Spin-echo Small-angle Neutron Scattering Research Articles

Simulation of spin-echo SANS (SESANS) using McStas on monochromatic and time of flight instruments

We conduct simulations of Spin Echo Small Angle Neutron Scattering (SESANS) by employing Monte Carlo methods to a setup using four magnetic Wollaston prisms. Our primary focus involves the validation of these models, encompassing monochromatic scenarios across various neutron wavelengths to ascertain the reliability of the simulations. Subsequently, we extend this validation to encompass simulations in time-of-flight mode. Our model consistently and precisely predicts the scattering patterns emanating from dilute spheres in both monochromatic and time-of-flight modes. Notably, it also accurately reproduces the intricate encoding associated with scattering occurring between the third and fourth magnetic Wollaston prism, which provides us with another approach to increase the solid angle coverage of a SESANS instrument. This validation process conclusively demonstrates the efficacy of our simulation methods. Importantly, it paves the way for simulating more intricate and realistic instrumental configurations, broadening the horizons for future research endeavours.

Revealing microscale bulk structures in polymer-carbon nanocomposites using spin-echo SANS.

We have used spin-echo small-angle neutron scattering (SESANS) to probe the hierarchy of structures present in polymer-carbon nanocomposites, with length scales spanning over three orders of magnitude, from 10 nm to 16 μm. The data processing and reduction show a unified approach across two SESANS instruments (TU Delft and Larmor at the ISIS neutron source) and yield consistent data that are able to be modelled using well-established hierarchical models in freely available software such as SasView. Using this approach, we are able to extend the measured length scales by over an order of magnitude compared to traditional scattering methods. This yields information about the structure in the bulk that is inaccessible with conventional scattering techniques (SANS/SAXS) and points to a way for interrogating and investigating polymer nanocomposites routinely across multiple length scales.

Simulations and concepts for a 2-D spin-echo modulated SANS (SEMSANS) instrument

The spin-echo small-angle neutron scattering (SESANS) technique utilises a series of inclined magnetic fields before and after the sample to encode the scattering angle into the polarisation to obtain a much higher resolution than in conventional SANS. The analogous technique (spin echo modulated SANS (SEMSANS)) implements spin manipulations before the sample only to encode the scattering into an intensity modulation. The technique can be combined with SANS to expand the length scale range probed from 1 nm to microns.Using McStas we show that using a series of four magnetic Wollaston prisms in two orthogonal pairs with a 90° rotation can be utilised to create SEMSANS modulations in 2-D. These modulations can also be of different periods in each encoding direction. This method can be applied to anisotropic scattering samples. Also this allows for the simultaneous measurement at two orthogonal independent spin-echo lengths. This technique yields directly information about the structure of oriented structures.

Magnetized FeSi film with micrometer thickness inserted with Cr layers as [formula omitted]-flippers for neutron spin-echo spectrometry

Magnetized soft ferromagnetic films with micrometer thickness can be used as π-flippers for a spin echo small-angle neutron scattering (SESANS) instrument. Two FeSi monolayers and two FeSi/Cr multilayers were fabricated using a direct-current magnetron sputtering technique. The thicknesses of the two FeSi monolayers were 114 nm and 1140 nm, respectively. The two FeSi/Cr multilayers with 2 and 20 periods, respectively, were composed of FeSi layers having thicknesses of 1000 nm and 100 nm, respectively, and 10 nm-thick Cr layers. Hysteresis loop measurements and X-ray diffraction measurements were used to characterize their magnetic properties and texture, respectively. Polarized neutron flipping efficiency measurements were conducted using the TPNR (Time-of-flight and Polarized Neutron Reflectometer) to determine the flipping efficiency of the FeSi/Cr multilayer with [100 nm FeSi/10 nm Cr]20. The experimental results show that the saturation magnetization of the FeSi-monolayers decreased and the coercivity increased as their thickness increased. The FeSi/Cr multilayer with [100 nm FeSi/10 nm Cr]20 had higher saturation magnetization (1300 emu/cm 3) and lower coercivity than those of [1000 nm FeSi/10 nm Cr]2, although the total thickness of the FeSi layers was almost the same, and its maximum flipping efficiency was up to 98% for polarized neutrons.

Radial spin echo small-angle neutron scattering method: concept and performance.

A novel spin echo small-angle neutron scattering (SESANS) concept based on a rotationally symmetric magnetic field geometry is introduced. The proposed method is similar to the conventional linear SESANS technique but uses longitudinal precession fields and field gradients in a radial direction, as typically found in neutron spin echo (NSE) spectrometers. Radial SESANS could thus be implemented as an add-on to NSE setups. The neutron trajectory through the instrument is encoded with the help of radial gradients generated by radial shifters, which are coils placed in the beam area similar to Fresnel coils. The present work introduces the setup of the instrument and explores its performance and the relationship between the encoded momentum transfer and the precession angle. The results indicate that radial SESANS is only sensitive to scattering along the radial direction and thus measures the projected correlation function along this direction as a function of the spin echo length, defined similarly to linear SESANS. For an evaluation of the performance of the setup, the case of scattering from solid spheres is considered and the results calculated for the radial and linear SESANS cases are compared. Also discussed is the implementation of the radial magnetic field geometry in spin echo modulated small-angle neutron scattering.

Exploring Nanoscale Structure in Perovskite Precursor Solutions Using Neutron and Light Scattering

Tailoring the solution chemistry of metal halide perovskites requires a detailed understanding of precursor aggregation and coordination. In this work, we use various scattering techniques, including dynamic light scattering (DLS), small angle neutron scattering (SANS), and spin–echo SANS (SESANS) to probe the nanostructures from 1 nm to 10 μm within two different lead-halide perovskite solution inks (MAPbI3 and a triple-cation mixed-halide perovskite). We find that DLS can misrepresent the size distribution of the colloidal dispersion and use SANS/SESANS to confirm that these perovskite solutions are mostly comprised of 1–2 nm-sized particles. We further conclude that if there are larger colloids present, their concentration must be <0.005% of the total dispersion volume. With SANS, we apply a simple fitting model for two component microemulsions (Teubner–Strey), demonstrating this as a potential method to investigate the structure, chemical composition, and colloidal stability of perovskite solutions, and we here show that MAPbI3 solutions age more drastically than triple cation solutions.

Design and simulations of spin-echo small angle neutron scattering spectrometer at CMRR

Current work presents the design and simulations of the spin-echo small-angle neutron scattering (SESANS) spectrometer at the 20 MW China Mianyang research reactor (CMRR)-based neutron center. Firstly, the components of the SESANS are introduced. Secondly, the Monte Carlo simulations of the key components for determining the technical parameters are presented. The bending radius of the focusing monochromator is set to 2.5 m. The length and radius of curvature of the S-Bender is set to 300 mm and 2.0 m, respectively. Accordingly, simulation results of the virtual spectrometer indicate that the neutron beam transmission is about 0.09 at wavelength of 0.4 nm. Thirdly, the finite element simulation and the testing of the magnetic field suggest that the optimized ampere-turns are 8400 and 8289.9, respectively. Accordingly, the simulation results indicate that the field integral homogeneity of main coil, V-coil, and field stepper are better than 2.91 × 10−6 T m, 2.3 × 10−6 T m, and 3.14 × 10−6 T m, respectively. Last, a multilayer flipper-permalloy with 100 nm FeSi and 10 nm Cr (or Ta) alternately sputtered on a Si wafer was designed and tested. Neutron experiments demonstrate that the maximum flipper efficiency reaches 0.98 and remains stable with increasing the strength of the main fields from 50 Gs to 200 Gs, when the corresponding wavelength is 0.31 nm. Based on the optimized parameters, the SESANS is under construction, and it will be completed at the end of 2021.

Spin-echo small-angle neutron scattering for multiscale structure analysis of food materials

Spin-echo small-angle neutron scattering (SESANS) yields structural information on length scales from 30 nanometres up till 20 micrometres. These length scales match nicely those of colloids, protein networks and fat droplets, which are present in many food materials. This makes SESANS an excellent probe to study food materials. An interesting feature of SESANS is the real space character of the raw data. Several examples of quantitative neutron scattering studies on food materials are shortly reviewed.

The microscopic distribution of hydrophilic polymers in interpenetrating polymer networks (IPNs) of medical grade silicone

By introducing hydrophilic polymers into silicone medical devices, highly beneficial biomedical properties can be realized. An established solution to introduce hydrophilic polymers is to form an interpenetrating polymer network (IPN) by performing the hydrogel synthesis in the presence of silicone swollen in supercritical carbon dioxide. The precise distribution of the two polymers is not known, and determining this is the goal of this study. Neutron scattering and microscopy were used to determine the distribution of the hydrophilic guest polymer. Atomic force microscopy revealed that the important length scale on the surface of these materials is 10–100 nm, and spin-echo small-angle neutron scattering (SESANS) on IPNs submerged in D2O revealed structures of the same scale within the interior and enabled quantification of their size. SESANS with hydration by D2O proved to be the only scattering technique that could determine the structure of the bulk of these types of materials, and it should be used as an important tool for characterizing polymer medical devices.

Revisiting neutron scattering data from deuterated milk

Deuterated milk (dried milk powder that has been dissolved in deuterated water, 2H2O or D2O) is a valuable material for determining the structure of dairy products by neutron scattering. This has primarily been used in the past to study the internal structure of casein micelles, and when longer length scales have been studied, interparticle interactions have been neglected. This will impact fits to the data over all length scales, which will hamper quantitative data analysis. Previously measured large length scale neutron scattering data from the literature, both ultra-small-angle neutron scattering (USANS) and spin-echo small-angle neutron scattering (SESANS) data, have been reanalyzed and improved fits have been obtained using a recently proposed model describing casein micelles as sticky spheres, rather than as hard spheres. This shows that these interactions will also be necessary for modeling neutron scattering data on deuterated milk.

Structural characterization of spray-dried microgranules by spin-echo small-angle neutron scattering

Spray-drying is a widely used industrial technique and has shown an immense potential in the fields of nanoscience and technology. This is due to its ability to synthesize microgranules consisting of correlated nanostructures using evaporation induced assembly through bottom-up approach. Although the nature of correlation among the constituent nanoparticles and their size distribution could earlier be obtained by conventional Small-angle Scattering (SAS) technique, a statistically averaged quantitative measure of the shell thickness and hollowness of the formed granules remained a challenge. In this work, we have used Spin-echo Small-angle Neutron Scattering (SESANS) technique to characterize spray-dried nanostructured microgranules having different hollowness. It is shown that this non-destructive technique provided precise quantification of the granular sizes and hollowness by utilizing polarization property of neutrons in real space directly.

Spin-echo Small Angle Neutron Scattering for a Compact Neutron Source Daria

Spin-echo small-angle neutron scattering (SESANS) technique is a method to measure the correlation function of the structural organization of materials from nano- to micrometer length scales. As this method does not require neither highly collimated beams nor high incident intensity it can be easily and effectively used at the low flux sources, such as compact accelerator-driven neutron sources. Here we describe an important science case for SESANS setup designed at the compact neutron source DARIA. It was shown that SESANS method is a sensitive tool to study the packaging of DNA in the nuclei of biological cells. The sensitivity of the SESANS signal crucially depends on the neutron wavelength. The pulse character of the compact neutron source suits ideally to these investigations as it implies changeable neutron wavelength in the range from 0.2 to 1.0 nm. Such option allows one to study in great detail the internal structure of the biological cell in the length scale from 10 nm to 100 μm.

Systematically quantifying oil–water microemulsion structures using (spin-echo) small angle neutron scattering

Microemulsion systems consisting of D2O, an alkane, an anionic internal olefin sulfonate surfactant, salt and secondary butyl alcohol (SBA) as co-solvent are studied in a systematic way. In four different sample sets, either the salt content, SBA content or alkane carbon number was varied in order to study the effects of the individual compounds on the structure sizes making up the microemulsion. Using complementary small-angle neutron scattering techniques SANS and Spin-Echo SANS, it was found that the microemulsion systems exhibit the largest structures in the optimum state (domain size of d/2 =144 nm in the model by Teubner and Strey), where the structure is considered bicontinuous. In comparison, at under- and over-optimum states where the structures consist of emulsified spherical droplets, the smallest measured diameter was 2R = 44 nm. Furthermore, the structure sizes in bicontinuous microemulsions decrease exponentially (down to d/2 =15 nm for pentadecane and 5 wt% SBA) as function of both SBA content and alkane carbon number. The observed trends in structure sizes combined with the trends observed in the area per surfactant molecule, are qualitatively explained with the extended Winsor R-ratio, the HLD-NAC model and surfactant film flexibility arguments.

Evolution of dispersion in the melt compounding of a model polymer nanocomposite system: A multi-scale study

We investigate the morphological development of polystyrene (PS)-C60 nanocomposites along the length of a prototype co-rotating twin-screw extruder with sampling capabilities. The effects of C60 concentration and output on the morphological evolution along the extruder are studied employing a suite of characterization techniques covering a wide range of length-scales, thereby shedding new light on the dispersion mechanism in this model system. We show that the relatively new spin-echo small-angle neutron scattering (SESANS) technique is well suited to probe both the distribution and the dispersion of C60. SESANS complements optical microscopy (OM) data as it covers sampling areas several orders of magnitude larger than OM. The multi-scale morphological information conveyed by OM, SESANS, SANS and rheological data shows that for larger outputs, C60 agglomerates are eroded as they travel along the extruder, resulting in C60 dispersion and distribution at both molecular and micrometric levels. The picture is more complex when smaller feed rates are used, as the evolution of C60 dispersion depends on the C60 loading. For larger C60 contents, agglomeration develops along the extruder, whereas dispersion is improved for smaller C60 contents. Overall, it is concluded that an over-high feed rate in extrusion does not necessarily result in a bigger size of the nanoparticle agglomerates because of the complex interplay between stresses and residence time.

Spin-echo small-angle neutron scattering (SESANS) studies of diblock copolymer nanoparticles.

Poly(glycerol monomethacrylate)-poly(benzyl methacrylate) (PGMA-PBzMA) diblock copolymer nanoparticles were synthesized via polymerization-induced self-assembly (PISA) using reversible addition-fragmentation chain-transfer (RAFT) aqueous emulsion polymerization in D2O. Such PISA syntheses produce sterically-stabilized nanoparticles in situ and can be performed at relatively high copolymer concentrations (up to 50 wt%). This PGMA-PBzMA formulation is known to form only spherical nanoparticles in water using aqueous emulsion polymerization (Macromolecules, 2014, 47, 5613-5623), which makes it an ideal model system for exploring new characterization methods. The polymer micelles were characterized using small-angle X-ray scattering (SAXS) and a recently developed form of neutron scattering, spin-echo small-angle neutron scattering (SESANS). As far as we are aware, this is the first report of a study of polymer micelles by SESANS, and the data agree well with reciprocal-space scattering. Using this technique enables characterization of the concentrated, as synthesized dispersions directly without dilution, and this will provide a method to study self-assembled polymer systems that have concentration dependent morphologies, while still maintaining the advantages of scattering techniques.

A Journey along the Extruder with Polystyrene:C60 Nanocomposites: Convergence of Feeding Formulations into a Similar Nanomorphology

We investigated the effect of the feeding formulation (premixed powders of pure components versus solvent-blended mixture) of polystyrene–C60 composites on the dispersion and reagglomeration phenomena developing along the barrel of a twin-screw extruder. The dispersion of C60 in the PS matrix is studied over different length scales using a combination of optical microscopy, spin-echo small-angle neutron scattering (SESANS), small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS). When a solvent-blended mixture is used as the feeding formulation, the inlet material contains essentially molecularly dispersed C60 as revealed by the nanodomains with very small phase contrast. However, C60 reagglomeration occurs along the extruder, creating a morphology still containing only nanodomains but with much higher phase contrast. In the case of mixed powders, the material evolves from the initial macroscopic mixture of pure polystyrene and C60 into a composite simultaneously containing micro- and nanoaggregates of C60 as well as C60 molecularly dispersed in the matrix. Our results show that the two different initial feeding formulations with widely different initial morphologies converge along the extruder, through opposite morphological pathways, into a similar final nanomorphology which is dictated by the interplay between the thermodynamics of the system and the flow. Correlations between the morphological evolution along the extruder and the thermorheological properties of the composites are identified.

High-strength bacterial cellulose–polyacrylamide hydrogels: Mesostructure anisotropy as studied by spin-echo small-angle neutron scattering and cryo-SEM

Submicron- and micron-scale structures of composite hydrogels based on bacterial cellulose (BC) and polyacrylamide (PAAm) were studied by spin-echo small-angle neutron scattering (SESANS) and cryo-scanning electron microscopy (cryo-SEM). These hydrogels possessing the structure of interpenetrating polymer network were synthesized via free-radical polymerization of acrylamide carried out in the pellicle of BC swollen in the reaction solution. No neutron scattering was observed for the samples swollen in heavy water to the equilibrium state, but the SESANS signal appeared when TbCl3 salt was added to the solvent. It is the unusual effect, which may be very helpful for SESANS studying of other hydrogel systems. The SESANS dependences obtained for these samples revealed the anisotropy of mesostructure for the hydrogels under investigation. Density inhomogeneities on the characteristic scale of 11.5±0.5μm were detected in one fixed orientation of the sample, i.e., with the growth plane of BC parallel to the plane formed by the neutron beam and the spin-echo length. The uniaxial anisotropy revealed agrees with a recently proposed model, which attributes this behavior to the existence of tunnel-like oriented structures inside BC. The evidence of such type of mesostructure anisotropy of BC and BC-PAAm hydrogels was obtained by using the cryo-SEM method.

Microstructure and rheology of globular protein gels in the presence of gelatin

The microstructure and rheological response of globular protein gels (whey protein isolate (WPI) and soy protein isolate (SPI)) in the presence of gelatin (type A, type B and hydrolyzed type A) was investigated. Microstructural information was obtained using a combination of confocal laser scanning microscopy (CLSM) and spin echo small-angle neutron scattering (SESANS). Addition of gelatin led to a coarsening of the globular protein gel structure and to a reduction in storage modulus of globular protein gels. The presence of hydrolyzed gelatin on the other hand did not induce these changes in the globular protein gels. Results were obtained at conditions where proteins only interact via hard body interactions. For these conditions it was concluded that the ratio of molecular sizes is the most important determinant for the occurrence or absence of rheological and microstructural changes in globular protein gels prepared in the presence of gelatin.

From nanopores to macropores: Fractal morphology of graphite

We present a comprehensive structural characterization of two different highly pure nuclear graphites that compasses all relevant length scales from nanometers to sub-mm. This has been achieved by combining several experiments and neutron techniques: Small Angle Neutron Scattering (SANS), high-resolution Spin Echo SANS (SESANS) and neutron imaging. In this way it is possible to probe an extraordinary broad range of 6 orders of magnitude in length from microscopic to macroscopic length scales. The results reveal a fractal structure that extends from ∼0.6nm to 0.6 mm and has surface and mass fractal dimensions both very close to 2.5, a value found for percolating clusters and fractured ranked surfaces in 3D.

Birefringent magnetic field system for experimental checking of neutron electroneutrality by the spin interferometry technique

We describe the structure design and present the results of experimental testing of a birefringent magnetic neutron prisms for spin-echo small-angle neutron scattering (SESANS). The SESANS setup, equipped with perfect single crystals for measuring diffraction-enhanced spin interference effects, must possess unprecedented sensitivity with respect to small external actions on a neutron and is intended for use in experiments for checking the neutron electroneutrality.