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Poly(N-isopropylmethacrylamide) (PNIPMAM) is a stimuliresponsive polymer, which in thin film geometry exhibits a volume-phase transition upon temperature increase in water vapor. The swelling behavior of PNIPMAM thin films containing magnesium salts in water vapor is investigated in view of their potential application as nanodevices. Both the extent and the kinetics of the swelling ratio as well as the water content are probed with in situ time-of-flight neutron reflectometry. Additionally, in situ Fourier-transform infrared (FTIR) spectroscopy provides information about the local solvation of the specific functional groups, while two-dimensional FTIR correlation analysis further elucidates the temporal sequence of solvation events. The addition of Mg(ClO4)2 or Mg(NO3)2 enhances the sensitivity of the polymer and therefore the responsiveness of switches and sensors based on PNIPMAM thin films. It is found that Mg(NO3)2 leads to a higher relative water uptake and therefore achieves the highest thickness gain in the swollen state.

Time-of-flight neutron reflectometry (ToF-NR) performed under different relative humidity conditions demonstrates that polymer brushes constituted by hydrophilic, cyclic macromolecules exhibit a more compact conformation with lower roughness as compared to linear brush analogues, due to the absence of dangling chain ends extending at the polymer-vapor interface. In addition, cyclic brushes feature a larger swelling ratio and an increased solvent uptake with respect to their linear counterparts as a consequence of the increased interchain steric repulsions. It is proposed that differences in swelling ratios between linear and cyclic brushes come from differences in osmotic pressure experienced by each brush topology. These differences stem from entropic constraints. The findings suggest that to correlate the equilibrium swelling ratios at different relative humidity for different topologies a new form of the Flory-like expression for equilibrium thicknesses of grafted brushes is needed., Macromolecular Rapid Communications, 44 (9), ISSN:1022-1336, ISSN:1521-3927

The KCl-modulated swelling of double thermoresponsive diblock copolymer (DBC) thin films in D2O atmosphere and their subsequent responsive behavior are investigated via spectral reflectance (SR), in situ time-of-flight neutron reflectometry (ToF-NR), and Fourier-transform infrared (FT-IR) spectroscopy. The copolymer consists of a short zwitterionic (poly(4-(N-(3-methacrylamidopropyl)-N,N- dimethylammonio) butane-1-sulfonate)) (PSBP) block and a long non-ionic poly(N-isopropylmethacrylamide) (PNIPMAM) block. DBC thin films are prepared via spin-coating from solutions containing 5 mM or devoid of KCl. The addition of KCl to the DBC thin films leads to a higher swelling ratio and D2O content during vapor treatment with D2O. Upon the subsequent heating of the hydrated DBC films, the films swell further and reach a maximum thickness before contracting. Two separate volume phase transition temperatures (VPTTs) are observed, namely where a further swelling plateau is reached (VPTTfs), and where contraction starts (VPTTc). Based on complementary SR studies of the effect of KCl on the swelling behavior of the respective PSBP and PNIPMAM homopolymer thin films, we conclude that the “further-swelling” period is mainly a consequence of the UCST-type phase transition of PSBP, whereas the “film contraction” period is due to the LCST-type phase of PNIPMAM in thin-film geometry. We observe that KCl reduces the VPTTc of the PNIPMAM blocks. Moreover, the salt migrates or aggregates inside the thin film upon heating,thereby forming a KCl enrichment layer in the intermediate section of the film. Furthermore, the observations by FT-IR prove that macroscopic and mesoscopic D2O absorption and desorption are correlated with the effect of KCl on hydration and de-hydration of the hydrophilic groups.

Monomeric alpha-synuclein (aSyn) is a well characterised as a lipid binding protein. aSyn is known to form amyloid fibrils which are also localised with lipids and organelles in so called Lewy bodies, insoluble structures found in Parkinson’s disease patient’s brains. It is still unclear under which conditions the aSyn-lipid interaction can start to become pathological. Previous work to address pathological interactions has focused on using synthetic lipid membranes, which lack the complexity of physiological lipid membranes which not only have a more complex lipid composition, but also contain lipid interacting proteins. Here, we investigate how either monomeric or fibrillar aSyn interact with physiological synaptic vesicles (SV) isolated from rodent brain. Using small angle neutron scattering and high-resolution imaging we observe that aSyn fibrils disintegrate SV, whereas aSyn monomers cause clustering of SV. Furthermore, SV enhance the aggregation rate of aSyn, however increasing the SV:aSyn ratio causes a reduction in aggregation propensity. SV lipids appear as an integrated part of aSyn fibrils and while the fibril morphology differs to aSyn fibrils alone, the core fibril structure remains the same. We finally demonstrate that lipid-associated aSyn fibrils are more easily taken up into cortical i3Neurons derived from induced pluripotent stem cells. Our study sheds light on differences between interactions of aSyn with synthetic lipid vesicles and physiological SV. We show how aSyn fibrils may enhance pathology by disintegrating SV, which in turn may have fatal consequences for neurons. Furthermore, disease burden may additionally be impacted by an increased uptake of lipid-associated aSyn by neurons, leading to more SV damage and enhancing aSyn aggregation.

The hydration and thermal response kinetics of the cross-linked thermoresponsive copolymer poly((diethylene glycol monomethyl ether methacrylate)-co-poly(ethylene glycol) methyl ether methacrylate), abbreviated as P(MEO2MA-co-OEGMA300), thin film on a hydrophobic polyacrylonitrile (PAN) substrate coating, which resembles a synthetic fabric, is probed by in situ neutron reflectivity (NR). The PAN and monomer (MEO2MA and OEGMA300) solutions are sequentially spin-coated onto a silicon (Si) substrate. Afterward, plasma treatment is applied to realize the cross-linking of PAN and monomers. The as-prepared cross-linked P(MEO2MA-co-OEGMA300) film on the hydrophobic PAN substrate coating presents a two-layer structure: a substrate-near layer, which is a mixture of PAN and P(MEO2MA-co-OEGMA300), and a main layer, which is composed of pure hydrophilic P(MEO2MA-co-OEGMA300). During hydration in D2O vapor atmosphere, the hydrophobic PAN component prevents the formation of D2O enrichment in the substrate-near layer. However, an additional vapor-near layer is observed on top of the main layer, which is enriched with D2O. The hydration process is constrained by the cross-linking points in the film, inducing the relaxation time to be longer than that in a spin-coated P(MEO2MA-co-OEGMA300) film. Because the as-prepared cross-linked film presents a transition temperature (TT) at 38 °C, the hydrated film switches to the collapsed state when the temperature is increased from 23 to 50 °C. The response to a thermal stimulus is also slower due to the existence of the internal cross-linking points as compared to the spin-coated film. Interestingly, no reswelling is observed at the end of the thermal stimulus, which can be also attributed to the presence of internal cross-linking points.

The swelling and solvation of 100-200 nm thin films of a diblock copolymer consisting of a short poly(methyl methacrylate) (PMMA) block and a long poly(N-isopropylacrylamide) (PNIPAM) block are investigated in mixed water/methanol vapors. The processes are followed in real time using spectral reflectance (SR), time-of-flight neutron reflectometry (ToF-NR), and Fourier transform infrared (FT-IR) spectroscopy, applying two neutron scattering contrast variation sequences. After hydration in pure water vapor, the vapor composition (relative to a flow rate of 1 L/min ≙ 100%) is changed to 70% water (D2O/H2O) and 30% methanol (CH3OH/CD3OH). Upon the mixed vapor stimulus, a two-step response is found, in which an initially enhanced swelling of the films is followed by a contraction. Differences in the solvent exchange kinetics found in ToF-NR experiments coincide with characteristic changes in the FT-IR spectra. While the initially enhanced swelling of the films is driven by the absorption of methanol, the film contraction is related to the release of both solvents, with almost no further change in solvent composition. In analogy to the coil-to-globule transition encountered in the polymer solution, these film response characteristics are attributed to the cononsolvency behavior of PNIPAM in water/methanol mixtures.

The water swelling and subsequent solvent exchange including co-nonsolvency behavior of thin films of a doubly thermo-responsive diblock copolymer (DBC) are studied via spectral reflectance, time-of-flight neutron reflectometry, and Fourier transform infrared spectroscopy. The DBC consists of a thermo-responsive zwitterionic (poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate)) (PSBP) block, featuring an upper critical solution temperature transition in aqueous media but being insoluble in acetone, and a nonionic poly(N-isopropylmethacrylamide) (PNIPMAM) block, featuring a lower critical solution temperature transition in water, while being soluble in acetone. Homogeneous DBC films of 50–100 nm thickness are first swollen in saturated water vapor (H2O or D2O), before they are subjected to a contraction process by exposure to mixed saturated water/acetone vapor (H2O or D2O/acetone-d6 = 9:1 v/v). The affinity of the DBC film toward H2O is stronger than for D2O, as inferred from the higher film thickness in the swollen state and the higher absorbed water content, thus revealing a pronounced isotope sensitivity. During the co-solvent-induced switching by mixed water/acetone vapor, a two-step film contraction is observed, which is attributed to the delayed expulsion of water molecules and uptake of acetone molecules. The swelling kinetics are compared for both mixed vapors (H2O/acetone-d6 and D2O/acetone-d6) and with those of the related homopolymer films. Moreover, the concomitant variations of the local environment around the hydrophilic groups located in the PSBP and PNIPMAM blocks are followed. The first contraction step turns out to be dominated by the behavior of the PSBP block, whereas the second one is dominated by the PNIPMAM block. The unusual swelling and contraction behavior of the latter block is attributed to its co-nonsolvency behavior. Furthermore, we observe cooperative hydration effects in the DBC films, that is, both polymer blocks influence each other’s solvation behavior.

Abnormal fast dehydration and rehydration of light- and thermo-dual-responsive copolymer films of poly(oligo(ethylene glycol) methyl ether methacrylate-co-6-(4-phenylazophenoxy)hexyl acrylate), abbreviated as P(OEGMA300-co-PAHA), are triggered by UV radiation. Both rapid kinetic processes are probed by in situ neutron reflectivity (NR). The transition temperatures (TTs) of P(OEGMA300-co-PAHA) are 53.0 (ambient conditions) and 52.5 °C (UV radiation, λ = 365 nm). Thin P(OEGMA300-co-PAHA) films show a random distribution of OEGMA300 and PAHA segments. They swell in a D2O vapor atmosphere at 23 °C (below TT) to a swelling ratio d/das-prep of 1.61 ± 0.01 and exhibit a D2O volume fraction φ(D2O) of 39.3 ± 0.5%. After being exposed to UV radiation for only 60 s, d/das-prep and φ(D2O) significantly decrease to 1.00 ± 0.01 and 13.4 ± 0.5%, respectively. Although the UV-induced trans-cis isomerization of the azobenzene in PAHA induces increased hydrophilicity, the configuration change causes a breaking of the intermolecular hydrogen bonds between OEGMA300 and D2O molecules and unexpected film shrinkage. As compared to thermal stimulus-induced dehydration, the present dehydration rate is 100 times faster. Removal of the UV radiation causes immediate rehydration. After 200 s, d/das-prep and φ(D2O) recover to their hydrated states, which is also 30 times faster than the initial hydration. At 60 °C (above TT), thin P(OEGMA300-co-PAHA) films switch to their collapsed state and are insensitive to UV radiation. Thus, the UV-induced fast dehydration and rehydration depend on the existence of hydrogen bonds.

The impact of thermal history on the kinetic response of thin thermoresponsive diblock copolymer poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol) methyl ether methacrylate), abbreviated as PMEO2MA-b-POEGMA300, films is investigated by in situ neutron reflectivity. The PMEO2MA and POEGMA300 blocks are both thermoresponsive polymers with a lower critical solution temperature. Their transition temperatures (TTs) are around 25 °C (TT1, PMEO2MA) and 60 °C (TT2, POEGMA300). Thus, by applying different temperature protocols (20 to 60 or 20 to 40 to 60 °C), the PMEO2MA-b-POEGMA300 thin films experience different thermal histories: the first protocol directly switches from a swollen to a collapsed state, whereas the second one switches first from a swollen to a semicollapsed and finally to a collapsed state. Although the applied thermal histories differ, the response and final state of the collapsed films are very close to each other. After the thermal stimulus, both films present a complicated response composed of an initial shrinkage, followed by a rearrangement. Interestingly, a subsequent reswelling of the collapsed film is only observed in the case of having applied a thermal stimulus of 20 to 40 °C. The normalized film thickness and the D2O amount of each layer in the PMEO2MA-b-POEGMA300 films are consistent at the end of the two different thermal stimuli. Hence, it can be concluded that the thermal history does not influence the final state of the PMEO2MA-b-POEGMA300 films upon heating. Based on this property, these thin films are especially suitable for the temperature switches on the nanoscale, which may experience different thermal histories.

Topological spin textures such as skyrmions hold high potential for use as magnetically active elements in diverse near-future applications. While skyrmions in metallic multilayers attract great attention in this context, unleashing the myriad potential of skyrmions for various applications requires the discovery and customization of alternative host system paradigms. Here we developed and applied a chemical method to synthesize octahedral particles of the chiral insulating skyrmion host Cu2OSeO3 with both narrow size distribution, and tailored dimensions approaching the nanoscale. Combining magnetometry and neutron scattering experiments with micromagnetic simulations, we show that the bulk phase diagram of Cu2OSeO3 changes dramatically below octahedral heights of 400 nm. Further particle size-dependent regimes are identified where various topological spin textures such as skyrmions, merons and bobbers can stabilize, prior to a lower critical octahedral height of approx. 190 nm below which no topological spin texture is found stable. These findings suggest conditions under which sparse topological spin textures confined to chiral magnet nanoparticles can be stable, and provide fresh potential for insulator-based application paradigms.

We present the results of a study of the vortex lattice in the heavy fermion superconductor ${\mathrm{CeCu}}_{2}{\mathrm{Si}}_{2}$, using small-angle neutron scattering (SANS). In this material at temperatures well below ${T}_{\mathrm{c}}\ensuremath{\sim}0.6$ K, the value of the upper critical field ${B}_{\mathrm{c}2}\ensuremath{\sim}2.2$ T is strongly limited by the Pauli paramagnetism of the heavy fermions. In this temperature region, our SANS data show an increase in the magnetization of the flux line cores with field, followed by a rapid fall near ${B}_{\mathrm{c}2}$. This behavior is the effect of Pauli paramagnetism and we present a theory-based model, which can be used to describe this effect in a range of materials. The pairing in ${\mathrm{CeCu}}_{2}{\mathrm{Si}}_{2}$ appears to arise from the effect of magnetic fluctuations, but the evidence for a $d$-wave order parameter is rather weak. We find that the vortex lattice structure in ${\mathrm{CeCu}}_{2}{\mathrm{Si}}_{2}$ is close to regular hexagonal. There are no phase transitions to square or rhombic structures; such transitions are expected for $d$-wave superconductors and observed in ${\mathrm{CeCoIn}}_{5}$; however, the temperature dependence of the SANS intensity indicates that both large and small gap values are present, most likely due to multiband $s$-wave superconductivity, rather than a nodal gap structure.

We study the evolution of the low-temperature field-induced magnetic defects observed under an applied magnetic field in a series of frustrated amorphous ferromagnets (Fe$_{1-x}$Mn$_{x}$)$_{75}$P$_{16}$B$_{3}$Al$_{3}$ (a-FeMn). Combining small-angle neutron scattering and Monte Carlo simulations, we show that the morphology of these defects resemble that of quasi-bidimensional spin vortices. They are observed in the reentrant spin-glass (RSG) phase, up to the critical concentration $x_{\rm C} \approx 0.36$ which separates the RSG and "true" spin glass (SG) within the low temperature part of the magnetic phase diagram of a-FeMn. These vortices systematically decrease in size with increasing magnetic field or decreasing the average exchange interaction, and they finally disappear in the SG sample ($x = 0.41$), being replaced by field-induced correlations over finite length scales. We argue that the study of these nanoscopic defects could be used to probe the nature of the critical line between the RSG and SG phases., Comment: 23 pages, 14 figures, includes supplement

The linear shrinkage behavior in thermoresponsive diblock copolymer films and its potential application in temperature sensors are investigated. The copolymer is composed of two thermoresponsive blocks with different transition temperatures (TTs): di(ethylene glycol) methyl ether methacrylate (MEO2MA; TT1 = 25 °C) and poly(ethylene glycol) methyl ether methacrylate (OEGMA300; TT2 = 60 °C) with a molar ratio of 1:1. Aqueous solutions of PMEO2MA-b-POEGMA300 show a three-stage transition upon heating as seen with optical transmittance and small-angle X-ray scattering: dissolution (T TT2). Due to the restrictions in the polymer chain arrangement introduced by the solid Si substrate, spin-coated PMEO2MA-b-POEGMA300 films exhibit an entirely different internal structure and transition behavior. Neutron reflectivity shows the absence of an ordered structure normal to the Si substrate in as-prepared PMEO2MA-b-POEGMA300 films. After exposure to D2O vapor for 3 h and then increasing the temperature above its TT1 and TT2, the ordered structure is still not observed. Only a D2O enrichment layer is formed close to the hydrophilic Si substrate. Such PMEO2MA-b-POEGMA300 films show a linear shrinkage between TT1 and TT2 in a D2O vapor atmosphere. This special behavior can be attributed to the synergistic effect between the restrained collapse of the PMEO2MA blocks by the still swollen POEGMA300 blocks and the impedance of chain arrangement by the Si substrate. Based on this unique behavior, spin-coated PMEO2MA-b-POEGMA300 films are further prepared into a temperature sensor by implementing Ag electrodes. Its resistance decreases linearly with temperature between TT1 and TT2.

The Guinier law for magnetic SANS on bulk ferromagnets is introduced and applied to the analysis of nanocrystalline cobalt. The magnetic-field-dependent Guinier radius reflects the characteristic microstructural size and depends on the magnetic interactions., Small-angle scattering of X-rays and neutrons is a routine method for the determination of nanoparticle sizes. The so-called Guinier law represents the low-q approximation for the small-angle scattering curve from an assembly of particles. The Guinier law has originally been derived for nonmagnetic particle-matrix-type systems and it is successfully employed for the estimation of particle sizes in various scientific domains (e.g. soft-matter physics, biology, colloidal chemistry, materials science). An important prerequisite for it to apply is the presence of a discontinuous interface separating particles and matrix. Here, the Guinier law is introduced for the case of magnetic small-angle neutron scattering and its applicability is experimentally demonstrated for the example of nanocrystalline cobalt. It is well known that the magnetic microstructure of nanocrystalline ferromagnets is highly nonuniform on the nanometre length scale and characterized by a spectrum of continuously varying long-wavelength magnetization fluctuations, i.e. these systems do not manifest sharp interfaces in their magnetization profile. The magnetic Guinier radius depends on the applied magnetic field, on the magnetic interactions (exchange, magnetostatics) and on the magnetic anisotropy-field radius, which characterizes the size over which the magnetic anisotropy field is coherently aligned into the same direction. In contrast to the nonmagnetic conventional Guinier law, the magnetic version can be applied to fully dense random-anisotropy-type ferromagnets.

Order-disorder transitions between glassy phases are common in nature and yet a comprehensive survey on the entailed structural changes is challenging since the constituents are in the micro-scale. Vortex matter in type-II superconductors is a model system where some of these experimental challenges can be tackled. Samples with point disorder present a glassy transition on increasing the density of vortices. A glassy yet quasi-crystalline phase, the Bragg glass, nucleates at low densities. The vortex glass stable at high densities is expected to be disordered, however its detailed structural properties remained experimentally elusive. Here we show that the vortex glass has large crystallites with in-plane positional displacements growing algebraically and short-range orientational order. Furthermore, the vortex glass has a finite and almost constant correlation length along the direction of vortices, in sharp contrast with strong entanglement. These results are important for the understanding of disorder-driven phase transitions in glassy condensed matter. Fil: Aragón Sánchez, Jazmín. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Cortés Maldonado, Raúl. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Cejas Bolecek, Néstor René. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Rumi, Gonzalo Agustín. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Pedrazzini, Pablo. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Dolz, Moira Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich". Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich"; Argentina Fil: Nieva, Gladys Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; Argentina Fil: Van Der Beek, Cornelis Jacominus. Université Paris Sud; Francia. Centre National de la Recherche Scientifique; Francia Fil: Konczykowski, Marcin. Ecole Polytechnique. Departement Physique. Laboratoire Des Solides Irradies; Francia Fil: Dewhurst, Charles D.. Institut Laue Langevin; Francia Fil: Cubitt, Robert. Institut Laue Langevin; Francia Fil: Kolton, Alejandro Benedykt. Comisión Nacional de Energía Atómica. Gerencia del Área Investigaciones y Aplicaciones No Nucleares. Gerencia de Física (CAB). Grupo de Teoría de Sólidos; Argentina Fil: Pautrat, Alain. École Nationale Supérieure d’Ingénieurs de Caen. Centre de Recherche; Francia Fil: Fasano, Yanina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; Argentina

In this paper we study consequences of the results of Kang et al. [Monoidal categorification of cluster algebras, J. Amer. Math. Soc. 31 (2018), 349–426] on a monoidal categorification of the unipotent quantum coordinate ring $A_{q}(\mathfrak{n}(w))$ together with the Laurent phenomenon of cluster algebras. We show that if a simple module $S$ in the category ${\mathcal{C}}_{w}$ strongly commutes with all the cluster variables in a cluster $[\mathscr{C}]$, then $[S]$ is a cluster monomial in $[\mathscr{C}]$. If $S$ strongly commutes with cluster variables except for exactly one cluster variable $[M_{k}]$, then $[S]$ is either a cluster monomial in $[\mathscr{C}]$ or a cluster monomial in $\unicode[STIX]{x1D707}_{k}([\mathscr{C}])$. We give a new proof of the fact that the upper global basis is a common triangular basis (in the sense of Qin [Triangular bases in quantum cluster algebras and monoidal categorification conjectures, Duke Math. 166 (2017), 2337–2442]) of the localization $\widetilde{A}_{q}(\mathfrak{n}(w))$ of $A_{q}(\mathfrak{n}(w))$ at the frozen variables. A characterization on the commutativity of a simple module $S$ with cluster variables in a cluster $[\mathscr{C}]$ is given in terms of the denominator vector of $[S]$ with respect to the cluster $[\mathscr{C}]$.

Silicon is a promising anode material for lithium ion batteries due to its ten times higher specific capacity compared to commercially used graphite anodes. However, silicon anodes suffer from strong capacity fading and low Coulombic efficiency during cycling. Here we analyzed crystalline silicon anodes by operando neutron reflectometry in combination with electrochemical impedance spectroscopy. The lithiation/delithiation processes were investigated over four cycles revealing a successive growth of the lithiated zone. Moreover, the loss of Coulombic efficiency could be directly correlated to a layer formation and its dissolution on the silicon surface that suppressed the insertion of lithium ions into the silicon anode. The comparison of the currents obtained by the scattering length density profiles and the potentiostat revealed that after an initial parasitic side reaction had occurred current losses of less than 5% could be achieved. While the lithiation was hindered by side reactions the delithiation process encountered no significant problems. The results obtained by electrochemical impedance spectroscopy suggested that a layer with high charge transfer resistance was formed after each delithiation step. Hence, these operando studies provide valuable insights into the correlation of surface formation processes and the loss in Coulombic efficiency.

The hydration and thermal response kinetics of the cross-linked thermoresponsive copolymer poly((diethylene glycol monomethyl ether methacrylate)

Graphite intercalation compounds (GICs) are a group of layered materials that are suitable as monochromators for cold neutrons. KC

We report the magnetic field dependence of the THz absorption and non-reciprocal directional dichroism spectra of BiFeO$_3$ measured on the three principal crystal cuts for fields applied along the three principal directions of each cut. From the systematic study of the light polarization dependence we deduced the optical selection rules of the spin-wave excitations. Our THz data, combined with small-angle neutron scattering results showed that i) an in-plane magnetic field rotates the $\mathbf{q}$ vectors of the cycloids perpendicular to the magnetic field, and ii) the selection rules are mostly determined by the orientation of the $\mathbf{q}$ vector with respect to the electromagnetic fields. We observed a magnetic field history dependent change in the strength and the frequency of the spin-wave modes, which we attributed to the change of the orientation and the length of the cycloidal $\mathbf{q}$ vector, respectively. Finally, we compared our experimental data with the results of linear spin-wave theory that reproduces the magnetic field dependence of the spin-wave frequencies and most of the selection rules, from which we identified the spin-polarization coupling terms relevant for the optical magnetoelectric effect.

The swelling of thin diblock copolymer (DBC) films is investigated in situ at 22 °C in pure water vapor as well as in mixed water / methanol vapor. The DBC consists of a zwitterionic poly(sulfobetaine) block, poly[3-((2-(methacryloyloxy)ethyl)-dimethylammonio) propane-1-sulfonate] (PSPE), and a nonionic poly(N-sopropylmethacrylamide) (PNIPMAM) block. The swelling in water vapor (either H2O or D2O) and the thin-film response to methanol vapor exchange (i.e., a part of the H2O vapor is exchanged by CD3OH vapor and a part of the D2O vapor is exchanged by CH3OH vapor) are followed with simultaneous time-offlight neutron reflectometry (ToF-NR) and spectral reflectance (SR) measurements. In situ Fourier transform infrared (FTIR)spectroscopy complements these data. Exposure to H2O vapor leads to a slightly higher degree of swelling and amount of absorbed H2O compared to D2O. Upon methanol exchange, the PSPE-b-PNIPMAM thin film undergoes two contractions, which are assigned to the specific responses of the individual polymer blocks of the DBC. Due to its isotope sensitivity, FTIR confirms these two separate contraction processes of the blocks on a molecular level and reveals the role of each polymer block during swelling in water vapor and upon the methanol exchange. Thus, four distinct film regimes with different thicknesses dependencies on the vapor composition can be established, thereby enabling a quarternary nanoswitch.

We report spatially resolved small-angle neutron-scattering measurements of the conical and skyrmion states of a bulk single crystal of nickel-substituted ${\mathrm{Cu}}_{2}{\mathrm{OSeO}}_{3}$, with a nominal concentration of Ni of 14%. We observe a significant spatial dependence of the structure of these magnetic states, characterized by increased disorder and misalignment with respect to the applied field as we approach the edge of the sample. Remarkably, the edge skyrmion state is also characterized by an extended stability towards lower temperatures. Surprisingly, in the same region of the sample, the metastable skyrmion state did not show simple decay. Instead, only a fraction of the scattered intensity appeared to decay, and the intensity therefore did not approach zero during our measurements. We suggest that the increased local disorder and the coexistence of conical and skyrmion states, induced by demagnetization effects at the edge of the sample, are responsible for the increased stability of this skyrmion state. We also infer that the unclear metastable behavior of the skyrmion lattice at the edge of the sample is due to the local geometry of the sample, which induces coexistence of different skyrmion states whose lifetimes are superimposed and difficult to separate in the data.

Magnetic skyrmions are nanosized topological spin textures stabilized by a delicate balance of magnetic energy terms. The chemical substitution of the underlying crystal structure of skyrmion-hosting materials offers a route to manipulate these energy contributions but also introduces additional effects such as disorder and pinning. While the effects of doping and disorder have been well studied in B20 metallic materials such as ${\mathrm{Fe}}_{1\ensuremath{-}x}{\mathrm{Co}}_{x}\mathrm{Si}$ and ${\mathrm{Mn}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{x}\mathrm{Si}$, the consequences of chemical substitution in the magnetoelectric insulator ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$ have not been fully explored. In this work we utilize a combination of AC magnetometry and small-angle neutron scattering to investigate the magnetic phase transition dynamics in pristine and Zn-substituted ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$. The results demonstrate that the first-order helical-conical phase transition exhibits two thermally separated behavioral regimes: at high temperatures, the helical and conical domains transform by large-scale, continuous rotations, while at low temperatures, the two phases coexist. Remarkably, the effects of pinning in the substituted sample are less prevalent at low temperatures compared to high temperatures, despite the reduction of available thermal activation energy. We attribute this behavior to the large, temperature-dependent, cubic anisotropy unique to ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$, which becomes strong enough to overcome the pinning energy at low temperatures. Consideration and further exploration of these effects will be crucial when engineering skyrmion materials towards future applications.

Magnetic skyrmions are vortex-like topological spin textures often observed in structurally chiral magnets with Dzyaloshinskii-Moriya interaction. Among them, Co-Zn-Mn alloys with a $\beta$-Mn-type chiral structure host skyrmions above room temperature. In this system, it has recently been found that skyrmions persist over a wide temperature and magnetic field region as a long-lived metastable state, and that the skyrmion lattice transforms from a triangular lattice to a square one. To obtain perspective on chiral magnetism in Co-Zn-Mn alloys and clarify how various properties related to the skyrmion vary with the composition, we performed systematic studies on Co$_{10}$Zn$_{10}$, Co$_9$Zn$_9$Mn$_2$, Co$_8$Zn$_8$Mn$_4$ and Co$_7$Zn$_7$Mn$_6$ in terms of magnetic susceptibility and small-angle neutron scattering measurements. The robust metastable skyrmions with extremely long lifetime are commonly observed in all the compounds. On the other hand, preferred orientation of a helimagnetic propagation vector and its temperature dependence dramatically change upon varying the Mn concentration. The robustness of the metastable skyrmions in these materials is attributed to topological nature of the skyrmions as affected by structural and magnetic disorder. Magnetocrystalline anisotropy as well as magnetic disorder due to the frustrated Mn spins play crucial roles in giving rise to the observed change in helical states and corresponding skyrmion lattice form., Comment: 70 pages, 19 figures

We investigate the macroscopic and microscopic physical properties of the solid solution of ${\mathrm{Ce}}_{1\ensuremath{-}x}{\mathrm{Pr}}_{x}\mathrm{AlGe}$. The series tunes from CeAlGe with its multi-$\stackrel{P\vec}{k}$ structure and a major moment in the $ab$ plane, to PrAlGe with an easy $c$-axis ferromagnetic ground state coexisting with a low density of nanoscale textured magnetic domain walls. Using AC, DC susceptibility, resistivity, specific heat, muon spin relaxation/rotation, and neutron scattering we analyze the magnetic ground state of the series. We provide further evidence supporting our previous claim for spin-glass-like properties in pure PrAlGe. With the introduction of Pr to CeAlGe the finite magnetic field required to stabilize the topological multi-$\stackrel{P\vec}{k}$ magnetic phase for $x=0$ becomes suppressed. The crossover between the two end-member ground states occurs in the vicinity of $x=0.3$, a region where we further anticipate the field-induced topological magnetic phase for $xl0.3$ to become the zero field ground state.

The impact of thermal history on the kinetic response of thin thermoresponsive diblock copolymer poly(diethylene glycol monomethyl ether methacrylate)

We present the results of a study of the vortex lattice (VL) of the nickel chalcogenide superconductor ${\mathrm{TlNi}}_{2}{\mathrm{Se}}_{2}$, using small angle neutron scattering. This superconductor has the same crystal symmetry as the iron arsenide materials. Previous work points to it being a two-gap superconductor, with an unknown pairing mechanism. No structural transitions in the vortex lattice are seen in the phase diagram, arguing against $d$-wave gap symmetry. Empirical fits of the temperature dependence of the form factor and penetration depth rule out a simple $s$-wave model, supporting the presence of nodes in the gap function. The variation of the VL opening angle with field is consistent with earlier reports of multiple gaps.

Neutron reflectivity is a powerful technique for characterizing interfaces in many areas of science. The traditional method of time of flight for measuring the wavelength of neutrons in a white beam is extremely wasteful, as the vast majority of neutrons must be absorbed in the choppers in order to produce a pulsed beam. A prism operates continuously, with a transmission up to two orders of magnitude higher than choppers. The wavelength-dependent deflection of the beam by the prism, coupled with a high spatial resolution detector, results in excellent wavelength resolution. The theory of how the resolution is considerably enhanced by curving the surface of the prism is described in detail for a real experimental arrangement. It is demonstrated how this can be used for faster neutron reflectometry, including the merging of different angles and subtraction of background. The technique shows considerable promise for neutron reflectivity, opening up new areas of science particularly in the realms of kinetics and small samples.

The vertical sample-plane reflectometer D17 at the Institut Laue–Langevin in Grenoble, France, has undergone several major upgrades since its commissioning, which are summarized in this article. The three major improvements are (i) a new focusing guide, increasing the usable flux on the sample by a factor of 2.5; (ii) a new beam polarizer and new spin flippers, allowing for the use of polarized neutrons in time-of-flight mode; and (iii) a new detector with a particularly uniform response under homogeneous exposure, improved stability and state-of-the-art detector electronics. The combination of these factors has paved the road to new possibilities in fast kinetic measurements, magnetism and off-specular scattering. Examples and scientific references for the new capabilities are presented.

Small-angle neutron scattering is used in combination with transport measurements to investigate the current-induced effects on the morphology of the intermediate mixed state domains in the intertype superconductor niobium. We report the robust self-organisation of the vortex lattice domains to elongated parallel stripes perpendicular to the applied current in a steady-state. The experimental results for the formation of the superstructure are supported by theoretical calculations, which highlight important details of the vortex matter evolution. The investigation demonstrates a mechanism of a spontaneous pattern formation that is closely related to the universal physics governing the intermediate mixed state in low-$\kappa$ superconductors., Comment: 15 pages, 9 figures

To enable a renewable energy future, electro- chemical energy storage remains as one of the main challenges of today’s society. Lithium-ion batteries have been shown to be of great potential in that respect, but they still suffer from safety instabilities arising from the use of flammable liquid electrolytes. Solid electrolytes are an interesting alternative that provide the required safety properties. We introduce a highly stable solid single-ion diblock copolymer electrolyte poly(deuterated styrene)- block-poly(poly(ethylene glycol) methyl ether styrene-co-lithium styrene sulfonyl(trifluoromethane sulfonyl)imide), denoted PS(d)-b-P(SPEG-co-STFSILi). Lithium metal batteries based on PS(d)-b-P(SPEG-co-STFSILi) are probed in operando with small-angle neutron scattering in order to investigate their suitability as safe batteries using lithium metal anodes. We compare cell operation when cycling at 0.5 C at 80 °C to 0.7 C at 90 °C, which represent severe working conditions for the battery. More than 200 cycles are performed, showing the inflation of the ionic pathways through cycling at 0.7 C, whereas at 0.5 C and 80 °C, battery performance and morphology remain unchanged.

The isothermal vacuum-induced dehydration of thin films made of poly(methoxy diethylene glycol acrylate) (PMDEGA), which were swollen under ambient conditions, is studied. The dehydration behavior of the homopolymer film as well as of a nanostructured film of the amphiphilic triblock copolymer polystyrene- block -poly(methoxy diethylene glycol acrylate)- block -polystyrene, abbreviated as PS- b -PMDEGA- b -PS, are probed, and compared to the thermally induced dehydration behavior of such thin thermo-responsive films when they pass through their LCST-type coil-to globule collapse transition. The dehydration kinetics is followed by in-situ neutron reflectivity measurements. Contrast results from the use of deuterated water. Water content and film thickness are significantly reduced during the process, which can be explained by Schott second order kinetics theory for both films. The water content of the dehydrated equilibrium state from this model is very close to the residual water content obtained from the final static measurements, indicating that residual water still remains in the film even after prolonged exposure to the vacuum. In the PS- b -PMDEGA- b -PS film that shows micro-phase separation, the hydrophobic PS domains modify the dehydration process by hindering the water removal, and thus retarding dehydration by about 30%. Whereas residual water remains tightly bound in the PMDEGA domains, water is completely removed from the PS domains of the block copolymer film.

We report a magnetic state in GaV4Se8 which emerges exclusively in samples with mesoscale polar domains and not in polar mono-domain crystals. It is manifested by a sharp anomaly in the magnetic susceptibility and the magnetic torque, distinct from other anomalies observed also in polar mono-domain samples upon transitions between the cycloidal, the Néel-type skyrmion lattice and the ferromagnetic states. We ascribe this additional transition to the transformation of distinct magnetic textures, confined to polar domain walls (DW), to the ferromagnetic (FM) state. The emergence of these DW-confined magnetic states is likely driven by the mismatch of different spin spirals, hosted by the adjacent domains. A clear anomaly in the magneto-current indicates that the DW-confined magnetic states also have strong contributions to the magnetoelectric response. We expect polar DWs to commonly host such confined magnetic edge states and, thus, offer a fertile ground to explore novel forms of magnetism.

Previous observations of metastable magnetic skyrmions have shown that close to the equilibrium pocket the metastable state has a short lifetime, and therefore, rapid cooling is required to generate a significant skyrmion population at low temperatures. Here, we report that the lifetime of metastable skyrmions in crystals of Cu2OSeO3 is extended by a factor of 50 with the introduction of only 2.5% zinc doping, allowing over 50% of the population to survive when field cooling at a rate of just 1 K/min. Our systematic study suggests that the lifetime enhancement is due to the increase in the pinning site density, rather than an alteration to the energy barrier of the decay process. We expect that doping can be exploited to control the lifetime of the metastable SkL state in other chiral magnets, offering a method of engineering skyrmion materials towards application in future devices.

We observe a hysteretic reorientation of the magnetic vortex lattice in the noncentrosymmetric superconductor ${\mathrm{Ru}}_{7}{\mathrm{B}}_{3}$, with the change in orientation driven by altering the magnetic field below ${T}_{\mathrm{c}}$. Normally a vortex lattice chooses either a single or degenerate set of orientations with respect to a crystal lattice at any given field or temperature, a behavior well described by prevailing phenomenological and microscopic theories. Here, in the absence of any typical VL structural transition, we observe a continuous rotation of the vortex lattice which exhibits a pronounced hysteresis and is driven by a change in magnetic field. We propose that this rotation is related to the spontaneous magnetic fields present in the superconducting phase, which are evidenced by the observation of time-reversal symmetry breaking, and the physics of broken inversion symmetry. Finally, we develop a model from the Ginzburg-Landau approach which shows that the coupling of these to the vortex lattice orientation can result in the rotation we observe.

Thermoresponsive films of poly(N-isopropyl methacrylamide) (PNIPMAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA) are compared with respect to their hydration and dehydration kinetics using in situ neutron reflectivity. Both as-prepared films present a homogeneous single-layer structure and have similar transition temperatures of the lower critical solution temperature type (TT, PNIPMAM 38 degrees C and PMDEGA 41 degrees C). After hydration in unsaturated D2O vapor at 23 degrees C, a D2O enrichment layer is observed in PNIPMAM films adjacent to the Si substrate. In contrast, two enrichment layers are present in PMDEGA films (close to the vapor interface and the Si substrate). PNIPMAM films exhibit a higher hydration capability, ascribed to having both donor (N-H) and acceptor (C=O) units for hydrogen bonds. "While the swelling of the PMDEGA films is mainly caused by the increase of the enrichment layers, the thickness of the entire PNIPMAM films increases with time. The observed longer relaxation time for swelling of PNIPMAM films is attributed to the much higher glass transition temperature of PNIPMAM. When dehydrating both films by increasing the temperature above the TT, they react with a complex response consisting of three stages (shrinkage, rearrangement, and reswelling). PNIPMAM films respond faster than PMDEGA films. After dehydration, both films still contain a large amount of D2O, and no completely dry film state is reached for a temperature above their TTs.

We report small angle neutron scattering (SANS) measurements of the skyrmion lattice in (Cu$_{0.976}$Zn$_{0.024}$)$_2$OSeO$_3$ under the application of an electric field. These measurements show an expansion of the skyrmion lattice stability region with electric field similar to that seen in pristine Cu$_2$OSeO$_3$. Furthermore, using time-resolved SANS, we observe the slow formation of skyrmions after an electric or magnetic field is applied, which has not been observed in pristine Cu$_2$OSeO$_3$ crystals. The measured formation times are dramatically longer than the corresponding skyrmion destruction times after the external field is removed, and increase exponentially from 100~s at 52.5~K to 10,000~s at 51.5~K. This thermally activated behaviour indicates an energy barrier for skyrmion formation of 1.57(2)~eV, the size of which demonstrates the huge cost for creating these complex chiral objects., 8 pages, 8 figures

A biskyrmion consists of two bound, topologically stable, skyrmion spin textures. These coffee-bean-shaped objects are observed in real space in thin plates using Lorentz transmission electron microscopy (LTEM). From LTEM imaging alone, it is not clear whether biskyrmions are surface-confined objects, or, analogous to skyrmions in noncentrosymmetric helimagnets, 3D tube-like structures in a bulk sample. Here, the biskyrmion form factor is investigated in single- and polycrystalline-MnNiGa samples using small-angle neutron scattering. It is found that biskyrmions are not long-range ordered, not even in single crystals. Surprisingly all of the disordered biskyrmions have their in-plane symmetry axis aligned along certain directions, governed by the magnetocrystalline anisotropy. This anisotropic nature of biskyrmions may be further exploited to encode information.

We present an operando neutron reflectometry study on the electrochemical incorporation of lithium into crystalline silicon for battery applications. Neutron reflectivity is measured from the ⟨100⟩ surface of a silicon single crystal which is used as a negative electrode in an electrochemical cell. The strong scattering contrast between Si and Li due to the negative scattering length of Li leads to a precise depth profile of Li within the Si anode as a function of time. The operando cell can be used to study the uptake and the release of Li over several cycles. Lithiation starts with the formation of a lithium enrichment zone during the first charge step. The uptake of Li can be divided into a highly lithiated zone at the surface (skin region) (x ∼ 2.5 in LixSi) and a much less lithiated zone deep into the crystal (growth region) (x ∼ 0.1 in LixSi). The total depth of penetration was less than 100 nm in all experiments. The thickness of the highly lithiated zone is the same for the first and second cycle, whereas the thickness of the less lithiated zone is larger for the second lithiation. A surface layer of lithium (x ∼ 1.1) remains in the silicon electrode after delithiation. Moreover, a solid electrolyte interface is formed and dissolved during the entire cycling. The operando analysis presented here demonstrates that neutron reflectivity allows the tracking of the kinetics of lithiation and delithiation of silicon with high spatial and temporal resolution.

The D33 small-angle neutron scattering (SANS) instrument at the Institut Laue–Langevin (ILL) is the most recent SANS instrument to be built at the ILL. In a project beginning in 2005 and lasting seven years, the concept has been developed, and the instrument designed, manufactured and installed. D33 was commissioned with neutrons during the second half of 2012, fully entering the ILL user programme in 2013. The scientific case required that D33 should provide a wide dynamic range of measured scattering vector magnitudeq, flexibility with regard to the instrument resolution, and the provision of polarized neutrons and3He spin analysis to facilitate and expand studies in magnetism. In monochromatic mode, a velocity selector and a flexible system of inter-collimation apertures define the neutron beam. A double-chopper system enables a time-of-flight (TOF) mode of operation, allowing an enhanced dynamicqrange (qmax/qmin) and a flexible wavelength resolution. Two large multitube detectors extend the dynamicqrange further, givingqmax/qmin≃ 25 in monochromatic mode and a very largeqmax/qmin> 1000 in TOF mode. The sample zone is large and flexible in configuration, accommodating complex and bulky sample environments, while the position of D33 is such as to allow high magnetic fields at the sample position. The instrument is of general purpose with a performance rivalling that of D22, and is well adapted for SANS studies in scientific disciplines as diverse as solution scattering in biology and soft matter and studies of physics, materials science and magnetism. This article provides a detailed technical description of D33 and its performance and characterization of the individual components, and serves as a technical reference for users of the instrument.

Magnetic skyrmions are topologically protected nanoscale spin textures with particle-like properties. In bulk cubic helimagnets, they appear under applied magnetic fields and condense spontaneously into a lattice in a narrow region of the phase diagram just below the magnetic ordering temperature, the so-called A-phase. Theory, however, predicts skyrmions to be locally stable in a wide range of magnetic fields and temperatures. Our neutron diffraction measurements reveal the formation of skyrmion states in large areas of the magnetic phase diagram, from the lowest temperatures up to the A-phase. We show that nascent and disappearing spiral states near critical lines catalyze topological charge changing processes, leading to the formation and destruction of skyrmionic states at low temperatures, which are thermodynamically stable or metastable depending on the orientation and strength of the magnetic field. Skyrmions are surprisingly resilient to high magnetic fields: the memory of skyrmion lattice states persists in the field polarized state, even when the skyrmion lattice signal has disappeared. These findings highlight the paramount role of magnetic anisotropies in stabilizing skyrmionic states and open up new routes for manipulating these quasi-particles towards energy-efficient spintronics applications.