performance properties of coatings based on an 86WC-10Co-4Cr composition obtained by the HVOF method at varying (150 L/min, 170 L/min, 190 L/min) oxygen flow rates were studied. The results showed that the coefficient of friction of coatings in gear oil remained almost unchanged with the variation in oxygen flow rate. However, microhardness increased significantly with an increasing oxygen flow rate, reaching a maximum at 190 L/min. An increasing oxygen flow rate was also accompanied by an increase in roughness and coating thickness, with a decrease in porosity, particularly notable at 190 L/min. Adhesion strength reached the maximum values for the A2 and A3 coatings under high loads. The phase composition of the coatings included WC, W2C and CoO phases irrespective of the oxygen flow rate, and their microstructure was characterized by a more homogeneous and dense structure. Thus, this study confirmed that the optimal oxygen flow rate for achieving an improved performance and tribological characteristics of 86WC-10Co-4Cr coatings is 190 L/min.

Surface Structure Formation in Plasma Cutting of Aluminum and Titanium Alloys Using Direct Current Straight and Reverse Polarity

Abstract The structural features and phase composition are examined in near-surface layers of specimens of Al-Mg, Al-Cu-Mg alloys and commercially pure titanium obtained by plasma cutting using direct current straight polarity (DCSP) and direct current reverse polarity (DCRP). It is found that the flows of molten metal ejected by the gas stream from the cut cavity during cutting form the fusion and heat-affected zones, whose structural morphology, phase composition, and thickness depend on both the selected material and the cutting mode. The fusion zone is thicker in specimens cut using DCRP than in those cut with DCSP. The thickness of the adjacent heat-affected zone is also the largest in the mode that provides a thicker fused layer. Aluminum alloy specimens cut in ambient air are characterized by the presence of oxygen in the near-surface layers. The lowest degree of oxidation is observed in Al-Mg alloy. Oxygen penetrates into the fused layer to a depth of 350–500 μm in Al-Cu-Mg and up to 200–250 μm in Al-Mg alloy. In titanium alloy, the thickness of oxide layers does not exceed 100–150 μm during straight polarity cutting and 200–250 μm during reverse polarity cutting. A thin brittle layer of TiO and TiO2 oxides is formed on the titanium alloy surface. It is shown that the generation of “water mist” around the plasma jet when cutting materials of all types with DCRP leads to a more intensive oxidation of metal, less thermal effect on the material, and reduced roughness of the cut face.

Full-scale insight into high-entropy ceramics from basic concepts, synthesis technologies, structural characteristics, and properties to application prospects

High-entropy ceramics (HECs) are an emerging material system that has gained significant attention and become a focal point of research due to their unique structure and outstanding performance. This paper provides a comprehensive examination of the basic concepts, synthesis methods, structural characteristics, unique properties, and application prospects of HECs. It begins with an overview of the basic concepts and historical context, followed by a detailed comparison of synthesis techniques, including both traditional and innovative approaches. The paper then analyzes the structural characteristics and phase compositions of HECs, particularly focusing on oxide, carbide, boride, and other non-oxide ceramics. In addition, it delves into the mechanical, thermal, electrical, and magnetic properties of HECs. The article also reviews the applications of HECs in high-temperature structural materials, functional materials, high-performance coatings, and biomedical implants. Finally, it discusses the future challenges and development pathways for HECs. By highlighting new applications and transformative possibilities, this study not only sheds light on cutting-edge research but also emphasizes the significant impact of HECs on sustainable material development. The integration of machine learning and artificial intelligence can further unlock the unique structural capabilities of HECs, offering substantial potential for advancements in emerging fields like new energy and biomedicine.

Regulations of Thermal Expansion Coefficients of Yb1−xAlxTaO4 for Environmental Barrier Coatings Applications

Environmental barrier coatings (EBCs) are widely used to protect ceramic matrix composites (CMCs, SiCf/SiC, and Al2O3f/Al2O3), and they should have low thermal expansion coefficients (TECs) matching the CMCs and excellent mechanical properties to prolong their lifetime. Current EBC materials have disadvantages of phase transitions and insufficient mechanical properties, which affect their working temperatures and lifetime. It is necessary to develop new oxide EBCs. Ytterbium tantalate (YbTaO4) is a stable and novel EBC material, and we have improved the mechanical properties and TECs of Yb1−xAlxTaO4 (x = 0.05, 0.1, 0.2, 0.3, 0.4, 0.5) ceramics by replacing Yb with Al. XRD, SEM, and EDS are used to verify the crystal and microstructures, and nano-indentation is used to measure the modulus and hardness when changes in TECs are measured within a thermal expansion device. The results show that the phase structure of Yb1−xAlxTaO4 (x = 0.05, 0.1, 0.2, 0.3, 0.4, 0.5) is stable at 25–1400 °C within air atmosphere, and their high-temperature TECs (6.4–8.9 × 10−6 K−1, 1400 °C) are effectively regulated by introductions of different contents of Al, which enlarge their engineering applications for SiCf/SiC and Al2O3f/Al2O3 CMCs. The evolutions of TECs are analyzed from structural characteristics and phase compositions, and the increased TECs make Yb1−xAlxTaO4 potential EBCs for Al2O3 matrixes. Due to the high bonding strength of Al–O bonds, hardness, as well as Young’s modulus, are enhanced with the increasing Al content, with Yb1−xAlxTaO4 (x = 0.05, 0.1, 0.2, 0.3, 0.4, 0.5) having a nano-hardness of 3.7–12.8 GPa and a Young’s modulus of 100.9–236.6 GPa. The TECs of YbTaO4 are successfully regulated to expand their applications, and they match those of Al2O3 and SiC matrixes, as well as displaying improved mechanical properties. This work promotes applications of YbTaO4 as potential EBCs and provides a new way to regulate the TECs of tantalates.

THE INFLUENCE OF TEMPERATURE TREATMENT ON THE STRUCTURAL-PHASE COMPOSITION OF SUPPORTED Со-Мо/Al2О3 CATALYTIC SYSTEMS

Using the method of impregnation in an excess of impregnating solution and subsequent temperature treatment in the temperature range of 100-400 °C, the synthesis of γ-modified catalytic systems based on transition metals (Co, Mo) supported on active aluminum oxide was carried out and their physicochemical properties were studied. A distinctive feature of these systems was the use of polyoxometalate complexes (molybdenum blues) obtained by mechanical activation of commercial molybdenum disulfide as a source of molybdenum. The carrier was obtained by high-temperature treatment of industrial pseudoboehmite powder AlOOH (Ishimbay Specialized Chemical Plant of Catalysts LLC). This approach makes it possible to significantly simplify the synthesis of catalytic systems. At the same time, the reagents and technologies used are publicly available and are produced on the territory of the Russian Federation on an industrial scale. The resulting systems are expected to be used in hydrotreating processes (hydrodesulfurization and hydrodenitrogenation) of diesel fractions. The synthesis included the stage of obtaining an impregnating solution by adding a weighed portion of cobalt nitrate to an alcohol solution of molybdenum blue, and the stage of directly impregnating the carrier in an excess of the impregnating solution. After impregnation, the systems were calcined at various temperatures in order to study the genesis of the active components and the effect of temperature treatment on various physicochemical properties. The synthesized systems were studied using various physicochemical methods (XRD, IR spectroscopy). It was found that to completely eliminate the nitro group from the system, a temperature treatment of at least 400 °C is necessary. It was also shown that molybdenum blue can act as a source of Mo. For citation: Zhirov N.А., Akimov Al.S., Sudarev Е.А., Akimov A.S. The influence of temperature treatment on the structural-phase composition of supported Со-Мо/Al2О3 catalytic systems. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 8. P. 44-49. DOI: 10.6060/ivkkt.20246708.3t.

The Influence of Bias Voltage on the Structure and Properties of TiZrNbMo Coating Deposited by Magnetron Sputtering

TiZrNbMo coatings have been deposited using the direct current pulsed magnetron sputtering method in an argon atmosphere. The synthesis processes have been conducted under various process parameters. The structure (chemical and phase composition) and mechanical properties of the obtained multicomponent coatings are investigated as a function of plasma modulation frequency (10 Hz and 1000 Hz) and substrate bias (0 to −150 V). It is the case that an increase in the substrate bias decreases the deposition rate and alters the coating’s chemical composition. The latter leads to a Ti concentration decrease and a simultaneous increase in Mo and Nb concentrations in the final coating material. X-ray diffraction measurements indicate a single-phase BCC structure, with grain size decreasing as substrate bias increases. This ultimately forms an amorphous–nanocrystalline structure at −150 V. The mechanical properties of the multicomponent TiZrNbMo coatings have been determined using the nanoindentation method. The maximum values of hardness (13.45 GPa) and elastic modulus (188.6 GPa) are achieved at a substrate bias of −150 V. We also show that the minimum elastic modulus (41.8 GPa) is achieved at an intermediate substrate bias of −100 V.

Effect of Mn content in the Ti/Zr-based AB2 Laves type alloys on their electrochemical performance

In this work, we studied the impact of Manganese content on the structural and electrochemical properties of the AB2 Laves phase alloys. These multicomponent alloys were composed of 7 individual constituents with a composition Ti0.15Zr0.85La0.03V0.12Mn0.7+xFe0.12Ni1.2 and a variable Manganese content, x = 0.021, 0.035, 0.070. The alloys were prepared using arc melting and rapid solidification techniques. These alloys were characterized by X-ray diffraction and Scanning Electron Microscopy with X-ray Energy Dispersive Spectroscopy allowing to probe the phase-structural composition of the alloys, their microstructures, and elemental distribution among the phase constituents. The rapidly solidified alloys exhibited refined microstructures with a more uniform elemental distribution compared to their as-cast counterparts, the latter containing larger grain sizes and clustered La-rich phases. C15 and C14 Laves type structures contributed to the phase-structural composition of the alloys, with their proportions influenced by the Manganese content and the chosen preparation method. The study revealed a multi-feature relationship between the Manganese content, the phase abundances, and the electrochemical performances, with notable disparities between as-cast and rapidly solidified alloys. The alloy containing 3 wt% Manganese demonstrated the highest discharge capacity and superior activation performance for both preparation methods, suggesting the best choice when optimizing the composition of the anodes for achieving the best battery performance. The highest hydrogen diffusion rate was observed for the alloy containing 10 wt% Manganese which can be related to the catalytic role of Manganese in the processes of hydrogen exchange when present in these alloys.

Characteristics of Si (C,N) Silicon Carbonitride Layers on the Surface of Ni-Cr Alloys Used in Dental Prosthetics.

Chromium- and cobalt-based alloys, as well as chrome-nickel steels, are most used in dental prosthetics. Unfortunately, these alloys, especially nickel-based alloys, can cause allergic reactions. A disadvantage of these alloys is also insufficient corrosion resistance. To improve the properties of these alloys, amorphous Si (C,N) coatings were deposited on the surfaces of metal specimens. This paper characterizes coatings of silicon carbide nitrides, deposited by the magnetron sputtering method on the surface of nickel-chromium alloys used in dental prosthetics. Depending on the deposition parameters, coatings with varying carbon to nitrogen ratios were obtained. The study analyzed their structure and chemical and phase composition. In addition, a study of surface wettability and surface roughness was performed. Based on the results obtained, it was found that amorphous coatings of Si (C,N) type with thicknesses of 2 to 4.5 µm were obtained. All obtained coatings increase the value of surface free energy. The study showed that Si (C,N)-type films can be used in dental prosthetics as protective coatings.

Magnesium borate whiskers/La2-XCeXZr2O7 catalysts preparation on cordierite honeycomb ceramic surfaces for soot catalytic oxidation͏

Magnesium borate whiskers were used to prepare a hierarchical microstructure on cordierite ceramic substrate through the precipitation-molten salt method. The La2-XCeXZr2O7 catalyst was then loaded onto the magnesium borate whiskers to form the hierarchical microstructure. The Ce-doped catalysts exhibited a significant improvement in the catalytic activity of soot combustion compared to the La2Zr2O7 catalyst. The study employed various techniques to characterize the structural morphology and phase composition, including scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Fourier transform-infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). The growth of Magnesium borate whiskers (Mg2B2O5) with diameters of 100–200 nm and lengths of 2–5 μm were grown and tightly bonded to the cordierite ceramic substrate to mimic the structure of human respiratory system cilia. This could improve the filtration efficiency of soot in car exhaust. BET analysis showed that the specific surface area of cordierite increased from 0.684 m2/g to 1.363 m2/g after whisker growth. The study confirmed that the whiskers were firmly attached to the cordierite ceramic substrate, as demonstrated by the binding strength experiments. The addition of Ce metal has been found to significantly enhance soot combustion due to the presence of more active oxygen species and superior mobility of lattice oxygen species with more oxygen vacancies. The catalyst's intrinsic redox property was characterized using X-ray photoelectron spectroscopy (XPS) and H2 temperature-programmed reduction (H2-TPR). The semi-quantitative thermogravimetric analysis (TG-DTG) and the temperature-programmed oxidation (TPO) of catalysts showed that Z-La1.9Ce0·1Zr2O7 exhibited the highest catalytic activity for soot combustion, with an ignition temperature of 268 °C, a peak temperature of 418 °C, and a temperature of 90 % soot conversion of 464 °C. Furthermore, cyclic stability experiments demonstrate that the Z-La1.9Ce0·1Zr2O7 catalyst exhibits excellent structural stability and consistent catalytic performance. This distinctive microstructure holds great potential for applications in the field of DPF.

Ultralow-Permittivity and Temperature-Stable Ba1-xCaxMg2Al6Si9O30 Dielectric Ceramics for C-Band Patch Antenna Applications.

Ca-substituted Ba1-xCaxMg2Al6Si9O30 ceramics were prepared to explore the relationships among their crystal structural parameters, phase compositions, dielectric properties, and coefficients of thermal expansion and applications in C-band antenna. The maximum solubility of Ba1-xCaxMg2Al6Si9O30 was located at x = 0.25, and Ba1-xCaxMg2Al6Si9O30 ceramics (0 ≤ x ≤ 0.25) crystallized in the space group P6/mcc. In Ba1-xCaxMg2Al6Si9O30 single-phase ceramics, εr was dominated by ionic polarizability and "rattling effects" of Ba2+ and Al(2)3+; Q × f was controlled by the roundness of [Si4Al2O18] inner rings and total lattice energy; and τf was affected by the bond valence of Si/Al(1)-O(1). Notably, the low average coefficients of thermal expansion (2.668 ppm/°C) at -150 °C ≤ T ≤ 850 °C and near-zero coefficients of thermal expansion (1.254 ppm/°C) at -150 °C ≤ T ≤ 260 °C were achieved for the Ba1-xCaxMg2Al6Si9O30 (x = 0.1) ceramic. Optimum microwave and terahertz dielectric properties were obtained for the Ba1-xCaxMg2Al6Si9O30 (x = 0.1) ceramic with εr = 5.80, Q × f = 31,174 at 13.99 GHz, τf = -7.10 ppm/°C, and εr = 5.71-5.85 at 0.2 THz ≤ f ≤ 1.0 THz. Also, the Ba1-xCaxMg2Al6Si9O30 (x = 0.1) ceramic substrate had been designed as a C-band patch antenna with a high simulated radiation efficiency (87.76%) and gain (6.30 dBi) at 7.70 GHz (|S11| = -38.41 dB).

Studying the Structural Phase Composition and Optical and Mechanical Properties of Al–Si–Re–O Coatings Deposited on Quartz Glass

Studying the Structural Phase Composition and Optical and Mechanical Properties of Al–Si–Re–O Coatings Deposited on Quartz Glass

Microstructure and Properties of Thin-Film Submicrostructures Obtained by Rapid Thermal Treatment of Nickel Films on Silicon

Nickel films of 40 nm thickness were obtained by means of magnetron sputtering on a single-crystalline silicon substrate. The films were subjected to rapid thermal treatment (RTT) for 7 s until the temperature increased from 200 to 550 °C. By means of the X-ray diffraction method, the structural-phase composition of nickel films before and after RTT was explored. The atomic force microscopy method due to direct contact with the surface under study, made it possible to accurately define the microstructure, roughness, specific surface energy and grain size of the nickel films before and after RTT, as well as to establish the relationship of these parameters with the phase composition and electrical properties of the films. Surface specific resistance was measured using the four-probe method. Based on XRD results, formation of Ni2Si and NiSi phases in the film was ascertained after RTT at 300 °C. At RTT 350–550 °C, only the NiSi phase was formed in the film. The microstructure and grain size significantly depend on the phase composition of the films. A correlation has been established between specific surface energy and resistivity with the average grain size after RTT at 350–550 °C, which is associated with the formation and constant restructuring of the crystal structure of the NiSi phase.

Strength characteristics and carbonation depth evolution of modified magnesium slag based solid waste storage backfill materials

CO2 storage is one of the effective ways to achieve China's 30·60 dual carbon goal. The study of the interaction between CO2 and storage backfill material lays a foundation for the long-term stability and gas tightness of CO2 storage. Based on the modified magnesium slag-based solid waste backfill material constructed by the storage, in order to explore the strength characteristics and carbonation depth evolution of the CO2 storage backfill material, the interaction between CO2 and the storage backfill material was analyzed from the perspectives of uniaxial compressive strength, carbonation depth test, pore structure distribution, microstructure and phase composition. The results show that carbonation can significantly improve the compressive strength of the storage backfill material, and the carbonation depth increases with the increase of carbonation time, and increases slowly after complete carbonation. The later the initial carbonation age, the faster the growth rate of compressive strength and carbonation depth, and the greater the growth rate. After high concentration CO2 curing, the diffusion rate and carbonation degree of the storage backfill material gradually decreased from the outside to the inside, and the calcium carbonate content also gradually decreased. The carbonation can significantly reduce the porosity of the sample, gradually transform from large pores to small pores, and the pore size distribution and pore structure are significantly improved. Therefore, the later the initial carbonation age is, the more beneficial the carbonation effect is for the long-term stability and air tightness development of the backfill material of the CO2 storage, which provides important theoretical guidance for the construction and storage method of the CO2 storage.

Сравнительный анализ термоупругих характеристик керамоматричных композиционных материалов, определенных по различным модельным представлениям структурно фазового состава матричного материала

A comparative analysis of thermoelastic characteristics of ceramic matrix composite materials (CMC) obtained by liquid and gas phase technologies, reinforced with two types of carbon fibers (CF), is carried out based on different model structural phase composition of the obtained matrix material. It is noted that when implementing the liquid phase siliconizing and using high modulus carbon fibers with high negative values of the absolute value of the coefficients of linear thermal expansion (CLTE), a simplified model of the matrix material consisting of only one SiC phase can be correctly used. When implementing PIP and CVI technologies, CMC with low modulus CF and CF with low negative CLTE values show the greatest sensitivity to an increase in matrix porosity. For CMC based on CF T800, the change in the longitudinal CLTE was about 66% with a porosity of 20%. An increase in porosity leads to a decrease in all elastic characteristics of the CMC, to the greatest extent for the transverse modulus of elasticity and the shear modulus.

Effect of Plasma Treatment on the Luminescent and Scintillation Properties of Thick ZnO Films Fabricated by Sputtering of a Hot Ceramic Target

The paper presents the results of a comprehensive study of the structural-phase composition, morphology, optical, luminescent, and scintillation characteristics of thick ZnO films fabricated by magnetron sputtering. By using a hot ceramic target, extremely rapid growth (~50 µm/h) of ZnO microfilms more than 100 µm thick was performed, which is an advantage for the industrial production of scintillation detectors. The effects of post-growth treatment of the fabricated films in low-temperature plasma were studied and a significant improvement in their crystalline and optical quality was shown. As a result, the films exhibit intense near-band-edge luminescence in the near-UV region with a decay time of <1 ns. Plasma treatment also allowed to significantly weaken the visible defect luminescence excited in the near-surface regions of the films. A study of the luminescence mechanisms in the synthesized films revealed that their near-band-edge emission at room temperature is formed by phonon replicas of free exciton recombination emission. Particularly, the first phonon replica plays the main role in the case of optical excitation, while upon X-ray excitation, the second phonon replica dominates. It was also shown that the green band peaking at ~510 nm (2.43 eV) is due to surface emission centers, while longer wavelength (>550 nm) green-yellow emission originates mainly from bulk parts of the films.

Effect of Geometrical Confinement on Ordering of Thermoplastic Polyurethanes with Crystallizable Hard and Soft Blocks

A series of multi-block thermoplastic polyurethanes incorporating different soft block structures was synthesized. This was achieved using a poly(butylene adipate) oligomer combined with its macrodiols of both an aromatic and aliphatic nature. The composition of the hard block included 1,6-hexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 1,4-butanediol. For the first time, the structural evolution and phase composition of both the hard and soft segments were analyzed during in situ thermal treatments. A combination of synchrotron small- and wide-angle X-ray scattering, differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy was used to determine the influence of the macrodiol’s nature and crystallization conditions on the polymorphic behavior of poly(butylene adipate). Using a new synthesis scheme, a relatively high degree of crystallinity for urethane blocks was achieved, which depended on the diisocyanate type in the structure of the soft segment. The hard segment domains imposed geometrical constraints on poly(butylene adipate), thereby altering its crystallization process compared to the neat oligomer. Thus, crystallization after annealing at a low temperature (80 °C) was fast, predominantly yielding a metastable β-phase. When heated to 180 °C, which was higher than the hard segment’s melting temperature, a phase-separated structure was observed. Subsequent crystallization was slower, favoring the formation of the stable α-PBA modification. The phase separation could be observed even after the hard block melting. Notably slow crystallization from an isotropic melt was documented after the disruption of phase separation at 230 °C.