Combining nuclear magnetic resonance and molecular dynamics simulations, we unravel the long-time dynamics of a paradigmatic colloid with strong dipole-dipole interactions. In a homogeneous magnetic field, ionic ferrofluids exhibit a stepwise association process from ensembles of monomers over stringlike chains to bundles of hexagonal zipped-chain patches. We demonstrate that attractive van der Waals interactions due to charge-density fluctuations in the magnetic particles play the key role for the dynamical stabilization of the hexagonal superstructures against thermal dissociation. Our results give insight into the dynamics of self-organization in systems dominated by dipolar interactions.

Although nuclear magnetic resonance (NMR) is one of the most powerful analytical techniques, it has not been widely used as a non-destructive, non-contact inline industrial sensor. A short background of NMR spectroscopy fundamentals and instrumentation is presented along with its potential applications and limitations for real-time analysis in the manufacturing sector. NMR signals are generated in the presence of a magnetic field normally produced by expensive large and heavy magnets which have been the major limiting factor in the use of NMR analysis in factories. However, the last decade has brought substantial advances in the development of cheaper, smaller, and lighter permanent magnets based on rare earth materials that use Halbach and unilateral configurations. Small and light cryogenic-free superconducting magnets are now offered in the market and are opening a new era in manufacturing. It is expected that soon NMR spectroscopy will be applied to monitor the chemical and physical properties of complex feedstock mixtures and reactions in real time which is the ultimate goal of precise process control.

No abstract

aWe have used low-field 1 H nuclear-magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) to investigate the aggregation dynamics of magnetic particles in ionic ferrofluids (IFFs) in the presence of magnetic field gradients. At the beginning of the experiments, the measured NMR spectra were broad and asymmetric, exhibiting two features attributed to different dynamical environments of water protons, depending on the local strength of the field gradients. Hence, the spatial redistribution of the magnetic particles in the ferrofluid caused by the presence of an external magnetic field in a time scale of minutes can be monitored in real time, following the changes in the features of the NMR spectra during a period of about an hour. As previously reported [Heinrich et al., Phys. Rev. Lett., 2011, 106, 208301], in the homogeneous magnetic field of a NMR spectrometer, the aggregation of the particles of the IFF proceeds in two stages. The first stage corresponds to the gradual aggregation of monomers prior to and during the formation of chain-like structures. The second stage proceeds after the chains have reached a critical average length, favoring lateral association of the strings into hexagonal zipped-chain superstructures or bundles. In this work, we focus on the influence of a strongly inhomogeneous magnetic field on the aforementioned aggregation dynamics. The main observation is that, as the sample is immersed in a certain magnetic field gradient and kept there for a time t inh , magnetophoresis rapidly converts the ferrofluid into an aggregation state which finds its correspondence to a state on the evolution curve of the pristine sample in a homogeneous field. From the degree of aggregation reached at the time t inh , the IFF sample just evolves thereafter in the homogeneous field of the NMR spectrometer in exactly the same way as the pristine sample. The final equilibrium state always consists of a colloidal suspension of zipped-chain bundles with the chain axes aligned along the magnetic field direction.