Van De Waals Research Articles

The electronic and magnetic properties modulated by ferroelectric polarization switching in two-dimensional VSeTe/Sc2CO2 van der Waals heterostructures.

Exploring multiferroic materials that combine magnetic and ferroelectric properties is scientifically interesting and has important technical implications for many functions of nanoscale devices. In this work, spintronics and magnetoelectric coupling devices are proposed in two-dimensional (2D) layered ferromagnetic (FM)/ferroelectric (FE) van de Waals (vdW) heterostructures, VSeTe/Sc2CO2, employing density functional theory (DFT) calculations. The results indicate that the VSeTe/Sc2CO2 vdW heterostructure changes from a metal to a semiconductor in Sc2CO2-P↑ and Sc2CO2-P↓ polarization states. At the same time, the charge at the interface of the VSeTe/Sc2CO2 heterostructure will also be redistributed with the transformation of the ferroelectric polarization state, resulting in the change of the distribution of the electronic states near the Fermi level, and thus the change in the magnetic anisotropy energy (EMAE) of the heterostructure. Interestingly, biaxial strain brings reversibility and non-volatile regulation to the heterostructure of semiconductors and metals. The results provide an effective way to fabricate magnetoelectric coupling devices with 2D multiferroic heterostructures.

Generalization of interfacial thermal conductance based on interfacial phonon localization

Interfacial energy transport is of great engineering and scientific importance. Traditional theoretical treatment based on phonon reflection and transmission only provides qualitative understanding of the interfacial thermal conductance (G). In the interface region, the material has gradual (covalent) or abrupt (van de Waals) physical structure transition, each transition features interface-region atomic interactions that are different from those of both adjoining sides. This difference makes the interface-region phonons extremely localized. Here, by constructing an “equivalent interfacial medium” (EIM) that accounts for the extremely localized phonon region, G can be described by a universal physical model that is characterized by an “interface characteristic temperature” (Θint) and energy carrier transfer time. The EIM model fits widely reported G ∼ T (T: temperature) data with high accuracy and provides remarkable prediction of G at different temperatures based on 2–3 experimental data points. Under normalized temperature (T/Θint) and interfacial thermal conductance (G/Gmax), all literature data of G can be universally grouped to a single curve. The EIM model provides a solid correlation between G and interfacial structure and is expected to significantly advance the physical understanding and design of interfacial energy transport toward high-efficiency energy conversion, transport, and micro/nanoelectronics.

Multimodal Spectroscopy Assays for Advanced Nano-Optics Approaches by Tuning Nano-Tool Surface Chemistry and Metal-Enhanced Fluorescence

In this research work, different chemical modifications were applied to gold nanoparticles and their use in enhanced non-classical light emitters based on metal-enhanced fluorescence (MEF) was evaluated. In order to achieve this, gold core–shell nanoparticles with silica shells were modified via multilayered addition and the incorporation of a covalently linked laser dye to develop MEF. Their inter-nanoparticle interactions were evaluated by using additional silica shell multilayers and modified cyclodextrin macrocycles. In this manner, the sizes and chemical surface interactions on the multilayered nanoarchitectures were varied. These optical active nanoplatforms led to the development of different nanoassembly sizes and luminescence behaviors. Therefore, the interactions and nanoassembly properties were evaluated by using various spectroscopic and nanoimaging techniques. Highly dispersible gold core–shell nanoparticles with diameters of 50–60 nm showed improved colloidal dispersion that led to single ultraluminescent gold core–shell nanoparticles with MEF. Then, the addition of variable silica lengths produced increased interactions and consequent nanoaggregation. However, the silanized nanoparticles were easily dispersible after agitation or sonication. Thus, their sizes were proportional only to the diameter and the van de Waals interaction did not affect their sizes in bulk. Then, the covalent linking of different concentrations of modified cyclodextrins was applied to the chemical surfaces by incorporating additional hydroxyl groups from the glucose monomeric unities of cyclodextrins. In this manner, variable larger-sized and inter-branched grafted gold core–shell silica nanoparticles were generated. The ultraluminescent properties were conserved due to the non-optical activity of the cyclodextrins. However, they generated enhanced ultraluminescence phenomena. Laser fluorescence microscopy nanoimaging showed enhanced resolutions in comparison to non-grafted supramolecular gold core–shell nanoparticles. The differences in their interactions and the sizes of the nanoassemblies were explained by their single nanoparticle diameters and the interacting chemical groups on their nanosurfaces. While the varied luminescence emissions generated were tuned by plasmonics, enhanced plasmonic phenomena and light scattering properties were seen depending on the type of nanoassembly. Thus, optically active and non-optically active materials led to different optical properties in the bright field and enhanced the excited state within the electromagnetic near-field of the gold nanotemplates. In this manner, it was possible to achieve high sensitivity by varying the spacer lengths and optical properties. Therefore, further perspectives regarding the design of nano-tools composed of light for various applications were discussed.

First-principles study on a Li-decorated two-dimensional g-C6N6 monolayer: A promising ambient temperature reversible H2 storage material

Designing novel materials that exhibit superior reversibility and function under ambient conditions can facilitate the development of hydrogen energy applications. Two-dimensional (2D) g-C6N6 monolayers show great potential for use in hydrogen storage owing to their nanoporous structure, ultralight mass, and flexible electronic structure. However, the hydrogen storage potential of these materials is limited by the naturally weak interaction between 2D materials and hydrogen molecules caused by van de Waals forces. To address this issue, we studied the hydrogen storage performance of the complex by decorating active Li ions on a 2D g-C6N6 substrate through first-principles calculations. Our results showed that modifying the Li ions did not cause the original planar structure to deform but rather induced more active sites for hydrogen adsorption by establishing an electrostatic field between the Li ions and the g-C6N6 monolayer. Through this modification, reversible hydrogen storage was achieved under ambient conditions with an average adsorption energy of −0.197 eV/H2 and a high gravimetric capacity of 5.88 wt%. The electronic properties of the material were systematically investigated, and the results suggested that the enhanced capacity of the Li@ g-C6N6 system to store hydrogen resulted from the formation of a polarization field and the induced electrostatic effect. Our research offers a new possibility for achieving reversible hydrogen energy storage at room temperature.

Energy, water, and protein folding: A molecular dynamics-based quantitative inventory of molecular interactions and forces that make proteins stable.

Protein folding energetics can be determined experimentally on a case-by-case basis but it is not understood in sufficient detail to provide deep control in protein design. The fundamentals of protein stability have been outlined by calorimetry, protein engineering, and biophysical modeling, but these approaches still face great difficulty in elucidating the specific contributions of the intervening molecules and physical interactions. Recently, we have shown that the enthalpy and heat capacity changes associated to the protein folding reaction can be calculated within experimental error using molecular dynamics simulations of native protein structures and their corresponding unfolded ensembles. Analyzing in depth molecular dynamics simulations of four model proteins (CI2, barnase, SNase, and apoflavodoxin), we dissect here the energy contributions to ΔH (a key component of protein stability) made by the molecular players (polypeptide and solvent molecules) and physical interactions (electrostatic, van der Waals, and bonded) involved. Although the proteins analyzed differ in length, isoelectric point and fold class, their folding energetics is governed by the same quantitative pattern. Relative to the unfolded ensemble, the native conformations are enthalpically stabilized by comparable contributions from protein-protein and solvent-solvent interactions, and almost equally destabilized by interactions between protein and solvent molecules. The native protein surface seems to interact better with water than the unfolded one, but this is outweighed by the unfolded surface being larger. From the perspective of physical interactions, the native conformations are stabilized by van de Waals and Coulomb interactions and destabilized by conformational strain arising from bonded interactions. Also common to the four proteins, the sign of the heat capacity change is set by interactions between protein and solvent molecules or, from the alternative perspective, by Coulomb interactions.

Electric field and strain tunable band gap and band alignments of MoSi2N4/MSe (M = In, Ga) van der Waals heterostructures

Using Van de Waals heterostructures (VDWH) to engineer novel electronic properties of two-dimensional (2D) material systems has proven to be a viable strategy in recent years. Given the excellent mechanical...

In vitro and in silico analyses reveal the interaction between LysM receptor-like kinase3 of Solanum tuberosum and the carbohydrate elicitor Riclin octaose.

As a carbohydrate elicitor, Riclin octaose (Rioc) activates the pattern-triggered immunity of Solanum tuberosum L., while how the plant perceives Rioc is unknown. Here, a pattern recognition receptor StLYK3 (LysM receptor-like kinase3) whose transcription level was significantly up-regulated after Rioc elicitation was investigated in vitro and in silico. The nucleotide that encoded the ectodomain of StLYK3 (StLYK3-ECD) was heterologously expressed in the Pichia pastoris strain GS115. The purified StLYK3-ECD had the molecular weight of 25.08kDa and pI of 5.69. Afterwards interaction between StLYK3-ECD and Rioc was analyzed by isothermal titration calorimetry. The molar ratio of ligand to receptor, dissociation constant, and enthalpy were 1.28±0.04, 26.7±3.1μM, and -45.0±1.8kJmol-1 , respectively. Besides, molecular dynamics results indicated that StLYK3-ECD contained three carbohydrate-binding motifs and the first two motifs probably contributed to the interaction with Rioc via hydrogen bond and van de Waals' forces. Amino acids containing hydroxyl, amidic, and sulfhydryl groups took the main portion in the docking site. Moreover, replacing the 92nd threonyl (T) of StLYK3-ECD with valyl (V) resulted in the alteration of the preferred docking site. The dissociation constant drastically increased to 841.6±232.4μM. In conclusion, StLYK3 was a potential receptor of Rioc.

Reconfigurable Multifunctional van der Waals Ferroelectric Devices and Logic Circuits.

Emerging reconfigurable devices are fast gaining popularity in the search for next-generation computing hardware, while ferroelectric engineering of the doping state in semiconductor materials has the potential to offer alternatives to traditional von-Neumann architecture. In this work, we combine these concepts and demonstrate the suitability of reconfigurable ferroelectric field-effect transistors (Re-FeFETs) for designing nonvolatile reconfigurable logic-in-memory circuits with multifunctional capabilities. Modulation of the energy landscape within a homojunction of a 2D tungsten diselenide (WSe2) layer is achieved by independently controlling two split-gate electrodes made of a ferroelectric 2D copper indium thiophosphate (CuInP2S6) layer. Controlling the state encoded in the program gate enables switching between p, n, and ambipolar FeFET operating modes. The transistors exhibit on-off ratios exceeding 106 and hysteresis windows of up to 10 V width. The homojunction can change from Ohmic-like to diode behavior with a large rectification ratio of 104. When programmed in the diode mode, the large built-in p-n junction electric field enables efficient separation of photogenerated carriers, making the device attractive for energy-harvesting applications. The implementation of the Re-FeFET for reconfigurable logic functions shows how a circuit can be reconfigured to emulate either polymorphic ferroelectric NAND/AND logic-in-memory or electronic XNOR logic with a long retention time exceeding 104 s. We also illustrate how a circuit design made of just two Re-FeFETs exhibits high logic expressivity with reconfigurability at runtime to implement several key nonvolatile 2-input logic functions. Moreover, the Re-FeFET circuit demonstrates high compactness, with an up to 80% reduction in transistor count compared to standard CMOS design. The 2D van de Waals Re-FeFET devices therefore exhibit promising potential for both More-than-Moore and beyond-Moore future of electronics, in particular for an energy-efficient implementation of in-memory computing and machine learning hardware, due to their multifunctionality and design compactness.

Thermodynamic quantities and phase transitions of five-dimensional de Sitter hairy spacetime* *Supported by the National Natural Science Foundation of China (12075143)

In this study, we take the mass, electric charge, hair parameter, and cosmological constant of five-dimensional de Sitter hairy spacetime as the state parameters of the thermodynamic system, and when these state parameters satisfy the first law of thermodynamics, the equivalent thermodynamic quantities of spacetime and the Smarr relation of five-dimensional de Sitter hairy spacetime are obtained. Then, we study the thermodynamic characteristics of the spacetime described by these equivalent thermodynamic quantities and find that de Sitter hairy spacetime has a phase transition and critical phenomena similar to those of van de Waals systems or charged AdS black holes. It is shown that the phase transition point of de Sitter hairy spacetime is determined by the ratio of two event horizon positions and the cosmic event horizon position. We discuss the influence of the hair parameter and electric charge on the critical point. We also find that the isochoric heat capacity of the spacetime is not zero, which is consistent with the ordinary thermodynamic system but differs from the isochoric heat capacity of AdS black holes, which is zero. Using the Ehrenfest equations, we prove that the critical phase transition is a second order equilibrium phase transition. Research on the thermodynamic properties of five-dimensional de Sitter hairy spacetime lays a foundation for finding a universal de Sitter spacetime thermodynamic system and studying its thermodynamic properties. Our universe is an asymptotically dS spacetime, and the thermodynamic characteristics of de Sitter hairy spacetime will help us understand the evolution of spacetime and provide a theoretical basis to explore the physical mechanism of the accelerated expansion of the universe.

Ultracompact single-nanowire-morphed grippers driven by vectorial Lorentz forces for dexterous robotic manipulations

Ultracompact and soft pairwise grippers, capable of swift large-amplitude multi-dimensional maneuvering, are widely needed for high-precision manipulation, assembly and treatment of microscale objects. In this work, we demonstrate the simplest construction of such robotic structures, shaped via a single-nanowire-morphing and powered by geometry-tailored Lorentz vectorial forces. This has been accomplished via a designable folding growth of ultralong and ultrathin silicon NWs into single and nested omega-ring structures, which can then be suspended upon electrode frames and coated with silver metal layer to carry a passing current along geometry-tailored pathway. Within a magnetic field, the grippers can be driven by the Lorentz forces to demonstrate swift large-amplitude maneuvers of grasping, flapping and twisting of microscale objects, as well as high-frequency or even resonant vibrations to overcome sticky van de Waals forces in microscale for a reliable releasing of carried payloads. More sophisticated and functional teamwork of mutual alignment, precise passing and selective light-emitting-diode unit testing and installation were also successfully accomplished via pairwise gripper collaborations. This single-nanowire-morphing strategy provides an ideal platform to rapidly design, construct and prototype a wide range of advanced ultracompact nanorobotic, mechanical sensing and biological manipulation functionalities.

Thermodynamics of phase transition in Reissner–Nordström–de Sitter spacetime

The Reissner-Nordstrm̈-de Sitter (RN-dS) spacetime can be considered as a thermodynamic system. Its thermodynamic properties are discussed that the RN-dS spacetime has phase transitions and critical phenomena similar to that of the Van de Waals system or the charged AdS black hole. The continuous phase transition point of RN-dS spacetime depends on the position ratio of the black hole horizon and the cosmological horizon. We discuss the critical phenomenon of the continuous phase transition of RN-dS spacetime according to Landau theory of continuous phase transition, that the critical exponent of spacetime is same as that of the Van de Waals system or the charged AdS black hole, which have universal physical meaning. We find that the order parameters are similar to those introduced in ferromagnetic systems. Our universe is an asymptotically dS spacetime, thermodynamic characteristics of RN-dS spacetime can help us understand the evolution of spacetime and provide a theoretical basis to explore the physical mechanism of accelerated expansion of the universe.

Anionic regulation and valence band convergence boosting the thermoelectric performance of Se-alloyed GeSb2Te4 single crystal

GeSb2Te4, a layer-structured pseudo-binary chalcogenide, is a promising thermoelectric material with low lattice thermal conductivity ensured by the van de Waals gap. However, its excessive hole concentration leads to low Seebeck coefficient and limited thermoelectric performance. Herein, GeSb2(Te1-xSex)4 (x = 0, 0.05, 0.07, 0.1, and 0.15) single crystals were grown via Bridgman method for thermoelectric performance investigation, with single crystals to utilize the anisotropic low lattice thermal conductivity, and Se-alloying as the strategy to optimize the thermoelectric performance. It was found that Se alloying increases the Seebeck coefficients, deriving from the reduced carrier concentrations due to the enlarged formation energy of intrinsic GeSb(A1), GeSb(A2), and VGe(A2) defects, as well as the simultaneous enhancement of density-of-states effective mass from a facilitated valence band convergence. Besides, Se-alloying also contributes to the reduction of the lattice thermal conductivity. With the forementioned benefits, a high figure of merit of 1.02 is obtained at 723 K in the out-of-plane direction of the crystal sample GeSb2(Te0.9Se0.1)4, and a 74% improvement on average zT is gained. The study of anionic regulation and valence band convergence in GeSb2Te4-based single crystal provides an effective pathway for performance optimization in related layer-structured thermoelectric materials.

Enzymatic hydrolysis lignin dissolution and low-temperature solvolysis in ethylene glycol

The dissolution and solvolysis processes of enzymatic hydrolysis lignin (EHL) in ethylene glycol are investigated. Ethylene glycol exhibits high EHL solubility and achieves complete EHL dissolution at room temperature. Gaussian simulation reveals that van de Waals interactions between ethylene glycol and EHL, including C-H⋯O and lone pair⋯π interactions, break the π-π stacking in EHL, achieving complete EHL dissolution. EHL is partly depolymerized in ethylene glycol at 200 °C even without a catalyst due to the strong van de Waals interactions. When NaOH and Ni are used as co-catalysts, EHL is efficiently depolymerized at 200 °C, and the overall monomer yield reaches 18.8 wt%. Fourier transform infrared spectroscopy (FT-IR) and molecular dynamics simulation results indicate that the adsorption of ethylene glycol over Ni surface hinders the adsorption of lignin fragments and monomers. Hence, EHL catalytic solvolysis in ethylene glycol occurs in the liquid phase, where OH− of NaOH promotes the EHL linkage breakage and active hydrogen atoms formed on Ni surface stabilize the active monomers.

DFT study of superlight ambient temperature reversible H2 storage media based on Li decorated on new planar BCN

A novel 2D pm-BCN monolayer with unique porous geometry, superlight mass, and superior stability is a promising candidate for hydrogen storage. However, pure 2D materials suffer from the weak Van de Waals interaction between the H2, and modification becomes necessary to improve their performance. Here, we design a new complex by decorating active Li ions on the 2D pm-BCN substrate. The decoration of Li can transfer a partial electron to the substrate pm-BCN, which enhances the original π bonding among pm-BCN and induce more active sites on it. Both Li and BCN can act as the adsorption sites. The H2 can realize reversible adsorption under an ambient condition with average adsorption energy of −0.20 eV/H2 and a gravimetric capacity of 6.34 wt%, which surpasses the targe value set by U.S. Department of Energy (DOE). Rigorous analysis of its electronic properties, including a partial density of states, charge density, and crystal orbital overlap population, illustrates that the polarization mechanism contributes to the enhancement of the hydrogen storage capacity of Li@pm-BCN.

Enabling molecular dynamics simulations of helium bubble formation in tritium-containing austenitic stainless steels: An Fe-Ni-Cr-H-He potential

Formation of helium bubbles impacts mechanical properties of materials used in nuclear applications. An Fe-Ni-Cr-H-He quinary potential capable of direct molecular dynamics simulations of nucleation and growth of helium bubbles from randomly-born helium interstitial atoms has been developed. This is accomplished by incorporating helium into an existing Fe-Ni-Cr-H quaternary potential while addressing three challenging paradoxes characterizing helium in austenitic stainless steels: (a) interstitial He atoms form tightly bound dimers and larger clusters in the lattice but He atoms are only bound by weak van de Waals forces in the pure gas phase, (b) He atoms diffuse readily in host metals yet significantly distort the lattice causing large volume expansions, and (c) He atoms prefer tetrahedral interstitial sites as opposed to the larger octahedral sites despite large repulsive interactions with metal atoms within the lattice. We demonstrate that our potential reproduces density functional theory results on important properties relevant to helium bubble nucleation and growth. In addition to molecular statics validation of static properties, molecular dynamics simulation tests establish that our potential leads to the nucleation of helium bubbles from an initial random distribution of He interstitial atoms while at the same time capturing the equation of state in the pure He phase.

Silane coupling agent impact on surface features of modification of basalt fibers and the rheological properties of basalt fiber reinforced asphalt

Rheological properties of fiber reinforced asphalt (FRA) can be significantly influenced by the surface properties of fibers. Modified basalt fibers are emerging materials used to enhance the performance of FRA. Silane coupling agents (SCAs) make it possible to introduce versatile surface features to basalt fibers (BFs). Six typical SCAs were tested and evaluated for modifications on the rheological properties of BF reinforced asphalt at different high-level temperatures. The specific characteristics of each modified BF was measured by dynamic surface tension meter, denoted as surface energy components (SFEC), calculated using two distinct methods, OWRK (dispersive-polar approach) and vOCG (acid-base approach). The semi-quantitative correlation between SFEC based on each method and rheological properties with regard to temperature response were detailed. Study results show that Van de Waals interaction and acid-base interaction is more suitable to describe the interaction between asphalt and basalt fibers, and the interaction mechanism changes when temperature increases. Our research provides a guidance in the modification of SCAs when used in combination with mineral fillers to improve the overall performance of asphalt mixtures. Additionally, a novel SCA carrying long chain alkanes (UP312) shows high potential for modifying mineral fillers with excellent water resistance and improvement in the rutting resistance of asphalt concrete.

Effect of surface Se concentration on stability and electronic structure of monolayer Bi2O2Se

Structural stability is one of the most fundamental issues to explore the applications of two-dimensional (2D) materials. Se-terminated bismuth oxychalcogenide, Bi2O2Se, attracts extensive attention as its quasi-2D nature, which links traditional three-dimensional (3D) and van de Waals 2D materials. Herein, we systematically constructed Bi2O2Se monolayers with different surface Se concentrations and studied their structural stability under different chemical environments. The stability of Bi2O2Se monolayer is found to be sensitive to the surface Se concentration, i.e., its formation energy decreases linearly until the Se concentration increases to 50% and then remains flat. Five monolayers with 0%, 12.5%, 50%, 87.5% and 100% Se concentrations are found to be highly stable at different chemical environments from Se-poor to Se-rich. Among them, the 50% Se concentration is high-symmetry with a neat BiO layer sandwiched between two Se layers, showing a direct-gap semiconducting nature. Structural deformation occurs in the other four Se concentrations, resulting in a p-type semiconductor characteristic with in-gap states. Scanning tunneling microscope simulations characterize the arrangement of atoms on the surfaces, and reflect the distribution of the local electronic structure. Our work is expected to provide further insight into the stability of Bi2O2Se monolayers and advance the understanding on other quasi-2D materials.

Generic prediction of exocytosis rate constants by size-based surface energies of nanoparticles and cells

Nanotechnology brings benefits in fields such as biomedicine but nanoparticles (NPs) may also have adverse health effects. The effects of surface-modified NPs at the cellular level have major implications for both medicine and toxicology. Semi-empirical and mechanism-based models aid to understand the cellular transport of various NPs and its implications for quantitatively biological exposure while avoiding large-scale experiments. We hypothesized relationships between NPs-cellular elimination, surface functionality and elimination pathways by cells. Surface free energy components were used to characterize the transport of NPs onto membranes and with lipid vesicles, covering both influences by size and hydrophobicity of NPs. The model was built based on properties of neutral NPs and cells, defining Van de Waals forces, electrostatic forces and Lewis acid–base (polar) interactions between NPs and vesicles as well as between vesicles and cell membranes. We yielded a generic model for estimating exocytosis rate constants of various neutral NPs by cells based on the vesicle-transported exocytosis pathways. Our results indicate that most models are well fitted (R2 ranging from 0.61 to 0.98) and may provide good predictions of exocytosis rate constants for NPs with differing surface functionalities (prediction errors are within 2 times for macrophages). Exocytosis rates differ between cancerous cells with metastatic potential and non-cancerous cells. Our model provides a reference for cellular elimination of NPs, and intends for medical applications and risk assessment.

Adsorption and diffusion properties of calcium ions at the van der Waals interface of NbSe2-graphene 2D heterostructure for multivalent battery applications: density functional theory calculations

Multivalent-ion batteries such as calcium-ion batteries show promise as a high-density alternative to lithium-ion batteries which currently dominate the portable electronics market. In this work, the adsorption and diffusion properties of calcium ion at the van der Waals (vdW) interface of the 2D heterostructure formed by vertically stacking NbSe2 monolayer and graphene were investigated via density functional theory (DFT) calculations. Results showed that calcium can be effectively adsorbed on the vdW interface of the 2D heterostructure, with the binding energy of most stable site at −2.77 eV, much higher than most metal ions’ binding on pristine graphene. Thus, the NbSe2-graphene 2D heterostructure reinforced the binding of calcium ions at the interface. It is revealed that due to the random stacking nature of NbSe2 and graphene, a multi-path minimum energy pathways were identified at the van de Waals region, with relatively low diffusion barriers of around 0.20–0.50 eV. These indicate the capabilities of the 2D vdW heterostructure for fast multivalent ionic mobility and charge-discharge rate, while maintaining strong binding at the vdW interface. The results reveal NbSe2-graphene 2D vdW heterostructure’s potential as a promising anode material for multivalent battery applications.

Rheology of Poly(glycidyl methacrylate) Macromolecular Nano Assemblies.

A recently reported combined polymerization process of glycidyl methacrylate, mediated by homometallic and heterobimetallic aluminium complexes, naturally produces nano-sized macromolecular assemblies. In this work, the morphological features and the rheological properties of these novel nanoassemblies are studied. The hydrodynamic sizes of the nanoparticles in the solution range from 10 to 40 nm (in numbers), but on a flat surface they adopt a characteristic thin disk shape. The dynamic moduli have been determined in a broad range of temperatures, and the time—temperature superposition applied to obtain master curves of the whole viscoelastic response from the glassy to the terminal regions. The fragility values obtained from the temperature dependence are of m ~40, typical of van de Waals liquids, suggesting a very effective packing of the macromolecular assemblies. The rheological master curves feature a characteristic viscoelastic relaxation with the absence of elastic intermediate plateau, indicating that the systems behaved as un-entangled polymers. The analysis of the linear viscoelastic fingerprint reveals a Zimm-like dynamics at intermediate frequencies typical of unentangled systems. This behaviour resembles that observed in highly functionalized stars, dendrimers, soft colloids and microgels.