Multidimensional nature of fluidized nanoparticle agglomerates.

We show that fluidized nanoparticle agglomerates are hierarchical fractal structures with three fractal dimensions: one characterizing sintered aggregates formed during nanoparticle synthesis, one that is also found in stored agglomerates and represents unbroken agglomerates, and one describing the large agglomerates broken during fluidization. This has been possible by using spin-echo small-angle neutron scattering-a relatively novel technique that, for the first time, allowed to characterize in situ the structure of fluidized nanoparticle agglomerates from 21 nm to ∼20 µm. The results show that serial agglomeration mechanisms in the gas phase can generate nanoparticle clusters with different fractal dimensions, contradicting the common approach that considers fluidized nanoparticle agglomerates as single fractals, in analogy to the agglomerates formed by micron-sized particles. This work has important implications for the fluidization field but also has a wider impact. Current studies deal with the formation and properties of clusters where the building blocks are particles and the structure can be characterized by only one fractal dimension. However, fluidized nanoparticle agglomerates are low-dimensional clusters formed by higher-dimensional clusters that are formed by low-dimensional clusters. This multifractality demands a new type of multiscale model able to capture the interplay between different scales.

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.

Simulations of foil-based spin-echo (modulated) small-angle neutron scattering with a sample using McStas.

For the further development of spin-echo techniques to label elastic scattering it is necessary to perform simulations of the Larmor precession of neutron spins in a magnetic field. The details of some of these techniques as implemented at the reactor in Delft are simulated. First, the workings of the magnetized foil flipper are simulated. A full virtual spin-echo small-angle neutron scattering instrument is built and tested without and with a realistic scattering sample. It is essential for these simulations to have a simulated sample that also describes the transmitted beam of unscattered neutrons, which usually is not implemented for the simulation of conventional small-angle neutron scattering (SANS) instruments. Finally, the workings of a spin-echo modulated small-angle neutron scattering (SEMSANS) instrument are simulated. The simulations are in good agreement with theory and experiments. This setup can be extended to include realistic magnetic field distributions to fully predict the features of future Larmor labelling elastic-scattering instruments. Configurations can now be simulated for more complicated combinations of SANS with SEMSANS.

Fabrication of artificial opals by electric-field-assisted vertical deposition.

We present a new technique for large-scale fabrication of colloidal crystals with controllable quality and thickness. The method is based on vertical deposition in the presence of a DC electric field normal to the conducting substrate. The crystal structure and quality are quantitatively characterized by microradian X-ray diffraction, scanning electron microscopy, and optical reflectometry. Attraction between the charged colloidal spheres and the substrate promotes growth of thicker crystalline films, while the best-quality crystals are formed in the presence of repulsion. Highly ordered thick crystalline layers with a small amount of stacking faults and a low mosaic spread can be obtained by optimizing the growth conditions.

Milk gelation studied with small angle neutron scattering techniques and Monte Carlo simulations.

The sol-gel transition of fat-free milk by acidification was studied with neutron scattering experiments and Monte Carlo simulations. Spin-echo small angle neutron scattering (SESANS) and ultrasmall angle neutron scattering (USANS) experiments were performed to measure the static structure of milk and yogurt, as well as the aggregation kinetics. Colloidal gelation was simulated from a reaction limited domain (RLCA) to the diffusion limited regime (DLCA) as cluster-cluster aggregation of adhesive, hard spheres on a three-dimensional lattice. Comparisons were drawn between experimental and numerical correlation functions. Milk was modeled as a suspension of casein micelles in water, and its structure was described with a dilute system of solid spheres with a log-normal distribution of sizes. The structure and formation of yogurt were described with a self-affine model, used for systems containing heterogeneities with a wide range of sizes. Simulation speed was increased by 1 order-of-magnitude using a new algorithm to eliminate dead time. Observations by SESANS and USANS of milk particle sizes and yogurt length scales were consistent and agreed well with literature. Kinetic USANS data yielded reliable information about the growth of typical length scale during aggregation. The simulation model predicted the measurement data qualitatively best staying close to the RLCA regime until large structures had formed. Correlation lengths were in good quantitative agreement, but longest simulated length scales were a of factor 2(1)/(2) below experimental findings. We conclude that small, mobile aggregates are formed during the first 3 h, mostly influencing the dimensionality of the system and that large, inert structures are formed from 2 up to 8 h, which determine the typical length scale.

Impact of water degumming and enzymatic degumming on gum mesostructure formation in crude soybean oil.

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.

Mesoporous Silica Formation Mechanisms Probed Using Combined Spin-Echo Modulated Small-Angle Neutron Scattering (SEMSANS) and Small-Angle Neutron Scattering (SANS).

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 two stage 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.

Polarization optimization of spin-echo small angle scattering instruments.

The polarization optimization in a small angle scattering spin-echo setup is considered, under the depolarization and phase errors that occur in field transition regions by improper adjustment of inclined magnetized foils as pi-flippers. Various correction procedures are discussed. In these setups with precession fields perpendicular to the beam directions, corrections can be reduced strongly by the use of pi-flippers, and for the remaining errors, correction coils can be constructed.

Quantitative Neutron Dark-field Imaging through Spin-Echo Interferometry.

Neutron dark-field imaging constitutes a seminal progress in the field of neutron imaging as it combines real space resolution capability with information provided by one of the most significant neutron scattering techniques, namely small angle scattering. The success of structural characterizations bridging the gap between macroscopic and microscopic features has been enabled by the introduction of grating interferometers so far. The induced interference pattern, a spatial beam modulation, allows for mapping of small-angle scattering signals and hence addressing microstructures beyond direct spatial resolution of the imaging system with high efficiency. However, to date the quantification in the small angle scattering regime is severely limited by the monochromatic approach. To overcome such drawback we here introduce an alternative and more flexible method of interferometric beam modulation utilizing a spin-echo technique. This novel method facilitates straightforward quantitative dark-field neutron imaging, i.e. the required quantitative microstructural characterization combined with real space image resolution. For the first time quantitative microstructural reciprocal space information from small angle neutron scattering becomes available together with macroscopic image information creating the potential to quantify several orders of magnitude in structure sizes simultaneously.

On characterization of anisotropic plant protein structures.

In this paper, a set of complementary techniques was used to characterize surface and bulk structures of an anisotropic Soy Protein Isolate (SPI)-vital wheat gluten blend after it was subjected to heat and simple shear flow in a Couette Cell. The structured biopolymer blend can form a basis for a meat replacer. Light microscopy and scanning electron microscopy provided a detailed view of structure formation over the visible surfaces of the SPI-gluten blend. Protein orientation in the direction of the flow was evident and fibrous formation appeared to exist on the macro- and micro-scale. Furthermore, according to texture analysis, the structured biopolymer obtained from the Couette Cell after processing at 95 °C and 30 RPM for 15 min has high tensile stress and strain anisotropy indices (∼2 and ∼1.8, respectively), comparable to those of raw meat (beef). The novel element in this work is the use of the neutron refraction method, utilizing spin-echo small angle neutron scattering (SESANS), to provide a look inside the anisotropic biopolymer blend complementing the characterization provided by the standard techniques above. With SESANS, it is possible to quantify the number of fibre layers and the orientation distribution of fibres. For a specimen thickness of 5 mm, the obtained number of fibre layers was 36 ± 4 and the standard deviation of the orientation distribution was 0.66 ± 0.04 radians. The calculated thickness of one layer of fibres was 138 µm, in line with SEM inspection.

Stability of aqueous food grade fibrillar systems against pH change.

We report that the stability of an aqueous food grade fibril system upon pH change is affected by the presence of peptides that are formed during the process of fibril formation. We discuss several other relationships between food relevant properties and nano-scale characteristics, and compare these relationships for aqueous fibril systems to those of oil based fibril systems. In such fibril systems, dynamics, self-organisation, and sensitivity to external conditions, play an important role. These aspects are common to complex systems in general and define the future challenge in relating functional properties of food to molecular scale properties of their ingredients.

Elucidation of density profile of self-assembled sitosterol + oryzanol tubules with small-angle neutron scattering.

Small-angle neutron scattering (SANS) experiments have been performed on self-assembled tubules of sitosterol and oryzanol in triglyceride oils to investigate details of their structure. Alternative organic phases (deuterated and non-deuterated decane, limonene, castor oil and eugenol) were used to both vary the contrast with respect to the tubules and investigate the influence of solvent chemistry. The tubules were found to be composed of an inner and an outer shell containing the androsterol group of sitosterol or oryzanol and the ferulic acid moieties in the oryzanol molecule, respectively. While the inner shell has previously been detected in SAXS experiments, the outer shell was not discernible due to similar scattering length density with respect to the surrounding solvent for X-rays. By performing contrast variation SANS experiments, both for the solvent and structurant, a far more detailed description of the self-assembled system is obtainable. A model is introduced to fit the SANS data; we find that the dimensions of the inner shell agree quantitatively with the analysis performed in earlier SAXS data (radius of 39.4 +/- 5.6 angstroms for core and inner shell together, wall thickness of 15.1 +/- 5.5 angstroms). However, the newly revealed outer shell was found to be thinner than the inner shell (wall thickness 8.0 +/- 6.5 angstroms). The changes in the scattering patterns may be explained in terms of the contrast between the structurant and the organic phase and does not require any subtle indirect effects caused by the presence of water, other than water promoting the formation of sitosterol monohydrate in emulsions with aqueous phases with high water activity.

Double stacking faults in convectively assembled crystals of colloidal spheres.

Using microradian X-ray diffraction, we investigated the crystal structure of convectively assembled colloidal photonic crystals over macroscopic (0.5 mm) distances. Through adaptation of Wilson's theory for X-ray diffraction, we show that certain types of line defects that are often observed in scanning electron microscopy images of the surface of these crystals are actually planar defects at 70.5 degrees angles with the substrate. The defects consist of two parallel hexagonal close-packed planes in otherwise face-centered cubic crystals. Our measurements indicate that these stacking faults cause at least 10% of stacking disorder, which has to be reduced to fabricate high-quality colloidal photonic crystals.

A small-angle neutron scattering study of cholic acid-based organogel systems.

Small-angle neutron scattering measurements were performed on some cholic acid-based gel systems in order to gain detailed information about the network structure. The presence of thin fibers with a radius of about 10-20 A was found for various gelators. Two types of interaction between different sorts of fibers were demonstrated, depending on the molecular structure of the gelator. The first type involves the presence of microcrystalline knots with a dimension of about 100-200 A between the fibers. Upon heating, this network gradually disintegrates. The second type involves loose entanglements between flattened fibers. The occurrence of these types of interaction is related to the length of the alkyl tail attached to cholic acid.

Spin control of the lifetime of an intramolecular charge-transfer excited state.

Triplet-sensitized generation of a long-lived intramolecular charge-separated excited state is described in an electron donor-acceptor molecule with a short distance between the donor and the acceptor. Time-resolved UV-Vis optical absorption spectroscopy shows that the lifetime of this triplet excited state is 1.4 micros in acetonitrile at 298 K, i.e. five orders of magnitude greater than that of the corresponding singlet charge-separated state. In slightly less polar alkane nitrile solvents, the local and CT triplet states coexist, which allows determination of their relative energies.