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We report process improvements for the fabrication of single-walled carbon nanotube ethylene-vinyl acetate transparent conductive films. CNT:EVA films demonstrate high resilience against folding and can replace the external dopant in a spiro-OMeTAD based hole selective contact of n-i-p perovskite solar cells achieving a steady-state efficiency of 16.3%. The adapted process is fully scalable, and compared to previous reports (Mazzotta et al., 2018) lowers the material cost dramatically and improves DC to optical conductivity ratio by two orders of magnitude to σdc/σop = 3.6 for pristine and σdc/σop = 15 for chemically doped films. We analyse the microstructure of our films via small angle neutron scattering and find a positive correlation between the long range packing density of the CNT:EVA films and the σdc/σop performance. Increasing monomer ratio and chain length of the EVA polymer improves resilience against bending strain, whereas no significant effect on the CNT wrapping and electrical conductivity of resulting films is found.

The neutron resonance spin echo (NRSE) technique has the potential to increase the Fourier time and energy resolution in neutron scattering by using radio-frequency (rf) neutron spin-flippers. However, aberrations arising from variations in the neutron path length between the rf flippers reduce the polarization. Here, we develop and test a transverse static-field magnet, a series of which are placed between the rf flippers, to correct for these aberrations. The prototype correction magnet was both simulated in an NRSE beamline using McStas, a Monte Carlo neutron ray-tracing software package, and measured using neutrons. The results from the prototype demonstrate that this static-field design corrects for transverse-field NRSE aberrations., 8 figures, 10 pages

Activity tests for synthetic antimicrobial compounds are often limited to the minimal inhibitory concentration assay using standard media and bacterial strains. In this study, a family of acrylamide copolymers that act as synthetic mimics of antimicrobial peptides were synthesized and shown to have a disruptive effect on bacterial membranes and structural integrity through microscopy techniques and membrane polarization experiments. The polymers were tested for their antimicrobial properties using media that mimic clinically relevant conditions. Additionally, their activity was compared in two different strains of the Gram-positive bacterium Staphylococcus aureus and the Gram-negative bacterium Pseudomonas aeruginosa. We showed that the medium composition can have an important influence on the polymer activity as there was a considerable reduction in minimal inhibitory concentrations against S. aureus grown in synthetic wound fluid (SWF), and against P. aeruginosa grown in synthetic cystic fibrosis sputum media (SCFM), compared to the concentrations in standard testing media. In contrast, we observed a complete loss of activity against P. aeruginosa in the serum-containing SWF. Finally, we made use of an emerging invertebrate in vivo model, using Galleria mellonella larvae, to assess toxicity of the polymeric antimicrobials, showing a good correlation with cell line toxicity measurements and demonstrating its potential in the evaluation of novel antimicrobial materials.\ud \ud

The stratum corneum's lipid matrix is a critical for the skin's barrier function and is primarily composed of ceramides (CERs), cholesterol (CHOL) and free fatty acids (FFAs). The lipids form a long periodicity phase (LPP), a unique trilayer unit cell structure. An enzyme driven pathway is implemented to synthesize these key lipids. If these enzymes are down- or upregulated as in inflammatory diseases, the final lipid composition is affected often altering the barrier function. In this study, we mimicked down regulation of enzymes involved in the synthesis of the sphingosine and CER amide bond. In a LPP lipid model, we substituted CER N-(tetracosanoyl)- sphingosine (CER NS) with either i) FFA C24 and free sphingosine, to simulate the loss of the CER amide bond, or ii) with FFA C24 and C18 to simulate the loss of the sphingosine headgroup. Our study shows the lipids in the LPP would not phase separate until at least 25% of the CER NS is substituted keeping the lateral packing and conformational ordering unaltered. Neutron diffraction studies showed that free sphingosine chains localized at the outer layers of the unit cell, while the remaining CER NS head group was concentrated in the inner headgroup layers. However, when FFA C18 was inserted, CER NS was dispersed throughout the LPP, resulting in an even distribution between the inner and outer water layers. The presented results highlight the importance of the CER NS headgroup structure and its interaction in combination with the carbon chain invariability for optimal lipid arrangement.

We investigate the effect of polymer tacticity on the phase behavior and phase separation of polymer mixtures by small-angle neutron scattering (SANS). Poly(α-methyl styrene-co-acrylonitrile) (PαMSAN) and deuterated poly(methyl methacrylate) (dPMMA) with two degrees of syndiotacticity were selected as a model partially miscible blend, as one of the most highly interacting systems known (defined by the temperature dependence of the blend’s interaction parameter). One-phase (equilibrium) and time-resolved, spinodal demixing experiments were analyzed by de Gennes’ random phase approximation (RPA) and Cahn–Hilliard–Cook (CHC) theory, respectively. The second derivative of the Gibbs free energy of mixing with respect to composition (G″ ≡ ∂2ΔGm/∂ϕ2) and corresponding χ parameter were obtained from both RPA and CHC analysis and found to correlate well across the phase boundary. We find that blends with higher PMMA syndiotacticity exhibit greater miscibility and a steeper G″ temperature dependence by ∼40%. The segment length of dPMMA with higher syndiotacticity was found to be a = 7.4 Å, slightly larger than 6.9 Å reported for lower syndiotacticity dPMMA. Consideration of thermal fluctuations is required for the self-consistent analysis of the nontrivial evolution of the spinodal peak position q* over time, corroborated by CHC model calculations. The temperature dependence of the mobility parameter, M, can be described by a “fast-mode” average of the diffusion coefficients of the blend constituents, except for quenches originating near the glass transition. A minimum demixing length scale of Λ ≈ 40 nm is obtained, in agreement with the theory for deeper quenches, but deviates at shallower quenches, whose origin we discuss. CHC correctly describes demixing length and time scales, except for quenches into the vicinity of the spinodal boundary. Our data demonstrate the significant effect of relatively minor polymer microstructure variations on polymer blend behavior across both sides of the phase boundary.

Water-lean CO2 capture solvents show promise for more efficient and cost-effective CO2 capture, although their long-term behavior in operation has yet to be well studied. New observations of extended structure solvent behavior show that some solvent formulations transform into a glass-like phase upon aging at operating temperatures after contact with CO2. The glassification of a solvent would be detrimental to a carbon-capture process due to plugging of infrastructure, introducing a critical need to decipher the underlying principles of this phenomenon to prevent it from happening. We present the first integrated theoretical and experimental study to characterize the nano-structure of metastable and glassy states of an archetypal single-component alkanolguanidine carbon-capture solvent and assess how minute changes in atomic-level interactions convert the solvent between metastable and glass-like states. Small-angle neutron scattering and neutron diffraction coupled with small- and wide-angle X-ray scattering analysis demonstrate that minute structural changes in solution precipitae reversible aggregation of zwitterionic alkylcarbonate clusters in solution. Our findings indicate that our test system, an alkanolguanidine, exhibits a first-order phase transition, similar to a glass transition, at approximately 40 °C-close to the operating absorption temperature for post-combustion CO2 capture processes. We anticipate that these phenomena are not specific to this system, but are present in other classes of colvents as well. We discuss how molecular-level interactions can have vast implications for solvent-based carbon-capture technologies, concluding that fortunately in this case, glassification of water-lean solvents can be avoided as long as the solvent is run above its glass transition temperature.

In this work, we studied TEMPO-oxidized cellulose nanofibril (OCNF) suspensions in the presence of diverse surfactants. Using a combination of small angle neutron scattering (SANS) and rheology, we compared the physical properties of the suspensions with their structural behavior. Four surfactants were studied, all with the same hydrophobic tail length but different headgroups: hexaethylene glycol mono-n-dodecyl ether (C12EO6, nonionic), sodium dodecyl sulfate (SDS, anionic), cocamidopropyl betaine (CapB, zwitterionic), and dodecyltrimethylammonium bromide (DTAB, cationic). Contrast variation SANS studies using deuterated version of C12EO6 or SDS, or by varying the D2O/H2O ratio of the suspensions (with CapB), allowed focusing only on the structural properties of OCNFs or surfactant micelles. We showed that, in the concentration range studied, for C12EO6, although the nanofibrils are concentrated thanks to an excluded volume effect observed in SANS, the rheological properties of the suspensions are not affected. Addition of SDS or CapB induces gelation for surfactant concentrations superior to the critical micellar concentration (CMC). SANS results show that attractive interactions between OCNFs arise in the presence of these anionic or zwitterionic surfactants, hinting at depletion attraction as the main mechanism of gelation. Finally, addition of small amounts of DTAB (below the CMC) allows formation of a tough gel by adsorbing onto the OCNF surface.

We examine the formation and growth of isolated myelin figures and microscale multilamellar tubules from isotropic micellar solutions of an anionic surfactant. Upon cooling, surfactant micelles transform into multilamellar vesicles (MLVs) whose contact is found to trigger the unidirectional growth of myelins. While the MLV diameter grows as dMLV ∝ t1/2, myelins grow linearly in time as LM ∝ t1, with a fixed diameter. Combining time-resolved small-angle neutron scattering (SANS) and optical microscopy, we demonstrate that the microscopic growth of spherical MLVs and cylindrical myelins stems from the same nanoscale molecular mechanism, namely, the surfactant exchange from micelles into curved lamellar structures at a constant volumetric rate. This mechanism successfully describes the growth rate of (nonequilibrium) myelin figures based on a population balance at thermodynamic equilibrium.

Oppositely charged polymer–surfactant complexes are frequently explored as a function of phase space defined by the charge ratio Z, (where Z = [+polymer]/[−surfactant]), commonly accessed through the surfactant concentration. Tuning the phase behaviour and related properties of these complexes is an important tool for optimising commercial formulations; hence, understanding the relationship between Z and bulk properties is pertinent. Here, within a homologous series of cationic hydroxyethyl cellulose (cat-HEC) polymers with minor perturbations in the degree of side chain charge modification, phase space is instead explored through [+polymer] at fixed Cpolymer. The nanostructures were characterised by small-angle neutron scattering (SANS) in D2O solutions and in combination with the oppositely charged surfactant sodium dodecylsulfate (h- or d-SDS). Scattering consistent with thin rods with an average radius of ∼7.7 Å and length of ∼85 Å was observed for all cat-HEC polymers and no significant interactions were shown between the neutral HEC polymer and SDS (CSDS < CMC). For the charge-modified polymers, interactions with SDS were evident and the radius of the formed complexes grew up to ∼15 Å with increasing Z. This study demonstrates a novel approach in which the Z phase space of oppositely charged polymer–surfactant complexes can be controlled at fixed concentrations.

Cyphochilus beetle scales are amongst the brightest structural whites in nature, being highly opacifying whilst extremely thin. However, the formation mechanism for the voided intra-scale structure is unknown. Here we report 3D x-ray nanotomography data for the voided chitin networks of intact white scales of Cyphochilus and Lepidiota stigma. Chitin-filling fractions are found to be 31 ± 2% for Cyphochilus and 34 ± 1% for Lepidiota stigma, indicating previous measurements overestimated their density. Optical simulations using finite-difference time domain for the chitin morphologies and simulated Cahn-Hilliard spinodal structures show excellent agreement. Reflectance curves spanning filling fraction of 5-95% for simulated spinodal structures, pinpoint optimal whiteness for 25% chitin filling. We make a simulacrum from a polymer undergoing a strong solvent quench, resulting in highly reflective (~94%) white films. In-situ X-ray scattering confirms the nanostructure is formed through spinodal decomposition phase separation. We conclude that the ultra-white beetle scale nanostructure is made via liquid–liquid phase separation. White beetle scales strongly scatter white light, whilst being very thin. Here, the authors measured the internal scale nanostructure for the beetles, Cyphochilus and L. stigma, and demonstrate that the optical structure can be simulated using liquid–liquid phase separation nanostructures, pointing to this as the formation mechanism.

Poly(methyl methacrylate) (PMMA) and poly(α-methyl styrene-co-acrylonitrile) (PαMSAN) form partially miscible blends with lower critical solution temperature (LCST) behaviour. We revisit this system using small angle neutron scattering (SANS), examining the effect of molecular weight (Mw) of deuterated PMMA (dPMMA), blend composition (φ) and temperature (T) in the homogeneous region. All data are well described by the Random Phase Approximation (RPA) theory, enabling us to determine thermodynamic and structural parameters, including the correlation length ξ, G00 (the second derivative of the free energy of mixing with respect to composition), and the statistical segment length a of each component. Phase boundaries are computed by extrapolation of G00 with temperature, to yield the spinodal, and inspection of Kratky plots to yield the binodal. For PαMSAN, a is determined to be 10.1±0.4 ˚A. Unsurprisingly, this system deviates strongly from Flory-Huggins expectations, exhibiting a minimal Mw dependence of the phase boundaries and φ-dependence of effective interaction parameter (˜χ). Comparison of G00 with values for other blend systems places PαMSAN/dPMMA in a class of highly interacting blends, expected from Cahn-Hilliard theory to yield small initial phase sizes upon spinodal demixing. This is confirmed experimentally, with an illustrative temperature jump resulting in an initial phase size of ' 30 nm.

Aqueous mixtures of anionic and nonionic/cationic surfactants can form non-trivial self-assemblies in solution and exhibit macroscopic responses. Here, we investigate the micellar phase of pure and mixed aqueous solutions of Sodium Dodecyl Sulfate (SDS) and Dimethyldodecyl Amine Oxide (DDAO) using a combination of Small Angle Neutron Scattering (SANS), Fourier-Transform Infrared Spectroscopy (FTIR) and rheological measurements. We examine the effect of temperature (0–60 °C), on the 20 wt% SDS micellar solutions with varying DDAO ( ⩽ 5 wt%), and seek to correlate micellar structure with zero-shear solution viscosity. SANS establishes the formation of prolate ellipsoidal micelles in aqueous solutions of pure SDS, DDAO and SDS/DDAO mixtures, whose axial ratio is found to increase upon cooling. Elongation of the ellipsoidal micelles of pure SDS is also induced by the introduction of the non-anionic DDAO, which effectively reduces the repulsive interactions between the anionic SDS head-groups. In FTIR measurements, the formation of elongated mixed ellipsoidal micelles is confirmed by the increase of ordering in the hydrocarbon chain tails and interaction between surfactant head-groups. We find that the zero-shear viscosity of the mixed surfactant solutions increases exponentially with decreasing temperature and increasing DDAO content. Significantly, a master curve for solution viscosity can be obtained in terms of micellar aspect ratio, subsuming the effects of both temperature and DDAO composition in the experimental range investigated. The intrinsic viscosity of mixed micellar solutions is significantly larger than the analytical and numerical predictions for Brownian suspensions of ellipsoidal colloids, highlighting the need to consider interactions of soft micelles under shear, especially at high concentrations.

Polymeric micelles, due to their easy preparation and versatile properties, have been widely applied as one of the most popular carriers for chemotherapeutic agents. Such micelles primarily prevent the leakage of drugs during transportation and thus protect healthy tissue. Controlled drug release, which releases the drugs at the site of interest using internal or external stimuli as triggers, can further improve the safety of the drug delivery process. In this paper, we investigate whether ionizing radiation can be used to initiate release, focusing on using Cerenkov light as a possible trigger. For this purpose, micelles composed of the degradable polymer poly(ϵ-caprolactone-b-ethylene glycol) (PCL-PEO) were first loaded with the photosensitizer chlorin e6 (Ce6) and subsequently exposed to gamma or X-ray radiation of varying radiation doses. The results reveal that Ce6 was released from the micelles under radiation, regardless of the energy of incident photons, showing that Cerenkov light was not the driving force behind the observed release. SANS measurements showed that the volume fraction of the micelles containing Ce6 was reduced after exposure to radiation. This change in volume fraction suggests that the number of micelles was reduced, which was probably responsible for the release of Ce6. The exact mechanism, however, remains unclear. Subsequently, the PCL-PEO micelles were loaded with Ce6 and one of the following drugs: doxorubicin (Dox), docetaxel (DTX), and paclitaxel (PTX). Under radiation exposure, Dox, which is quite stable in single-loaded micelles, shows an enhanced release profile in the presence of Ce6, while DTX and PTX remained in the micelles, regardless of the presence of Ce6.

The modulated intensity by zero effort small-angle neutron scattering (MI-SANS) technique is used to measure scattering with a high energy resolution on samples normally ill-suited for neutron resonance spin echo. The self-diffusion constant of water is measured over a q–t range of 0.01–0.2 Å−1 and 70–500 ps. In addition to demonstrating the methodology of using time-of-flight MI-SANS instruments to observe diffusion in liquids, the results support previous measurements on water performed with different methods. This polarized neutron technique simultaneously measures the intermediate scattering function for a wide range of time and length scales. Two radio frequency flippers were used in a spin-echo setup with a 100 kHz frequency difference in order to create a high-resolution time measurement. The results are compared with self-diffusion measurements made by other techniques and the general applicability of MI-SANS at a pulsed source is assessed.

The first measurements of magnetic correlation functions are presented using time-of-flight Spin-echo modulated small angle neutron scattering (SEMSANS) on the Larmor instrument at the ISIS pulsed neutron source. The accessible length scale is beyond that of the conventional SANS. A simplified model is presented to calculate the expected correlation functions for various magnetisation fields applied to the sample. As an example, we present the experimental data of a soft iron sample at various configurations of magnetisation field.

In-situ Neutron Diffraction and Small-Angle Neutron Scattering (SANS) are employed for the first time simultaneously in order to reveal the interaction between the austenite to ferrite phase transformation and the precipitation kinetics during isothermal annealing at 650 and at 700 °C in three steels with different vanadium (V) and carbon (C) concentrations. Austenite-to-ferrite phase transformation is observed in all three steels at both temperatures. The phase transformation is completed during a 10 h annealing treatment in all cases. The phase transformation is faster at 650 than at 700 °C for all alloys. Additions of vanadium and carbon to the steel composition cause a retardation of the phase transformation. The effect of each element is explained through its contribution to the Gibbs free energy dissipation. The austenite-to-ferrite phase transformation is found to initiate the vanadium carbide precipitation. Larger and fewer precipitates are detected at 700 than at 650 °C in all three steels, and a larger number density of precipitates is detected in the steel with higher concentrations of vanadium and carbon. After 10 h of annealing, the precipitated phase does not reach the equilibrium fraction as calculated by ThermoCalc. The external magnetic field applied during the experiments, necessary for the SANS measurements, causes a delay in the onset and time evolution of the austenite-to-ferrite phase transformation and consequently on the precipitation kinetics.

Interphase precipitation occurring during solid-state phase transformations in micro-alloyed steels is generally studied through transmission electron microscopy, atom probe tomography, and ex situ measurements of Small-Angle Neutron Scattering (SANS). The advantage of SANS over the other two characterization techniques is that SANS allows for the quantitative determination of size distribution, volume fraction, and number density of a statistically significant number of precipitates within the resulting matrix at room temperature. However, the performance of ex situ SANS measurements alone does not provide information regarding the probable correlation between interphase precipitation and phase transformations. This limitation makes it necessary to perform in situ and simultaneous studies on precipitation and phase transformations in order to gain an in-depth understanding of the nucleation and growth of precipitates in relation to the evolution of austenite decomposition at high temperatures. A furnace is, thus, designed and developed for such in situ studies in which SANS measurements can be simultaneously performed with neutron diffraction measurements during the application of high-temperature thermal treatments. The furnace is capable of carrying out thermal treatments involving fast heating and cooling as well as high operation temperatures (up to 1200 °C) for a long period of time with accurate temperature control in a protective atmosphere and in a magnetic field of up to 1.5 T. The characteristics of this furnace give the possibility of developing new research studies for better insight of the relationship between phase transformations and precipitation kinetics in steels and also in other types of materials containing nano-scale microstructural features. This work was financially supported equally by the Technology Foundation TTW, as part of the Netherlands Organization for Scientific Research (NWO), and Tata Steel Europe through the Grant No. 14307 under the Project No. S41.5.14548 in the framework of the Materials Innovation Institute (M2i) Partnership Program. The experiments performed at ISIS Neutron and Muon Source were supported by beam-time allocation from the Netherlands Organization for Scientific Research (NWO) through Project No. 721.012.102 (LARMOR) with Experiment No. RB1869024.

The development of direct probes of entanglement is integral to the rapidly expanding field of complex quantum materials. Here we test the robustness of entangled neutrons as a quantum probe by measuring the Clauser-Horne-Shimony-Holt contextuality witness while varying the beam properties. Specifically, we show that the mode entanglement of the spin and path subsystems of individual neutrons prepared in two different experiments using two different apparatuses persists even after varying the entanglement length, coherence length, and neutron energy difference of the paths. The two independent apparatuses acting as entangler-disentangler pairs are static-field magnetic Wollaston prisms and resonance-field radio-frequency flippers. Our results show that the spatial and energy properties of the neutron beam may be significantly altered without reducing the contextuality witness value below the Tsirelson bound, meaning that maximum entanglement is preserved. We also show that two paths may be considered distinguishable even when the path states significantly overlap. Therefore, we have shown that our experimental results are consistent with the distinguishable subsystem assumption down to a separation of less than 100 nm, proving entanglement and the contextual nature of reality on short length scales. This work is the key step in the realization of the modular, robust technique of entangled neutron scattering, which can extract entanglement information from a sample without the knowledge of the microscopic sample Hamiltonian: only semiquantitative knowledge of the correlation lengths of the relevant degrees of freedom and the timescales of the characteristic dynamics is required.

Hypothesis Surfactants have been widely used as adjuvants in agri-sprays to enhance the solubility of pesticides in foliar spray deposits and their mobility through leaf cuticles. Previously, we have characterised pesticide solubilisation in nonionic surfactant micelles, but what happens when pesticides become solubilised in anionic, cationic and zwitterionic and their mixtures with nonionic surfactants remain poorly characterised. Experiments To facilitate characterisations by SANS and NMR, we used nonionic surfactant hexaethylene glycol monododecyl ether (C12E6), anionic sodium dodecylsulphate (SDS), cationic dodecyltrimethylammonium bromide (DTAB) and zwitterionic dodecylphosphocholine (C12PC) as model adjuvant systems to solubilise 3 pesticides, Cyprodinil (CP), Azoxystrobin (AZ) and Difenoconazole (DF), representing different structural features. The investigation focused on the influence of solubilisates in driving changes to the micellar nanostructures in the absence or presence of electrolytes. NMR and NOESY were applied to investigate the solubility and location of each pesticide in the micelles. SANS was used to reveal subtle changes to the micellar structures due to pesticide solubilisation with and without electrolytes. Findings Unlike nonionic surfactants, the ionic and zwitterionic surfactant micellar structures remain unchanged upon pesticide solubilisation. Electrolytes slightly elongate the ionic surfactant micelles but have no effect on nonionic and zwitterionic surfactants. Pesticide solubilisation could alter the structures of the binary mixtures of ionic/zwitterionic and ionic/nonionic micelles by causing elongation, shell shrinkage and dehydration, with the exact alteration being determined by the molar ratio in the mixture.

We have designed, built, and validated a (quasi)-simultaneous measurement platform called NUrF, which consists of neutron small-angle scattering, UV-visible, fluorescence, and densitometry techniques. In this contribution, we illustrate the concept and benefits of the NUrF setup combined with high-performance liquid chromatography pumps to automate the preparation and measurement of a mixture series of Brij35 nonionic surfactants with perfluorononanoic acid in the presence of a reporter fluorophore (pyrene).

The file attached to this record is the author's final peer reviewed version. The Publisher's final version can be found by following the DOI link. Coacervation is widely used in formulations to induce a beneficial character to the formulation, but nonequilibrium effects are often manifest. Electrophoretic NMR (eNMR), pulsed-gradient spin-echo NMR (PGSE-NMR), and small-angle neutron scattering (SANS) have been used to quantify the interaction between low molecular cationic poly(diallyldimethylammonium chloride) (PDADMAC) and the anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a model for the precursor state to such nonequilibrium processes. The NMR data show that, within the low surfactant concentration one-phase region, an increasing surfactant concentration leads to a reduction in the charge on the polymer and a collapse of its solution conformation, attaining minimum values coincident with the macroscopic phase separation boundary. Interpretation of the scattering data reveals how the rodlike polymer changes over the same surfactant concentration window, with no discernible fingerprint of micellar type aggregates, but rather with the emergence of disklike and lamellar structures. At the highest surfactant concentration, the emergence of a weak Bragg peak in both the polymer and surfactant scattering suggests these precursor disk and lamellar structures evolve into paracrystalline stacks which ultimately phase separate. Addition of the nonionic surfactant hexa(ethylene glycol) monododecyl ether (C12E6) to the system seems to have little effect on the PDADMAC/SDS interaction as determined by NMR, merely displacing the observed behavior to lower SDS concentrations, commensurate with the total SDS present in the system. In other words, PDADMAC causes the disruption of the mixed SDS/C12E6 micelle, leading to SDS-rich PDADAMC/surfactant complexes coexisting with C12E6-rich micelles in solution.

International audience; The initial formation stages of surfactant-templated silica thin films which grow at the air−water interface were studied using combined spin−echo modulated small-angle neutron scattering (SEMSANS) and small-angle neutron scattering (SANS). The films are formed from either a cationic surfactant or nonionic surfactant (C16EO8) in a dilute acidic solution by the addition of tetramethoxysilane. Previous work has suggested a twostage formation mechanism with mesostructured particle formation in the bulk solution driving film formation at the solution surface. From the SEMSANS data, it is possible to pinpoint accurately the time associated with the formation of large particles in solution that go on to form the film and to show their emergence is concomitant with the appearance of Bragg peaks in the SANS pattern, associated with the two-dimensional hexagonal order. The combination of SANS and SEMSANS allows a complete depiction of the steps of the synthesis that occur in the subphase.

Various theories beyond the Standard Model predict new particles with masses in the sub-eV range with very weak couplings to ordinary matter which can possess spin-dependent couplings to electrons and nucleons. We report null results of a search for possible exotic spin-dependent couplings of the neutron which could be induced by the exchange of light weakly coupled bosons or spin-gravity coupling conducted using a spin-echo neutron spectrometer. We constrain the products ${g}_{A}^{2}$ and ${g}_{A}{g}_{V}$ of the axial vector coupling of the neutron to the matter of the Earth through the exchange of a weakly coupled vector boson for force ranges between the metre scale and the radius of the Earth. We also constrain the constants in some theories of exotic spin-gravity couplings.

The vertical depth distributions of amine oxide surfactants, N,N-dimethyldodecyl amine N-oxide (DDAO) and N,N-dimethyltetradecyl amine N-oxide (DTAO), in poly(vinyl alcohol) (PVA) films were explored using neutron reflectometry (NR). In both binary and plasticized films, the two deuterated surfactants formed a single monolayer on the film surface with the remaining surfactant homogeneously distributed throughout the bulk of the film. Small-angle neutron scattering and mechanical testing revealed that these surfactants acted like plasticizers in the bulk, occupying the amorphous regions of PVA and reducing its glass-transition temperature. NR revealed little impact of plasticizer (glycerol) incorporation on the behavior of these surfactants in PVA. The surfactant molecular area in the segregated monolayer was smaller for DTAO than for DDAO, indicating that the larger molecule was more densely packed at the surface. Surface tension was used to assess the solution behavior of these surfactants and the effect of glycerol incorporation. Determination of molecular area of each surfactant on the solution surface revealed that the structures of the surface monolayers are remarkably consistent when water is placed by the solid PVA. Incorporation of glycerol caused a decrease of molecular area for DDAO and increase in molecular area for DTAO both in solution and in PVA. This suggests that the head group interactions, which normally limit the minimum area per adsorbed molecule, are modified by the length of the alkyl tail.

D- and L-arginine-based polyamidoamino acids, called D- and L-ARGO7, retain the chirality and acid/base properties of the parent -amino acids and show pH-dependent self-structuring in water. The ability of the ARGO7 chiral isomers to selectively interact with chiral biomolecules and/or surfaces was studied by choosing sodium deoxycholate (NaDC) as a model chiral biomolecule for its ability to self-assembly into globular micelles, showing enantio-selectivity. To this purpose, mixtures of NaDC with D-, L- or D,L-ARGO7, respectively, in water were analysed by circular dichroism (CD) spectroscopy and small-angle neutron scattering (SANS) at different levels of acidity expressed in terms of pD and concentrations. Differences in the CD spectra indicated chiral discrimination for NaDC/ARGO7 mixtures in the gel phase (pD 7.30) but not in the solution phase (pD 9.06). SANS measurements confirmed large scale structural perturbation induced by this chiral discrimination in the gel phase yet no modulation of the structure in the solution phase. Together, these techniques shed light on the mechanism by which ARGO7 stereoisomers modify the morphology of NaDC micelles as a function of pH. This work demonstrates chirality-dependent interactions that drive structural evolution and phase behaviour of NaDC, opening the way for designing novel smart drug delivery systems.

Food chemistry 311, 126017 - (2020). doi:10.1016/j.foodchem.2019.126017, Phospholipid gum mesostructures formed in crude soybean oil after water degumming (WD) and enzymatic degumming (ED) were studied at a range of phospholipid and water concentrations. For ED, phospholipase C (PLC), phospholipase A2 (PLA2) and a mixture of phospholipases Purifine 3G (3G) were used. Both WD and ED resulted in lamellar liquid-crystalline phases, however, of different topology. The dependence of the bilayer spacings (as observed by SANS and SAXS) on the ratio between amount of water and amphiphilic lipids differed for WD and PLA2 ED vs PLC and 3G ED. This difference was also observed for dynamics at molecular scale as observed by time-domain (TD) NMR and attributed to partial incorporation of diglycerides and free fatty acids into gum bilayers after PLC and 3G ED. Feasibility of using TD-NMR relaxometry for quantification of the gum phase and estimation of degumming efficiency was demonstrated., Published by Elsevier, New York, NY [u.a.]

Pronounced fibres are formed through simple shearing of a dense calcium caseinate dispersion. Both mechanical tests and scanning electron microscopy images demonstrate that the material is anisotropic. It is hypothesised that calcium caseinate aggregates, under shear, align into micro-fibres and bundle further into a hierarchical structure. Yet no direct evidence at the sub-micron length scale can support the assumption. Small angle neutron scattering (SANS) experiments were conducted on calcium caseinate samples prepared at different conditions. Analysis of the SANS data revealed that the micro-fibres have a diameter of ∼100nm and a length of ∼300nm. The addition of enzyme and air contributed to longer and thinner micro-fibres. Furthermore, the extent of fibre alignment at the micro-scale and the macroscopic anisotropy index followed the same trends with varying processing conditions. It is concluded that the material does indeed possess a hierarchical structure and the micro-fibres are responsible for the anisotropy on the macro-scale.

Mechanical interlocking of molecules (catenation) is a nontrivial challenge in modern synthetic chemistry and materials science1,2. One strategy to achieve catenation is the design of pre-annular molecules that are capable of both efficient cyclization and of pre-organizing another precursor to engage in subsequent interlocking3–9. This task is particularly difficult when the annular target is composed of a large ensemble of molecules, that is, when it is a supramolecular assembly. However, the construction of such unprecedented assemblies would enable the visualization of nontrivial nanotopologies through microscopy techniques, which would not only satisfy academic curiosity but also pave the way to the development of materials with nanotopology-derived properties. Here we report the synthesis of such a nanotopology using fibrous supramolecular assemblies with intrinsic curvature. Using a solvent-mixing strategy, we kinetically organized a molecule that can elongate into toroids with a radius of about 13 nanometres. Atomic force microscopy on the resulting nanoscale toroids revealed a high percentage of catenation, which is sufficient to yield ‘nanolympiadane’10, a nanoscale catenane composed of five interlocked toroids. Spectroscopic and theoretical studies suggested that this unusually high degree of catenation stems from the secondary nucleation of the precursor molecules around the toroids. By modifying the self-assembly protocol to promote ring closure and secondary nucleation, a maximum catenation number of 22 was confirmed by atomic force microscopy. Nanoscale toroids with a high percentage of poly-catenation and radii of up to about 13 nm are kinetically organized using fibrous supramolecular assemblies with intrinsic curvature and a solvent-mixing strategy.

Fullerene derivatives are used in a wide range of applications including as electron acceptors in solution-processable organic photovoltaics. We report agglomeration of fullerene derivatives in optically opaque solutions of PC61BM and PC71BM, with concentrations ranging from 30 mg mL-1 up to 90 mg mL-1, in different solvents with relevance to organic photovoltaics, using a novel neutron scattering technique, Spin-Echo Small Angle Neutron Scattering (SESANS). From SESANS, agglomerates with correlation lengths larger than 1 μm are found in some PC61BM solutions, in contrast no agglomerates are seen in PC71BM solutions. These results clearly show that PC71BM is fundamentally more soluble than PC61BM in the solvents commonly used in photovoltaic inks and corroborating similar observations previously achieved using other experimental techniques. Computer models are presented to study the energetics of solution and agglomeration of both species, ascribing the difference to a kinetic effect probably related to the larger anisotropy of PC71BM. Also, this work showcases the power of SESANS to probe agglomerates of fullerene derivatives in completely opaque solutions for agglomerates of the order of one to several microns.

The precipitation kinetics of vanadium carbides and its interaction with the austenite-to-ferrite phase transformation is studied in two micro-alloyed steels that differ in vanadium and carbon concentrations by a factor of two, but have the same vanadium-to-carbon atomic ratio of 1:1. Dilatometry is used for heat-treating the specimens and studying the phase transformation kinetics during annealing at isothermal holding temperatures of 900, 750 and 650 °C for up to 10 h. Small-Angle Neutron Scattering (SANS) and Atom Probe Tomography (APT) measurements are performed to study the vanadium carbide precipitation kinetics. Vanadium carbide precipitation is not observed after annealing for 10 h at 900 and 750 °C, which is contrary to predictions from thermodynamic equilibrium calculations. Vanadium carbide precipitation is only observed during or after the austenite-to-ferrite phase transformation at 650 °C. The precipitate volume fraction and mean radius continuously increase as holding time increases, while the precipitate number density starts to decrease after 20 min, which corresponds to the time at which the austenite-to-ferrite phase transformation is finished. This indicates that nucleation and growth are dominant during the first 20 min, while later precipitate growth with soft impingement (overlapping diffusion fields) and coarsening take place. APT shows gradual changes in the precipitate chemical composition during annealing at 650 °C, which finally reaches a 1:1 atomic ratio of vanadium-to-carbon in the core of the precipitates after 10 h.

Here, we describe new developments in the study of electrodeposition processes with time-resolved dynamic neutron reflectivity (NR) methods to achieve insights into the differences between growth of metal films using a range of electrochemical control functions. We show that the temporal resolution has increased from 1 to 2 h per data set (in our previous studies) to approximately 8 min. We have studied the electrochemical deposition of copper and silver as thin-film metals onto a gold electrode substrate from a deep eutectic solvent using potentiodynamic (PD), potentiostatic (PS) and galvanostatic (GS) electrochemical control functions. In particular, we have utilised novel developments in neutron reflectivity methods to acquire real-time data for the growing metal films. Event mode capture of neutron scattering events, as a function of momentum transfer vector, Q, during electrochemical growth has enabled time-resolved measurement of the neutron reflectivity, R(Q), profiles of the growing metal films. Subsequent fitting and iterative optimisation of the R(Q,t) data reveals the thickness, roughness and relative density (spatially resolved solvent content) of the metal film during growth. These data show that the different electrochemical growth methodologies exhibit different trends in thickness, roughness and solvation. Silver films show an increasing roughness trend with time but these trends are largely independent of growth method. In contrast, the roughness of copper films, grown under similar conditions, shows a strong dependency on growth method with PS methods producing smoothest films. These conclusions are confirmed by ex-situ AFM measurements. The fitted NR data show that the Cu and Ag films contain between 5 and 10% volume fraction solvent. Furthermore, we have explored different NR data fitting methodologies in order to process the large numbers of data sets produced. Gratifyingly, the different methodologies and starting conditions yield a very consistent picture of metal film growth.

This paper presents 2D mapping of residual strains, induced by cold expansion and laser shock peening processing of aluminium alloy samples, by using Bragg edge neutron transmission. Neutron transmission uses information contained in the neutron beam transmitted through a sample. It is shown that neutron transmission strain mapping with high spatial resolution can provide important insights into the distribution of residual strains associated with processing of materials. The residual strain field around a cold-expanded hole can be revealed in detail, as can be the residual strain profile associated with laser peening. Results are correlated with measurements obtained by conventional neutron diffraction and incremental hole drilling. The residual strain variation around the cold-expanded hole and the depth of compressive residual strain generated by the peening process were captured with high spatial resolution, showing the advantages of neutron transmission over other well-established strain measurement methods by non-destructively generating a map of residual strains over a large area. Keywords: Neutron transmission, Residual strain, Strain mapping, Bragg edge analysis, Cold expansion, Laser shock peening

A method dubbed grating-based holography was recently used to determine the structure of colloidal fluids in the rectangular grooves of a diffraction grating from X-ray scattering measurements. Similar grating-based measurements have also been recently made with neutrons using a technique called spin-echo small-angle neutron scattering. The analysis of the X-ray diffraction data was done using an approximation that treats the X-ray phase change caused by the colloidal structure as a small perturbation to the overall phase pattern generated by the grating. In this paper, the adequacy of this weak phase approximation is explored for both X-ray and neutron grating holography. It is found that there are several approximations hidden within the weak phase approximation that can lead to incorrect conclusions from experiments. In particular, the phase contrast for the empty grating is a critical parameter. While the approximation is found to be perfectly adequate for X-ray grating holography experiments performed to date, it cannot be applied to similar neutron experiments because the latter technique requires much deeper grating channels.

The uncertainties and the stability of a neutron sensitive MCP/Timepix detector when operating in the event timing mode for quantitative image analysis at a pulsed neutron source were investigated. The dominant component to the uncertainty arises from the counting statistics. The contribution of the overlap correction to the uncertainty was concluded to be negligible from considerations based on the error propagation even if a pixel occupation probability is more than 50%. We, additionally, have taken into account the multiple counting effect in consideration of the counting statistics. Furthermore, the detection efficiency of this detector system changes under relatively high neutron fluxes due to the ageing effects of current Microchannel Plates. Since this efficiency change is position-dependent, it induces a memory image. The memory effect can be significantly reduced with correction procedures using the rate equations describing the permanent gain degradation and the scrubbing effect on the inner surfaces of the MCP pores.

The properties of a hydrogel are controlled by the underlying network that immobilizes the solvent. For gels formed by the self-assembly of a small molecule, it is common to show the primary fibres that entangle to form the network by microscopy, but it is difficult to access information about the network. One approach to understand the network is to examine the effect of the concentration on the rheological properties, such that G′∝ cx, where G′ is the storage modulus and c is the concentration. A number of reports link the exponent x to a specific type of network. Here, we discuss a small library of gels formed using functionalized dipeptides, and describe the underlying networks of these gels, using microscopy, small angle scattering and rheology. We show that apparently different networks can give very similar values of x.

Fullerene derivatives are used in a wide range of applications including as electron acceptors in solution-processable organic photovoltaics. We report agglomeration of fullerene derivatives in optically opaque solutions of PC

The development of qualitatively new measurement capabilities is often a prerequisite for critical scientific and technological advances. The dramatic progress made by modern probe techniques to uncover the microscopic structure of matter is fundamentally rooted in our control of two defining traits of quantum mechanics: discreteness of physical properties and interference phenomena. Magnetic Resonance Imaging, for instance, exploits the fact that protons have spin and can absorb photons at frequencies that depend on the medium to image the anatomy and physiology of living systems. Scattering techniques, in which photons, electrons, protons or neutrons are used as probes, make use of quantum interference to directly image the spatial position of individual atoms, their magnetic structure, or even unveil their concomitant dynamical correlations. None of these probes have so far exploited a unique characteristic of the quantum world: entanglement. Here we introduce a fundamentally new quantum probe, an entangled neutron beam, where individual neutrons can be entangled in spin, trajectory and energy. Its tunable entanglement length from nanometers to microns and energy differences from peV to neV will enable new investigations of microscopic magnetic correlations in systems with strongly entangled phases, such as those believed to emerge in unconventional superconductors. We develop an interferometer to prove entanglement of these distinguishable properties of the neutron beam by observing clear violations of both Clauser-Horne-Shimony-Holt and Mermin contextuality inequalities in the same experimental setup. Our work opens a pathway to a future era of entangled neutron scattering in matter., Comment: 11 pages, 4 figures

We report the spontaneous formation of multilamellar vesicles (MLVs) from low concentration (

To investigate long length scale structures using neutron scattering, real space techniques have shown certain advantages over the conventional methods working in reciprocal space. As one of the real space measurement techniques, spin echo modulated small angle neutron scattering (SEMSANS) has attracted attention, due to its relaxed constraints on sample environment and the possibility to combine SEMSANS and a conventional small angle neutron scattering instrument. In this report, we present the first implementation of SEMSANS at a pulsed neutron source and discuss important corrections to the data due to the sample absorption. These corrections allow measurements made with different neutron wavelengths and SEMSANS configurations to be overlaid and give confidence that the measurements provide an accurate representation of the density correlations in the sample.

We report on the structural evaluation of high fat fish oil-in-water emulsions emulsified with sodium caseinate (CAS) and phosphatidylcholine (PC). The microemulsions contained 70% (w/w) fish oil with 1.05–1.4% (w/w) CAS and 0.4–1.75% (w/w) PC and were studied by the combination of light scattering together with small-angle X-ray and neutron scattering (SAXS/SANS). Aqueous CAS forms aggregates having a denser core of about 100 kDa and less dense shell about 400 kDa with the hard sphere diameter of 20.4 nm. PC appears as multilayers whose coherence length spans from 40 to 100 nm. PC monolayer separates oil and water phases. Moreover, 80% CAS particles are loosely bound to the interface but are not forming continuous coverage. The distance between aggregated CAS particles in microemulsion is increased compared to CAS aggregates in pure CAS-in-water system. PC multilayers become larger in the presence of oil-water interface compared to the pure PC mixtures. Bilayers become larger with increasing PC concentration. This study forms a structural base for the combination of CAS and PC emulsifiers forming a well-defined thin and dense PC layer together with thick but less dense CAS layer, which is assumed to explain its better oxidative stability compared to single emulsifiers.