The term “pseudo‐single domain” (PSD) has been used to describe the transitional state in rock magnetism that spans the particle size range between the single domain (SD) and multidomain (MD) states. The particle size range for the stable SD state in the most commonly occurring terrestrial magnetic mineral, magnetite, is so narrow (~20–75 nm) that it is widely considered that much of the paleomagnetic record of interest is carried by PSD rather than stable SD particles. The PSD concept has, thus, become the dominant explanation for the magnetization associated with a major fraction of particles that record paleomagnetic signals throughout geological time. In this paper, we argue that in contrast to the SD and MD states, the term PSD does not describe the relevant physical processes, which have been documented extensively using three‐dimensional micromagnetic modeling and by parallel research in material science and solid‐state physics. We also argue that features attributed to PSD behavior can be explained by nucleation of a single magnetic vortex immediately above the maximum stable SD transition size. With increasing particle size, multiple vortices, antivortices, and domain walls can nucleate, which produce variable cancellation of magnetic moments and a gradual transition into the MD state. Thus, while the term PSD describes a well‐known transitional state, it fails to describe adequately the physics of the relevant processes. We recommend that use of this term should be discontinued in favor of “vortex state,” which spans a range of behaviors associated with magnetic vortices.

Interpretations of palaeomagnetic observations assume that naturally occurring magnetic particles can retain their primary magnetic recording over billions of years. The ability to retain a magnetic recording is inferred from laboratory measurements, where heating causes demagnetization on the order of seconds. The theoretical basis for this inference comes from previous models that assume only the existence of small, uniformly magnetized particles, whereas the carriers of palaeomagnetic signals in rocks are usually larger, non-uniformly magnetized particles, for which there is no empirically complete, thermally-activated model. This study has developed a thermally-activated numerical micromagnetic model that can quantitatively determine the energy barriers between stable states in nonuniform magnetic particles on geological time scales. We examine in detail the thermal stability characteristics of equidimensional cuboctahedral magnetite and find that contrary to previously published theories, such non-uniformly magnetized particles provide greater magnetic stability than their uniformly magnetized counterparts. Hence, non-uniformly magnetized grains, which are commonly the main remanence carrier in meteorites and rocks, can record and retain highfidelity magnetic recordings over billions of years.micromagnetics | paleomagnetism | geomagnetism S ince the 1900s magnetic recordings observed in rocks and meteorites have been studied to understand the evolution of the Earth and the Solar System. The validity of the findings from these studies depends on a theoretical understanding of rock-magnetic recordings provided by Néel (1, 2) and numerous experimental studies, for example, Strangway et. al. (3) and Evans and Wayman (4). The overwhelming evidence from these authors was that stable natural magnetic remanence (NRM) in rocks resides within ultrafine, uniformly magnetized particles, called single domain (SD) particles. Néel's theory (1, 2) for the behavior of thermally-activated SD particles describes a unique relationship between thermal and temporal stability and gave confidence that palaeomagnetic recordings that become unstable (unblocked) only at high temperatures, retain magnetic recordings from the time of their mineral crystallization, possibly as far back in time as four billion years ago.However, in the 1970s and 80s the widespread use of hysteresis parameters to characterize magnetic mineralogy (5) found that the majority of magnetic particles in rocks are not in uniform magnetic states, but are larger in size (80 -1000 nm) and contain complex magnetic states that are not described by either SD theory or the multidomain theory of micron-sized particles (2, 6). The term pseudo-single-domain (PSD) was coined for such particles and much effort was spent in determining the origin of their magnetic fidelity (Dunlop Psark, 1977, Moon and Merrill, 1985). Due to the complexity of the problem it has not been possible to determine the temporal stability of magnetisation in PSD grains on geological time scales fro...

Magnetite (Fe3O4) is an important magnetic mineral to Earth scientists, as it carries the dominant magnetic signature in rocks, and the understanding of its magnetic recording fidelity provides a critical tool in the field of palaeomagnetism. However, reliable interpretation of the recording fidelity of Fe3O4 particles is greatly diminished over time by progressive oxidation to less magnetic iron oxides, such as maghemite (γ-Fe2O3), with consequent alteration of remanent magnetization potentially having important geological significance. Here we use the complementary techniques of environmental transmission electron microscopy and off-axis electron holography to induce and visualize the effects of oxidation on the magnetization of individual nanoscale Fe3O4 particles as they transform towards γ-Fe2O3. Magnetic induction maps demonstrate a change in both strength and direction of remanent magnetization within Fe3O4 particles in the size range dominant in rocks, confirming that oxidation can modify the original stored magnetic information.

A "process map" for the hydrothermal synthesis (HS) of single crystalline R-Fe 2 O 3 nanorods from aqueous FeCl 3 is presented, as a function of temperature, time, and phosphate concentration, as assessed using the combined techniques of X-ray diffractometry, transmission electron microscopy, selected area electron diffraction, Fourier transform infrared spectrometry, and X-ray photoelectron spectroscopy. The process map provides insight into the nature of intermediate β-FeOOH nanorod precipitation, dissolution and subsequent R-Fe 2 O 3 growth, along with the effect of PO 4 3anion concentration on the R-Fe 2 O 3 particle shape. Increasing the processing temperature in the absence of a surfactant promoted the dissolution of initially formed β-FeOOH nanorods and the nucleation and growth of equiaxed R-Fe 2 O 3 nanoparticles with rhombohedral morphology. Increasing additions of phosphate surfactant resulted in a shape change of the R-Fe 2 O 3 nanoparticles into lenticular R-Fe 2 O 3 nanorods with increasing aspect ratio but with progressive inhibition of R-Fe 2 O 3 phase formation. Increasing the synthesis temperature in the presence of PO 4 3anions was associated with the recovery of well-defined single crystal, lenticular nanorods. Increasing the time of synthesis in the presence of PO 4 3anions was similarly associated with the progressive formation and dissolution of β-FeOOH and the growth of well-defined lenticular R-Fe 2 O 3 nanorods. An HS processing temperature of 200 °C and an Fe 3+ -PO 4 3molar ratio of 31.5 yielded optimized crystalline lenticular R-Fe 2 O 3 nanorods with an aspect ratio of ∼7. Chemical analysis indicated that some P was retained within the bulk of the developed R-Fe 2 O 3 nanorods.

The hydrothermal growth mechanism of α-Fe₂O₃ nanorods has been investigated using a novel valve assisted pressure autoclave. This approach has facilitated the rapid quenching of hydrothermal suspensions into liquid nitrogen, providing 'snapshots' representative of the near in situ physical state of the synthesis reaction products as a function of known temperature. Examination of the acquired samples using complementary characterisation techniques of transmission electron microscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy (FT-IR) has provided fundamental insight into the anisotropic crystal growth mechanism of the lenticular α-Fe₂O₃ nanorods.An intermediate ß-FeOOH phase was observed to precipitate alongside small primary α-Fe₂O₃ nanoparticles. Dissolution of the ß-FeOOH phase with increasing temperature, in accordance with Ostwald's rule of stages, led to the release of Fe³+ anions back into solution to supply the growth of α-Fe₂O₃ nanoparticles, which in turn coalesced to form lenticular α-Fe₂O₃ nanorods. The critical role of the PO₄³⁻ surfactant on mediating the lenticular shape of the α-Fe₂O₃ nanorods is emphasised. Strong phosphate anion absorption on α-Fe₂O₃ crystal surfaces stabilised the primary α-Fe₂O₃ nanoparticle size to < 10 nm. FT-IR investigation of the quenched reaction products provided evidence for PO₄³⁻ absorption on the α-Fe₂O₃ nanoparticles in the form of mono or bi-dentate (bridging) surface complexes on surfaces normal and parallel to the crystallographic α-Fe₂O₃ c-axis, respectively. Monodentate PO₄³⁻ absorption is considered weaker and hence easily displaced during growth, as compared to absorbed PO₄³⁻ bi-dentate species, which implies the α-Fe₂O₃ c-planes are favoured for the oriented attachment of primary α-Fe₂O₃ nanoparticles, resulting in the development of filamentary features which act as the basis of growth, defining the shape of the lenticular α-Fe₂O₃ nanorods.