Exfoliation Resistance,Microstructure, and Oxide Formation Mechanisms of the White Oxide Layer on CP Ti and Ti–Nb–Ta–Zr Alloys

We found that specific biomedical Ti and its alloys, such as CP Ti, Ti–29Nb–13Ta–4.6Zr, and Ti–36Nb–2Ta–3Zr–0.3O, form a bright white oxide layer after a particular oxidation heat treatment. In this paper, the interfacial microstructure of the oxide layer on Ti–29Nb–13Ta–4.6Zr and the exfoliation resistance of commercially pure (CP) Ti, Ti–29Nb–13Ta–4.6Zr, and Ti–36Nb–2Ta–3Zr–0.3O were investigated. The alloys investigated were oxidized at 1273 or 1323 K for 0.3–3.6 ks in an air furnace. The exfoliation stress of the oxide layer was high in Ti–29Nb–13Ta–4.6Zr and Ti–36Nb–2Ta–3Zr–0.3O, and the maximum exfoliation stress was as high as 70 MPa, which is almost the same as the stress exhibited by epoxy adhesives, whereas the exfoliation stress of the oxide layer on CP Ti was less than 7 MPa, regardless of duration time. The nanoindentation hardness and frictional coefficients of the oxide layer on Ti–29Nb–13Ta–4.6Zr suggested that the oxide layer was hard and robust enough for artificial tooth coating. The cross-sectional transmission electron microscopic observations of the microstructure of oxidized Ti–29Nb–13Ta–4.6Zr revealed that a continuous oxide layer formed on the surface of the alloys. The Au marker method revealed that both in- and out-diffusion occur during oxidation in Ti–29Nb–13Ta–4.6Zr and Ti–36Nb–2Ta–3Zr–0.3O, whereas only out-diffusion governs oxidation in CP Ti. The obtained results indicate that the high exfoliation resistance of the oxide layer on Ti–29Nb–13Ta–4.6Zr and Ti-36Nb-2Ta-3Zr-0.3O are attributed to their dense microstructures composing of fine particles, and a composition-graded interfacial microstructure. On the basis of the results of our microstructural observations, the oxide formation mechanism of the Ti–Nb–Ta–Zr alloy is discussed.     

Evaluation of Drug-Loading Ability of Poly(Lactic Acid)/Hydroxyapatite Core–Shell Particles

Poly(lactic acid)/hydroxyapatite (PLA/HAp) core–shell particles are prepared using the emulsification method. These particles are safe for living organisms because they are composed of biodegradable polymers and biocompatible ceramics. These particles are approximately 50–100 nm in size, and their hydrophobic substance loading can be controlled. Hence, PLA/HAp core–shell particles are expected to be used as drug delivery carriers for hydrophobic drugs. In this work, PLA/HAp core–shell particles with a loading of vitamin K₁ were prepared, and their drug-loading ability was evaluated. The particles were 40–80 nm in diameter with a PLA core and a HAp shell. The particle size increased with an increase in the vitamin K₁ loading. The drug-loading capacity (LC) value of the particles, an indicator of their drug-loading ability, was approximately 250%, which is higher than the previously reported values. The amount of vitamin K₁ released from the particles increased as the pH of the soaking solution decreased because the HAp shell easily dissolved under the acidic conditions. The PLA/HAp particles prepared in this work were found to be promising candidates for drug delivery carriers because of their excellent drug-loading ability and pH sensitivity.     

Investigation of the Implementation of Laser Surface Alloying of Cu with Cr–WC

This paper presents research on the microstructure and mechanical properties of an alloyed composite copper (Cu) surface layer, reinforced with a mixture of chromium–tungsten carbide (Cr–WC) powders. Copper alloying was performed using a high-power diode laser (HPDL). In the tests, three mixtures of powders with different percentage contents (75%Cr 25%WC, 50%Cr 50%WC, 25%Cr 75%WC) were injected into the melting pool during the laser surface alloying process. Microstructural evolution and the properties of the surface layer of copper after laser alloying were investigated. Structural investigations were performed using light microscopy, scanning and transmission electron microscopy (SEM, TEM) and X-ray diffraction (XRD). Microhardness and wear resistance of the modified surface layer were examined as well. After laser treatment the applied powders appear as uniformly distributed particles in the alloyed zone as well as nanoscale precipitates in the Cu matrix. Several types of precipitate characteristics, in terms of morphology, structure and chemical composition, were observed. Laser alloying of the surface layer modified the microstructure, which resulted in an increase in the hardness of the surface layers compared to the base material.     

Preparation,Characterization and Tailoring Properties of Poly(Vinyl Chloride) Composites with the Addition of Functional Halloysite–Lignin Hybrid Materials

In this article, halloysite–lignin hybrid materials (HL) were designed and obtained. The weak hydrogen bonds found between the components were determined based on Fourier transform infrared spectroscopy (FTIR), proving the achievement of class I hybrid systems. The HL systems were characterized by very good thermal stability and relatively good homogeneity, which increased as the proportion of the inorganic part increased. This was confirmed by analyzing scanning electron microscope (SEM) images and assessing particle size distributions and polydispersity indexes. Processing rigid poly(vinyl chloride) (PVC) with HL systems with a content of up to 10 wt% in a Brabender torque rheometer allowed us to obtain composites with a relatively homogeneous structure confirmed by SEM observations; simultaneously, a reduction in the fusion time was noted. An improvement in PVC thermal stability of approximately 40 °C for composites with HL with a ratio of 1:5 wt/wt was noted. Regardless of the concentration of the HL system, PVC composites exhibited inconsiderably higher Young’s modulus, but the incorporation of 2.5 wt% of fillers increased Charpy impact strength by 5–8 kJ/m² and doubled elongation at break. This study demonstrated that favorable mechanical properties of PVC composites can be achieved, especially with an HL system with a ratio of 5:1 wt/wt.     

Improving the Thermomechanical Properties of Poly(lactic acid) via Reduced Graphene Oxide and Bioderived Poly(decamethylene 2,5-furandicarboxylate)

Polylactide (PLA) is the most widely used biopolymer, but its poor ductility and scarce gas barrier properties limit its applications in the packaging field. In this work, for the first time, the properties of PLA solvent-cast films are improved by the addition of a second biopolymer, i.e., poly(decamethylene 2,5-furandicarboxylate) (PDeF), added in a weight fraction of 10 wt%, and a carbon-based nanofiller, i.e., reduced graphene oxide (rGO), added in concentrations of 0.25–2 phr. PLA and PDeF are immiscible, as evidenced by scanning electron microscopy (SEM) and Fourier-transform infrared (FTIR) spectroscopy, with PDeF spheroidal domains showing poor adhesion to PLA. The addition of 0.25 phr of rGO, which preferentially segregates in the PDeF domains, makes them smaller and considerably rougher and improves the interfacial interaction. Differential scanning calorimetry (DSC) confirms the immiscibility of the two polymer phases and highlights that rGO enhances the crystallinity of both polymer phases (especially of PDeF). Thermogravimetric analysis (TGA) highlights the positive impact of rGO and PDeF on the thermal degradation resistance of PLA. Quasi-static tensile tests evidence that adding 10 wt% of PDeF and a small fraction of rGO (0.25 phr) to PLA considerably enhances the strain at break, which raises from 5.3% of neat PLA to 10.0% by adding 10 wt% of PDeF, up to 75.8% by adding also 0.25 phr of rGO, thereby highlighting the compatibilizing role of rGO on this blend. On the other hand, a further increase in rGO concentration decreases the strain at break due to agglomeration but enhances the mechanical stiffness and strength up to an rGO concentration of 1 phr. Overall, these results highlight the positive and synergistic contribution of PDeF and rGO in enhancing the thermomechanical properties of PLA, and the resulting nanocomposites are promising for packaging applications.     

The Effect of Heat Treatment on the Tribological Properties and Room Temperature Corrosion Behavior of Fe–Cr–Al-Based OPH Alloy

The microstructure, mechanical, tribological, and corrosion properties of Fe–Cr–Al–Y-based oxide-precipitation-hardened (OPH) alloy at room temperature are presented. Two OPH alloys with a composition of 0.72Fe–0.15Cr–0.06Al–0.03Mo–0.01Ta–0.02Y₂O₃ and 0.03Y₂O₃ (wt.%) were prepared by mechanical alloying with different milling times. After consolidation by hot rolling, the alloys presented a very fine microstructure with a grain size of approximately 180 nm. Such a structure is relatively brittle, and its mechanical properties are enhanced by heat treatment. Annealing was performed at three temperatures (1000 °C, 1100 °C, and 1200 °C), with a holding time from 1 to 20 h. Tensile testing, wear testing, and corrosion testing were performed to evaluate the effect of heat treatment on the behavior and microstructural properties. The grain size increased almost 10 times by heat treatment, which influenced the mechanical properties. The ultimate tensile strength increased up to 300% more compared to the initial state. On the other hand, heat treatment has a negative effect on corrosion and wear resistance.     

A Study on the Electromagnetic–Thermal Coupling Effect of Cross-Slot Frequency Selective Surface

In high-power microwave applications, the electromagnetic-thermal effect of frequency selective surface (FSS) cannot be ignored. In this paper, the electromagnetic-thermal coupling effects of cross-slot FSS were studied. We used an equivalent circuit method and CST software to analyze the electromagnetic characteristics of cross-slot FSS. Then, we used multi-field simulation software COMSOL Multiphysics to study the thermal effect of the FSSs. To verify the simulation results, we used a horn antenna with a power of 20 W to radiate the FSSs and obtain the stable temperature distribution of the FSSs. By using simulations and experiments, it is found that the maximum temperature of the cross-slot FSS appears in the middle of the cross slot. It is also found that the FSS with a narrow slot has severer thermal effect than that with a wide slot. In addition, the effects of different incident angles on the temperature variation of FSS under TE and TM polarization were also studied. It is found that in TE polarization, with the increase in incident angle, the maximum stable temperature of FSS increases gradually. In TM polarization, with the increase in incident angle, the maximum stable temperature of FSS decreases gradually.     

Double-layer structure of the Pt(111)–aqueous electrolyte interface

We present detailed measurements of the double-layer capacitance of the Pt(111)–electrolyte interface close to the potential of zero charge (PZC) in the presence of several different electrolytes consisting of anions and cations that are considered to be nonspecifically adsorbed. For low electrolyte concentrations, we show strong deviations from traditional Gouy–Chapman–Stern (GCS) behavior that appear to be independent of the nature of the electrolyte ions. Focusing on the capacitance further away from PZC and the trends for increasing ion concentration, we observe ion-specific capacitance effects that appear to be related to the size or hydration strength of the ions. We formulate a model for the structure of the electric double layer of the Pt(111)–electrolyte interface that goes significantly beyond the GCS theory. By combining two existing models, namely, one capturing the water reorganization on Pt close to the PZC and one accounting for an attractive ion–surface interaction not included in the GCS model, we can reproduce and interpret the main features the experimental capacitance of the Pt(111)–electrolyte interface. The model suggests a picture of the double layer with an increased ion concentration close to the interface as a consequence of a weak attractive ion–surface interaction, and a changing polarizability of the Pt(111)–water interface due to the potential-dependent water adsorption and orientation.

A molecular-level understanding of the electric double layer is important in order to understand many electrochemical processes and interfacial phenomena (1). Being an important catalytic material, platinum is one of the best-studied electrode materials, but detailed studies of its double-layer structure are remarkably scarce. The reason for the absence of detailed studies may lie in the fact that, except for Pt(111), none of the low-index planes of platinum exhibit a double-layer window, in which the metal is bare of adsorbates and can be considered ideally polarizable (2). The absence of a double-layer window, in which neither hydrogen or hydroxyl are adsorbed to the surface, renders the capacitance a combination of capacitive and pseudocapacitive contributions that is difficult to unequivocally separate, impeding detailed quantitative studies. Although the Pt(111) surface exhibits a small double-layer window in the range of 0.4 V to 0.6 V versus the reversible hydrogen electrode (RHE), in which the interface is considered free of adsorbates and ideally polarizable (2), the available capacitance data shows that under these conditions, even Pt(111) does not follow the expected textbook behavior (3).In the absence of any specific adsorption, the capacitance of the electric double layer of an ideally polarizable interface is expected to follow the Gouy–Chapman–Stern (GCS) model (4, 5). The GCS theory divides the total capacitance of the electric double layer Ctot into an “inner layer” or “Stern” capacitance Ci and the diffuse Gouy–Chapman capacitance C_GC:1CGCS=1Ci+1CGC .[1]The Gouy–Chapman capacitance CGC is computed by deriving the concentration of ions in the double layer from a Poisson–Boltzmann distribution including only electrostatic interactions. In the case of a symmetric electrolyte, this gives rise to the following expression for CGC:CGC(E)=(2z2e2εsε0ckBT)12cosh(ze(E−Epzc)2kBT),[2] where E is the potential at the Stern layer, Epzc is the potential of zero charge (PZC) of the interface, z is the charge number of the electrolyte ions, e is the unit of charge, εs is the dielectric constant of the solvent, ε0 is the vacuum permittivity, c is the bulk concentration of the electrolyte, kB is the Boltzmann constant, and T is the temperature. This expression should be accurate in the limit of (very) low electrolyte concentration close to the PZC, and it should be the dominant contribution to the capacitance at low electrolyte concentrations.Classical work by Grahame on the double layer of a mercury electrode in various electrolytes has confirmed the applicability of the GCS model at low electrolyte concentration (4, 6). However, in recent experiments, we have shown that the Pt(111)–perchloric acid interface, which is traditionally considered to be ideally polarizable, has a much higher differential capacitance than predicted by GCS theory and that the concentration-dependent capacitance does not follow the predictions of the GCS theory (3). In our original publication, we tentatively attributed this behavior to an (attractive) interaction between the ions and the electrode, which is not accounted for in GCS theory. More recently, we also developed a mean-field model (7), in which we showed that relatively weak ion–surface interaction strengths are sufficient to reproduce the observed experimental observations. A similar conclusion was reached in a recent theory paper by Schmickler (8).To improve our understanding of the nature of this interaction and the associated anomalous behavior of the diffuse double layer of Pt(111), we extend our capacitance measurements here to a range of electrolytes with different monovalent anions and cations, which are all considered to be nonspecifically adsorbed (Li⁺, Na⁺, K⁺, Cs⁺, ClO₄⁻, F⁻, and CH₃SO₃⁻). Combining these experimental investigations with theoretical modeling allows us to put forward a more refined model for the double-layer structure of Pt(111), in which both an attractive ion–surface interaction and field-dependent water adsorption to the interface play a central role. We believe that the significance of our model likely goes beyond the Pt(111)–electrolyte interface, as the interactions are not specific to that interface. Therefore, our results are an important step toward resolving the true structure of the electric double layer.     

Functional Materials Based on Cyclometalated Platinum(II) β-Diketonate Complexes: A Review of Structure–Property Relationships and Applications

Square planar organoplatinum(II) complexes have garnered immense interest in the area of materials research. The combination of the Pt(II) fragment with mono-, bi- tri- and tetradentate organic ligands gives rise to a large variety of complexes with intriguing properties, especially cyclometalated Pt(II) complexes in which ligands are connected through covalent bonds demonstrate higher stability, excellent photoluminescence properties, and diverse applications. The properties and applications of the Pt(II)-based materials can be smartly fine-tuned via a judicious selection of the cyclometalating as well as ancillary ligands. In this review, attempts have been made to provide a brief review of the recent developments of neutral Pt(II) organometallic complexes bearing bidentate cyclometalating ligands and β-diketonate ancillary ligands, i.e., (C^N)Pt(O^O) and (C^C)Pt(O^O) derivatives. Both small (monomeric, dimeric) and large (polymeric) materials have been considered. We critically assessed the role of functionalities (ligands) on photophysical properties and their impact on applications.     

Elastic Properties and Energy Loss Related to the Disorder–Order Ferroelectric Transitions in Multiferroic Metal–Organic Frameworks [NH4][Mg(HCOO)3] and [(CH3)2NH2][Mg(HCOO)3]

Elastic properties are important mechanical properties which are dependent on the structure, and the coupling of ferroelasticity with ferroelectricity and ferromagnetism is vital for the development of multiferroic metal–organic frameworks (MOFs). The elastic properties and energy loss related to the disorder–order ferroelectric transition in [NH₄][Mg(HCOO)₃] and [(CH₃)₂NH₂][Mg(HCOO)₃] were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The DSC curves of [NH₄][Mg(HCOO)₃] and [(CH₃)₂NH₂][Mg(HCOO)₃] exhibited anomalies near 256 K and 264 K, respectively. The DMA results illustrated the minimum in the storage modulus and normalized storage modulus, and the maximum in the loss modulus, normalized loss modulus and loss factor near the ferroelectric transition temperatures of 256 K and 264 K, respectively. Much narrower peaks of loss modulus, normalized loss modulus and loss factor were observed in [(CH₃)₂NH₂][Mg(HCOO)₃] with the peak temperature independent of frequency, and the peak height was smaller at a higher frequency, indicating the features of first-order transition. Elastic anomalies and energy loss in [NH₄][Mg(HCOO)₃] near 256 K are due to the second-order paraelectric to ferroelectric phase transition triggered by the disorder–order transition of the ammonium cations and their displacement within the framework channels, accompanied by the structural phase transition from the non-polar hexagonal P6₃22 to polar hexagonal P6₃. Elastic anomalies and energy loss in [(CH₃)₂NH₂][Mg(HCOO)₃] near 264 K are due to the first-order paraelectric to ferroelectric phase transitions triggered by the disorder–order transitions of alkylammonium cations located in the framework cavities, accompanied by the structural phase transition from rhombohedral R3¯c to monoclinic Cc. The elastic anomalies in [NH₄][Mg(HCOO)₃] and [(CH₃)₂NH₂][Mg(HCOO)₃] showed strong coupling of ferroelasticity with ferroelectricity.     

Influence of Fabrication Method and Surface Modification of Alumina Ceramic on the Microstructure and Mechanical Properties of Ceramic–Elastomer Interpenetrating Phase Composites (IPCs)

The paper presents experimental results of the work conducted to improve the adhesion between alumina ceramics and urea-urethane elastomer in the interpenetrating phase composites (IPCs), in which these two phases are interpenetrating three-dimensionally and topologically throughout the microstructure. Measurements of the contact angle, surface roughness, and shear tests were used to evaluate the effectivity and select the quantity of a silane coupling agent and the ceramic fabrication method. The tests were conducted using samples of dense alumina ceramic obtained by three- or four-step methods. In the four-step process, hot isostatic pressing (HIP) was applied additionally. As a result of the coupling agent coat and HIP application, the ceramic substrate wettability by the elastomer was improved. The water contact angle was reduced from 80 to 60%. In the next step, porous ceramic preforms were fabricated using HIP sintering and a solution of silane coupling agent treated their surface. The composites were produced using vacuum-pressure infiltration of porous alumina ceramics by urea-urethane elastomer in liquid form. The influence of the coupling agent application on the microstructure and mechanical properties of the composites was estimated. The microstructure of the composites was identified using SEM microscopy and X-ray tomography. As a result of using the coupling agent, residual porosity decreased from 7 to 2%, and compressive strength, as well as stress at a plateau, increased by more than 20%, from 25 to 33 MPa and from 15 to 24 MPa, respectively, for the composites fabricated by infiltration ceramic preforms with 40% of porosity.     

The Effect of (Mg,Zn)12Ce Phase Content on the Microstructure and the Mechanical Properties of Mg–Zn–Ce–Zr Alloy

The quantitative study of rare earth compounds is important for the improvement of existing magnesium alloy systems and the design of new magnesium alloys. In this paper, the effective separation of matrix and compound in Mg–Zn–Ce–Zr alloy was achieved by a low-temperature chemical phase separation technique. The mass fraction of the (Mg, Zn)₁₂Ce compound was determined and the effect of the (Mg, Zn)₁₂Ce phase content on the heat deformation organization and properties was investigated. The results show that the Mg–Zn–Ce compound in both the as-cast and the homogeneous alloys is (Mg, Zn)₁₂Ce. (Mg, Zn)₁₂Ce phase formation depends on the content and the ratio of Zn and Ce elements in the initial residual melt of the eutectic reaction. The Zn/Ce mass ratios below 2.5 give the highest compound contents for different Zn contents, 5.262 wt.% and 7.040 wt.%, respectively. The increase in the amount of the (Mg, Zn)₁₂Ce phase can significantly reduce the critical conditions for dynamic recrystallization formation. Both the critical strain and the stress decrease with increasing rare earth content. The reduction of the critical conditions and the particle-promoted nucleation mechanism work together to increase the amount of dynamic recrystallization. In addition, it was found that alloys with 6 wt.% Zn elements tend to undergo a dynamic recrystallization softening mechanism, while alloys with 3 wt.% Zn elements tend to undergo a dynamic reversion softening mechanism.     

The Effect of Surface Substrate Treatments on the Bonding Strength of Aluminium Inserts with Glass-Reinforced Poly(phenylene) Sulphide

Materials composed of a polymer matrix reinforced with carbon/glass fibres providing lightweight and superior mechanical properties are widely used as structural components for automotive and aerospace applications. However, such parts need to be joined with various metal alloys to obtain better mechanical performance in many structural elements. Many studies have reported enhancements in polymer–metal bonding using adhesives, adhesive/rivet combined joints, and different surface treatments. This study investigated the influences of various surface treatments on the adhesion between glass-reinforced poly(phenylene) sulphide (PPS) and aluminium alloy during the injection over-moulding process. Adhesion strength was evaluated via the shear test. Correlations for the shear strength of the polymer–metal with different metal–substrate treatments were studied. Since the strongest bonding was attained in the treatment with the highest roughness, this value, as it determines the level of micromechanical interlocking of connected materials, seems to be a critical factor affecting the adhesion strength. Three-dimensional (3D) topographic images characterized with a 3D optical microscope indicated that there was a meaningful influence exerted by the interface topologies of the aluminium substrates used for the over-moulding process. The results further indicated that increases in a substrate’s surface energy in connection with atmospheric plasma treatments negatively influence the final level of the bonding mechanism.     

Influence of Carbon on the Microstructure Evolution and Hardness of Fe–13Cr–xC (x = 0–0.7 wt.%) Stainless Steel

The influence of carbon on the phase transformation behavior of stainless steels with the base chemical composition Fe–13Cr (wt.%), and carbon concentrations in the range of 0–0.7 wt.%, was studied at temperatures between −196 °C and liquidus temperature. Based on differential scanning calorimetry (DSC) measurements, the solidification mode changed from ferritic to ferritic–austenitic as the carbon concentration increased. The DSC results were in fair agreement with the thermodynamic equilibrium calculation results. In contrast to alloys containing nearly 0% C and 0.1% C, alloys containing 0.2–0.7% C exhibited a fully austenitic phase stability range without delta ferrite at high temperatures. Quenching to room temperature (RT) after heat treatment in the austenite range resulted in the partial transformation to martensite. Due to the decrease in the martensite start temperature, the fraction of retained austenite increased with the carbon concentration. The austenite fraction was reduced by cooling to −196 °C. The variation in hardness with carbon concentration for as-quenched steels with martensitic–austenitic microstructures indicated a maximum at intermediate carbon concentrations. Given the steady increase in the tetragonality of martensite at higher carbon concentrations, as confirmed by X-ray diffraction measurements, the variation in hardness with carbon concentration is governed by the amount and stability of austenite.     

Influence of the β− Radiation/Cold Atmospheric-Pressure Plasma Surface Modification on the Adhesive Bonding of Polyolefins

The goal of this research was to examine the effect of two surface modification methods, i.e., radiation cross-linking and plasma treatment, on the adhesive properties and the final quality of adhesive bonds of polypropylene (PP), which was chosen as the representative of the polyolefin group. Polymer cross-linking was induced by beta (accelerated electrons—β⁻) radiation in the following dosages: 33, 66, and 99 kGy. In order to determine the usability of β⁻ radiation for these applications (improving the adhesive properties and adhesiveness of surface layers), the obtained results were compared with values measured on surfaces treated by cold atmospheric-pressure plasma with outputs 2.4, 4, and 8 W. The effects of both methods were compared by several parameters, namely wetting contact angles, free surface energy, and overall strength of adhesive bonds. Furthermore, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) were conducted. According to our findings the following conclusion was reached; both tested surface modification methods significantly altered the properties of the specimen’s surface layer, which led to improved wetting, free surface energy, and bond adhesion. Following the β⁻ radiation, the free surface energy of PP rose by 80%, while the strength of the bond grew in some cases by 290% in comparison with the non-treated surface. These results show that when compared with cold plasma treatment the beta radiation appears to be an effective tool capable of improving the adhesive properties and adhesiveness of PP surface layers.     

Fluorescently Labeled Gadolinium Ferrate/Trigadolinium Pentairon(III) Oxide Nanoparticles: Synthesis,Characterization, In Vivo Biodistribution,and Application for Visualization of Myocardial Ischemia–Reperfusion Injury

Various gadolinium compounds have been proposed as contrasting agents for magnetic resonance imaging (MRI). In this study, we suggested a new synthesis method of gadolinium ferrate/trigadolinium pentairon(III) oxide nanoparticles (GF/TPO NPs). The specific surface area of gadolinium ferrate (GdFeO₃) and trigadolinium pentairon(III) oxide (Gd₃Fe₅O₁₂) nanoparticles was equal to 42 and 66 m²/g, respectively. The X-ray diffraction analysis confirmed that the synthesized substances were GdFeO₃ and Gd₃Fe₅O₁₂. The gadolinium content in the samples was close to the theoretically calculated value. The free gadolinium content was negligible. Biodistribution of the GF/TPO NPs was studied in rats by fluorescent imaging and Fe²⁺/Fe³⁺ quantification demonstrating predominant accumulation in such organs as lung, kidney, and liver. We showed in the in vivo rat model of myocardial ischemia–reperfusion injury that GF/TPO NPs are able to target the area of myocardial infarction as evidenced by the significantly greater level of fluorescence. In perspective, the use of fluorescently labeled GF/TPO NPs in multimodal imaging may provide basis for high-resolution 3D reconstruction of the infarcted heart, thereby serving as unique theranostic platform.     

An Enhanced Understanding of the Powder Bed Fusion–Laser Beam Processing of Mg-Y3.9wt%-Nd3wt%-Zr0.5wt% (WE43) Alloy through Thermodynamic Modeling and Experimental Characterization

Powder Bed Fusion–Laser Beam (PBF–LB) processing of magnesium (Mg) alloys is gaining increasing attention due to the possibility of producing complex biodegradable implants for improved healing of large bone defects. However, the understanding of the correlation between the PBF–LB process parameters and the microstructure formed in Mg alloys remains limited. Thus, the purpose of this study was to enhance the understanding of the effect of the PBF–LB process parameters on the microstructure of Mg alloys by investigating the applicability of computational thermodynamic modelling and verifying the results experimentally. Thus, PBF–LB process parameters were optimized for a Mg WE43 alloy (Mg-Y_3.9wt%-Nd_3wt%-Zr_0.5wt%) on a commercially available machine. Two sets of process parameters successfully produced sample densities >99.4%. Thermodynamic computations based on the Calphad method were employed to predict the phases present in the processed material. Phases experimentally established for both processing parameters included α-Mg, Y₂O₃, Mg₃Nd, Mg₂₄Y₅ and hcp-Zr. Phases α-Mg, Mg₂₄Y₅ and hcp-Zr were also predicted by the calculations. In conclusion, the extent of the applicability of thermodynamic modeling was shown, and the understanding of the correlation between the PBF–LB process parameters and the formed microstructure was enhanced, thus increasing the viability of the PBF–LB process for Mg alloys.     

The Composites of PCL and Tetranuclear Titanium(IV)–Oxo Complex with Acetylsalicylate Ligands—Assessment of Their Biocompatibility and Antimicrobial Activity with the Correlation to EPR Spectroscopy

In our research, we have focused on the biological studies on composite materials produced by the dispersion of titanium(IV)–oxo complex (TOC) with acetylsalicylate ligands in a poly(ε-caprolactone) (PCL) matrix, which is a biodegradable thermoplastic polymer increasingly used in the production of medical devices. Using PCL as a matrix for the biologically active compounds, such as antimicrobial agents, antibiotics or other active medical substances, from which these individuals can be gradually released is fully understable. Composites of PCL + nTOC (n = 10, 15 and 20 wt.%) have been produced and, in such a form, the biological properties of TOCs have been estimated. Direct and indirect cytotoxicity studies have been performed in vitro on L929 and human umbilical vein endothelial cells (HUVEC) cell lines. The antibacterial and antifungal activity of the PCL + TOC samples have been assessed against two Staphylococcus aureus (ATCC 6538 and ATCC 25923) reference strains, two Escherichia coli (ATCC 8739 and ATCC 25922) reference strains and yeast of Candida albicans ATCC 10231. Obtained results have been correlated with electron paramagnetic resonance (EPR) spectroscopy data. We could conclude that photoexcitation by visible light of the surface of PCL + nTOC composite foils lead to the formation of different paramagnetic species, mainly O⁻, which slowly disappears over time; however, their destructive effect on bacteria and cells has been proven.     

Temperature and Infill Density Effects on Thermal,Mechanical and Shape Memory Properties of Polylactic Acid/Poly(ε-caprolactone) Blends for 4D Printing

Polylactic acid (PLA)/poly(ε-caprolactone) (PCL) blends have exhibited good shape memory properties and degradable characteristics in various 4D printing fields such as biomedicine, flexible electronics, and soft robotics, where the service temperature fluctuates easily by environment temperature and polymer characteristics. In this work, printed PLA/PCL 4D samples with different infill densities were prepared by material extrusion printing of pre-extruded filaments and characterized under different temperatures. The results show that the microstructures of printed samples are not influenced by printing process and have similar unique orientation as that of filaments. The thermal properties are stable and show obvious phase transition temperatures, while the mechanical properties decrease slightly in low temperature region and then decrease rapidly when temperature is over 60 °C. The increase in infill density can further improve the storage modulus more than 40% and have no significant influence on the thermal properties. The printed samples also exhibit good shape memory performances with fast recovery speeds less than 22 s. Furthermore, a two-step model is provided to predict the effective modulus of printed PLA/PCL samples and agrees well with experimental data. The results prove that temperature and infill density have different influences on the thermal, mechanical and shape memory properties of PLA/PCL blends.     

Effect of Partial Ba Substitutions on the Crystallization of Sr2TiSi2O8 (STS) Glass–Ceramics and on the Generation of a SAW Signal at High Temperatures

Because of their characteristics, including a d₃₃ of 10–15 pC/N and high stability up to temperatures over 1000 °C, polar glass–ceramics containing fresnoite crystals can be regarded as highly effective materials for applications requiring piezoelectricity at high temperatures. In the present paper we investigate barium substitutions in an Sr-fresnoite (STS) glass–ceramic. Two aspects are studied: first, the effect of the substitution on the preferential orientation of the crystallization, and second, the ability of the glass–ceramics to generate and propagate surface acoustic waves (SAW) at high temperatures. XRD analyses show that a 10 at.% substitution of Ba allows us to keep a strong preferential orientation of the (00l) planes of the fresnoite crystals down to more than 1 mm below the surfaces. Higher substitution levels (25 and 50 at.%), induce a non-oriented volume crystallization mechanism that competes with the surface mechanism. SAW devices were fabricated from glass–ceramic substrates with 0, 10 and 25 at.% Ba substitutions. Temperature testing reveals the high stability of the frequency and delay for all of these devices. The glass–ceramic with a 10 at.% Ba substitution gives the strongest amplitude of the SAW signal. This is attributed to the high (00l) preferential orientation and the absence of disoriented volume crystallization.