Partial Crystallization Research Articles

Effect of annealing on the tribological behavior of Zr-based bulk metallic glass

Bulk Metallic Glasses (BMGs) are promising materials for several applications owing to their high elastic limit and resistance to permanent deformation. However, BMGs have lower wear resistance than their crystalline counterparts during dry sliding. The formation of a composite material with crystalline phases dispersed in the BMG matrix through devitrification and partial crystallization at elevated temperatures has recently been proposed as an effective way to improve the wear resistance. However, our understanding of the origin of the improved wear behavior of annealed BMGs is still elusive. Here, a systematic evaluation of the effect of annealing temperature (from temperatures lower than the BMG glass transition temperature to temperatures higher than the BMG recrystallization temperature) on the friction and wear response of a Zr-based BMG, namely Vit105 (Zr52.5Cu17.9Ni14.6Al10Ti5), was performed. The results indicate that annealing Vit105 improves its wear resistance while also reducing the steady-state friction response when the annealing temperature is close to the glass transition temperature. Notably, the formation of a transfer film on the sapphire countersurface is highly dependent on the applied normal load and sliding time. Finally, the wear mechanism was found to be strongly dependent on the annealing temperature as a transition from a predominantly adhesive wear mechanism to an abrasive-dominated one was observed as the annealing temperature crossed the glass transition temperature. Altogether, the results of this work aid to our understanding of the tribological behavior of Zr-based BMGs in general, while also providing clues to strategies for the effective use of BMGs in tribological applications.

An Enhanced Bioactive Glass Composition with Improved Thermal Stability and Sinterability.

The development of new bioactive glasses (BGs) with enhanced bioactivity and improved resistance to crystallization is crucial for overcoming the main challenges faced by commercial BGs. Most shaping processes require thermal treatments, which can induce partial crystallization, negatively impacting the biological and mechanical properties of the final product. In this study, we present a novel bioactive glass composition, S53P4_MSK, produced by a melt-quench route. This novel composition includes magnesium and strontium, known for their therapeutic effects, and potassium, recognized for improving the thermal properties of bioactive glasses. The thermal properties were investigated through differential thermal analysis, heating microscopy and sintering tests from 600 °C to 900 °C. These characterizations, combined with X-ray diffraction analysis, demonstrated the high sinterability without crystallization of S53P4_MSK, effectively mitigating related issues. The mechanical properties-elastic modulus, hardness and fracture toughness-were evaluated on the sintered sample by micro-indentation, showing high elastic modulus and hardness. The bioactivity of the novel BG was assessed following Kokubo's protocol and confirmed by scanning electron microscopy, X-ray energy dispersive spectroscopy, and Raman spectroscopy. The novel bioactive glass composition has shown high sinterability without crystallization at 700 °C, along with good mechanical properties and bioactivity.

Crystallization Kinetics of an Equimolar Liquid Crystalline Mixture and Its Components

This new equimolar mixture comprises the liquid crystalline compounds MHPOBC and partially fluorinated 3F2HPhF6. The phase sequence of the mixture was determined by differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction, and broadband dielectric spectroscopy. The enantiotropic smectic A*, C*, and CA* phases were observed for the mixture. Only partial crystallization of the mixture was observed during cooling at 2–40 K/min, and the remaining smectic CA* phase underwent vitrification. In contrast, the crystallization of the pure components was complete or almost complete for the same range of cooling rates. The kinetics of the non-isothermal and isothermal crystallization of the mixture and its pure components were investigated by differential scanning calorimetry. The non-isothermal data were analyzed by the isoconversional method, while the isothermal data were analyzed using the Avrami model. As is typical, the nucleation-controlled crystallization kinetics were observed.

Generalized <i>Р—Т</i> path and fluid regime of exhumation of metapelites of the central zone of the Limpopo complex, south Africa

The P–T paths of exhumation of Precambrian granulite complexes at the craton boundaries usually include two stages: sub-isothermal decompression and a decompression–cooling stage with a more gentle P–T path. Our goal is to understand the possible causes of the change in the slope of the P–T path of exhumation of the Central Zone (CZ) of the Limpopo granulite complex (South Africa), located between the Kaapvaal and Zimbabwe cratons. For this purpose, rocks (mainly, metapelites) from various structural positions within the Central Zone, i.e. dome structures, regional crossfolds, local and regional shear-zones, were studied. Metapelites are gneisses of similar bulk composition. Relics of leucosomes composed of quartz-feldspar aggregates with garnet and biotite are variously manifested in rocks, and melanocratic areas enriched in cordierite usually mark micro-shear-zones that envelope and/or break garnet porphyroblasts. Study of polymineral (crystallized melt and fluid) inclusions in garnet, its zoning with respect to the major (Mg, Fe, Ca) and some trace (P, Cr, Sc) elements, fluid inclusions in quartz, as well as phase equilibria modeling (PERPLE_X) showed that rocks coexisted with granite melts and aqueous-carbonic-salt fluids (aH2O = 0.74–0.58) at the peak of metamorphism at 800–850°C and 10–11 kbar. Partial melting initiated sub-isothermal exhumation of rocks to 7.5–8 kbar during diapirism of granitic magmas in the Neoarchean (2.65–2.62 Ga). This is reflected in the specific zoning of garnet grains in terms of the grossular content. A change in the rheology of rocks as a result of partial removal and crystallization of the melt activated shear-zones during further exhumation to 6–5.5 kbar along the P–T decompression–cooling path of 95–100°/kbar, reflecting a slower uplift of rocks in the middle crust. This process was resumed due to thermal effects and interaction of rocks with aqueous fluids (aH2O 0.85) in the Paleoproterozoic (~2.01 Ga). Such a scenario of metamorphic evolution implies that the Limpopo granulite complex, in general, and its Central Zone, in particular, are the result of the evolution of an ultra-hot orogen, where vertical tectonic movements associated with diapirism were conjugate with horizontal tectonic processes caused by the convergence of continental blocks.

Processes controlling magma fertility at Buenavista del Cobre porphyry copper deposit (Cananea, México): A new petrogenetic model based on zircon U-Pb dating and apatite geochemistry

The Buenavista del Cobre is a world-class porphyry Cu-Mo deposit located in the Cananea Mining District, northern Sonora, México. Using zircon U-Pb dating, we show that the Proterozoic Cananea Granite, unconformably overlain regionally by Paleozoic limestones hosting skarn deposits underlies the present-day pit. We also present new crystallization ages for host rocks of copper mineralization in the District, dating for the first time a volcanic rock of the Henrietta Formation at 186.8 ± 1.1/3.0 Ma and the El Torre Syenite at 176.3 ± 1.1/2.9 Ma. Zircon U-Pb dating of the different porphyritic bodies reveals that the magmatic activity at Buenavista del Cobre lasted at least 4 Myr, from 59.7 ± 0.5/1.1 Ma to 56.1 ± 0.2/0.9 Ma. The deposit is composed by several porphyry intrusions referred to as “ore-rich” and “ore-poor” based on their individual metal contributions, which provides the opportunity to study the origin and processes enhancing magma fertility in an individual deposit. Combining our new geochronological dataset with geochemistry of apatite from the different porphyries allows us to propose a new petrogenetic model for the Buenavista del Cobre deposit. As the apatite Eu and Ce anomalies overlap with no clear difference between the ore-rich and ore-poor intrusions, we propose that the magmatic oxidation states of the magmas were similar. However, differences in apatite REE signatures, as well as variations in apatite Sr compositions between the two groups suggest that fractional crystallization processes in the parental magma influence the fertility of the porphyries. Additionally, apatite Cl contents of ore-rich porphyry intrusions are higher (>0.4 wt%) than the ore-poor intrusions (<0.2 wt%), suggesting an important role of the initial Cl content of the magmas in the mineralization process. These observations give new insights on the petrogenetic processes at origin of porphyry magma fertility. We propose that the evolution of the parental melt by fractional crystallization of hydrous minerals (hornblende) at upper crustal levels induced low H2O content of the residual magma, resulting in the formation of ore-poor porphyries. In contrast, we suggest that fractionation of anhydrous minerals (plagioclase) increased the H2O content in the residual melt, leading to the formation of ore-rich porphyries. Our new data allow us to propose an original genetic model for the Buenavista del Cobre deposit, which involves two cycles of supply, cooling and partial crystallization. This contribution shows that petrogenetic processes controlling porphyry copper magmas fertility are recorded in the composition of apatite at the deposit scale and highlights the importance of considering apatite geochemistry as an exploration tool.

Partial crystallization in Pd-BMG systems: From understanding structure towards influencing functionality through temperature-time series

Small quantities of crystalline domains created in an amorphous matrix are seen as an active driver for enhanced properties in bulk metallic glasses (BMGs). We investigated partial crystallization and phase transformations through a series of isotherms at 370°C performed on amorphous Pd-based BMG samples with the nominal composition of Pd43Cu27Ni10P20 (Pd-BMG) and a density of 9.425 g/cm3. X-ray based methods such as X-ray diffraction (XRD) and phase enhanced micro-computed tomography (μ-CT) have been pushed to their limits for studying atomic structure and morphology, while time available before crystallization has additionally been investigated via differential scanning calorimetry (DSC), and are combined with optical microscopy (OM), scanning electron microscopy (SEM), and hardness measurements for their mechanical properties. We reveal that Pd-based BMG samples isothermally treated at 370 °C start to crystallize after 20 min and still undergo phase transformations and recrystallization even after being fully crystalline after 60 min of the isothermal treatment. Interestingly, 3D phase enhanced micro-computed tomography shows a clear separation of two domains of slightly different densities. We highlight X-ray tomographic scans, allowing the 3D spatial visualization of extremely low-density contrast in different material domains, thus providing a multi-scale physical description of the Pd-BMG system. Interesting is the fact, that the re-crystallization is not homogenous and the crystalline domains can reach large size of (100–200 μm) in an amorphous matrix.

Structure transformation in amorphous Fe-B ribbon under laser scanning

Amorphous Fe86B14 alloy produced by the melt quenching technique was processed by pulsed fibber laser in scanning mode with various scanning speed and laser power. X-ray diffraction method was used to study the laser-induced structure evolution in the amorphous ribbon. Nanosized grains of α-Fe phase were observed as a result of partial crystallization.

Interaction behaviour of alloy 690 upon exposure to P2O5 containing borosilicate glass at simulated vitrification conditions

This study investigates the interaction between alloy 690 and two types of glasses: pristine borosilicate and P2O5-containing borosilicate glass, at typical glass pouring temperatures encountered during the vitrification of high-level radioactive waste in the back-end of Nuclear Fuel Cycle (NFC). Partial crystallization of both glasses was observed at the alloy 690/glass interface, with certain, though not entirely identical, crystalline phases forming at the interface. The density of these crystalline phases is significantly higher than that of the surrounding glass, which raises concerns about these reaction products settling at the bottom of the furnace. Such sedimentation could potentially obstruct the freeze valve, thereby halting the vitrification process. Additionally, intergranular grooves on the alloy surface exposed to P2O5-containing borosilicate glass were found to disappear with prolonged exposure. This phenomenon is attributed to the strong corrosive action of the highly basic and oxidizing P2O5-bearing glass, leading to the peeling away of the entire exposed surface of alloy 690.

A New Approach Toward Extreme Thermal Stability of Femtosecond Laser Induced Modifications in Glasses

AbstractImprinting thermally stable transformations by femtosecond laser in glass would benefit the development of optical sensors dedicated to harsh environments including combustors, nuclear reactors, aircraft engines, or metal/ceramic manufacturing processes. While glass brings undeniable assets over refractory crystalline materials like shaping ability (e.g., optical fiber form), one key challenge is to prevent the erasure of induced transformations at high temperatures and for long periods. In this article, the role of glass composition and viscosity to achieve modifications stable at high temperatures is first reviewed, providing a comprehensive roadmap for engineers in optics and photonics. While silica appears to be the candidate of choice, it is revealed that binary aluminosilicates can compete and sometimes surpass it. The hypothesis is formulated and investigated that a hybrid glass‐crystalline nano‐structuring can imprint ultra‐stable modifications inside glass. Laser‐induced modifications in Al2O3‐SiO2 and ZrO2‐Al2O3‐SiO2 glasses reveal a partial crystallization, shaped into a lamellar structure and orientable with laser light polarization. These birefringent structures can withstand temperatures up to 1300 °C for 30 minutes. Even after erasure, a positive index contrast persists, up to 1650 °C for binary 60Al2O3‐40SiO2 (mol%). This is the first observation of this kind of persisting index contrast, paving the way to ultra‐stable glass‐based optical waveguiding.

Trace element abundances in mineral phases and the groundmass of ocean island basalts

Incompatible trace elements are important tracers in igneous petrogenesis for determining processes acting: (i) prior to partial melting on magma sources; (ii) during partial melting, fractional crystallization or contamination of magmas, and (iii) after emplacement of lavas or intrusive rocks close to Earth's surface. Of particular interest are the high field strength elements (HFSE: Ti, Zr, Nb, Hf, Ta) which are incompatible elements with high valence states that are also relatively immobile in aqueous fluids. Abundances of Ti, Ta, and Nb (TITAN) in ocean island basalts (OIB) have been suggested to reflect recycled oceanic crust in mantle source regions, due to retention of these elements in subducted eclogitic rutile. Some of these elements have also been used to determine ‘canonical’ trace element ratios, such as Nb/U and Ta/U, that are considered invariant during petrogenetic processes. In this contribution, we present an extensive set of in situ trace element data for olivine, clinopyroxene, oxide minerals and groundmass for a suite of well-studied ocean island basalt (OIB) lavas from the Canary Islands, Azores, Samoa, Tubuai and La Réunion. The data were obtained using laser-ablation inductively coupled plasma mass spectrometry, and we also report a new open-source reduction routine for abundance determination using this method. Mineral-groundmass partitioning behavior is determined for olivine, clinopyroxene and oxides, showing that these are consistent with published partition coefficients for clinopyroxene and olivine, but are more variable for oxide phases. This variability is due to the wide variety of oxide phases possible in OIB (e.g., Cr-spinel, ilmenite, titanomagnetite) and their formation within the crystallization sequence. The new data shows that Nb and Ta budgets are dominated by fine-grained groundmass, as are most other incompatible trace elements, while the Ti budget is divided between clinopyroxene, oxide and groundmass. Modally reconstructed TITAN anomalies closely reproduce bulk rock compositions in samples with >40 % groundmass. Olivine and clinopyroxene fractional crystallization have negligible effects on TITAN anomalies, while oxide fractionation has more marked effects, with Ti anomalies being most affected. Variability in the HFSE in OIB and their association with other elements (e.g., Nb/U and Ta/U) can reflect source characteristics, although careful screening for petrogenetic effects should be done prior to ascribing significance to TITAN anomalies or canonical trace element ratios.

Solid-liquid phase behaviour of novel kosmotrope/chaotrope binary mixtures involving sarcosine

The concept of deep eutectic solvents (DESs) has been recently applied to osmolytes (kosmotropes or chaotropes), small organic molecules responsible for stabilization of proteins and other biomolecules in various biological systems. In this study the combinations of the kosmotrope sarcosine (Sar) with chaotrope urea (U) or guanidine hydrochloride (G) across various molar ratios was studied experimentally by the differential scanning calorimetry and infrared spectroscopy. Theoretical prediction of thermodynamic interaction terms based on screening of the charge density was used to support interpretation of experimental findings. Phase diagrams were constructed for both Sar-U and Sar-G systems and eutectic behaviour was identified. Neither of the two systems showed depression of the eutectic temperature compared to its ideal solution values, and therefore neither of the systems could be classified as a deep eutectic solvent in the classical sense. The Sar-G system did show at least partial crystallization of its eutectic solution upon cooling. However, the eutectic solution of the Sar-U system remained amorphous at decreased temperatures, and the phenomenon was attributed to be kinetic in nature and originating from strong intermolecular hydrogen bonding interactions of the components. Thus, it was speculated that the role of osmolytes in stabilizing cellular biomolecules might not come from the thermodynamics only.

Optimizing Manufacturing of Zr–Cu–AI–NI Metallic Glasses via Laser Metal Deposition

Recently, it was discovered that the cutting-edge technique known as laser powder bed fusion (LPBF) is the best way to produce Zr-based bulk glasses made of metal (BMGs). While LPBF gives greater versatility, current state-of-the-art production techniques like copper mold casting and arc-melting have limits when it comes to implementing complicated designs. Furthermore, LPBF enables a delicate balance to be struck between producing intricate characteristics and sustaining suitable temperatures all through the whole operation. Because of its exceptional features and practical availability, this research focuses on optimizing the process variables for a specific Zr-based alloy, AMZ4, which is produced by additive manufacturing in order to optimize both its mechanical and thermal characteristics. Belonging to the class of zirconium-based alloys known as bulk metallic glasses (BMG), Zr57Cu15Ni10AI5 (or Vit-106) has an excellent glass-forming ability and shows great promise. By casting, a BMG alloy may be transformed into workpieces that are about one centimeter in size in all three dimensions. Nevertheless, crystallization is induced when the cast size is further increased since it reduces the cooling rate. By building a workpiece from many melt sections with the cooling rate maintained above the critical one, selective laser melt (SLM) is an established technique for overcoming size restrictions for BMGs. Partially crystallized BMG is now an issue with SLM-obtained components. The effect of SLM process variables on partial crystallization is investigated in this paper. You may regulate the size and intensity of the inclusion by altering the speed of the laser scanning. Microhardness and wear resistance may be improved by incorporating submicron crystalline inclusions into the amorphous matrix by SLM.

Thermal Weathering of 3D-Printed Lunar Regolith Simulant Composites.

The production of lunar regolith composites is a promising venture, especially when enabled by extrusion-based additive manufacturing techniques such as direct ink write. However, both three-dimensional (3D) printing production and usage of polymer composites containing regolish on the lunar surface are challenges due to harsh environmental conditions such as severe thermal cycling. While thermal degradation in polymer composites under thermal cycling has been studied, there is limited understanding of how polymer properties impact the mechanical performance of lunar regolith composites when both printing and usage are carried out under extreme thermal conditions. Here, we aim to bridge that gap through the creation of composites containing a lunar Highlands regolith simulant suspended in an ultraviolet (UV) curable binder, which were printed at -30 °C and thermally cycled between weekly lunar day (127 °C) and weekly night (-190 °C) temperatures. We validate that thermal stresses cause both physical and chemical degradation since the regolith simulant composites become stiffer, more porous, and show yellowing after exposure to thermal cycling. Moreover, we indicate that chemical degradation mechanisms seem to compete with residual polymerization in certain formulations. We attribute this phenomenon to partial crystallization of monomer species during printing at -30 °C, resulting in low vinyl bond conversion during initial curing. The results presented here shed light on the intricate interplay between thermal stresses, uncured polymer properties, and degradation mechanisms, which can help guide future use cases of regolith composites for lunar infrastructure needs.

Peculiar photoelectrochemical activity of zinc oxide and tin dioxide

Zinc oxide thin films made by pulsed reactive magnetron sputtering combined with RF ECWR plasma on FTO or ITO substrates exhibit high photoelectrochemical activity for water splitting under UV light, but are unstable against photocorrosion. It can be suppressed by a protective layer of SnO2 made by atomic layer deposition. The SnO2 layer is quasi-amorphous in the as-received state, but the thermal treatment causes partial crystallization to cassiterite, without significant change of the optical band gap. Ferrocene in acetonitrile electrolyte solution is a useful redox probe for the blocking-quality tests of thin films of n-semiconductors. Both ZnO and SnO2 are sensitive to irreversible electrochemical doping at potentials negative to the flatband potential. The flipping of electrochemical work functions of the Zn-terminated (0001) and O-terminated (000–1) faces of ZnO (wurtzite) takes place in acetonitrile vs. aqueous electrolyte solutions. The potentials for photocurrent onset are near the flatband potentials in an aqueous electrolyte solution for both ZnO and SnO2.

Design of FDM fabricated poly-lactic acid parts with forced-air cooling speed as the new control parameter to tune its shape memory effect

Poly lactic acid (PLA) as one of the shape memory polymers has extensively been used as the material in the 3D printing by fused deposition modeling process. In this study, we introduced the forced-air cooling speed as new control parameter in the fabrication process. A commercial material extrusion printer was retrofitted with a control module of forced-air cooling system. The shape memory effects of the PLA printed in different cooling speeds from 0–5 m s−1 were first measured by submerging the printed coupon specimens into water bath at recovery temperature. It is found that the changes in dimensions were mainly anisotropic and dependent of the raster angle in printing, in addition to the controlled cooling speed. The shape memory strains were roughly in linear trend with the magnitude of cooling air speed. In other words, the shape memory effect of the PLA can be easily controlled by the cooling air speed in fabrication. X-ray diffraction measurement on the specimens before and after recovery treatment confirmed the shape memory effect was related to the partial crystallization of molecular structure. Moreover, the different cooling air speeds also induced different thermal stresses in the printed specimens which manifest its important role in the total shape memory strain. Finally, the proposed theoretical beam formulation for the recovery bending deflection was shown to have good prediction accuracy comparing with experimental measurements.

Porphyrin Photosensitizers into Polysaccharide-Based Biopolymer Hydrogels for Topical Photodynamic Therapy: Physicochemical and Pharmacotechnical Assessments.

Photodynamic therapy (PDT) is an emerging treatment modality that utilizes light-sensitive compounds, known as photosensitizers, to produce reactive oxygen species (ROS) that can selectively destroy malignant or diseased tissues upon light activation. This study investigates the incorporation of two porphyrin structures, 5-(4-hydroxy-3-methoxyphenyl)-10,15,20-tris-(4-acetoxy-3-methoxyphenyl) porphyrin (P2.2.) and 5,10,15,20-tetrakis-(4-acetoxy-3-methoxyphenyl) porphyrin (P2.1.), into hydroxypropyl cellulose (HPC) hydrogels for potential use in topical photodynamic therapy (PDT). The structural and compositional properties of the resulting hydrogels were characterized using advanced techniques such as Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), atomic force microscopy (AFM), UV-Visible (UV-Vis) spectroscopy, and fluorescence spectroscopy. FTIR spectra revealed a slight shift of the main characteristic absorption bands corresponding to the porphyrins and their interactions with the HPC matrix, indicating successful incorporation and potential hydrogen bonding. XRD patterns revealed the presence of crystalline domains within the HPC matrix, indicating partial crystallization of the porphyrins dispersed within the amorphous polymer structure. TGA results indicated enhanced thermal stability of the HPC-porphyrin gels compared to 10% HPC gel, with additional weight loss stages corresponding to the thermal degradation of the porphyrins. Rheological analysis showed that the gels exhibited pseudoplastic behavior and thixotropic properties, with minimal impact on the flow properties of HPC by P2.1., but notable changes in viscosity and shear stress with P2.2. incorporation, indicating structural modifications. AFM imaging revealed a homogeneous distribution of porphyrins, and UV-Vis and fluorescence spectroscopy confirmed the retention of their photophysical properties. Pharmacotechnical evaluations showed that the hydrogels possessed suitable mechanical properties, optimal pH, high swelling ratios, and excellent spreadability, making them ideal for topical application. These findings suggest that the porphyrin-incorporated HPC hydrogels have significant potential as effective therapeutic agents for topical applications.

Complex dynamics of partially freezable confined water revealed by combined experimental and computational studies

We investigate water dynamics in mesoporous silica across partial crystallization by combining broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and molecular dynamics simulations (MDS). Exploiting the fact that not only BDS but also NMR field-cycling relaxometry and stimulated-echo experiments provide access to dynamical susceptibilities in broad frequency and temperature ranges, we study both the fully liquid state above the melting point Tm and the dynamics of coexisting water and ice phases below this temperature. It is found that partial crystallization leads to a change in the temperature dependence of rotational correlation times τ, which occurs in addition to previously reported dynamical crossovers of confined water and depends on the pore diameter. Furthermore, we observe that dynamical susceptibilities of water are strongly asymmetric in the fully liquid state, whereas they are much broader and nearly symmetric in the partially frozen state. Finally, water in the nonfreezable interfacial layer below Tm does not exhibit a much debated dynamical crossover at ∼220 K. We argue that its dynamics is governed by a static energy landscape, which results from the interaction with the bordering silica and ice surfaces and features a Gaussian-like barrier distribution. Consistently, our MDS analysis of the motional mechanism reveals a hopping motion of water in thin interfacial layers. The rotational correlation times of the confined ice phases follow Arrhenius laws. While the values of τ depend on the pore diameter, freezable water in various types of confinements and mixtures shows similar activation energies of Ea ≈ 0.43 eV.

Competition between bead boundary fusion and crystallization kinetics in material extrusion-based additive manufacturing

Assembling polymer beads into well-defined 3D geometries through a layer by layer deposition process, such as material extrusion additive manufacturing, remains challenging due to the complex interplay between the several kinetics involved (flow, inter-beads diffusion/fusion, cooling, solidification, etc). Here, we explore the influence of physical parameters like bead cross section geometry, partial bead fusion (also called bead coalescence or bead welding) and crystallization kinetics on the 3D printing of isotactic polypropylene as a model semi-crystalline polymer. New methods for the characterization of printed stacks cross sections, interlayer cohesion and viscoelastic coalescence are introduced. Our results demonstrate how printing conditions, through input parameters like layer height and nozzle temperature, can greatly affect interlayer cohesion in relation to polymer interdiffusion at the interface. We show that the relevant timescale for fusion is mainly driven by the polymer’s rheology, and that fusion is many-fold faster under Hertzian compression, i.e. due to the effect of contact pressure. Quantitative description of the influence of the extrusion nozzle and build platform temperatures on the crystallization time of printed beads highlights how the processability window is defined by the competition between fusion and crystallization. Our approach therefore provides a framework for the optimization of process parameters based on the physical processes involved during the production run of semi-crystalline polymers.

Tailoring of structural and optical properties of GeOx thin films using 100 MeV Si ions

In the present work, the effects of 100 MeV Si ions on the structural and optical properties of GeOx thin films have been investigated. Thin films of Germanium oxide (GeOx) were deposited onto silicon substrates using electron beam evaporation technique. Subsequently, 100 MeV Si7+ ions were used to irradiate as-deposited films at different fluences ranging from 5 × 1012 to 2 × 1013 ions/cm2. As-deposited films are amorphous as evident from XRD and Raman results. After irradiation with a fluence of 5 × 1012 ions/cm2 the films show partial crystallization. The strong photoluminescence (PL) exhibited from as-deposited and irradiated films is in ultraviolet (UV) and blue region. The blue shift was observed in PL bands after ion beam irradiation. PL band intensity was found to vary with irradiation fluence. The possible mechanism of variation in the PL emission from GeOx thin films with Si ion irradiation has been studied.

Effect of MnO2 Nanoparticles Stabilized with Cocamidopropyl Betaine on Germination and Development of Pea (Pisum sativum L.) Seedlings.

This study aimed to synthesize, characterize, and evaluate the effect of cocamidopropyl betaine-stabilized MnO2 nanoparticles (NPs) on the germination and development of pea seedlings. The synthesized NPs manifested as aggregates ranging from 50-600 nm, comprising spherical particles sized between 19 to 50 nm. These particles exhibited partial crystallization, indicated by peaks at 2θ = 25.37, 37.62, 41.18, 49.41, 61.45, and 65.79°, characteristic of MnO2 with a tetragonal crystal lattice with a I4/m spatial group. Quantum chemical modelling showed that the stabilization process of MnO2 NPs with cocamidopropyl betaine is energetically advantageous (∆E > 1299.000 kcal/mol) and chemically stable, as confirmed by the positive chemical hardness values (0.023 ≤ η ≤ 0.053 eV). It was revealed that the interaction between the MnO2 molecule and cocamidopropyl betaine, facilitated by a secondary amino group (NH), is the most probable scenario. This ascertain is supported by the values of the difference in total energy (∆E = 1299.519 kcal/mol) and chemical hardness (η = 0.053 eV). These findings were further confirmed using FTIR spectroscopy. The effect of MnO2 NPs at various concentrations on the germination of pea seeds was found to be nonlinear and ambiguous. The investigation revealed that MnO2 NPs at a concentration of 0.1 mg/L resulted in the highest germination energy (91.25%), germinability (95.60%), and lengths of roots and seedlings among all experimental samples. However, an increase in the concentration of preparation led to a slight growth suppression (1-10 mg/L) and the pronounced inhibition of seedling and root development (100 mg/L). The analysis of antioxidant indicators and phytochemicals in pea seedlings indicated that only 100 mg/L MnO2 NPs have a negative effect on the content of soluble sugars, chlorophyll a/b, carotenoids, and phenols. Conversely, lower concentrations showed a stimulating effect on photosynthesis indicators. Nevertheless, MnO2 NPs at all concentrations generally decreased the antioxidant potential of pea seedlings, except for the ABTS parameter. Pea seedlings showed a notable capacity to absorb Mn, reaching levels of 586.5 μg/L at 10 mg/L and 892.6 μg/L at 100 mg/L MnO2 NPs, surpassing the toxic level for peas according to scientific literature. However, the most important result was the observed growth-stimulating activity at 0.1 mg/L MnO2 NPs stabilized with cocamidopropyl betaine, suggesting a promising avenue for further research.