Basal Plane Research Articles

Water-mediated chelation dynamics of dicarboxylic acid functionalized TiO2 nanoparticles for β-nucleation enhancement in isotactic polypropylene composites

ABSTRACT Isotactic polypropylene (iPP) is the most prominent form of polypropylene, and β-phase is the most resistant to impact compared to the crystalline forms. However, β-phase is the least frequently obtained under conventional operating conditions. TiO2 nanoparticles were functionalized with dicarboxylic acids as nucleating agents to promote β-crystal formation in iPP. The effects of three dicarboxylic acids – glutaric, pimelic, and azelaic – were characterized on TiO2-modified surfaces. Additionally, the interactions between TiO2 and water molecules, crucial for the formation of chelating or bridging linkages, were analyzed using Fourier Transform Infrared spectroscopy. For pimelic and azelaic acids at the polymer processing temperature, the carboxyl group band disappeared, suggesting a transition of the acid-calcium union from a bridging to a chelating linkage due to the presence of water molecules. These molecules help maintain the stability of the chains during processing. X-ray diffraction (XRD) analysis confirmed a higher content of β-crystalline structures in iPP when modified with pimelic and azelaic acids. The research indicates that water molecules, desorbed during manufacturing, facilitate the chelating form, thereby enhancing β-nucleation and improving the surface properties of iPP composites. These β-nucleated PP composites represent a promising material solution for medical device applications, offering a compelling combination of enhanced properties and cost-effectiveness.

A Reduced-Symmetry Pd2L4 Cage from a Heterotopic Dipyridyl Ligand.

Two dipyridyl ligands, L3,3 and L3,4, have been used in combination with palladium(II) in the construction of metallosupramolecular species that show anion-dependent behavior in solution. A rare example of a low-symmetry (C2h) lantern-type cage is formed in one instance, [Pd2(L3,3)4]4+, while the isomeric ligand yields a larger double-walled square complex, [Pd4(L3,4)8]8+. [Pd2(L3,3)4](NO3)4 was isolated in crystalline form revealing two anions within the interior of the C2h-symmetry cage. The cage itself is held together by hydrogen bonding between "head-to-tail" pairs of ligands that reinforces the symmetry generated by the ditopic ligands. In solution, the cage with NO3- has sharp 1H nuclear magnetic resonance (NMR) signals at room temperature, while the BF4- analogue has broad signals that sharpen at higher temperatures or upon addition of (Bu4N)(NO3), highlighting the importance of the anion in templating or otherwise influencing self-assembly in solution. Altering the substitution position of one of the pyridyl rings yields a more "open" complex, with [Pd4(L3,4)8](NO3)8 being isolated as a crystalline solid. The double-walled square complex has a greater Pd···Pd separation due to the increased angle that the pyridyl groups subtend at the core of the ligand. NMR spectroscopy and mass spectrometry studies suggest a single species in the presence of nitrate but multiple species with tetrafluoroborate.

Suppression of stacking-fault expansion in 4H-SiC diodes by helium implantation

Abstract Bipolar degradation is a critical problem in SiC devices, caused by the expansion of single Shockley stacking faults (1SSFs) from basal plane dislocations. This paper presents the effects of helium implantation on the suppression of 1SSFs expansion. The fabricated PiN diodes were analyzed using current-voltage characteristics and electroluminescence imaging. The results show that helium implantation can effectively suppress 1SSFs expansion without significantly degrading diode performance. We consider that this suppression is due to the pinning of dislocations by point defects introduced during helium implantation, and the reduction of carrier lifetime may also play a role in suppressing 1SSFs expansion.

Compressive Properties and Energy Absorption Characteristics of Co-Continuous Interlocking PDMS/PLA Lattice Composites

Co-continuous interlocking lattice structures usually present superior compressive properties and energy absorption characteristics. In this study, co-continuous interlocking polydimethylsiloxane/polylactic acid (PDMS/PLA) lattice composites were designed with different strut diameters, and successfully manufactured by combining the fused deposition modeling (FDM) technique and the infiltration method. This fabrication method can realize the change and control of structure parameters. The effects of the strut diameter on the compressive properties and energy absorption behavior of PDMS/PLA lattice composites were investigated by using quasi-static compression tests. The compressive properties of the co-continuous interlocking PDMS/PLA lattice composites can be adjusted in a narrow density range by a linear correlation. The energy absorption density of the co-continuous interlocking PDMS/PLA lattice composites increases with the increase in the PLA strut diameter and presents a higher efficiency peak and wider plateau region. The PLA lattice acts as a skeleton and plays an important role in bearing the compressive load and in energy absorption. The indexes of the compressive properties/energy absorption characteristics and PLA volume fraction of co-continuous interlocking PDMS/PLA lattice composites show linear relationships in logarithmic coordinates. The effect of the PLA volume fraction increasing on the plateau stress is more sensitive than the compressive strength and energy absorption density.

Dispersion Analysis of Plane Wave Propagation in Lattice-Based Mechanical Metamaterial for Vibration Suppression

Phononic crystals based on lattice structures provide important wave dispersion characteristics as band structures, showing excellent compatibility with additive manufacturing. Although the lattice structures have shown the potential for vibration suppression, a design guideline to control the frequency range of the bandgap has not been well established. This paper studies the dispersion characteristics of plane wave propagation in lattice-based mechanical metamaterials to realize effective vibration suppression for potential aerospace applications. Triangular and hexagonal periodic lattice structures are mainly studied in this paper. The influence of different geometric parameters on the bandgap characteristics is investigated. A finite element approach with Floquet–Bloch’s principles is implemented to effectively evaluate the dispersion characteristics of waves in lattice structures, which is validated numerically and experimentally with a 3D-printed lattice plate. Based on numerical studies with the developed analysis framework, the influences of the geometric parameters of lattice plate structures on dispersion characteristics can mainly be categorized into three patterns: change in specific branches related to in-plane or out-of-plane vibrations, upward/downward shift in frequency range, and drastic change in dispersion characteristics. The results obtained from the study provide insight into the design of band structures to realize vibration suppression at specific frequencies for engineering applications.

Study on the preparation of Nano-Fe3O4 by steel pickling waste liquor and its effective removal of Cr (VI) from wastewater

In order to comprehensively treat and utilize steel pickling waste liquor (SPWL), this study used SPWL as raw material to prepare two different crystalline forms of Nano-Fe3O4 by co-precipitation and precipitation-oxidation methods, and investigated their removal effect on Cr(VI) in wastewater. The two kinds of Nano-Fe3O4 were characterized using SEM, XRD, and VSM, and the results showed that the Nano-Fe3O4 synthesized by the co-precipitation method has better properties. The two kinds of Nano-Fe3O4 were used to remove Cr(VI) in wastewater, the adsorption capacity could reach 38.38 mg/g and 15.83 mg/g, respectively. Five adsorption kinetic models and five isothermal adsorption models were used to study the adsorption mechanism of Fe3O4 on Cr(VI). The adsorption process of Cr(VI) by Nano-Fe3O4 was explained well using the pseudo-second-order and Freundlich isotherm model, and the results showed that the adsorption process mainly involved physical and chemical adsorption. Through the characterization analysis before and after the reaction, the removal mechanism of Cr(VI) by Nano-Fe3O4 prepared from SPWL is mainly attributed to electrostatic adsorption and reduction reaction. According to the market survey and analysis, the production cost is reduced by at least 58.33 % compared to that of Nano-Fe3O4 prepared using analytical purity in the market. Therefore, the preparation of Nano-Fe3O4 by steel pickling waste liquor provides an economical and effective way to remove heavy metal ions in wastewater.

First-principles investigation of lanthanides diffusion in HCP zirconium via vacancy-mediated transport

The diffusion of lanthanide fission products plays an important role in the growth of the fuel-cladding chemical interaction (FCCI) region in metallic fuels. The use of a Zr interdiffusion barrier may mitigate the transport of lanthanides from the fuel to the cladding, but the efficacy of such a liner is not yet known. In this paper, the stability and vacancy-mediated diffusion of La, Ce, Pr, and Nd in hexagonal close-packed (HCP) Zr is investigated via density functional theory (DFT) calculations and self-consistent mean field (SCMF) analysis. DFT is used to calculate the formation, binding, and migration energies of vacancies and vacancy-solute pairs. The DFT energetics are used in the KineCluE code to calculate the Onsager transport coefficients. La is found to be the fastest diffusing species in HCP Zr and experiences an almost isotropic diffusion behavior. The other three species (Ce, Pr, and Nd) demonstrate anisotropic diffusion where the diffusion in the basal planes is significantly faster than that along the c-axis. The calculated lanthanide diffusivities in HCP Zr are fitted to an Arrhenius relation and the activation energies and prefactors are reported for the first time. Furthermore, the vacancy drag and the segregation tendencies were analyzed using the calculated off-diagonal transport coefficients. According to our vacancy-mediated diffusion model, lanthanides are expected to be enriched at vacancy sinks at low temperatures, while at high temperatures, lanthanides are depleted at sinks and will preferably diffuse into the bulk. The enrichment/depletion transition temperature depends on the diffusion direction (basal or axial) and hence will be controlled by the grain texture and orientation.

Mechanical characterization and puncture resistance of 3D‐printed PLA lattice structures

Mechanical characterization and puncture resistance of <scp>3D</scp>‐printed <scp>PLA</scp> lattice structures

Improved thermal stability and electrical conductivity of dysprosium doped barium zirconium cerate electrolyte

Acceptor-doped perovskites based on the BaCeO3 have been extensively investigated as promising candidates for proton-conducting electrolyte at intermediate temperatures. This operational regime is characterized by proton conduction facilitated via hydroxyl protons that effectively occupy vacancies of oxide ions within the perovskite crystal lattice structure. While the trade-off parameters (proton conductivity and chemical stability) concern the utility of cerium-based electrolytes, acceptor doped compounds hinder the mobility of protons due to dopant-charge and dopant-host interactions. However, Dy-doped compounds reveal a promising behavior relative to most acceptor substituents with marginal constraints at higher doping concentration. As a result, a threshold doping range is essential to combat material inconsistencies such as cationic disorder to proton trapping effect. Therefore in the present study we synthesize the single-phase dysprosium and zirconium co-doped barium cerate at different doping concentrations (BaCe0.8-xZr0.2DyxO3-δ (x = 0.0–0.20)) to showcase the chemical inertness of the compound against oxidizing and reducing atmospheres preserving high ionic conductivity. According to our experimental outcomes, higher ionic conductivity among wet atmospheric conditions suggests the role of moisture to contribute additional charge carriers among the Dy-doped samples via explicitly generated oxygen vacancies. As a result, BaCe0.65Zr0.2Dy0.15O3-δ demonstrates a highest total conductivity, reaching 2.44 x 10-2 S cm−1 at 575 °C, with an associated activation energy of 0.61 eV within the temperature range of 300–600 °C. The study also reveals the optimal operating temperature of the proton conducting electrolyte to avoid mixed ionic (H+ and O2–) conduction.

Lattice Manipulation with Di-Tertiary Ammonium Spacer in Bismuth Bromide Perovskite Directs Efficient Charge Transport and Suppressed Ion Migration for Photodetector Applications.

Bismuth halide hybrid perovskites have emerged as promising alternatives to their lead halide homologs because of high chemical stability, low toxicity, and structural diversity. However, their advancements in optoelectronic field are plagued with poor charge transport, due to considerable microstrain triggered by bulky spacer. Herein, the di-tertiary ammonium spacer (N,N,N',N'-tetramethyl-1,4-butanediammonium, TMBD) is explored to direct stable 1D bismuth bromide lattice structure with relaxed microstrain. Compared to the primary pentamethylenediamine (PD)2+, the (TMBD)2+ adopting alternating alignment enables a unique H-bonds mode to distort the configuration of inorganic layers to form corner-sharing [BiBr5] near-regular chains with narrower bandgap, lower exciton binding energy, and reduced carrier-lattice interactions, thereby facilitating charge-carrier transport. Moreover, the (TMBD)2+ spacers largely suppress ion migration in perovskite lattice, as substantiated by the experimental and theoretical investigations. Consequently, (TMBD)BiBr5 single crystal photodetector delivers a 185-fold increase in current on/off ratio with respect to (PD)BiBr5 under white light irradiation, considerable responsivity (≈82.97mA W-1), detectivity (≈8.06 ×1011 Jones) under weak light (0.02mW cm-2) irradiation, in the top rank of the reported hybrid bismuth halide perovskites. This finding offers novel design criterion for high-performance lead-free perovskites.

Predicting and Optimizing the Dimensions of Rod in Lattice Structures Fabricated by Laser Powder Bed Fusion

Laser powder bed fusion (LPBF) is a highly effective method for manufacturing complex parts and is widely used in industry for creating lattice structures. However, during the manufacturing process, the actual dimensions and shapes of the lattice structure rod often deviate significantly from the design model due to limited understanding of the structure-process-property relationship in LPBF. This makes it difficult to carry out targeted structural design and process planning based on the technical characteristics of LPBF. This paper investigates the relationship between melt pool dimensions and lattice structure rod dimensions through theoretical analyses. Based on melt pool dimensions obtained with the help of numerical simulation, a prediction model for the actual dimensions of lattice structure rod is established. We design experiments to validate the accuracy of the predictive model, using LPBF to fabricate rods with varying inclinations, dimensions, and cross-sectional shapes. The actual dimensions are measured under a microscope and compared with the predicted dimensions. The results indicate a difference of no more than 0.1mm. Furthermore, the experiments reveal a correlation between scan path curvature and actual dimensions. Based on this correlation, the dimensional prediction model is corrected, resulting in an improved generalization performance of the model for parts with varying scan paths. Based on the dimension prediction model, we propose an optimization method to modify the CAD dimensions of the rod to ensure the consistency between the actual and designed dimensions of the rod.

The Chinese Knot inspired anisotropic TC4 lattice Structures: Ultra-high specific strength in engineering materials

Lattice structures possess high specific strength, multi-functionality through innovative structural designs. Here, we proposed an efficient method for the construction of lattice structures by elongating two-dimensional planar patterns along the load direction, which enabled the efficient utilization of 100 % materials for load bearing. Inspired by Chinese Knot (CK), a series of meticulously crafted TC4 lattice structures were fabricated by using selective laser melting. These structures feature nine tubular units arranged in a 3 × 3 matrix interconnected by sixteen parallel plates, and their failure modes were subsequently investigated by uniaxial compression tests. The results show that the specific compressive strength of the CK structure enhances as increasing the density. The detachment between the plate and tube, and the buckling of the plate, lead to the premature failure, which in turn leads to substantial variations in strength, estimated at approximately 80 MPa at ∼ 1.5 g/cm3. When the thickness of the plate exceeds 0.5 mm, and the tube wall thickness exceeds 0.04 mm, the CK structures show high stability and exhibit a 45° shear failure mode. Notably, the specific strength of the CK structure can surpass 330 MPa∙cm3/g, which represents the peak level of specific compressive strength compared to the current TC4 lattice structures.

The corrosion behavior of AZ91 bulk alloy and thin films

Purpose The purpose of this study is to campare the corrosion behavior of Az91 films and bulk sample, in the objective to provide reference for the corrosion resistance improvement of Mg alloys. Design/methodology/approach AZ91 films with various thickness values are produced by magnetron sputtering technique, and the corrosion behavior was characterized by immersion tests and electrochemical measurements. Findings The AZ91 films exhibited a preferred orientation with basal planes parallel to the surface and increased densification with the increase of thickness, and a superior corrosion resistance for the AZ91 films compared with the bulk sample. Originality/value The preferred (0002) basal planes in AZ91 films benefited the corrosion resistance and the nanoscale AZ91 films facilitated the development of a dense passivation film. Consequently, AZ91 film exhibited a superior corrosion resistance.

Effect of Unit Cell Rotation on Mechanical Performance of Selective Laser Melted Gyroid Structures for Bone Tissue Engineering

Gyroid lattice structures, inspired by the natural interconnectivity of human bone, show promise in bone tissue engineering (BTE). This study explores the mechanical properties, and failure mechanisms of selective laser melted (SLM) Gyroid Ti6Al4V lattice structures with varying unit cell rotation angles (RA) of 0∘ (G0), 30∘ (G30), and 60∘ (G60) around the x-axis. The study assesses their mechanical and energy absorption properties through quasi-static compression testing and elastoplastic finite element (FE) analysis. Despite similar relative densities for all designed lattices, the RA variation significantly impacts mechanical performance. G30 exhibits superior load-bearing capacity, with higher modulus of elasticity, yield strength, ultimate strength, and plateau stress. It also has the highest energy absorption capacity, while G60 shows the highest surface area (SA) and surface area-to-volume ratio (SA/VR). These findings highlight the potential of Gyroid lattices for bone replacements due to their tunable mechanical and biological responses.

Random fields-triggered strain enhancement in BNT-based materials

Bi0.5Na0.5TiO3 is regarded a potential alternative to lead-based piezoelectric materials due to its large electro-strain. Generally, the improved electro-strain is considered to arise from a relaxor-ferroelectric transition, and the random fields play a critical role. In this study, to investigate the effect of random electric field or strain field on the strain value, the dopant Sb5+, Ta5+, Zr4+, and Hf4+ are introduced into the Bi0.5(Na0.8K0.2)0.5Ti1-xBxO3 matrix, respectively. The 1% Ta5+ doped sample has the largest unipolar electro-strain, up to 0.49%, followed by the 3% Zr4+ doped sample (~0.448%). The electro-strain of 1% Sb5+ and 3% Hf4+ samples are 0.404% and 0.377%, respectively. The results show the random electric field or strain field can effectively regulate the relaxor-ferroelectric transition temperature, which enhances strain, but the strain value cannot be determined directly. The strain value is determined by the lattice structure before and after the electric field is applied.

Unveiling the Influence of Antimony Substitution on the Surface Properties and Adsorption Behavior of Ferrihydrite: From Molecular Mechanisms to Environmental Implications.

Antimony(V) substitution is common in secondary ferrihydrite, especially in mining areas and tailings. However, its impact on the adsorption behavior of ferrihydrite is still unclear. Therefore, this study investigated the influential mechanisms of Sb(V) substitution on the lattice structure and surface properties of Sb-substituted ferrihydrite (SbFh), and its adsorption of coexisting Sb(OH)6-. Antimony(V) is substituted at Fe1 sites and is primarily distributed on the surface. Substitution has opposing effects on the outer- and inner-sphere complexation of Sb(OH)6-. On one hand, substituted-Sb(V) transfers more positive charges to ≡FeOH, reducing the number of H bonds. Subsequently, the charge saturation of ≡FeOH decreases, surface charge increases, and outer-sphere complexation is promoted. On the other hand, the elevated bond valence of Sb-O increases charge saturation of ≡FeOH, reducing the charge capacity that ≡FeOH can accommodate from inner-sphere complexes. Thus, inner-sphere complexation is inhibited. Inner-sphere complexation plays a more important role, and Sb(OH)6- adsorption is inhibited. Additionally, the primary complexation modes of Sb(OH)6- transform from bidentate to monodentate complexation. This research has important implications for understanding the environmental behavior of ferrihydrite, as well as the fate and bioavailability of antimony in mining areas and tailings.

Insight view of thermal, mechanical and structural behavior of novel double perovskites Ba2XSbO6 (X = Sc, Y): A DFT based study

The study of double perovskite structures Ba2XSbO6 (X = Sc, Y) is carried out using the first principles algorithms within the framework of Density Functional Theory (DFT). The results showed that these compounds possess a cubic perovskite structure with the lattice space group Fm-3m generally represented by the group No. 225. The band structure of these compounds confirms their insulating nature. The calculated values of elastic parameters determined the brittle nature of Ba2ScSbO6 and Ba2YSbO6 compounds. Positive frequencies of the phonon dispersion curve indicates that these double perovskites are dynamically stable, with one acoustic and ten optical phonon modes having the combination of Raman active, Infrared active and optically inactive modes. The transport properties of these materials including electrical and thermal conductivity, as well as their thermoelectric power have been investigated. Additionally, the figure of merit was calculated to assess the suitability of double perovskites for thermoelectric devices and advanced technological applications.

Mechanochemical synthesis of nitrogen-modified microscale zero-valent iron for efficient Cr(VI) removal: The role of lattice strain

Lattice engineering of Fe0 based on heteroatom doping holds great promise in water purification owing to their tunable geometric and electronic structure. However, there is limited understanding of how nitrogen atom in Fe0 lattice structure affects its local microenvironment and corresponding reactivity toward target contaminants. Herein, microscale zero-valent iron with interstitial N doping (N-mZVI) was successfully prepared by a facile mechanochemical method for heavy metal pollution control. N-mZVI exhibited excellent reactivity for Cr(VI) elimination, and both removal efficiency and conversion rate could reach 100 %, which was 8.06 and 2.73 times higher than that of pristine ball milled mZVI, respectively. Besides, the rate constant of various heavy metals sequestration (Cr(VI), Ni(II), Pb(II), Cu(II), and Cd(II)) over N-mZVI was 61.3 ∼ 115.6-fold faster than that of pristine ball milled mZVI. N-mZVI was also demonstrated to be pH-universal, long-term stability, and environmental applicability. Experimental results and theoretical calculations indicated that tensile strain induced by interstitial N doping expanded Fe0 lattice and weakened the lattice Fe-Fe interaction, thus significantly accelerating electron transport dynamics in Fe0 core. Meanwhile, iron nitride species on the surface of N-mZVI promoted electron transfer from iron shell layer to heavy metals. This work comprehensively investigates the structure–property relationships of lattice engineering-based N-mZVI, and provides a new insight into rational design of modified mZVI with high reactivity.

Thionitrosyl Complexes of Rhenium and Technetium with PPh3 and Chelating Ligands—Synthesis and Reactivity

In contrast to corresponding nitrosyl compounds, thionitrosyl complexes of rhenium and technetium are rare. Synthetic access to the thionitrosyl core is possible by two main approaches: (i) the treatment of corresponding nitrido complexes with S2Cl2 and (ii) by reaction of halide complexes with trithiazyl chloride. The first synthetic route was applied for the synthesis of novel rhenium and technetium thionitrosyls with the metals in their oxidation states “+1” and “+2”. [MVNCl2(PPh3)2], [MVNCl(PPh3)(LOMe)] and [MVINCl2(LOMe)] (M = Re, Tc; {LOMe}− = (η5-cyclopentadienyl)tris(dimethyl phosphito-P)cobaltate(III)) complexes have been used as starting materials for the synthesis of [ReII(NS)Cl3(PPh3)2] (1), [ReII(NS)Cl3(PPh3)(OPPh3)] (2), [ReII(NS)Cl(PPh3)(LOMe)]+ (4a), [ReII(NS)Cl2(LOMe)] (5a), [TcII(NS)Cl(PPh3)(LOMe)]+ (4b) and [TcII(NS)Cl2(LOMe)] (5b). The triphenylphosphine complex 1 is partially suitable as a precursor for ongoing ligand exchange reactions and has been used for the synthesis of [ReI(NS)(PPh3)(Et2btu)2] (3a) (HEt2btu = N,N-diethyl-N′-benzoyl thiourea) containing two chelating benzoyl thioureato ligands. The novel compounds have been isolated in crystalline form and studied by X-ray diffraction and spectroscopic methods including IR, NMR and EPR spectroscopy and (where possible) mass spectrometry. A comparison of structurally related rhenium and technetium complexes allows for conclusions about similarities and differences in stability, reaction kinetics and redox behavior between these 4d and 5d transition metals.

A Study on the Growth of Highly Qualified Superconducting YBa2Cu3O7 Thin Films and Correlation Between Lattice Structure and Critical Temperature

A Study on the Growth of Highly Qualified Superconducting YBa₂Cu₃O₇ Thin Films and Correlation Between Lattice Structure and Critical Temperature