Effect of Phase Transitions in Polymer Solutions on the Magnetic Response of Embedded Nanoparticles

Doping complex polymer solutions with magnetic nanoparticles opens up a class of functional materials. However, a distinct decrease in the degree of magnetic in-field alignment of nanoparticles upon crystallization of the carrier liquid is observed, which could pose a crucial hindrance for the preparation of such hybrid materials. To understand their behavior in detail, including their performance over extended temperature ranges and their structural transformations in the presence of external fields, it is useful to employ direct methods that provide information on the particle length scale. Here, we aim to understand the quasi-static magnetic behavior of magnetic particles in complex fluid environments employing aqueous solutions of poly(ethylene glycol) as model systems and discuss their thermomagnetic behavior under the influence of phase transitions. For this purpose, magnetically blocked nanoparticles based on cobalt ferrite (CoFe2O4) are utilized as tracer particles in temperature-dependent magnetization measurements complemented by differential scanning calorimetry (DSC). Following this approach, a detailed understanding of the impact of thermal phase transitions such as (eutectic) melting and freezing as well as glass transitions on the mobility of the particles is obtained at different concentration regimes

Size effects on rotational particle diffusion in complex fluids as probed by Magnetic Particle Nanorheology

Rheological approaches based on micro- or nanoscopic probe objects are of interest due to the low volume requirement, the option of spatially resolved probing, and the minimal-invasive nature often connected to such probes. For the study of microstructured systems or biological environments, such methods show potential for investigating the local, size-dependent diffusivity and particle–matrix interactions. For the latter, the relative length scale of the used probes compared to the size of the structural units of the matrix becomes relevant. In this study, a rotational-dynamic approach based on Magnetic Particle Nanorheology (MPN) is used to extract size- and frequency-dependent nanorheological properties by using an otherwise well-established polymer model system. We use magnetically blocked CoFe2O4 nanoparticles as tracers and systematically vary their hydrodynamic size by coating them with a silica shell. On the polymer side, we employ aqueous solutions of poly(ethylene glycol) (PEG) by varying molar mass M and volume fraction ϕ. The complex Brownian relaxation behavior of the tracer particles in solutions of systematically varied composition is investigated by means of AC susceptometry (ACS), and the results provide access to frequency dependent rheological properties. The size-dependent particle diffusivity is evaluated based on theoretical descriptions and macroscopic measurements. The results allow the classification of the investigated compositions into three regimes, taking into account the probe particle size and the length scales of the polymer solution. While a fuzzy cross-over is indicated between the well-known macroscopic behavior and structurally dominated spectra, where the hydrodynamic radius is equal to the radius of gyration of the polymer (rh ∼ Rg), the frequency-related scaling behavior is dominated by the correlation length ξ respectively by the tube diameter a in entangled solutions for rh < Rg

Recipe for High Moment Materials with Rare-earth and 3d Transition Metal Composites

Materials with high volume magnetization are perpetually needed for the generation of sufficiently large magnetic fields by writer pole of magnetic hard disks, especially for achieving increased areal density in storage media. In search of suitable materials combinations for this purpose, we have employed density functional theory to predict the magnetic coupling between iron and gadolinium layers separated by one to several monolayers of 3d transition metals (Sc-Zn). We demonstrate that it is possible to find ferromagnetic coupling for many of them and in particular for the early transition metals giving rise to high moment. Cr and Mn are the only elements able to produce a significant ferromagnetic coupling for thicker spacer layers. We also present experimental results on two trilayer systems Fe/Sc/Gd and Fe/Mn/Gd. From the experiments, we confirm a ferromagnetic coupling between Fe and Gd across a 3 monolayers Sc spacer or a Mn spacer thicker than 1 monolayer. In addition, we observe a peculiar dependence of Fe/Gd magnetic coupling on the Mn spacer thickness

Strain- and field-induced anisotropy in hybrid elastomers with elongated filler nanoparticles

The implementation of anisotropy to functional materials is a key step towards future smart materials. In this work, we evaluate the influence of preorientation and sample architecture on the strain-induced anisotropy in hybrid elastomers containing covalently attached elongated magnetic filler particles. Accordingly, silica coated spindle-type hematite nanoparticles are incorporated into poly(dimethylsiloxane)-based elastomers, and two types of composite architectures are compared: on the one hand a conventional architecture of filled, covalently crosslinked elastomers, and on the other hybrid elastomers that are crosslinked exclusively by covalent attachment of the polymer chains to the particle surface. By the application of external strain and with magnetic fields, the orientational order of the elongated nanoparticles can be manipulated, and we investigate the interplay between strain, magnetic order, and orientational order of the particles by combining 2D small angle X-ray scattering experiments under strain and fields with Mossbauer spectroscopy under similar conditions, and supplementary angular-dependent magnetization experiments. The converging information is used to quantify the order in these interesting materials, while establishing a direct link between the magnetic properties and the spatial orientation of the embedded magnetic nanoparticles

Superparamagnetic nanoparticles with LC polymer brush shell as efficient dopants for ferronematic phases

Liquid crystal (LC) based magnetic materials consisting of LC hosts doped with functional magnetic nanoparticles enable optical switching of the mesogens at moderate magnetic field strengths and thereby open the pathway for the design of novel smart devices. A promising route for the fabrication of stable ferronematic phases is the attachment of a covalently bound LC polymer shell onto the surface of nanoparticles. With this approach, ferronematic phases based on magnetically blocked particles and the commercial LC 4-cyano-4 '-pentylbiphenyl (5CB) liquid crystal were shown to have a sufficient magnetic sensitivity, but the mechanism of the magneto-nematic coupling is unidentified. To get deeper insight into the coupling modes present in these systems, we prepared ferronematic materials based on superparamagnetic particles, which respond to external fields with internal magnetic realignment instead of mechanical rotation. This aims at clarifying whether the hard coupling of the magnetization to the particle's orientation (magnetic blocking) is a necessary component of the magnetization-nematic director coupling mechanism. We herein report the fabrication of a ferronematic phase consisting of surface-functionalized superparamagnetic Fe3O4 particles and 5CB. We characterize the phase behavior and investigate the magneto-optical properties of the new ferronematic phase and compare it to the ferronematic system containing magnetically blocked CoFe2O4 particles to get information about the origin of the magneto-nematic coupling

Scale-dependent particle diffusivity and apparent viscosity in polymer solutions as probed by dynamic magnetic nanorheology

In several upcoming rheological approaches, including methods of micro- and nanorheology, the measurement geometry is of critical impact on the interpretation of the results. The relative size of the probe objects employed (as compared to the intrinsic length scales of the sample to be investigated) becomes of crucial importance, and there is increasing interest to investigate the dynamic processes and mobility in nanostructured materials. A combination of different rheological approaches based on the rotation of magnetically blocked nanoprobes is used to systematically investigate the size-dependent diffusion behavior in aqueous poly(ethylene glycol) (PEG) solutions with special attention paid to the relation of probe size to characteristic length scales within the polymer solutions. We employ two types of probe particles: nickel rods of hydrodynamic lengthL(h)between 200 nm and 650 nm, and cobalt ferrite spheres with diameterd(h)between 13 nm and 23 nm, and examine the influence of particle size and shape on the nanorheological information obtained in model polymer solutions based on two related, dynamic-magnetic approaches. The results confirm that as long as the investigated solutions are not entangled, and the particles are much larger than the macromolecular correlation length, a good accordance between macroscopic and nanoscopic results, whereas a strong size-dependent response is observed in cases where the particles are of similar size or smaller than the radius of gyrationR(g)or the correlation length xi of the polymer solution