Preferential Direction Research Articles

Science Teachers’ Pedagogical Orientations Versus Students’ Preferred Orientations in Pakistan

Previous studies have sufficiently debated science teachers’ pedagogical orientations (PO); however, research on students’ preferred or desired orientations is scarce. This study determined students’ preferred teaching orientations in relationship with their teachers’ PO. The sample included 313 grade VIII students and 94 teachers from middle schools in Peshawar-Pakistan. Three vignettes from the Pedagogy of Science Teaching Tests (POSTT) were used to find PO. Data was analyzed using frequency count, means, and t-test. The findings revealed students’ and teachers’ preferences for didactic direct and active direct orientations. However, the choice of orientation varied with the nature of the topic. The students and teachers showed the least preference for open inquiry orientation. A significant positive correlation existed between teachers’ PO and teaching experience, and a negative correlation existed between students’ preferred orientations and academic achievement in the general science subject. Interestingly, students with higher test scores preferred teacher-centered instead of student-centered orientations. The study suggests improving teacher education programs to train science teachers in inquiry orientations and its proper integration with science content at all levels.

Influence of different drilling forces on drill bit wear in automated drilling of concrete with industrial robots

AbstractThis article investigates the effect of different drilling forces on drill bit wear and their effects on drilling time within the context of the development of a drilling robot for on‐site construction applications. The study explores variations in three force levels (80, 120, 160 N), three directional orientations (upwards, downwards, horizontal), four drill bit diameters (8, 10, 12, 16 mm), and two concrete strength types (C25/30, C70/85). The findings indicate that while there is little divergence in drill bit wear across force levels, the influence of concrete strength is undeniable. Furthermore, drilling time increases, by 7 % to 11 % after 37.5 m drilling depth and up to 68% after 150 m depending on the drilling configuration. In conclusion, the study reveals a notable discrepancy between the progressive increase in drilling time and the relatively stable progression of drill bit wear, particularly in achieving code‐compliant boreholes.

Depth Profiles of Crystallinity and Preferential Orientation and Surface Characteristics of Sputter‐Deposited CeO2 Thin Film Buffer Layers on Sapphire Substrates Evaluated Through Two‐Dimensional Grazing‐Incidence X‐Ray Diffraction

ABSTRACTTwo‐dimensional grazing‐incidence wide‐angle X‐ray diffraction data were acquired from CeO2 thin films serving as buffer layers on r‐cut sapphire substrates to investigate the depth profiles of crystallinity and preferential orientation as well as surface conditions. The thin film samples were sputter‐deposited under different conditions. Data were obtained at an X‐ray wavelength of 0.100 nm at 0.02° intervals from 0.06° to 0.30° at the grazing‐incidence angle. A 60‐nm‐thick CeO2 thin film sputter‐deposited under Ar (Ar‐60) and a 100‐nm‐thick CeO2 thin film sputter deposited using 10 vol.% O2 in Ar (O+Ar‐100) were found to have partially oriented three‐dimensional bulk crystal structures with preferential orientation in the (100) direction near the surface. The lattice constant for the Ar‐60 film was found to be approximately 0.30% smaller than that for a CeO2 standard, whereas the lattice constant for the O+Ar‐100 film was approximately 0.50% larger. Lattice mismatch between the CeO and CeO2 on the substrate surface is evidently not an issue based on the lattice constants near the surface. Hence, both films could be considered to represent optimal buffer layers for YBa2Cu3O6+δ thin film growth. However, even in the case of a CeO2 thin film suitable for use as a buffer layer, the difference in lattice constants between the interior and surface of an Ar‐60 film was found to be relatively small, whereas that for an O+Ar‐100 film was relatively large. These results show that it is important to analyze the film surface in detail by reducing the incidence angle to less than 0.1°.

Analysis of Magnetic Anisotropy Constants Obtained from Hall Data Using Generalized Sucksmith Thompson Method on NiCo<sub>2</sub>O<sub>4</sub>(001) Films with Tilted Preferential Direction

Analysis of Magnetic Anisotropy Constants Obtained from Hall Data Using Generalized Sucksmith Thompson Method on NiCo<sub>2</sub>O<sub>4</sub>(001) Films with Tilted Preferential Direction

Macrocycle Unidirectional Transport Along a Linear Molecule by a Two-Step Chemical Reaction Sequence.

Chemical systems displaying directional motions are relevant to the operation of artificial molecular machines. Herein we present the functioning of a molecule capable of transporting a cyclic species in a preferential direction. Our system is based on a linear, non-symmetric, positively charged molecule. This cation integrates into its structure two different reactive regions. On one side features a bulky ester group that can be exchanged by a smaller substituent; the other extreme contains an acid/base responsive moiety that plays a dual role, as part of the recognition motif and as a terminal group. In the acidic state, a dibenzo-24-crown-8 ether slides into the linear component attracted by the positively charged recognition site. It does this selectively through the extreme that contains the azepanium group, since the other side is sterically hindered. After base addition, intermolecular interactions are lost; however, the macrocycle is unable to escape from the linear component since the energy barrier to slide over the neutral azepane is too large. Therefore, a metastable mechanically interlocked molecule is formed. A second reaction, now on the ester functionality, exchanges the bulky mesityl for a methyl group, small enough to allow macrocycle dissociation, completing the directional transit of the ring along the track.

Impact of molecular architecture and draw ratio on enhancement of targeted mechanical properties of machine direction oriented polyethylene films produced after blown film extrusion

Conventional multi-material multi-layer flexible packaging offers excellent properties. However, it has recycling challenges, necessitating a shift to mono-material multi-layer flexible packaging for example all-polyethylene (PE) packaging which can be tailored through various synthesis and processing methods for different layers. In this work, we study how the key molecular properties (number-average molecular weight ( Mn), weight-average molecular weight ( M w), molecular weight distribution (MWD), comonomer content (short chain branching)) and machine direction orientation (MDO) process draw ratio (MDX) influence the final morphology and mechanical properties of MDO-PE films which are intended as the outer layer of mono-material all-polyethylene multi-layer flexible packaging. Five PE grades and various blends were extruded and blown into films. Selected blown films were machine direction oriented to obtain the final MDO-PE films. Furthermore, one selected PE blown film was processed at different MDO process draw ratios while keeping other process parameters constant. From the molecular properties point of view, the higher molecular weight fractions provide a higher possibility for uniform stretching whereas lower molecular weight fractions provide a higher natural draw ratio and therefore higher modulus and stiffness enhancement. Further, the results show that increasing MDO process draw ratio leads to more fibrillation and increased crystallinity. Consequently, the tensile modulus and stiffness at the higher draw ratios increase as well and are comparable to conventionally used polymers in outer layers of multilayer flexible packaging. Thus, this work demonstrates that MDO-PE films with enhanced modulus can provide sufficient stiffness for the design of outer layer of mono-material multi-layer all-PE packaging which presents higher potential for mechanical recyclability.

Investigation of Effect of Part-Build Directions and Build Orientations on Tension-Tension Mode Fatigue Behavior of Acrylonitrile Butadiene Styrene Material Printed Using Fused Filament Fabrication Technology.

This article explores the fatigue characteristics of acrylonitrile butadiene styrene (ABS) components fabricated using fused filament fabrication (FFF) additive manufacturing technology. ABS is frequently used as a polymeric thermoplastic material in open-source FFF machines for a variety of engineering applications. However, a comprehensive understanding of the mechanical properties and execution of FFF-processed ABS components is necessary. Currently, there is limited knowledge regarding the fatigue behavior of ABS components manufactured using FFF AM technology. The primary target of this study is to evaluate the results of part-build directions and build orientation angles on the tensile fatigue behavior exhibited by ABS material. To obtain this target, an empirical investigation was carried out to assess the influence of building angles and orientation on the fatigue characteristics of ABS components produced using FFF. The test samples were printed in three distinct directions, including Upright, On Edge, and Flat, and with varying orientation angles ([0°, 90°], [15°, 75°], [30°, 60°], [45°]), using a 50% filling density. The empirical data suggest that, at each printing angle, the On-Edge building orientation sample exhibited the most prolonged vibrational duration before fracturing. In this investigation, we found that the On-Edge printing direction significantly outperformed the other orientations in fatigue life under cyclic loading with 1592 loading cycles when printed with an orientation angle of 15°-75°. The number of loading cycles was 290 and 39 when printed with the same orientation angle for the Flat and Upright printing directions, respectively. This result underscores the importance of orientation in the mechanical performance of FFF-manufactured ABS materials. These findings enhance our comprehension of the influence exerted by building orientation and building angles on the fatigue properties of FFF-produced test samples. Moreover, the research outcomes supply informative perspectives on the selection of building direction and building orientation angles for the design of 3D-printed thermoplastic components intended for fatigue cyclic-loading applications.

Bimodal grain structure, phase transformation, and mechanical properties of a Mg-Gd-Y-Zn-Zr alloy during hot extrusion

In this study, we investigated the evolution of grain structures and second phases of a Mg-9.5Gd-4Y–2Zn-0.3Zr alloy during two-stage deformation that took place in the metal during hot extrusion, as well as their effects on its mechanical properties. We found that the alloy exhibited a bimodal grain structure consisting of equiaxed dynamic recrystallized (DRXed) grains and elongated unDRXed grains. As the extrusion process progressed, DRX occurred on a large scale, resulting in an increase in the proportion of DRXed grains from 17.8% to 93.2%, and a reduction in average grain size from 80.3 μm to 9.41 μm. The grain orientation also underwent a transition from a single orientation of an extrusion direction (ED) parallel to <0001> (i.e. ED//<0001>) to mixed orientations of ED//<01–10> and ED//<0001>. The primary mechanism of dynamic recrystallization (DRX) during extrusion involved particle-stimulated nucleation (PSN) accompanied by both continuous and discontinuous DRX. The Mg-9.5Gd-4Y–2Zn-0.3Zr alloy mainly contained intergranular 18R-long period stacking order (LPSO) phases and intragranular 14H-LPSO. As the extrusion process progressed, 18R-LPSO changed from blocky to lamellar to accommodate deformation, and β-Mg5(Gd,Y) phase particles dynamically precipitated along DRXed grain boundaries. The 14H-LPSO phase was found to be primarily distributed within coarse unDRXed grains. As deformation via extrusion progressed, the quantity of 14H-LPSO gradually decreased. Ultimately, with the gradual dissolution of Mg5(Gd,Y), 14H-LPSO reprecipitated within the recrystallized grain boundaries. As the extrusion process progressed, both the yield strength (YS) and elongation (EL) increased from 132.6 MPa to 287.6 MPa and from 10.8% to 15.5%, respectively. This was mainly attributed to the significant reduction in grain size and second phase size.

Optimization of Triply Periodic Minimal Surface Heat Exchanger to Achieve Compactness, High Efficiency, and Low-Pressure Drop

With advancements in additive manufacturing (AM) techniques, high-quality triply periodic minimal surface (TPMS) structures can now be produced. TPMS walled heat exchangers (HX) hold significant potential for industrial applications and are receiving increasing attention. This paper explores the impact of various TPMS design variables on flow and thermal performance to optimize TPMS heat exchangers for compactness, high efficiency, and low pressure drop. The design variables examined include the type of TPMS lattice, unit cell size, wall thickness, aspect ratio, TPMS orientation, and equivalent thickness. The study reveals that the flow and heat transfer performance of TPMS structures are significantly affected by these design variables. For the Gyroid, Diamond, and SplitP lattices, performance is nearly identical when the surface-to-volume ratio is kept constant. The average velocity of the fluid in the TPMS HX should be 0.3 m/s. The corresponding Re is between 300~800. Thin wall thickness, small equivalent thickness, and flat lattice configurations can significantly reduce pressure drop while maintaining the overall heat transfer coefficient. Additionally, the angle between the flow direction and TPMS orientation can increase pressure drop. Three aluminum heat exchangers were successfully printed using an AM machine, and testing results are comparable with theoretical prediction.

Characterization of polyethylene films drawn by machine direction orientation and consequences on their photooxidation

The effect of uniaxial drawing by Machine Direction Orientation (MDO) on polyethylene films was first studied by complementary analytical methods. XRD and polarized FTIR spectroscopy revealed the transformation of the initial spherulitic structure of PE into microfibrils composed of small crystalline blocks connected by amorphous chains oriented along the drawing direction. No stress-induced crystallization was observed upon MDO processing, but the permeability to oxygen was reduced by 30 % owing to this morphology change. In a second time, the effect of photooxidation on undrawn and MDO-drawn films was studied. There was no difference in the photooxidation kinetics and stoichiometry between them. A slight reorganization of the polymer structure due to physical ageing was observed before any photooxidation, but no change in orientation occurred upon photochemical ageing. Finally, the oxygen permeability of undrawn and MDO-drawn films decreased owing to the changes brought by photooxidation, especially the formation of polar functions within the initially apolar polyethylene and the occurrence of chemicrystallization.

Full‐field effect of flow‐induced fiber orientation during compression molding of carbon fiber sheet molding compounds

AbstractAn image‐based fiber orientation analysis technique has been employed to study the effect of initial charge coverage and preferential fiber alignment on the flow‐induced fiber orientations in carbon fiber sheet molding compounds (SMCs). The initial charge coverage area exhibited minimal fiber reorientation while significant fiber alignment in the flow direction was observed in the regions of greatest flow. Novel subsurface analysis using the same full‐field orientation analysis technique also showed the presence of a skin‐core structure with greater flow‐induced fiber alignment at the mold surfaces, while the core retained more of the initial fiber orientation distribution. Edge effects were also revealed by this analysis at the mold walls. Tensile testing from two orthogonal directions showed that panels molded from lower charge coverage resulted in better mechanical performance and lower anisotropy. Moreover, by encouraging charge flow in the preform's preferential alignment direction, high tensile stiffness and strength in the preferred direction were achieved (56.7 GPa and 238.9 MPa, respectively) at 30% fiber volume fraction. This provides a practical demonstration of the value in controlling fiber orientation, with respect to charge positioning and mold flow, to maximize and tailor the composite performance of SMCs typically used for automotive applications.Highlights Low‐cost scanning technique is extended to assess internal fiber orientations Full‐field orientations are measured before and after molding Investigation of how charge size and shape can affect orientations Combining effects of flow and initial orientation to tailor SMC performance Circular statistics provides a thorough analysis of orientation distributions

Evolution of the Tn4371 ICE family: traR-mediated coordination of cargo gene upregulation and horizontal transfer.

ICEKKS102Tn4677 carries a bph operon for the mineralization of polychlorinated biphenyls (PCBs)/biphenyl and belongs to the Tn4371 ICE (integrative and conjugative element) family. In this study, we investigated the role of the traR gene in ICE transfer. The traR gene encodes a LysR-type transcriptional regulator, which is conserved in sequence, positioning, and directional orientation among Tn4371 family ICEs. The traR belongs to the bph operon, and its overexpression on solid medium resulted in modest upregulation of traG (threefold), marked upregulation of xis (80-fold), enhanced ICE excision and, most notably, ICE transfer frequency. We propose the evolutional roles of traR, which upon insertion to its current position, might have connected the cargo gene activation and ICE transfer. This property of ICE, i.e., undergoing transfer under environmental conditions that lead to cargo gene activation, would instantly confer fitness advantages to bacteria newly acquiring this ICE, thereby resulting in efficient dissemination of the Tn4371 family ICEs.IMPORTANCEOnly ICEKKS102Tn4677 is proven to transfer among the widely disseminating Tn4371 family integrative and conjugative elements (ICEs) from β and γ-proteobacteria. We showed that the traR gene in ICEKKS102Tn4677, which is conserved in the ICE family with fixed location and direction, is co-transcribed with the cargo gene and activates ICE transfer. We propose that capturing of traR by an ancestral ICE to the current position established the Tn4371 family of ICEs. Our findings provide insights into the evolutionary processes that led to the widespread distribution of the Tn4371 family of ICEs across bacterial species.

Simultaneous carbon fiber layer thickness and direction measurement and identification using a novel eddy current sensor and simplified multi-scale 1D-ResNet network

A novel eddy current sensor, featuring a triangular excitation coil and three rectangular receiving coils, is proposed for simultaneously detecting carbon fiber layer thickness and directions in the manufacturing process of carbon fiber reinforced polymer (CFRP) materials. It can disclose various carbon fiber layers and directions based on the signals obtained from the three receiving coils. However, classification of carbon fiber layers and directions proves challenging due to the complexity of signal features resulting from different combinations of carbon fiber layers and directions. To address this issue, we propose the use of a simplified multi-scale 1D-ResNet network. Comparative analysis reveals that our proposed network achieves higher train and validation accuracy compared to single-scale 1D-ResNet networks and different layers 1D-ResNet networks. Furthermore, the proposed simplified network not only achieves high classification accuracy with 100% and 99.7% for carbon fiber layers and directions, respectively, but also requires less training time compared to multi-scale 1D-ResNet networks. The novel eddy current sensor proposed in this study enables accurate recognition of carbon fiber layers and their directional orientation through the implementation of a simplified multi-scale 1D-ResNet network in the manufacturing process of CFRP materials. This innovation significantly enhances the quality of CFRP materials during manufacturing, ensuring their strength aligns with predetermined orientations.

Measuring linear birefringence via rotating-sample transmission Stokes spectropolarimetry

Linear birefringence is a fundamental property of optically anisotropic media, defined by the difference in refractive index experienced by light polarized along orthogonal directions. It is usually manifested in microscopically aligned molecular systems, where a preferential direction of light–matter interaction is created. For instance, the anisotropic structure of calcite crystal causes the famous double-refraction phenomenon. Another common example is commercial adhesive tapes, which are polymeric materials possessing birefringent properties due to their manufacturing processes. The intrinsic relation between birefringence and molecular alignment forges a new analytical route to study materials such as polymeric thin films. Therefore, the capacity of measuring linear birefringence and its fast axis is of paramount importance for the science of anisotropic molecular systems. In this contribution, a comprehensive approach to acquire linear birefringence using rotating-sample transmission Stokes spectropolarimetry is presented and applied to transparent adhesive tapes as a case study. The experimental setup comprises a thermal light source and a spectropolarimeter capable of determining wavelength distributions of Stokes parameters. The samples are carefully aligned in a rotating mount and subjected to a fixed broadband vertically polarized light beam. Then, the transmitted light is analyzed using a rotating retarder type of spectropolarimeter. Through systematic variation of the sample’s angular position, the Stokes parameters of transmitted light are measured for each transmitted wavelength as a function of the sample’s angular position. The linear retardance and fast axis direction relative to the tape’s long axis are then determined from the modulation of Stokes parameters over sample rotation. The model derivation, experimental procedure, and signal processing protocol are described in detail, and the approach is verified with a simple correlation between linear retardance and the number of stacked layers of tape.

Heterogeneous microstructure of γ-irradiated pre-oxidized PAN fiber revealed by microfocus SR-SAXS reconstruction and molecular simulation.

The microstructure plays a crucial role in the manufacturing and application of polyacrylonitrile fibers, which serve as precursors for carbon fibers. Synchrotron radiation small angle x-ray scattering (SR-SAXS) is a non-destructive and precise technique for analyzing fiber structures. This study employed one-dimensional SR-SAXS mapping to extract key structural parameters such as periodicity, lamellae thickness, and the extent of amorphous regions, as well as the directional orientation in γ-irradiated, pre-oxidized polyacrylonitrile fibers. The analysis revealed a three-layered structure comprising a surface skin, a transitional layer, and a central core. Notably, the lamellar thickness exhibits a "U"-shaped distribution, while the long-period structures, amorphous regions, and orientational properties demonstrate a "wave-like" pattern. Within this structure, the skin exhibits a higher level of orientation, with the orientation decreasing progressively from the skin toward the core layer. The structure of the layered crystal was further corroborated by the morphological analysis. In addition, molecular simulations were performed to propose the mechanisms underlying the formation of this layered structure. This comprehensive investigation using SR-SAXS and one-dimensional mapping provides detailed insights into the microstructural and morphological characteristics of polyacrylonitrile fibers, which can inform future advancements in material processing and refinement techniques for the production of advanced fibers.

Coupling stress and transmissivity to define equivalent directional hydraulic conductivity of fractured rocks

A DFN (Discrete Fracture Network) modelling approach is developed to couple stresses with fracture transmissivities and to evaluate large scale rock mass hydraulic conductivity. The transmissivity-stress coupling relies on a negative exponential correlation between normal stress acting on a fracture and fracture transmissivity, bounded by residual and maximal apertures. The remote stresses and the local stress fluctuations induced by the fractures themselves are combined in a semi-analytical approach to compute the normal stress acting on each fracture of a DFN. Directional equivalent hydraulic conductivities are numerically computed in all directions from a spherical permeameter setup. The resulting properties are first a cloud of points, where each point defines a direction and an equivalent hydraulic conductivity. The distribution of equivalent hydraulic conductivities is analyzed to define mean values, preferential directions and anisotropy ratio. The entire workflow is developed in the numerical platform DFN.lab. The capacity of the method to investigate the impact of the in-situ stresses on the rock mass hydraulic conductivity is illustrated for fracturing and in-situ stress conditions similar to the conditions at the Forsmark site in Sweden. We find that the stress fluctuations induced by the fractures have a significant impact on the resulting hydraulic conductivity field. They limit the anisotropy ratio to values close to a factor of 3 while the transmissivity distribution is correlated to orientations and spans several orders of magnitude. Sensitivity analyses, performed by changing the parameters of the transmissivity-stress law, show quantitatively how the directional hydraulic conductivities are rather controlled by the orientations of the in-situ stresses or by the underlying connectivity structure of the DFN.

Ultrahigh Thermal Rectification at Small Temperature Difference Achieved by Near‐Field Thermal Photon Manipulation

AbstractThermal diodes, which allow heat to flow in a preferential direction, are an essential component of thermal circuitry and will find applications in many fields ranging from thermal photon controls to quantum information. The quality of a thermal diode is defined by the thermal rectification ratio (TRR). Here, an ultrahigh TRR exceeding 105 at a small temperature difference (1–5 K) is presented based on near‐field thermal photon (NFTP) manipulation, by utilizing asymmetric gap‐variated dual terminals based on graphene/Si heterostructures and materials with contrasting thermal expansion coefficients. Analyses of the photon tunneling probability show that the colossal TRR comes from coupled and decoupled graphene surface plasmon polaritons under opposite temperature biases, remaining robust across a wide operating temperature range. Further enhancement can be achieved by tuning the Fermi level of graphene. This work demonstrates the significance of asymmetry in NFTP manipulation for thermal diode performance, achieving an ultrahigh TRR, which is at least three orders higher than the state‐of‐the‐art structures at the same small temperature difference (1–5 K), and is comparable to state‐of‐the‐art electronic diodes.

Bimodal structure formation and texture transition mechanism in laser remelted Mg–Al-based alloy

Texture inheritance, texture weakening, and a complete texture transition within different solidified molten pool (MP) have been achieved by manipulating various processing parameters of conduction mode in laser remelted magnesium-aluminum (Mg–Al)-based AZ31 alloy. At a low laser power (P = 100 W), restricted number of temperature gradient directions on moving solid/liquid (S/L) interfaces within small MP leads to strong texture inheritance. Tilting angles 20°–45° away from building direction (B.D.) in {0001} plane is a preferential growth direction of texture inheritance. In contrast, spontaneous texture weakening has occurred due to frequently varied temperature gradient directions within increasing MP size in higher P cases. Meanwhile, increasing scanning speed V has a significant effect on weakening the texture as well as refining grains in the solidified MP. Furthermore, fine grains formation with random orientations in MP bottom at both high P (400 W) and high V (20, 30, and 50 mm/s) leads to the occurrence of a bimodal structure, which is affected by solidification characteristics as well as thermal convection. For the case of the highest P and the highest V, a texture transition has occurred as tilting angles of 45°–90° away from B.D. in {0001} plane within MP, compared to 0°–45° texture of base material for the Mg–Al-based alloy in the study.

Kinetics of the bcc to hcp phase transition in [formula omitted]-oriented single crystal iron under ramp compression

Non-Equilibrium Molecular Dynamics simulations have been used to investigate the kinetics of the bcc to hcp phase transition in ramp-compressed [001]-oriented single crystal iron in the presence of defects consisting in micro-voids. Depending on the ramp maximum pressure, the microstructure of the daughter hcp phase is observed to be strongly affected by the plastic activity in the parent bcc phase. The hcp phase is first nucleated around the pre-existing microvoids, then it grows along preferential crystal directions and the subsequent volume reduction induces a local relaxation of the pressure. The velocity of the bcc-hcp phase boundary is shown to increase gradually with maximum pressure up to supersonic values. For high over-compression beyond the transition onset pressure, the phase transformation becomes almost instantaneous and essentially independent of the initial defects. Meanwhile, the ramp wave steepens with propagation distance and evolves into a shock front, up to the over-driven regime classically observed in both experiments and hydrodynamic, macro-scale simulations.

Understanding the Role of Solvent on the Growth of Zinc Oxide: Insight from Experiment and Molecular Dynamics Simulations.

The controlled synthesis of nanoparticles with tailored shapes and morphologies has garnered significant attention, driven by the ever-growing demand for advanced materials with defined properties. In nanoparticle formation, various parameters influence the final product, and among these, the solvent plays a pivotal role, as it constitutes the major component of the reaction medium. In this work, the critical role of solvents in controlling the growth of zinc oxide (ZnO) nanoparticles was investigated, with a focus on simple primary alcoholic solvents as the reaction medium. A model reaction based on the direct solvolysis of anhydrous zinc acetylacetonate was employed to probe the influence of different primary alcohols, specifically methanol, ethanol, and their mixture. A substantial difference in the preferential growth direction of the ZnO nanocrystals in methanol and ethanol was observed through XRD and was further proven through TEM. Thereby, in ethanol, a preferential growth in the [001] direction was observed, resulting in short nanorods as primary particles, while this growth was inhibited in methanol, leading to platelet- or sheet-like primary particles. To unravel the underlying mechanisms responsible for the observed solvent-dependent variations, molecular dynamics (MD) simulations were employed using an optimized interface force field to model the ZnO-alcohol interaction. These simulations provide valuable insights into the preferential adsorption of the solvent molecules onto the polar (0001) and (0001̅) and nonpolar (101̅0) ZnO surfaces, shedding light on the fundamental interactions driving the shape control phenomenon. Essentially, the experimental observations on primary particle morphology could be explained well by the adsorption behavior determined by the MD simulations. Furthermore, this report provides an extensive comparison with various similar reaction systems for ZnO synthesis, deriving correlations with the findings from the model system. These insights contribute to a deeper understanding of the intricate interplay between solvent properties and nanoparticle growth, offering a valuable toolkit for designing and optimizing the synthesis of ZnO nanoparticles with specific shapes and functionalities.