Structure and dynamics in suspensions of magnetic platelets.

In this research, we employ Brownian dynamics simulations, density functional theory, and mean-field theory to explore the profound influence of shape anisotropy of magnetic nanoplatelets on suspension magnetic response. Each platelet is modelled as an oblate cylinder with a longitudinal point dipole, with an emphasis on strong dipolar interactions conducive to self-assembly. We investigate static structural and magnetic properties, characterising the system through pair distribution function, static structure factor, and cluster-size distribution. The findings demonstrate that shape-specific interactions and clustering lead to significant changes in reorientational relaxation times. Under zero field, distinctive modes in the dynamic magnetic susceptibility identify individual particles and particle clusters. In the presence of an applied field, the characteristic relaxation time of clusters increases, while that of single particles decreases. This research provides insights into the intricate interplay between shape anisotropy, clustering, and magnetic response in platelet suspensions, offering valuable perspectives for recent experimental observations.

Relating the length of a magnetic filament with solvophobic, superparamagnetic colloids to its properties in applied magnetic fields.

The idea of creating polymer-like structures by crosslinking magnetic nanoparticles (MNPs) opened an alternative perspective on controlling the rheological properties of magnetoresponsive systems, because unlike suspensions of self-assembled MNPs, whose cluster sizes are sensitive to temperature, magnetic filaments (MFs) preserve their initial topology. Considering the length scales characteristic of single-domain nanoparticles used to create MFs, the MNPs can be both ferro- and superparamagnetic. Moreover, steric or electrostatic stabilization might not fully screen van der Waals interactions. In this paper, using coarse-grained molecular dynamics simulations, we investigate the influence of susceptibility of superparamagnetic MNPs-their number and central attraction forces between them-on the polymeric, structural, and magnetic properties of MFs with varied backbone rigidity. We find that, due to the general tendency of MFs with superparamagnetic monomers to bend, reinforced for colloids with a high susceptibility, properties of MFs vary greatly with chain length.

Controlling the coarsening dynamics of ferrogranular networks by means of a vertical magnetic field.

We are exploring in experiments the aggregation process in a shaken granular mixture of glass and magnetized steel beads, filled in a horizontal vessel, after the shaking amplitude is suddenly decreased. Then the magnetized beads form a transient network that coarsens in time into compact clusters, resembling a viscoelastic phase separation [Tanaka, J. Phys.: Condens. Matter 12, R207 (2000)0953-898410.1088/0953-8984/12/15/201], where attached beads represent the slow phase. Here we investigate how a homogeneous magnetic field oriented in vertical direction impedes the emergence and growth of the networks. With increasing field amplitude this phase is replaced by a fluctuating arrangement of repelling, isolated steel beads. The experimental results are compared with those of computer simulations. Coarse-grained molecular dynamics confirms the impact of an applied magnetic field on the structural transitions and allows us to investigate long-time regimes and magnetic response not yet accessible in the experiment. It turns out that an applied magnetic field has different impacts, depending on it strength. It can be used either to slow down the dynamics of the structural transitions without changing the type of the resulting phases and only affecting the amount and sizes of clusters, or to fully impede the formation of network-like and compact aggregates of steel beads.

Multicore-based ferrofluids in zero field: initial magnetic susceptibility and self-assembly mechanisms.

The necessity to improve magnetic building blocks in magnetic nano-structured soft materials stems from a fascinating potential these materials have in bio-medical applications and nanofluidics. Along with practical reasons, the interplay of magnetic and steric interactions on one hand, and entropy, on the other, makes magnetic soft matter fundamentally challenging. Recently, in order to tailor magnetic response of the magnetic particle suspensions, the idea arose to replace standard single-core nanoparticles with nano-sized clusters of single-domain nanoparticles (grains) rigidly bound together by solid polymer matrix - multicore magnetic nanoparticles (MMNPs). To pursue this idea, a profound understanding of the MMNP interactions and self-assembly is required. In this work we present a computational study of the MMNP suspensions and elucidate their self-assembly and magnetic susceptibility. We show that depending on the magnetic moment of individual grains the suspensions exhibit qualitatively distinct regimes. Firstly, if the grains are moderately interacting, they contribute to a significant decrease of the remanent magnetisation of MMNPs and as such to a decrease of the magnetic susceptibility, this way confirming previous findings. If the grains are strongly interacting, instead, they serve as anchor points and support formation of grain clusters that span through several MMNPs, leading to MMNP cluster formation and a drastic increase of the initial magnetic response. Both the topology of the clusters and their size distribution in MMNP suspensions is found to be notably different from those formed in conventional magnetic fluids or magnetorheological suspensions.

Switching-field and first-order-reversal-curve distribution measurements in magnetic elastomers by molecular dynamics simulations: Accounting for polydispersity.

In this work we employ molecular dynamics simulations to investigate the first-order-reversal-curve distribution and switching-field distribution of magnetic elastomers. We model magnetic elastomers in a bead-spring approximation with permanently magnetized spherical particles of two different sizes. We find that a different fractional composition of particles affects the magnetic properties of elastomers obtained as a result. We prove that the hysteresis of the elastomer can be attributed to the broad energy landscape with multiple shallow minima and caused by dipolar interactions.

The influence of anisotropy on the microstructure and magnetic properties of dipolar nanoplatelet suspensions.

In recent years, there has been an increasing interest in magnetic nanoparticles with non-spherical shapes. This is largely due to their broad span of tuneable properties, which allow for tailoring of the colloidal properties by altering the magnetic anisometry or shape anisotropy of the nanoparticle. Although extensive research has gone into novel synthesis methods, the theoretical and analytical treatment of magnetic colloidal suspensions still predominantly focuses on spherical particles. This paper explores the microstructure and initial static magnetic susceptibility of systems of anisometric dipolar magnetic nanoplatelets in order to understand the applicability of dipolar sphere-based theories and models for such systems. We find that the microstructure as characterized by the particle distribution and magnetic clustering of platelets diverges significantly from that of spheres both quantitatively and qualitatively. We find lower initial static magnetic susceptibilities in nanoplatelet systems than in comparable suspensions of dipolar spheres. At lower values of the magnetic coupling constant, this can be accounted for by applying corrections to the volume fraction. However, this approach is less accurate for systems with stronger magnetic interactions. By providing predictions of and explanations for the observed effects, we aim to facilitate the use of magnetic nanoplatelet suspensions in the broad range of applications.

Magnetostatic response and field-controlled haloing in binary superparamagnetic mixtures.

Nowadays, magnetoresponsive soft materials, based not simply on magnetic nanoparticles but rather on multiple components with distinct sizes and magnetic properties in both liquid and polymeric carriers, are becoming more and more widespread due to their unique and versatile macroscopic response to an applied magnetic field. The variability of the latter is related to a complex interplay of the magnetic interactions in a highly nonuniform internal field caused by spatial inhomogeneity in multicomponent systems. In this work, we present a combined analytical and simulation study of binary superparamagnetic systems containing nanoclusters and dispersed single-domain nanoparticles in both liquid and solid carrier matrices. We investigate the equilibrium magnetic response of these systems for wide ranges of concentrations and interaction energies. It turns out that, while the magnetization of a binary solid can be both above and below that of an ideal superparamagnetic gas, depending on the concentration of the dispersed phase and the interparticle interactions, the system in a liquid carrier is highly magnetically responsive. In liquid, a spatial redistribution of the initially homogeneously dispersed phase in the vicinity of the nanocluster is observed, an effect that is reminiscent of the so-called haloing effect previously observed experimentally on micro- and milliscales.

Rheology of a Nanopolymer Synthesized through Directional Assembly of DNA Nanochambers, for Magnetic Applications.

We present a numerical study of the effects of monomer shape and magnetic nature of colloids on the behavior of a single magnetic filament subjected to the simultaneous action of shear flow and a stationary external magnetic field perpendicular to the flow. We find that based on the magnetic nature of monomers, magnetic filaments exhibit a completely different phenomenology. Applying an external magnetic field strongly inhibits tumbling only for filaments with ferromagnetic monomers. Filament orientation with respect to the flow direction is in this case independent of monomer shape. In contrast, reorientational dynamics in filaments with superparamagnetic monomers are not inhibited by applied magnetic fields, but enhanced. We find that the filaments with spherical, superparamagnetic monomers, depending on the flow and external magnetic field strength, assume semipersistent, collapsed, coiled conformations, and their characteristic time of tumbling is a function of field strength. However, external magnetic fields do not affect the characteristic time of tumbling for filaments with cubic, superparamagnetic monomers, but increase how often tumbling occurs.

Structural transitions and magnetic response of supramolecular magnetic polymerlike structures with bidisperse monomers.

Supramolecular magnetic polymerlike (SMP) structures are nanoscaled objects that combine the flexibility of polymeric conformations and controllability of magnetic nanoparticles. The advantage provided by the presence of permanent cross-linkers is that even at high temperature, a condition at which entropy dominates over magnetic interactions, the length and the topology of the SMP structures are preserved. On cooling, however, preexistent bonds constrain thermodynamically equilibrium configurations, making a low-temperature regime for SMP structures worth investigating in detail. Moreover, making SMP structures with perfectly monodisperse monomers has been a challenge. Thus, the second open problem in the application of SMP structures is the missing understanding of the polydispersity impact on their structural and magnetic properties. Here extensive Langevin dynamics simulations combined with parallel tempering method are used to investigate SMP structures of four different types, i.e., chainlike, Y-like, X-like, and ringlike, composed of monomers of two different sizes. Our results show that the presence of small particles in SMP structures can qualitatively change the magnetic response at low temperature, making those structures surprisingly more magnetically responsive than their monodisperse counterparts.

Nanopolymers for magnetic applications: how to choose the architecture?

Directional assembly of nanoscale objects results in morphologies that can broadly be classified as supra-molecular nanopolymers. Such morphologies, given a functional choice of the monomers used as building blocks, can be of ubiquitous utility in optical, magnetic, rheological, and medical applications. These applications, however, require a profound understanding of the interplay between monomer shape and bonding on one side, and polymeric properties - on the other. Recently, we fabricated nanopolymers using cuboid DNA nanochambers, as they not only allow fine-tuning of the resulting morphologies but can also carry magnetic nanoparticles. However, it is not known if the cuboid shape and inter-cuboid connectivity restrict the equilibrium confirmations of the resulting nanopolymers, making them less responsive to external stimuli. In this work, using Molecular Dynamics simulations, we perform an extensive comparison between various nanopolymer architectures to explore their polymeric properties, and their response to an applied magnetic field if magnetic nanoparticles are embedded. We explain the impact of monomer shape and bonding on the mechanical and magnetic properties and show that DNA nanochambers can build highly responsive and magnetically controllable nanopolymers.

Magneto-elastic coupling as a key to microstructural response of magnetic elastomers with flake-like particles.

Using the combination of experiment and molecular dynamics simulations, we investigate structural transformations in magnetic elastomers with NdFeB flake-like particles, caused by applied moderate magnetic fields. We explain why and how those transformations depend on whether or not the samples are initially cured by a short-time exposure to a strong field. We find that in a cured sample, a moderate magnetic field leads mainly to in-place flake rotations that are fully reversed once the applied field is switched off. In contrast, in an initially non-cured sample the flakes perform both translation and rotations under the influence of a moderate applied field that lead to the formation of chain-like structures that remain such even if the field is switched off.

Flux and separation of magneto-active superballs in applied fields.

The term "active matter" describes a class of out-of-equilibrium systems, whose ability to transform environmental to kinetic energy is sought after in multiple fields of science. A challenge that still remains is to craft nanometer-sized active particles, whose motion can be efficiently directed by externally applied bio-noninvasive stimuli. Adding a magnetic component and therefore being able to direct the motion of active nanoparticles with an applied magnetic field is one of the promising solutions in the field. In this study, we employ molecular dynamics simulations to predict an external field-induced flow that arises in mixtures of magneto-active nanosized cubic and spherical particles with distinct mutual orientations between magnetization and propulsion. We explain why the flux of the suspended particles in the field direction does not only depend on the angle between the active force, driving a particle forward, and the orientation of its magnetization, but also on particle shape and inter-particle interactions. Our results show that by tuning those parameters, one can achieve complete separation of particles according to their magnetization orientation. Based on our findings, along with optimizing the cargo properties of magneto-active nano-units, the actual composition of the magneto-active particle suspension can be characterized.

Divalent Multilinking Bonds Control Growth and Morphology of Nanopolymers.

Assembly of nanoscale objects into linear architectures resembling molecular polymers is a basic organization resulting from divalent interactions. Such linear architectures occur for particles with two binding patches on opposite sides, known as Janus particles. However, unlike molecular systems where valence bonds can be envisioned as pointlike interactions nanoscale patches are often realized through multiple molecular linkages. The relationship between the characteristics of these linkages, the resulting interpatch connectivity, and assembly morphology is not well-explored. Here, we investigate assembly behavior of model divalent nanomonomers, DNA nanocuboid with tailorable multilinking bonds. Our study reveals that the characteristics of individual molecular linkages and their collective properties have a profound effect on nanomonomer reactivity and resulting morphologies. Beyond linear nanopolymers, a common signature of divalent nanomonomers, we observe an effective valence increase as linkages lengthened, leading to the nanopolymer bundling. The experimental findings are rationalized by molecular dynamics simulations.

Self-diffusion in bidisperse systems of magnetic nanoparticles.

In the present paper, we study the self-diffusion of aggregating magnetic particles in bidisperse ferrofluids. We employ density functional theory (DFT) and coarse-grained molecular dynamics (MD) simulations to investigate the impact of granulometric composition of the system on the cluster self-diffusion. We find that the presence of small particles leads to the overall increase of the self-diffusion rate of clusters due the change in cluster size and composition.

Adsorption transition of a grafted ferromagnetic filament controlled by external magnetic fields.

Extensive Langevin dynamics simulations are used to characterize the adsorption transition of a flexible magnetic filament grafted onto an attractive planar surface. Our results identify different structural transitions at different ratios of the thermal energy to the surface attraction strength: filament straightening, adsorption, and the magnetic flux closure. The adsorption temperature of a magnetic filament is found to be higher in comparison to an equivalent nonmagnetic chain. The adsorption has been also investigated under the application of a static homogeneous external magnetic field. We found that the strength and the orientation of the field can be used to control the adsorption process, providing a precise switching mechanism. Interestingly, we have observed that the characteristic field strength and tilt angle at the adsorption point are related by a simple power law.

Directing the Diffusion of a Nonmagnetic Nanosized Active Particle with External Magnetic Fields.

With the help of molecular dynamics simulations we show that an arbitrary nonmagnetic active particle with a size below one micrometer, being immersed in a suspension of magnetic nanoparticles, can diffuse faster along the direction of an applied field than perpendicular to the latter. This effect is demonstrated in monodisperse and polydisperse systems of magnetic nanoparticles for magnetic fields of moderate strength. The ability to direct a nonmagnetic active particle along the magnetic field stems from the formation of chains of magnetic nanoparticles aligned with the field direction. Such chains form effective channels through which the active particle can diffuse. We combine the investigations of the diffusion and transport efficiency of the active particle parallel and perpendicular to the field with the structural analysis of the magnetic nanoparticle system and find that the ability to direct an active particle of a given size can be maximized by changing magnetic particle concentration. The optimal transport efficiency is achieved at a concentration of magnetic material that provides a mean width of the effective tunnels that matches the effective size of the active particle.

Correction: Characterisation of the magnetic response of nanoscale magnetic filaments in applied fields.

Correction for 'Characterisation of the magnetic response of nanoscale magnetic filaments in applied fields' by Deniz Mostarac et al., Nanoscale, 2020, DOI: .

Characterisation of the magnetic response of nanoscale magnetic filaments in applied fields.

Incorporating magnetic nanoparticles (MNPs) within permanently crosslinked polymer-like structures opens up the possibility for synthesis of complex, highly magneto-responsive systems. Among such structures are chains of prealigned magnetic (ferro- or super-paramagnetic) monomers, permanently crosslinked by means of macromolecules, which we refer to as magnetic filaments (MFs). In this paper, using molecular dynamics simulations, we encompass filament synthesis scenarios, with a compact set of easily tuneable computational models, where we consider two distinct crosslinking approaches, for both ferromagnetic and super-paramagnetic monomers. We characterise the equilibrium structure, correlations and magnetic properties of MFs in static magnetic fields. Calculations show that MFs with ferromagnetic MNPs in crosslinking scenarios where the dipole moment orientations are decoupled from the filament backbone, have similar properties to MFs with super-paramagnetic monomers. At the same time, magnetic properties of MFs with ferromagnetic MNPs are more dependent on the crosslinking approach than they are for ones with super-paramagnetic monomers. Our results show that, in a strong applied field, MFs with super-paramagnetic MNPs have similar magnetic properties to ferromagnetic ones, while exhibiting higher susceptibility in low fields. We find that MFs with super-paramagnetic MNPs have a tendency to bend the backbone locally rather than to fully stretch along the field. We explain this behaviour by supplementing Flory theory with an explicit dipole-dipole interaction potential, with which we can take in to account folded filament configurations. It turns out that the entropy gain obtained through bending compensates an insignificant loss in dipolar energy for the filament lengths considered in the manuscript.

Self-assembly of charged colloidal cubes.

In this work, we show how and why the interactions between charged cubic colloids range from radially isotropic to strongly directionally anisotropic, depending on tuneable factors. Using molecular dynamics simulations, we illustrate the effects of typical solvents to complement experimental investigations of cube assembly. We find that in low-salinity water solutions, where cube self-assembly is observed, the colloidal shape anisotropy leads to the strongest attraction along the corner-to-corner line, followed by edge-to-edge, with a face-to-face configuration of the cubes only becoming energetically favorable after the colloids have collapsed into the van der Waals attraction minimum. Analysing the potential of mean force between colloids with varied cubicity, we identify the origin of the asymmetric microstructures seen in experiment.

The structure of clusters formed by Stockmayer supracolloidal magnetic polymers.

Unlike Stockmayer fluids, that prove to undergo gas-liquid transition on cooling, the system of dipolar hard or soft spheres without any additional central attraction so far has not been shown to have a critical point. Instead, in the latter, one observes diverse self-assembly scenarios. Crosslinking dipolar soft spheres into supracolloidal magnetic polymer-like structures (SMPs) changes the self-assembly behaviour. Moreover, aggregation in systems of SMPs strongly depends on the constituent topology. For Y- and X-shaped SMPs, under the same conditions in which dipolar hard spheres would form chains, the formation of very large loose gel-like clusters was observed (E. Novak et al., J. Mol. Liq. 271, 631 (2018)). In this work, using molecular dynamics simulations, we investigate the self-assembly in suspensions of four topologically different SMPs --chains, rings, X and Y-- whose monomers interact via Stockmayer potential. As expected, compact drop-like clusters are formed by SMPs in all cases if the central isotropic attraction is introduced, however, their shape and internal structure turn out to depend on the SMPs topology.