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Ferromagnetic liquid droplets with adjustable magnetic properties

Significance Structured functional liquids combine mechanical versatility of fluids with solid-state properties, such as ferromagnetism, and offer a route to synthesize and control magnetic liquids for adaptive liquid robotics. Studies on these intriguing materials are only in their nascent state, and a profound understanding of the physical state is still lacking. We use hydrodynamics experiments to probe how the magnetization of ferromagnetic liquid droplets, governed by the assembly and jamming of magnetic nanoparticles at liquid–liquid interfaces, and their response to external stimuli can be tuned by chemical, structural, and magnetic means. Our results highlight the leading role of structural short-range order on magnetic properties, which provide a path toward nano-patterning structured liquids.

36 MATERIALS SCIENCE↗

Ballistic Ejection of Microdroplets from Overpacked Interfacial Assemblies

Spontaneous emulsification, resulting from the assembly and accumulation of surfactants at liquid–liquid interfaces, is an interfacial instability where microdroplets are generated and diffusively spread from the interface until complete emulsification. Here, it is shown that an external magnetic field can modulate the assembly of paramagnetic nanoparticle surfactants (NPSs) at liquid–liquid interfaces to trigger an oversaturation in the areal density of the NPSs at the interface, as evidenced by a marked reduction in the interfacial tension, γ, and corroborated with a magnetostatic continuum theory. Despite the significant reduction in γ, the presence of the magnetic field does not cause stable interfaces to become unstable. Upon rapid removal of the field, however, an explosive ejection of a plume of microdroplets from the surface occurs, a dynamical interfacial instability which is termed explosive emulsification. Further, this explosive event rapidly reduces the areal density of the NPSs to its pre-field level, stabilizing the interface. The ability to externally suppress or trigger the explosive emulsification and controlled generation of tens of thousands of microdroplets, uncovers an efficient energy storage and release process, that has potential applications for controlled and directed delivery of chemicals and remotely controlled soft microrobots, taking advantage of the ferromagnetic nature of the microdroplets.

36 MATERIALS SCIENCE↗

Effect of Dipole Interactions on Blocking Temperature and Relaxation Dynamics of Superparamagnetic Iron-Oxide (Fe 3 O 4 ) Nanoparticle Systems

The effects of dipole interactions on magnetic nanoparticle magnetization and relaxation dynamics were investigated using five nanoparticle (NP) systems with different surfactants, carrier liquids, size distributions, inter-particle spacing, and NP confinement. Dipole interactions were found to play a crucial role in modifying the blocking temperature behavior of the superparamagnetic nanoparticles, where stronger interactions were found to increase the blocking temperatures. Consequently, the blocking temperature of a densely packed nanoparticle system with stronger dipolar interactions was found to be substantially higher than those of the discrete nanoparticle systems. The frequencies of the dominant relaxation mechanisms were determined by magnetic susceptibility measurements in the frequency range of 100 Hz–7 GHz. The loss mechanisms were identified in terms of Brownian relaxation (1 kHz–10 kHz) and gyromagnetic resonance of Fe 3 O 4 (~1.12 GHz). It was observed that the microwave absorption of the Fe 3 O 4 nanoparticles depend on the local environment surrounding the NPs, as well as the long-range dipole–dipole interactions. These significant findings will be profoundly important in magnetic hyperthermia medical therapeutics and energy applications.

36 MATERIALS SCIENCE↗

Activation and Assembly of Plasmonic-Magnetic Nanosurfactants for Encapsulation and Triggered Release

Multifunctional surfactants hold great potentials in catalysis, separation, and biomedicine. Highly active plasmonic-magnetic nanosurfactants are developed through a novel acid activation treatment of Au–Fe 3 O 4 dumbbell nanocrystals. The activation step significantly boosts nanosurfactant surface energy and enables the strong adsorption at interfaces, which reduces the interfacial energy one order of magnitude. Mediated through the adsorption at the emulsion interfaces, the nanosurfactants are further constructed into free-standing hierarchical structures, including capsules, inverse capsules, and two-dimensional sheets. The nanosurfactant orientation and assembly structures follow the same packing parameter principles of surfactant molecules. Furthermore, nanosurfactants demonstrate the capability to disperse and encapsulate homogeneous nanoparticles and small molecules without adding any molecular surfactants. The assembled structures are responsive to external magnetic field, and triggered release is achieved using an infrared laser by taking advantage of the enhanced surface plasmon resonance of nanosurfactant assemblies. Finally, solvent and pH changes are also utilized to achieve the cargo release.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

2022 American Conference on Neutron Scattering (ACNS 2022)

The 11th American Conference on Neutron Scattering (ACNS 2022) will be held on June 5-9, 2022, in Boulder, CO. The Conference will provide essential information on the breadth and depth of current neutron-related research worldwide. Hosted by the Neutron Scattering Society of America, this year’s Conference will feature a combination of invited and contributed talks, poster sessions, and tutorials. Topics of the conference are: Advances in Neutron Facilities, Instrumentation and Software: Developments in sources, instrumentation, sample environments and control software. Hard Condensed Matter: Magnetism, correlated metals, quantum/topological materials, superconductors, ferroelectrics, multiferroics, glasses, and disorder phenomena. Submissions outlining examples of neutron scattering in industrial and engineering applications involving hard condensed matter systems are also encouraged. Soft Matter: Neutron studies of soft materials and related fields including in situ and in operando studies. Polymers, surfactants, emulsions, gels, nanoparticles, colloidal suspensions and more. Submissions of computational studies or applications of machine learning beneficial to neutron scattering experiments, as well as examples of neutron scattering in industrial and engineering applications are strongly encouraged. Biology, Biophysics and Biotechnology: Neutron studies of biological and biologically relevant systems. Proteins, bio membranes, biological assemblies, natural materials, nucleic acids, drug-delivery platforms and biomedical systems. Submissions of computational studies or applications of machine learning beneficial to biological neutron scattering experiments, as well as examples of neutron scattering in applied research involving biological systems, are strongly encouraged. Materials Chemistry and Energy: Neutron-based studies of functional materials and materials for energy applications. Examples include porous materials such as metal organic frameworks (MOFs), zeolites; phosphors; novel pigments; electrolytes; catalysts; ionic conductors/cathode materials; photovoltaic materials (hybrid perovskites); thermoelectrics; magnetocalorics/electrocalorics. Structural Materials and Engineering: Neutron scattering studies of materials and engineering processes including structural materials, concrete and metals, as well as engineering processes including combustion, corrosion, additive manufacturing, and others. Neutron Physics: Fundamental physical studies of the neutron and related areas. Emerging Applications in Neutron Scattering: Machine Learning and Data Science: Advances in computing power have contributed to rapidly evolving machine learning and data science fields that can be leveraged to the benefit of the neutron scattering community. The purpose of this session is to highlight recent advances in machine learning and data science and to serve as the foundation of a parallel data and computation track highlighting computation advances and applications in neutron scattering throughout the conference.

36 MATERIALS SCIENCE↗

Detection and Mitigation of Radionuclides in the Environment: Toward a Clean Ecosystem

This research describes a straightforward approach to producing surface-engineered nanomaterials for the detection and mitigation of radionuclides generated in nuclear facilities. Here, a micelle forming surfactant ligand, namely cetyltrimethylammonium bromide (CTAB), was engineered on the surface of iron oxide nanoparticles and explored for the removal of radioactive materials, such as pertechnetate (TcO 4 – ), from aqueous environments. A series of analytical tools were employed to characterize the nanocomposite materials, such as SEM, EDS, UV-Vis spectroscopy, DLS, and PALS, and evaluated for their ability to capture a model analyte, perrhenate (ReO 4 – ) ions. The iron oxide magnetic nanoparticles retain their magnetic properties after surface functionalization and can be easily manipulated and collected with a magnet. Therefore, these nanocomposite materials can be used to remotely remediate environments by scavenging and collecting radionuclide species at the desired location.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

CHAPTER 9. Bijels the Easy Way

Spinodal decomposition is not the only way to make a bijel. Indeed, while spinodal decomposition produces structures with a potentially useful morphology, it can be challenging to make bijels using this method and the resulting systems can be hard to process and manipulate. Furthermore, exploiting the functional properties of the assembled particle monolayer is extremely challenging. Here, we show how the assembly of nanoparticle surfactants at the liquid–liquid interface can be used to kinetically trap liquids into a wealth of complex structures without using spinodal decomposition. We apply liquid three-dimensional printing and moulding methods, along with patterned substrates with controllable wetting properties, to build all-liquid devices with applications in chemical synthesis, separation, and purification. The functional properties of the assembled nanomaterials can be exploited to produce interfacially structured liquids that are plasmonically and magnetically responsive. Finally, we conclude by arguing that, while the field shows great promise, efforts need to be made to translate liquid bicontinuous systems out of the laboratory and into meaningful, real-world applications, as well applications in more ‘exotic’ disciplines, such as synthetic biology.

36 MATERIALS SCIENCE↗

Catalytic Enhancement of Inductively Heated Fe 3 O 4 Nanoparticles by Removal of Surface Ligands

Abstract Heat management in catalysis is limited by each material's heat transfer efficiencies, resulting in energy losses despite current thermal engineering strategies. In contrast, induction heating of magnetic nanoparticles (NPs) generates heat at the surface of the catalyst where the reaction occurs, reducing waste heat via dissipation. However, the synthesis of magnetic NPs with optimal heat generation requires interfacial ligands, such as oleic acid, which act as heat sinks. Surface treatments using tetramethylammonium hydroxide (TMAOH) or pyridine are used to remove these ligands before applications in hydrophilic media. In this study, Fe 3 O 4 NPs are surface treated to study the effect of induction heating on the catalytic oxidation of 1‐octanol. Whereas TMAOH was unsuccessful in removing oleic acid, pyridine treatment resulted in a roughly 2.5‐fold increase in heat generation and product yield. Therefore, efficient surfactant removal has profound implications in induction heating catalysis by increasing the heat transfer and available surface sites.

Moura, Natalia S.↗

Hollow nanoparticles with hybrid double layers

The present invention discloses the morphology of hollow, double-shelled submicrometer particles generated through a rapid aerosol-based process. The inner shell is an essentially hydrophobic carbon layer of nanoscale dimension (5-20 nm), and the outer shell is a hydrophilic silica layer of approximately 5-40 nm, with the shell thickness being a function of the particle size. The particles are synthesized by exploiting concepts of salt bridging to lock in a surfactant (CTAB) and carbon precursors together with iron species in the interior of a droplet. This deliberate negation of surfactant templating allows a silica shell to form extremely rapidly, sealing in the organic species in the particle interior. Subsequent pyrolysis results in a buildup of internal pressure, forcing carbonaceous species against the silica wall to form an inner shell of carbon. The incorporation of magnetic iron oxide into the shells opens up applications in external stimuli-responsive nanomaterials.

John, Vijay T.↗

Local and long-range atomic/magnetic structure of non-stoichiometric spinel iron oxide nanocrystallites

Spinel iron oxide nanoparticles of different mean sizes in the range 10–25 nm have been prepared by surfactant-free up-scalable near- and super-critical hydrothermal synthesis pathways and characterized using a wide range of advanced structural characterization methods to provide a highly detailed structural description. The atomic structure is examined by combined Rietveld analysis of synchrotron powder X-ray diffraction (PXRD) data and time-of-flight neutron powder-diffraction (NPD) data. The local atomic ordering is further analysed by pair distribution function (PDF) analysis of both X-ray and neutron total-scattering data. It is observed that a non-stoichiometric structural model based on a tetragonal γ-Fe 2 O 3 phase with vacancy ordering in the structure (space group P 4 3 2 1 2) yields the best fit to the PXRD and total-scattering data. Detailed peak-profile analysis reveals a shorter coherence length for the superstructure, which may be attributed to the vacancy-ordered domains being smaller than the size of the crystallites and/or the presence of anti-phase boundaries, faulting or other disorder effects. The intermediate stoichiometry between that of γ-Fe 2 O 3 and Fe 3 O 4 is confirmed by refinement of the Fe/O stoichiometry in the scattering data and quantitative analysis of Mössbauer spectra. The structural characterization is complemented by nano/micro-structural analysis using transmission electron microscopy (TEM), elemental mapping using scanning TEM, energy-dispersive X-ray spectroscopy and the measurement of macroscopic magnetic properties using vibrating sample magnetometry. Notably, no evidence is found of a Fe 3 O 4 /γ-Fe 2 O 3 core-shell nanostructure being present, which had previously been suggested for non-stoichiometric spinel iron oxide nanoparticles. Finally, the study is concluded using the magnetic PDF (mPDF) method to model the neutron total-scattering data and determine the local magnetic ordering and magnetic domain sizes in the iron oxide nanoparticles. The mPDF data analysis reveals ferrimagnetic collinear ordering of the spins in the structure and the magnetic domain sizes to be ∼60–70% of the total nanoparticle sizes. The present study is the first in which mPDF analysis has been applied to magnetic nanoparticles, establishing a successful precedent for future studies of magnetic nanoparticles using this technique.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗