Narrowly distributed crystal orientation in biomineral vaterite

Biominerals formed by animals provide skeletal support, and many other functions. They were previously shown to grow by aggregation of amorphous nanoparticles, but never to grow ion-by-ion from solution, which is a common growth mechanism for abiotic crystals. We analyze vaterite CaCO3 multi crystalline spicules from the solitary tunicate Herdmania momus, with Polarization dependent Imaging Contrast PIC mapping, scanning and aberration corrected transmission electron microscopies. The first fully quantitative PIC mapping data, presented here, measured 0{\deg} 30{\deg} angle spreads between immediately adjacent crystals. Such narrowly distributed crystal orientations demonstrate that crystallinity does not propagate from one crystal to another 0{\deg} angle spreads, nor that new crystals with random orientation 90{\deg} nucleate. There are no organic layers at the interface between crystals, hence a new, unknown growth mechanism must be invoked, with crystal nucleation constrained within 30{\deg}. Two observations are consistent with crystal growth from solution: vaterite microcrystals express crystal faces, and are smooth at the nanoscale after cryo fracture. The observation of 30{\deg} angle spreads, lack of interfacial organic layers, and smooth fracture figures broadens the range of known biomineralization mechanisms and may inspire novel synthetic crystal growth strategies. Spherulitic growth from solution is one possible mechanism consistent with all these observations.Comment: Chemistry of Materials 201

Nacre tablet thickness records formation temperature in modern and fossil shells

Nacre, the iridescent outer lining of pearls and inner lining of many mollusk shells, is composed of periodic, parallel, organic sheets alternating with aragonite (CaCO_3) tablet layers. Nacre tablet thickness (TT) generates both nacre's iridescence and its remarkable resistance to fracture. Despite extensive studies on how nacre forms, the mechanisms controlling TT remain unknown, even though they determine the most conspicuous of nacre's characteristics, visible even to the naked eye. Thermodynamics predicts that temperature (T) will affect both physical and chemical components of biomineralized skeletons. The chemical composition of biominerals is well-established to record environmental parameters, and has therefore been extensively used in paleoclimate studies. The physical structure, however, has been hypothesized but never directly demonstrated to depend on the environment. Here we observe that the physical TT in nacre from modern and fossil shallow-water shells of the bivalves Pinna and Atrina correlates with T as measured by the carbonate clumped isotope thermometer. Based on the observed TT vs. T correlation, we anticipate that TT will be used as a paleothermometer, useful to estimate paleotemperature in shallow-water paleoenvironments. Here we successfully test the proposed new nacre TT thermometer on two Jurassic Pinna shells. The increase of TT with T is consistent with greater aragonite growth rate at higher T, and with greater metabolic rate at higher T. Thus, it reveals a complex, T-dependent biophysical mechanism for nacre formation

Ultrafast domain dilation induced by optical pumping in ferromagnetic CoFe/Ni multilayers

Ultrafast optical pumping of systems with spatially nonuniform magnetic textures is known to cause far-from-equilibrium spin transport effects, such as the broadening of domain-walls. Here, we study the dynamics of labyrinth domain networks in ferromagnetic CoFe/Ni multilayers subject to a femtosecond optical pump and find an ultrafast domain dilation by 6% within 1.6 ps. This surprising result is based on the unambiguous determination of a harmonically-related shift of ultrafast magnetic X-ray diffraction for the first- and third-order rings. Domain dilation is plausible from conservation of momentum arguments, whereby inelastic scattering from a hot, quasi-ballistic, radial current transfers momentum to the magnetic domains. Our results suggest a potentially rich variety of unexpected physical phenomena associated with far-from-equilibrium inelastic electron-magnon scattering processes in the presence of spin textures

Narrowly Distributed Crystal Orientation in Biomineral Vaterite

Biominerals formed by animals provide skeletal support and many other functions. They were previously shown to grow by aggregation of amorphous nanoparticles but never to grow ion-by-ion from solution, which is a common growth mechanism for abiotic crystals. We analyze vaterite (CaCO3) multicrystalline spicules from the solitary tunicate Herdmania momus, with polarization-dependent imaging contrast (PIC)-mapping and scanning and aberration-corrected transmission electron microscopies. The first fully quantitative PIC-mapping data, presented here, measured 0-30°angle spreads between immediately adjacent crystals. Such narrowly distributed crystal orientations demonstrate that crystallinity does not propagate from one crystal to another (0°angle spreads), nor that new crystals with random orientation (90°) nucleate. There are no organic layers at the interface between crystals; hence, a new, unknown growth mechanism must be invoked, with crystal nucleation constrained within 30°. Two observations are consistent with crystal growth from solution: vaterite microcrystals express crystal faces and are smooth at the nanoscale after cryo-fracture. The observation of 30° angle spreads, lack of interfacial organic layers, and smooth fracture figures broadens the range of known biomineralization mechanisms and may inspire novel synthetic crystal growth strategies. Spherulitic growth from solution is one possible mechanism consistent with all these observations

The nature of the ultrafast magnetic phase transition in nickel revealed by correlating EUV-MOKE and ARPES spectroscopies

By correlating time- and angle-resolved photoemission (Tr-ARPES) and time-resolved transverse- magneto-optical Kerr effect (Tr-TMOKE) measurements, both at extreme ultraviolet (EUV) wavelengths, we uncover the nature of the ultrafast photoinduced magnetic phase transition in Ni. This allows us to explain the ultrafast magnetic response of Ni at all laser fluences - from a small reduction of the magnetization at low laser fluences, to complete quenching at high laser fluences. We provide an alternative explanation to the fluence-dependent recovery timescales commonly observed in ultrafast magneto-optical spectroscopies on ferromagnets: it is due to the bulk-averaging effect and different depths of sample exhibit distinct dynamics, depending on whether a magnetic phase transition is induced. We also show evidence of two competing channels with two distinct timescales in the recovery process, that suggest the presence of coexisting phases in the material

Critical behavior within 20 fs drives the out-of-equilibrium laser-induced magnetic phase transition in nickel

It has long been known that ferromagnets undergo a phase transition from ferromagnetic to paramagnetic at the Curie temperature, associated with critical phenomena such as a divergence in the heat capacity. A ferromagnet can also be transiently demagnetized by heating it with an ultrafast laser pulse. However, to date, the connection between out-of-equilibrium and equilibrium phase transitions, or how fast the out-of-equilibrium phase transitions can proceed, was not known. By combining time-and angle-resolved photoemission with time-resolved transverse magneto-optical Kerr spectroscopies, we show that the same critical behavior also governs the ultrafast magnetic phase transition in nickel. This is evidenced by several observations. First, we observe a divergence of the transient heat capacity of the electron spin system preceding material demagnetization. Second, when the electron temperature is transiently driven above the Curie temperature, we observe an extremely rapid change in the material response: The spin system absorbs sufficient energy within the first 20 fs to subsequently proceed through the phase transition, whereas demagnetization and the collapse of the exchange splitting occur on much longer, fluence-independent time scales of similar to 176 fs. Third, we find that the transient electron temperature alone dictates the magnetic response. Our results are important because they connect the out-of-equilibrium material behavior to the strongly coupled equilibrium behavior and uncover a new time scale in the process of ultrafast demagnetization

Direct measurement of the static and transient magneto-optical permittivity of cobalt across the entire M-edge in reflection geometry by use of polarization scanning

The microscopic state of amagnetic material is characterized by its resonant magneto-optical response through the off-diagonal dielectric tensor component epsilon(xy). However, the measurement of the full complex epsilon(xy) in the extreme ultraviolet spectral region covering the M absorption edges of 3d ferromagnets is challenging due to the need for either a careful polarization analysis, which is complicated by a lack of efficient polarization analyzers, or scanning the angle of incidence in fine steps. Here, we propose and demonstrate a technique to extract the complex resonant permittivity epsilon(xy) simply by scanning the polarization angle of linearly polarized high harmonics to measure the magneto-optical asymmetry in reflection geometry. Because this technique is more practical and faster to experimentally implement than previous approaches, we can directly measure the full time evolution of epsilon(xy)(t) during laser-induced demagnetization across the entire M-2,M-3 absorption edge of cobalt with femtosecond time resolution. We find that for polycrystalline Co films on an insulating substrate, the changes in epsilon(xy) are uniform throughout the spectrum, to within our experimental precision. This result suggests that, in the regime of strong demagnetization, the ultrafast demagnetization response is primarily dominated by magnon generation. We estimate the contribution of exchange-splitting reduction to the ultrafast demagnetization process to be no more than 25%.Web of Science972art. no. 02443