Polymorphism in the Ruddlesden-Popper Nickelate La3Ni2O7: Discovery of a Hidden Phase with Distinctive Layer Stacking.

We report the discovery of a novel form of Ruddlesden-Popper (RP) nickelate that stands as the first example of long-range, coherent polymorphism in this class of inorganic solids. Rather than the well-known, uniform stacking of perovskite blocks ubiquitously found in RP phases, this newly discovered polymorph of the bilayer RP phase La3Ni2O7 adopts a novel stacking sequence in which single-layer and trilayer blocks of NiO6 octahedra alternate in a "1313" sequence. Crystals of this new polymorph are described in space group Cmmm, although we note evidence for a competing Imam variant. Transport measurements at ambient pressure reveal metallic character with evidence of a charge density wave transition with an onset at T ≈ 134 K. The discovery of such polymorphism could reverberate to the expansive range of science and applications that rely on RP materials, particularly the recently reported signatures of superconductivity in bilayer La3Ni2O7 with Tc as high as 80 K above 14 GPa.

X-ray-induced piezoresponse during X-ray photon correlation spectroscopy of PbMg1/3Nb2/3O3.

X-ray photon correlation spectroscopy (XPCS) holds strong promise for observing atomic-scale dynamics in materials, both at equilibrium and during non-equilibrium transitions. Here an in situ XPCS study of the relaxor ferroelectric PbMg1/3Nb2/3O3 (PMN) is reported. A weak applied AC electric field generates strong response in the speckle of the diffuse scattering from the polar nanodomains, which is captured using the two-time correlation function. Correlated motions of the Bragg peak are also observed, which indicate dynamic tilting of the illuminated volume. This tilting quantitatively accounts for the observed two-time speckle correlations. The magnitude of the tilting would not be expected solely from the modest applied field, since PMN is an electrostrictive material with no linear strain response to the field. A model is developed based on non-uniform static charging of the illuminated surface spot by the incident micrometre-scale X-ray beam and the electrostrictive material response to the combination of static and dynamic fields. The model qualitatively explains the direction and magnitude of the observed tilting, and predicts that X-ray-induced piezoresponse could be an important factor in correctly interpreting results from XPCS and nanodiffraction studies of other insulating materials under applied AC field or varying X-ray illumination.

Thermal Hysteresis and Ordering Behavior of Magnetic Skyrmion Lattices.

The physics of phase transitions in two-dimensional (2D) systems underpins research in diverse fields including statistical mechanics, nanomagnetism, and soft condensed matter. However, many aspects of 2D phase transitions are still not well understood, including the effects of interparticle potential, polydispersity, and particle shape. Magnetic skyrmions are chiral spin-structure quasi-particles that form two-dimensional lattices. Here, we show, by real-space imaging using in situ cryo-Lorentz transmission electron microscopy coupled with machine learning image analysis, the ordering behavior of Néel skyrmion lattices in van der Waals Fe3GeTe2. We demonstrate a distinct change in the skyrmion size distribution during field-cooling, which leads to a loss of lattice order and an evolution of the skyrmion liquid phase. Remarkably, the lattice order is restored during field heating and demonstrates a thermal hysteresis. This behavior is explained by the skyrmion energy landscape and demonstrates the potential to control the lattice order in 2D phase transitions.

Harnessing interpretable and unsupervised machine learning to address big data from modern X-ray diffraction.

The information content of crystalline materials becomes astronomical when collective electronic behavior and their fluctuations are taken into account. In the past decade, improvements in source brightness and detector technology at modern X-ray facilities have allowed a dramatically increased fraction of this information to be captured. Now, the primary challenge is to understand and discover scientific principles from big datasets when a comprehensive analysis is beyond human reach. We report the development of an unsupervised machine learning approach, X-ray diffraction (XRD) temperature clustering (X-TEC), that can automatically extract charge density wave order parameters and detect intraunit cell ordering and its fluctuations from a series of high-volume X-ray diffraction measurements taken at multiple temperatures. We benchmark X-TEC with diffraction data on a quasi-skutterudite family of materials, (CaxSr[Formula: see text])3Rh4Sn13, where a quantum critical point is observed as a function of Ca concentration. We apply X-TEC to XRD data on the pyrochlore metal, Cd2Re2O7, to investigate its two much-debated structural phase transitions and uncover the Goldstone mode accompanying them. We demonstrate how unprecedented atomic-scale knowledge can be gained when human researchers connect the X-TEC results to physical principles. Specifically, we extract from the X-TEC-revealed selection rules that the Cd and Re displacements are approximately equal in amplitude but out of phase. This discovery reveals a previously unknown involvement of [Formula: see text] Re, supporting the idea of an electronic origin to the structural order. Our approach can radically transform XRD experiments by allowing in operando data analysis and enabling researchers to refine experiments by discovering interesting regions of phase space on the fly.

Isotropic Nature of the Metallic Kagome Ferromagnet Fe3Sn2 at High Temperatures.

Anisotropy and competing exchange interactions have emerged as two central ingredients needed for centrosymmetric materials to exhibit topological spin textures. Fe3Sn2 is thought to have these ingredients as well, as it has recently been discovered to host room temperature skyrmionic bubbles with an accompanying topological Hall effect. We present small-angle inelastic neutron scattering measurements that unambiguously show that Fe3Sn2 is an isotropic ferromagnet below TC≈660 K to at least 480 K - the lower temperature threshold of our experimental configuration. Fe3Sn2 is known to have competing magnetic exchange interactions, correlated electron behavior, weak magnetocrystalline anisotropy, and lattice anisotropy; all of these features are thought to play a role in stabilizing skyrmions in centrosymmetric systems. Our results reveal that at elevated temperatures, there is an absence of magnetocrystalline anisotropy and that the system behaves as a typical exchange ferromagnet with a spin stiffness DT=0 K=271±9 meV Å2.

Simultaneous First-Order Valence and Oxygen Vacancy Order/Disorder Transitions in (Pr0.85Y0.15)0.7Ca0.3CoO3-δ via Analytical Transmission Electron Microscopy.

Perovskite cobaltites have been studied for years as some of the few solids to exhibit thermally driven spin-state crossovers. The unanticipated first-order spin and electronic transitions recently discovered in Pr-based cobaltites are notably different from these conventional crossovers, and are understood in terms of a unique valence transition. In essence, the Pr valence is thought to spontaneously shift from 3+ toward 4+ on cooling, driving subsequent transitions in Co valence and electronic/magnetic properties. Here, we apply temperature-dependent transmission electron microscopy and spectroscopy to study this phenomenon, for the first time with atomic spatial resolution, in the prototypical (Pr0.85Y0.15)0.70 Ca0.30CoO3-δ. In addition to the direct spectroscopic observation of charge transfer between Pr and Co at the 165 K transition (on both the Pr and O edges), we also find a simultaneous order/disorder transition associated with O vacancies. Remarkably, the first-order valence change drives a transition between ordered and random O vacancies, at constant O vacancy density, demonstrating reversible crystallization of such vacancies even at cryogenic temperatures.

Chloride-bridged, defect-dicubane {Ln4} core clusters: syntheses, crystal structures and magnetic properties.

Three chloride-bridged lanthanide compounds, [Ln4Cl6(CH3OH)12(OH)2]·4Cl·2CH3OH [Ln = Gd (), Dy () and Er ()], have been unexpectedly isolated by the reactions of LnCl3·6H2O and N,N'-bis(salicylidene)-1,2-(phenylene-diamine) (H2L). X-ray crystallographic analysis reveals a triclinic cell with a unique defect-dicubane {Ln4} core and the structure across this series is nominally isomorphic. Measurements of direct current magnetic susceptibility and isothermal magnetization give insight into the relevant cluster Hamiltonians for , , and , and alternating current susceptibility shows slow relaxation in , but not in or down to 2 K and up to 1 kHz.

Role of random electric fields in relaxors.

PbZr(1-x)Ti(x)O3 (PZT) and Pb(Mg1/3Nb2/3)(1-x)Ti(x)O3 (PMN-xPT) are complex lead-oxide perovskites that display exceptional piezoelectric properties for pseudorhombohedral compositions near a tetragonal phase boundary. In PZT these compositions are ferroelectrics, but in PMN-xPT they are relaxors because the dielectric permittivity is frequency dependent and exhibits non-Arrhenius behavior. We show that the nanoscale structure unique to PMN-xPT and other lead-oxide perovskite relaxors is absent in PZT and correlates with a greater than 100% enhancement of the longitudinal piezoelectric coefficient in PMN-xPT relative to that in PZT. By comparing dielectric, structural, lattice dynamical, and piezoelectric measurements on PZT and PMN-xPT, two nearly identical compounds that represent weak and strong random electric field limits, we show that quenched (static) random fields establish the relaxor phase and identify the order parameter.

Surgical stabilization of flail chest injuries with MatrixRIB implants: a prospective observational study.

BACKGROUND: Surgical stabilization of flail chest injury with generic osteosynthesis implants remains challenging. A novel implant system comprising anatomic rib plates and intramedullary splints may improve surgical stabilization of flail chest injuries. This observational study evaluated our early clinical experience with this novel implant system to document if it can simplify the surgical procedure while providing reliable stabilization. METHODS: Twenty consecutive patients that underwent stabilization of flail chest injury with anatomic plates and intramedullary splints were prospectively enrolled at two Level I trauma centres. Data collection included patient demographics, injury characterization, surgical procedure details and post-operative recovery. Follow-up was performed at three and six months to assess pulmonary function, durability of implants and fixation and patient health. RESULTS: Patients had an Injury Severity Score of 28±10, a chest Abbreviated Injury Score of 4.2±0.4 and 8.5±2.9 fractured ribs. Surgical stabilization was achieved on average with five plates and one splint. Intra-operative contouring was required in 14% of plates. Post-operative duration of ventilation was 6.4±8.6 days. Total hospitalization was 15±10 days. At three months, patients had regained 84% of their expected forced vital capacity (%FVC). At six months, 7 of 15 patients that completed follow-up had returned to work. There was no mortality. Among the 91 rib plates, 15 splints and 605 screws in this study there was no hardware failure and no loss of initial fixation. There was one incidence of wound infection. Implants were removed in one patient after fractures had healed. CONCLUSIONS: Anatomic plates eliminated the need for extensive intraoperative plate contouring. Intramedullary rib splints provided a less-invasive fixation alternative for single, non-comminuted fractures. These early clinical results indicate that the novel implant system provides reliable fixation and accommodates the wide range of fractures encountered in flail chest injury.

Biplanar fixation of a locking plate in the diaphysis improves construct strength.

BACKGROUND: Elevation of a locking plate over the bone surface not only supports biological fixation, but also decreases the torsional strength of the fixation construct. Biplanar fixation by means of a staggered screw hole arrangement may combat this decreased torsional strength caused by plate elevation. This biomechanical study evaluated the effect of biplanar fixation on the torsional strength of locking plate fixation in the femoral diaphysis. METHODS: Custom titanium plates were manufactured with either a linear or staggered hole pattern to evaluate planar and biplanar fixation, respectively. Fixation strength under torsional loading was evaluated in surrogates of the femoral diaphysis representative of osteoporotic and non-osteoporotic bone. Furthermore, fixation strength was determined for plate fixation with unicortical or bicortical locking screws. Five specimens per configuration were loaded to failure in torsion to determine their strength, stiffness, and failure mode. FINDINGS: In osteoporotic bone, biplanar fixation was 32% stronger (P=0.01) than planar fixation when unicortical screws were used and 9% stronger (P=0.02) when bicortical screws were used. In non-osteoporotic bone, biplanar fixation was 55% stronger (P<0.001) than planar fixation when unicortical screws were used and 42% (P<0.001) stronger when bicortical screws were used. INTERPRETATION: A biplanar screw configuration improves the torsional strength of diaphyseal plate fixation relative to a planar configuration in both osteoporotic and normal bone. With biplanar fixation, unicortical screws provide the same fixation strength as bicortical screws in non-osteoporotic bone.

Complications of anterior cruciate ligament reconstruction.

Injury to the anterior cruciate ligament (ACL) can result in recurrent instability, impairment, and progressive joint damage in athletes who return to high-risk sports activities. ACL reconstruction often is indicated. With refinement of surgical techniques and accelerated rehabilitation, the number of complications following ACL reconstruction has greatly decreased since the 1980s. Nevertheless, ACL reconstruction remains a complex procedure with multiple steps and many possible complications. Understanding the incidence and etiology of the more common complications associated with ACL reconstruction during the preoperative and postoperative periods is important to manage (if not avoid) the risk of these complications.

Prospective trial of a treatment algorithm for the management of the anterior cruciate ligament-injured knee.

BACKGROUND: Specific guidelines for operative versus nonoperative management of anterior cruciate ligament injuries do not yet exist. HYPOTHESIS: Surgical risk factors can be used to indicate whether reconstruction or conservative management is best for an individual patient. STUDY DESIGN: Prospective nonrandomized controlled clinical trial; Level of evidence, 2. METHODS: Patients were classified as high, moderate, or low risk using preinjury sports participation and knee laxity measurements. Early anterior cruciate ligament reconstruction (within 3 months of injury) was recommended to high-risk patients and conservative care to low-risk patients. It was recommended that moderate-risk patients have either early reconstruction or conservative care, according to the day of presentation. Assessment of subjective outcomes, activity, physical measurements, and radiographs was performed at mean follow-up of 6.6 years. RESULTS: Early phase conservative management resulted in more late phase meniscus surgery than did early phase reconstruction at all risk levels (high risk, 25% vs 6.5%; moderate risk, 37% vs 7.7%, P = .01; low risk, 16% vs 0%). Early- and late-reconstruction patients' Tegner scores increased from presurgery to follow-up (P < .001) but did not return to preinjury levels. Early-reconstruction patients had higher rates of degenerative change on radiographs than did nonreconstruction patients (P < .05). CONCLUSIONS: Early phase reconstruction reduced late phase knee laxity, risk of symptomatic instability, and the risk of late meniscus tear and surgery. Moderate- and high-risk patients had similar rates of late phase injury and surgery. Reconstruction did not prevent the appearance of late degenerative changes on radiographs. Relationship between bone contusion on initial magnetic resonance images and the finding of degenerative changes on follow-up radiographs were not detected. The treatment algorithm used in this study was effective in predicting risk of late phase knee surgery.