Practical applications of small-angle neutron scattering.

Recent improvements in beam-line accessibility and technology have led to small-angle neutron scattering (SANS) becoming more frequently applied to materials problems. SANS has been used to study the assembly, dispersion, alignment and mixing of nanoscale condensed matter, as well as to characterise the internal structure of organic thin films, porous structures and inclusions within steel. Using time-resolved SANS, growth mechanisms in materials systems and soft matter phase transitions can also be explored. This review is intended for newcomers to SANS as well as experts. Therefore, the basic knowledge required for its use is first summarised. After this introduction, various examples are given of the types of soft and hard matter that have been studied by SANS. The information that can be extracted from the data is highlighted, alongside the methods used to obtain it. In addition to presenting the findings, explanations are provided on how the SANS measurements were optimised, such as the use of contrast variation to highlight specific parts of a structure. Emphasis is placed on the use of complementary techniques to improve data quality (e.g. using other scattering methods) and the accuracy of data analysis (e.g. using microscopy to separately determine shape and size). This is done with a view to providing guidance on how best to design and analyse future SANS measurements on materials not listed below

Porous 'Ouzo-effect' silica-ceria composite colloids and their application to aluminium corrosion protection.

By exploiting spontaneous emulsification to prepare porous SiO(2) particles, we report the formation of porous CeO(2)@SiO(2) hybrid colloids and their incorporation into a silica-zirconia coating to improve the corrosion protection of aluminium

The power of branched chains: optimising functional molecular materials

The power of branched alkyl substituents to alter material properties is known to soft matter chemistry, with examples found in both surfactants and ionic liquids. Here, we highlight their potency in organic molecular/polymeric materials with optoelectronic applications. Attaching branched alkyl chains to the active p-conjugated core modulates core–core interactions and thus softens the material. This can lead to optimised assemblies with improved optoelectronic properties. By increasing the number and volume of the flexible chains, individual cores can be isolated, yielding functional organic liquids with bulk optical properties the same as the intrinsic molecular characteristics obtained for their dilute solutions. These liquid materials can accommodate dopants to offer diverse and tuneable emission colours, and provide an easily applicable flexible and foldable continuous layer for future optoelectronic media

Alkylated-C-60 based soft materials: regulation of self-assembly and optoelectronic properties by chain branching

Derivatization of fullerene (C60) with branched aliphatic chains softens C60-based materials and enables the formation of thermotropic liquid crystals and room temperature nonvolatile liquids. This work demonstrates that by carefully tuning parameters such as type, number and substituent position of the branched chains, liquid crystalline C60 materials with mesophase temperatures suited for photovoltaic cell fabrication and room temperature nonvolatile liquid fullerenes with tunable viscosity can be obtained. In particular, compound 1, with branched chains, exhibits a smectic liquid crystalline phase extending from 84 °C to room temperature. Analysis of bulk heterojunction (BHJ) organic solar cells with a ca. 100 nm active layer of compound 1 and poly(3-hexylthiophene) (P3HT) as an electron acceptor and an electron donor, respectively, reveals an improved performance (power conversion efficiency, PCE: 1.6 ± 0.1%) in comparison with another compound, 10 (PCE: 0.5 ± 0.1%). The latter, in contrast to 1, carries linear aliphatic chains and thus forms a highly ordered solid lamellar phase at room temperature. The solar cell performance of 1 blended with P3HT approaches that of PCBM/P3HT for the same active layer thickness. This indicates that C60 derivatives bearing branched tails are a promising class of electron acceptors in soft (flexible) photovoltaic devices

Doped-carbon electrocatalysts with trimodal porosity from a homogeneous polypeptide gel

One of the biggest challenges for materials science is to design facile routes to structurally complex materials, which is particularly important for global applications such as fuel cells. Doped nanostructured carbons are targeted as noble metal-free electrocatalysts for this purpose. Their intended widespread use, however, necessitates simple and robust preparation methods that do not compromise on material performance. Here, we demonstrate a versatile one-pot synthesis of nitrogen-doped carbons that exploits the templating ability of biological polymers. Starting with just metal nitrates and gelatin, multiphase C/Fe3C/MgO nanomaterials are formed, which are then etched to produce active carbon electrocatalysts with accessible trimodal porosity. These show remarkable performance in the oxygen reduction reaction – a key process in proton exchange membrane fuel cells. The activity is comparable to commercial platinum catalysts and shows improved stability with reduced crossover effects. This simple method offers a new route to widely applicable porous multicomponent nanocomposites

Supramolecular copolymerization driven by integrative self-sorting of hydrogen-bonded rosettes.

Molecular recognition to preorganize noncovalently polymerizable supramolecular complexes is a characteristic process of natural supramolecular polymers, and such recognition processes allow for dynamic self-alteration, yielding complex polymer systems with extraordinarily high efficiency in their targeted function. We herein show an example of such molecular recognition-controlled kinetic assembly/disassembly processes within artificial supramolecular polymer systems using six-membered hydrogen-bonded supramolecular complexes (rosettes). Electron-rich and poor monomers are prepared that kinetically coassemble through a temperature-controlled protocol into amorphous coaggregates comprising a diverse mixture of rosettes. Over days, the electrostatic interaction between two monomers induces an integrative self-sorting of rosettes. While the electron-rich monomer inherently forms toroidal homopolymers, the additional electrostatic interaction that can also guide rosette association allows helicoidal growth of supramolecular copolymers that are comprised of an alternating array of two monomers. Upon heating, the helicoidal copolymers undergo a catastrophic transition into amorphous coaggregates via entropy-driven randomization of the monomers in the rosette

Self-folding of supramolecular polymers into bioinspired topology.

Folding one-dimensional polymer chains into well-defined topologies represents an important organization process for proteins, but replicating this process for supramolecular polymers remains a challenging task. We report supramolecular polymers that can fold into protein-like topologies. Our approach is based on curvature-forming supramolecular rosettes, which affords kinetic control over the extent of helical folding in the resulting supramolecular fibers by changing the cooling rate for polymerization. When using a slow cooling rate, we obtained misfolded fibers containing a minor amount of helical domains that folded on a time scale of days into unique topologies reminiscent of the protein tertiary structures. Thermodynamic analysis of fibers with varying degrees of folding revealed that the folding is accompanied by a large enthalpic gain. The self-folding proceeds via ordering of misfolded domains in the main chain using helical domains as templates, as fully misfolded fibers prepared by a fast cooling rate do not self-fold

The aggregation of an alkyl-C60 derivative as a function of concentration, temperature and solvent type.

Contrast-variation small-angle neutron scattering (CV-SANS), small-angle X-ray scattering (SAXS), nuclear magnetic resonance (NMR) measurements of diffusion and isothermal titration calorimetry (ITC) are used to gain insight into the aggregation of an alkyl-C60 derivative, molecule 1, in n-hexane, n-decane and toluene as a function of concentration and temperature. Results point to an associative mechanism of aggregation similar to other commonly associating molecules, including non-ionic surfactants or asphaltenes in non-aqueous solvents. Little aggregation is detected in toluene, but small micelle-like structures form in n-alkane solvents, which have a C60-rich core and alkyl-rich shell. The greatest aggregation extent is found in n-hexane, and at 0.1 M the micelles of 1 comprise around 6 molecules at 25 °C. These micelles become smaller when the concentration is lowered, or if the solvent is changed to n-decane. The solution structure is also affected by temperature, with a slightly larger aggregation extent at 10 °C than at 25 °C. At higher concentrations, for example in solutions of 1 above 0.3 M in n-decane, a bicontinuous network becomes apparent. Overall, these findings aid our understanding of the factors driving the assembly of alkyl-p-conjugated hydrophobic amphiphiles such as 1 in solution and thereby represent a step towards the ultimate goal of exploiting this phenomenon to form materials with well-defined order

Nuclear magnetic resonance and small-angle X-ray scattering studies of mixed sodium dodecyl sulfate and N,N-dimethyldodecylamine N-oxide aqueous systems performed at low temperatures

Surfactant crystallisation is important in many applications in the food, consumer product and medical sectors. However, these processes are not well understood. In particular, surfactant crystallisation can be detrimental to the stability of detergent formulations, such as dish liquid products, resulting in a turbid solution that fails appearance criteria. With the rising global demand for detergent products, understanding the factors that influence formulation stability is of increasing importance. To enable industry to build more robust formulations, it is important to understand the underlying chemistry of the crystallisation process. Here, a model system containing anionic (sodium dodecyl sulfate, SDS) and amphoteric (N,N-dimethyldodecylamine N-oxide, DDAO) surfactants, at concentrations typical of dish liquid products, is studied. Variable temperature 1H nuclear magnetic resonance (NMR) spectroscopy and small-angle X-ray scattering (SAXS) is used to probe the compositional and structural properties of this system, as a function of pH. On cooling, at pH 9, a mixture of hydrated crystals, predominately composed of SDS, and micelles containing both surfactants, have been observed prior to complete freezing. At pH 2, both surfactants appear to undergo a simultaneous phase transition, resulting in the removal of micelles and the formation of hydrated crystals of mixed composition