Small-angle Neutron Scattering Measurements Research Articles

Probing the adsorption of nonionic micelles on different-sized nanoparticles by scattering techniques.

The interaction of nanoparticles with surfactants is extensively used in a wide range of applications from enhancing colloidal stability to phase separation processes as well as in the synthesis of noble functional materials. The interaction is highly specific depending on the charged nature of the surfactant. In the case of nonionic surfactants, the micelles adsorb on the surface of nanoparticles. The adsorption of nonionic surfactant C12E10 as a function of surfactant concentration for two different sizes of anionic silica nanoparticles (16 and 27 nm) has been examined using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). SANS measurements have been carried out under different contrast-matched conditions, where nanoparticles, as well as surfactant micelles, have been contrast-matched to the solvent. The adsorption of micelles is determined from the contrast-matched condition of silica nanoparticles with the solvent. SANS data under surfactant contrast-matched condition suggest that there is no modification in the structure and/or interaction of the silica nanoparticles in presence of nonionic micelles. The adsorption of micelles on nanoparticles is found to follow an exponential behavior with respect to the surfactant concentration. These results are consistent with the variation of hydrodynamic size of nanoparticle-surfactant system in DLS. The study on different-sized nanoparticles shows that the lower curvature enhances the packing fraction whereas the loss of surface-to-volume ratio suppresses the fraction of adsorbed micelles with the increase in the nanoparticle size. The adsorption coefficient has higher value for the larger size of the nanoparticles. In the mixed system of two sizes of nanoparticles, no preferential selectivity of micelle adsorption is observed.

A correspondence between the Flory–Rehner theory for microgels and the Daoud–Cotton model for polymer-grafted nanoparticles

Poly(N-isopropyl acrylamide) (PNIPAM) is a commonly investigated thermoresponsive polymer that exhibits a number of interesting physical behaviors. Here, we use small-angle neutron scattering (SANS) measurements to determine the conformation of PNIPAM in two regions of the chain when it is grafted at moderate grafting densities to the surface of SiO2 nanoparticles (rNP ≈ 10 nm). At these grafting densities, polymer chains may adopt two primary conformations, depending on the specific value of the second virial coefficient, the molecular weight of the chains, and other properties. The nanoparticles are studied in D2O and ethanol-d6 to ascertain the effect of solvent quality on the chain conformation in both the inner and outer regions of the brush. The SANS measurements are interpreted using a modified Daoud–Cotton model that connects the Flory–Rehner theory of microgel thermodynamics to the structure of polymer-grafted nanoparticles.

3D printed spherical environmental chamber for neutron reflectometry and grazing-incidence small-angle neutron scattering experiments.

In neutron scattering on soft matter, an important concern is the control and stability of environmental conditions surrounding the sample. Complex sample environment setups are often expensive to fabricate or simply not achievable by conventional workshop manufacturing. We make use of state-of-the-art 3D metal-printing technology to realize a sample environment for large sample sizes, optimized for investigations on thin film samples with neutron reflectometry (NR) and grazing-incidence small-angle neutron scattering (GISANS). With the flexibility and freedom of design given by 3D metal-printing, a spherical chamber with fluidic channels inside its walls is printed from an AlSi10Mg powder via selective laser melting (SLM). The thin channels ensure a homogeneous heating of the sample environment from all directions and allow for quick temperature switches in well-equilibrated atmospheres. In order to optimize the channel layout, flow simulations were carried out and verified in temperature switching tests. The spherical, edgeless design aids the prevention of condensation inside the chamber in case of high humidity conditions. The large volume of the sample chamber allows for high flexibility in sample size and geometry. While a small-angle neutron scattering (SANS) measurement through the chamber walls reveals a strong isotropic scattering signal resulting from the evenly orientated granular structure introduced by SLM, a second SANS measurement through the windows shows no additional background originating from the chamber. Exemplary GISANS and NR measurements in time-of-flight mode are shown to prove that the chamber provides a stable, background free sample environment for the investigation of thin films.

The Large-Area Detector for Small-Angle Neutron Scattering on iMATERIA at J-PARC

An area detector with a central hole structure was built up for small-angle neutron scattering (SANS) on the iMATERIA instrument at Japan Proton Accelerator Research Complex (J-PARC). Linear position-sensitive detector tubes filled with 3He gas were arranged in three layers leaving a central hole. As a result of the calibration process, a SANS measurement with wide q-range from 0.007 Å−1 to 4.3 Å−1 was achieved in double-frame operation, supplying neutrons with wavelengths from 1 Å to 10 Å. As a merit of this central hole structure, neutron transmission can be measured simultaneously to reduce experimental time and effort. This is ideal for time-resolved studies, in which the sample transmission can be time-dependent, throughout the whole experiment. Additionally, the data storage system in ‘event mode’ format provides an excellent platform for such time-resolved experiments.

In situ magnetorheological SANS setup at Institut Laue-Langevin

A magnetorheological sample environment is presented that allows for in situ magnetic field and shear flow during small-angle neutron scattering (SANS) measurements and is now available at the Institut Laue-Langevin (ILL). The setup allows performing simultaneous magnetorheological measurements together with the investigation of structural and magnetic changes on the nanometer length scale underlying the rheological response of ferrofluids. We describe the setup consisting of a commercial rheometer and a custom-made set of Helmholtz coils and show exemplarily data on the field and shear flow alignment of a dispersion of hematite nanospindles in water.Graphical abstractA magnetorheological sample environment is presented that allows for in-situ magnetic field and shear flow during Small-Angle Neutron Scattering (SANS) measurements and is now available at the Institut Laue-Langevin (ILL).

Role of Protein-Water Interface in the Stacking Interactions of Granum Thylakoid Membranes-As Revealed by the Effects of Hofmeister Salts.

The thylakoid membranes of vascular plants are differentiated into stacked granum and unstacked stroma regions. The formation of grana is triggered by the macrodomain formation of photosystem II and light-harvesting complex II (PSII-LHCII) and thus their lateral segregation from the photosystem I—light-harvesting complex I (PSI-LHCI) super-complexes and the ATP-synthase; which is then stabilized by stacking interactions of the adjacent PSII-LHCII enriched regions of the thylakoid membranes. The self-assembly and dynamics of this highly organized membrane system and the nature of forces acting between the PSII-LHCII macrodomains are not well understood. By using circular dichroism (CD) spectroscopy, small-angle neutron scattering (SANS) and transmission electron microscopy (TEM), we investigated the effects of Hofmeister salts on the organization of pigment-protein complexes and on the ultrastructure of thylakoid membranes. We found that the kosmotropic agent (NH4)2SO4 and the Hofmeister-neutral NaCl, up to 2 M concentrations, hardly affected the macro-organization of the protein complexes and the membrane ultrastructure. In contrast, chaotropic salts, NaClO4, and NaSCN destroyed the mesoscopic structures, the multilamellar organization of the thylakoid membranes and the chiral macrodomains of the protein complexes but without noticeably affecting the short-range, pigment-pigment excitonic interactions. Comparison of the concentration- and time-dependences of SANS, TEM and CD parameters revealed the main steps of the disassembly of grana in the presence of chaotropes. It begins with a rapid diminishment of the long-range periodic order of the grana membranes, apparently due to an increased stacking disorder of the thylakoid membranes, as reflected by SANS experiments. SANS measurements also allowed discrimination between the cationic and anionic effects—in stacking and disorder, respectively. This step is followed by a somewhat slower disorganization of the TEM ultrastructure, due to the gradual loss of stacked membrane pairs. Occurring last is the stepwise decrease and disappearance of the long-range chiral order of the protein complexes, the rate of which was faster in LHCII-deficient membranes. These data are interpreted in terms of a theory, from our laboratory, according to which Hofmeister salts primarily affect the hydrophylic-hydrophobic interactions of proteins, and the stroma-exposed regions of the intrinsic membrane proteins, in particular—pointing to the role of protein-water interface in the stacking interactions of granum thylakoid membranes.

The benefits of a Bayesian analysis for the characterization of magnetic nanoparticles

Magnetic nanoparticles offer a unique potential for various biomedical applications, but prior to commercial usage a standardized characterization of their structural and magnetic properties is required. For a thorough characterization, the combination of conventional magnetometry and advanced scattering techniques has shown great potential. In the present work, we characterize a powder sample of high-quality iron oxide nanoparticles that are surrounded with a homogeneous thick silica shell by DC magnetometry and magnetic small-angle neutron scattering (SANS). To retrieve the particle parameters such as their size distribution and saturation magnetization from the data, we apply standard model fits of individual data sets as well as global fits of multiple curves, including a combination of the magnetometry and SANS measurements. We show that by combining a standard least-squares fit with a subsequent Bayesian approach for the data refinement, the probability distributions of the model parameters and their cross correlations can be readily extracted, which enables a direct visual feedback regarding the quality of the fit. This prevents an overfitting of data in case of highly correlated parameters and renders the Bayesian method as an ideal component for a standardized data analysis of magnetic nanoparticle samples.

Small-angle neutron scattering (SANS) characterization of 13.5 Cr oxide dispersion strengthened ferritic steel for fusion applications

Abstract Small-angle neutron scattering (SANS) has been utilized for micro-structural investigation on laboratory heats of oxide dispersion strengthened (ODS) 13.5 Cr wt % ferritic steel, with 0.3 wt% Y2O3 and with variable Ti and W contents. The results show that increasing the Ti content from 0.2 to 0.4 wt% a distribution of nano-clusters develops, tentatively identified as Y2Ti2O7, with average radii as small as 6.5 A and volume fractions increasing from 0.021 to 0.032. The measured SANS cross-sections show also the growth of much larger defects, possibly Cr oxides. Furthermore, the ratio of magnetic to nuclear SANS components shows that the defect composition varies both with their size and with the Ti and the W content. These results are in qualitative agreement with transmission electron microscopy (TEM) observations, showing a striking influence of Ti addition on particle size refinement. However, while TEM is limited in statistics and minimum observable size of the Ti-rich nano-clusters, the defect distributions obtained by these SANS measurements provide complementary information useful for morphological characterization of the micro-structure in the investigated material.

Molecular exchange in spherical diblock copolymer colloids synthesised by polymerisation-induced self-assembly

To study molecular exchange between colloids requires the preparation of suitably labelled species. Deuterium isotopic labelling has been used to prepare two chemically identical yet isotopically distinguishable poly(lauryl methacrylate)-poly(methyl methacrylate) (PLMA-PMMA) diblock copolymer colloids by polymerisation-induced self-assembly (PISA) directly in an alkane solvent. Molecular exchange should be detectable by performing small-angle neutron scattering (SANS) measurements on the dispersions. SANS measurements were performed on fully hydrogenous PLMA39-PMMA57 and deuterated core PLMA39-P(MMA-d8)57 colloids. They were mixed in equal amounts and heated to determine if molecular exchange occurred. PISA syntheses are often thermally initiated, and diblock copolymers self-assemble at elevated temperature, making this an important parameter to study. Experimental data for the mixture were compared to predicted curves for exchanged and non-exchanged colloids. The scattering of a mixture of fully hydrogenous and deuterated core copolymers does not disappear upon molecular exchange, due to the remaining contrast between the stabiliser and the core and solvent even after the cores fully exchange. By simultaneously fitting the SANS data from dispersions before mixing and using these parameters to constrain fitting the SANS data of mixtures, the molecular exchange between diblock copolymer micelles upon heating is clearly observed.

Small-angle neutron scattering quantification of phase separation and the corresponding embrittlement of a super duplex stainless steel after long-term aging at 300°C

Small-angle neutron scattering (SANS) was applied to quantify the nanostructural evolution during spinodal decomposition in a 25Cr-7Ni (wt.%) super duplex stainless steel isothermally aged at 300 °C, for up-to 48,000 h. Prior to the application on the 25Cr-7Ni alloy, the SANS methodology was validated by comparing results from SANS measurements on binary Fe-Cr alloys with atom probe tomography results. SANS results on the 25Cr-7Ni alloy indicated that decomposition wavelength decreased from 5.1 nm to 4.5 nm, whereas the amplitude increased from 15.0 to 33.4 at.%. This quantitative nanostructural evolution correlated to a hardening of the ferrite phase by 190 HV and a reduction of the sub-size Charpy-V impact toughness from 60 J to 25 J.

On the kinetics of gamma prime (γ’) precipitation and its strengthening mechanism in Alloy 617 during a long-term thermal aging

The changes in the mechanical properties and the microstructure of solid-solution-strengthened Ni-Cr-Co-Mo Alloy 617 during an extended thermal aging at 750 °C from 200 h up to 32,000 h are investigated. It is shown that thermal aging leads to the formation of nanoscale γ’ precipitates, which affect the strengthening of the γ-matrix and thus overall mechanical properties of Alloy 617. Small-Angle Neutron Scattering (SANS) measurements indicate that about 3 vol.% of nanoscale γ’ precipitates with an average radius below 20 nm is formed after thermal aging for only 200 h. The volume fraction of these precipitates does not increase dramatically reaching about 6% after 32,000 h, however, their size does change significantly reaching the average of about 100 nm after 32,000 h. The kinetics of the coarsening of the present nanoscale γ’ precipitates is shown to follow the classical Lifshitz–Slyozov–Wagner (LSW) theory for diffusion-controlled precipitate Ostwald ripening. Furthermore, SANS measurements of the microstructure-averaged volume fraction and size of present nanoscale γ’ precipitates allow for an investigation of the strengthening mechanisms of the formed nanoscale γ’ precipitates. It is found that the Jackson–Reed order strengthening model, which accounts for shearing of precipitates by the strongly coupled dislocation pairs agrees with the experimental observations.

Synthesis, aggregation and adsorption behaviour of a thermoresponsive pentablock copolymer

AbstractPoly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer (Pluronic F127) was modified by introducing poly(N‐isopropylacrylamide) (PNIPAM) at both the PEO ends, and the pentablock copolymer (PNIPAM41–F127–PNIPAM41, PN41) so prepared was characterized using gel permeation chromatography and 1H NMR spectroscopy. The degree of polymerization of NIPAM blocks at the two ends was 41. The solution behaviour and microstructure of PN41 aggregates in water were examined using UV–visible spectroscopy, micro‐differential scanning calorimetry and small‐angle neutron scattering (SANS) and compared with F127. Two lower critical solution temperatures (LCSTs) were observed for the pentablock copolymer, corresponding to PPO and PNIPAM blocks, respectively. The adsorption of PN41 on thiol‐grafted hydrophobic gold surfaces at various temperatures was investigated using a quartz crystal microbalance. It was found that the adsorption behaviour and mechanism of PN41 were mainly determined by the interactions of the pentablock copolymers with different chain conformations in dilute aqueous solutions at various temperatures. SANS measurements were used to determine the temperature‐dependent structural evolution of polymer micelles in aqueous solution. A NOESY study revealed that above the LSCT of PNIPAM, the interaction of PPO and PNIPAM protons increases and the distance between PPO and PNIPAM decreases. © 2019 Society of Chemical Industry

On the Kinetics of Gamma Prime (R') Precipitation and its Strengthening Mechanism in Alloy 617 During a Long-Term Thermal Aging

The changes in the mechanical properties and the microstructure of Alloy 617 during an extended thermal aging at 750 °C from 200 h up to 32,000 h are investigated. It is shown that formation of nanoscale r' precipitates [Ni3(Al,Ti)] and their consequent coarsening significantly affect the strengthening of the r-matrix and thus overall mechanical properties of Alloy 617. Small-Angle Neutron Scattering (SANS) measurements confirms that about 3 vol.% of nanoscale r' precipitates with an average radius below 20 nm is formed after thermal aging for only 200 h. The volume fraction of formed precipitates does not increase dramatically reaching about 6% after 32,000 h, however, their size does change significantly reaching the average of about 100 nm after 32,000 h. The kinetics of the coarsening of the present nanoscale r' precipitates is shown to follow the classical Lifshitz-Slyozov-Wagner (LSW) theory for diffusion-controlled precipitate Ostwald ripening. SANS measurements of the microstructure-averaged volume fraction and size of present nanoscale r' precipitates allowed us to investigate strengthening mechanisms of the formed nanoscale r' precipitates. It is found that the Jackson-Reed order strengthening model, which accounts for shearing of precipitates by the strongly coupled dislocation pairs describes well the experimental observations (increment of the yield strength).

Self-Assembled Nanostructure of C60-Amphiphilic Molecules Complex in Aqueous Solution: A Small Angle Neutron Scattering Study

In this research, self-assembled nanostructures of C60-agents dispersed in water were investigated using the small angle neutron scattering (SANS) technique. SANS measurements of the C60-agent (surfactant and block copolymers) dispersions showed that clumps of several C60 molecules remain aggregated after ultrasonication and that the C60 aggregates are encapsulated by the agent (surfactants or polymers), existing as a stable dispersion in water. While the shell thickness of dispersed C60-agents (2.04 nm-3.41 nm) differs according to the surfactants and polymers, the formation of C60 aggregates with 4 or 5 fullerenes, where the radius of the C60 aggregates ca. 0.67 nm was not affected. The UV-vis spectrum of the dispersions further supports the formation of C60 aggregates.

Interaction of precipitation with austenite-to-ferrite phase transformation in vanadium micro-alloyed steels

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.

Amphiphilic Bottlebrush Block Copolymers: Analysis of Aqueous Self-Assembly by Small-Angle Neutron Scattering and Surface Tension Measurements

A systematic series of 16 amphiphilic bottlebrush block copolymers (BCPs) containing polystyrene and poly(N-acryloylmorpholine) (PACMO) side chains were prepared by a combination of atom-transfer radical polymerization (ATRP), photoiniferter polymerization, and ring-opening metathesis polymerization (ROMP). The grafting-through method used to prepare the polymers enabled a high degree of control over backbone and side-chain molar masses for each block. Surface tension measurements on the self-assembled amphiphilic bottlebrush BCPs in water revealed an ultralow critical micelle concentration (cmc), 1–2 orders of magnitude lower than linear BCP analogues on a molar basis, even for micelles with >90% PACMO content. Combined with coarse-grained molecular dynamics simulations, fitting of small-angle neutron scattering traces (SANS) allowed us to evaluate solution conformations for individual bottlebrush BCPs and micellar nanostructures for self-assembled macromolecules. Bottlebrush BCPs showed an increase in a...

Interaction of salicylic acid analogues with Pluronic® micelles: Investigations on micellar growth and morphological transition

The aqueous solutions of PEO-PPO-PEO type triblock copolymers (Pluronic® P123, P103 and P105) with variations in their total molecular weight and block contribution are investigated for encapsulation of drugs. Two drugs, namely Aspirin (AS) and 5-Methyl Salicylate (MS) having different partition coefficient was studied. The changes in size and micellar dynamics due to formation of drug-polymer complexes are investigated using dynamic light scattering (DLS), dynamic surface tension (DST), Nuclear Magnetic Resonance (NMR) and Small angle neutron scattering (SANS) measurements. Increase in apparent hydrodynamic diameter (Dh) measured by DLS suggests the growth of micelles, which is equally supported by calculated micellar parameters from SANS measurements. The solubilization of drugs within micelles alters the diffusivity of the monomers due to stronger hydrophobic forces leading to highly stable aggregates as concluded by dynamic surface tension measurements. The significant increase in micellar size was noticed in presence of MS, while AS had less prominent effect on micellar growth. The preferential partitioning of drug into the hydrophobic micellar core is the driving force for the possible formation of higher morphologies. The hydrophobic interactions between MS and P123 are confirmed by 1H NMR. The differences in molecular interactions leading to distinct morphological behavior are explained by the localization of drug within nanocarriers.

VC-Precipitation Kinetics Studied by Small-Angle Neutron Scattering in Nano-Steels

Nanosteels are used in automotive applications to accomplish resource-efficiency while providing high-tech properties. Quantitative data and further understanding on the precipitation kinetics in Nanosteels can contribute to fulfil this goal. Small-Angle Neutron Scattering measurements are performed on a Fe-C-Mn-V steel, previously heat-treated in a dilatometer at 650°C for several holding times from seconds to 10 hours. The evolution of the precipitate volume fraction, size distribution and number density is calculated by fitting the experimental Small-Angle Neutron Scattering curves. The effect of phase transformation on precipitation kinetics is also discussed. Complementary Transmission Electron Microscopy, Scanning Electron Microscopy and Inductively Coupled Plasma Optical Emission Spectroscopy measurements are performed to support the Small-Angle Neutron Scattering data analysis.

Micro-structural effects of irradiation temperature and helium content in neutron irradiated B-alloyed Eurofer97-1 steel

The micro-structural effects of different neutron irradiation temperatures and helium contents, for 16 dpa dose, have been investigated by means of small-angle neutron scattering (SANS) in B-alloyed ferritic/martensitic steel Eurofer97-1 (0.12 C, 9 Cr, 0.2 V, 1.08 W wt%, B concentrations up to 1000 ppm); due to B transmutations, fusion relevant He/dpa values are expected to be produced under neutron irradiation. SANS measurements have been carried out on a sample irradiated at 350 °C, with estimated helium content of 5600 appm, and compared to previous SANS results, obtained on two other irradiated samples of this same B-alloyed steel. These new measurements confirm that for such high helium contents the SANS cross-section increases in order of magnitude and the magnetic SANS component is strongly reduced, compared to lower helium content (400 appm). Such effects are attributed to increase in helium bubbles density and to the presence of micro-cavities, produced after dissolution of large B-carbides. The SANS data analysis procedure has been improved, also thanks to the additional information provided by the new measurements, and more accurate helium bubble size distributions have been obtained for all the investigated samples. For 5600 appm helium content, bubble volume fractions are found of 0.025 for the sample irradiated at 350 °C and of 0.041 for the previously investigated sample irradiated at 400 °C, significantly increasing with the irradiation temperature. These values are approximately one order of magnitude larger than the value of 0.003 previously found for the sample with 400 appm helium. The size distributions are compared with electron microscopy observations of these same samples. It appears that the occurrence of complex micro-structural changes in irradiated Eurofer97-1 steel should be taken in due account when considering its application under high He/dpa ratio values.

1.5 GPa compact double-wall clamp cell for SANS and NSE studies at low temperatures and high magnetic fields

We have developed and realised a compact high-pressure clamp cell of the piston-cylinder type for Small Angle Neutron Scattering (SANS) and Neutron Spin Echo (NSE) spectroscopy measurements. The cell can pressurise φ5 mm samples up to 1.5 GPa. It is non-magnetic, produces a sufficiently low and flat SANS background with a relatively good neutron transmission and can be used in combination with polarised neutrons. The cell accommodates samples of up to 55 mm3 in volume and adopts a two-layer geometry: a TiZr body (outer layer) and a CuBe2 insert (inner layer). Its design is very compact and can be employed inside cryomagnets featuring a sample bore greater than φ30 mm. We present the cell and illustrate its performances with a series of neutron scattering experiments performed on single-crystalline MnSi.