Two high‐resolution, general‐purpose, small‐angle neutron scattering instruments have been constructed at the National Institute of Standards and Technology's Center for Neutron Research. The instruments are 30 m long and utilize mechanical velocity selectors, pinhole collimation and high‐data‐rate two‐dimensional position‐sensitive neutron detectors. The incident wavelength, wavelength resolution and effective length of the instruments are independently variable, under computer control, and provide considerable flexibility in optimizing beam intensity and resolution. The measurement range of the instruments extends from 0.0015 to 0.6 Å−1 in scattering wavevector, corresponding to structure in materials from 10 Å to nearly 4000 Å. The design and characteristics of the instruments, and their modes of operation, are described, and data are presented which demonstrate their performance.

Small‐angle scattering (SAS) curves are characterized by two main features: the Guinier region and the Porod region. Standard linear plots are available to fit SAS data and obtain a radius of gyration and a Porod exponent. A new Guinier–Porod empirical model is introduced to fit SAS data from spherical as well as nonspherical objects such as rods or platelets. It also applies to shapes intermediate between spheres and rods or between rods and platelets. The new model is used to fit SAS data from a Pluronic solution that sequentially forms unimers, then spherical micelles, then cylindrical micelles, then lamellar micelles upon heating. This single model can fit structures associated with all four phases as well as the intermediate structures.

The clustering phenomenon has been observed in many macromolecular systems. Poly-(ethylene oxide) solutions are characterized by a clustering effect that has been extensively discussed in the literature. Its origin has remained elusive. Using small-angle neutron scattering from PEO solutions in various deuterated solvents, the possible causes of clustering that have been given in the literature are analyzed here. These include impurities in water, possible PEO crystallization, a subtle phase transition whereby a concentrated phase coexists with free polymer coils, hydrogen-bond physical crosslinking, and finally chain ends effect. We have shown that under the experimental conditions considered here (4% PEO weight fraction) the mostly forgotten chain ends effect is at the origin of clustering in poly(ethylene oxide) solutions.

Bottlebrush polymers are highly branched macromolecules with potential applications in antifouling coatings, rheological modifiers, and drug delivery systems. However, the solution conformation of bottlebrush polymers has been studied in only a limited set of materials made primarily by grafting-from polymerization. Here we present small-angle neutron scattering (SANS) measurements on a series of polystyrene bottlebrush polymers with varying side-chain and backbone lengths in d 8-toluene to analyze their size, shape, and conformation. Bottlebrush polymers with 2–7 kg mol–1 polystyrene side chains (degree of polymerization DP = 14–54) and poly(oxanorbornene) backbones (DP = 10–264) were synthesized using reversible addition–fragmentation chain transfer (RAFT) followed by a ring-opening metathesis polymerization (ROMP) grafting-through synthesis scheme. Analysis by Guinier–Porod, rigid cylinder, and flexible cylinder models provided estimates of the bottlebrush polymer length, radius, and stiffness. The bottlebrush polymer cross-sectional area depends primarily on side-chain DP, and the radius of gyration R g exhibits a power-law dependence with side-chain DP. We also observe a sphere-to-cylinder transition with increasing backbone DP, with the transition occurring at a backbone DP of approximately 120 for the polystyrene bottlebrush polymers studied. The maximum molecular dimension for the series studied varies from 25 to 350 nm.

The poly(ethylene oxide) (PEO)/water system is investigated using small-angle neutron scattering (SANS). This system associates to form hydrogen-bonded clusters at high enough concentrations. Two correlation lengths are observed: one long range representing cluster sizes and the other short range representing polymer chain correlations. Clusters are formed at a volume fraction of 4% hPEO in D 2O. An LCST transition is obtained between a mixed phase (through hydrogen bonding) and a demixed twophase region. Solvent deuteration is seen to enhance hydrogen bonding. Deuteration of the polymer backbone is seen to enhance hydrophobic interactions. The average polymer contrast match method fails due to the isotopic dependence of specific interactions. Pressure was seen to lower the LCST by breaking hydrogen bonds. At even higher temperature (beyond the boiling point of water) a UCST transition was observed.

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Sodium dodecyl sulfate (SDS) surfactants form micelles when dissolved in water. These are formed of a hydrocarbon core and hydrophilic ionic surface. The small-angle neutron scattering (SANS) technique was used with deuterated water (D2O) in order to characterize the micelle structure. Micelles were found to be slightly compressed (oblate ellipsoids) and their sizes shrink with increasing temperature. Fits of SANS data to the Mean Spherical Approximation (MSA) model yielded a calculated micelle volume fraction which was lower than the SDS surfactant (sample mixing) volume fraction; this suggests that part of the SDS molecules do not participate in micelle formation and remain homogeneously mixed in the solvent. A set of material balance equations allowed the estimation of the SDS fraction in the micelles. This fraction was found to be high (close to one) except for samples around 1 % SDS fraction. The micelle aggregation number was found to decrease with increasing temperature and/or decreasing SDS fraction.

Small amphiphilic molecules, also known as hydrotropes, are too small to form micelles in aqueous solutions. However, aqueous solutions of nonionic hydrotropes show the presence of a dynamic, loose, non-covalent clustering in the water-rich region, This clustering can be viewed as "micelle-like structural fluctuations". Although these fluctuations are short ranged (approximately 1 nm) and short lived (10 ps-50 ps), they may lead to thermodynamic anomalies. In addition, many experiments on aqueous solutions of hydrotropes show the occasional presence of mesoscale (approximately 100 nm) inhomogeneities. We have combined results obtained from molecular dynamics simulations, small-angle neutron scattering, and dynamic light-scattering experiments carried out on tertiary butyl alcohol (hydrotrope)-water solutions and on tertiary butyl alcohol-water-cyclohexane (hydrophobe) solutions to elucidate the nature and structure of these inhomogeneities. We have shown that stable mesoscale inhomogeneities occur in aqueous solutions of nonionic hydrotropes only when the solution contains a third, more hydrophobic, component. Moreover, these inhomogeneities exist in ternary systems only in the concentration range where structural fluctuations and thermodynamic anomalies are observed in the binary water-hydrotrope solutions. Addition of a hydrophobe seems to stabilize the water-hydrotrope structural fluctuations, and leads to the formation of larger (mesoscopic) droplets. The structure of these mesoscopic droplets is such that they have a hydrophobe-rich core, surrounded by a hydrogen-bonded shell of water and hydrotrope molecules. These droplets can be extremely long-lived, being stable for over a year. We refer to the phenomenon of formation of mesoscopic droplets in aqueous solutions of nonionic hydrotropes containing hydrophobes, as mesoscale solubilization. This phenomenon may represent a ubiquitous feature of nonionic hydrotropes that exhibit clustering in water, and may have important practical applications in areas, such as drug delivery, where the replacement of traditional surfactants may be necessary.