Small Angle Neutron Scattering of Aerogels: Simulations and Experiments

A numerical simulation of silica aerogels is performed using diffusion-limited cluster-cluster aggregation of spheres inside a cubic box (with periodic boundary conditions). The volume fraction $c$ is taken to be sufficiently large to get a gel structure at the end of the process. In the case of monodisperse spheres, the wavevector dependent scattered intensity $I(q)$ is calculated from the product of the form factor $P(q)$ of a sphere by the structure factor $S(q)$, which is related to the Fourier transform of $g(r)-1$, where $g(r)$ is the pair correlation function between sphere centers. The structure factor $S(q)$ exhibits large-$q$ damped oscillations characteristics of the short range (intra-aggregate) correlations between spheres. These oscillations influence the $I(q)$ curve in the $q$-region between the fractal regime and the Porod regime and quantitative comparisons are made with experiments on colloidal aerogels. Moreover, at small-$q$ values, $S(q)$ goes through a maximum characteristic of large range (inter-aggregate) correlations. Quantitative fits of the maximum in the experimental $I(q)$ curves of base-catalyzed aerogel are presented. In the case of polydisperse spheres, $I(q)$ is calculated directly from a single aggregate simulation. It is shown that increasing polydispersity shifts the location of the cross-over between the fractal and Porod regimes towards low $q$-value.Comment: RevTex, 9 pages + 11 postscript figures, compressed using "uufiles". Proceeding of the 4th International Simposium on Aerogels (To appear in J. of Non-Cryst. Solids

Crystal structure and high-field magnetism of La2CuO4

Neutron diffraction was used to determine the crystal structure and magnetic ordering pattern of a La2CuO4 single crystal, with and without applied magnetic field. A previously unreported, subtle monoclinic distortion of the crystal structure away from the orthorhombic space group Bmab was detected. The distortion is also present in lightly Sr-doped crystals. A refinement of the crystal structure shows that the deviation from orthorhombic symmetry is predominantly determined by displacements of the apical oxygen atoms. An in-plane magnetic field is observed to drive a continuous reorientation of the copper spins from the orthorhombic b-axis to the c-axis, directly confirming predictions based on prior magnetoresistance and Raman scattering experiments. A spin-flop transition induced by a c-axis oriented field previously reported for non-stoichiometric La2CuO4 is also observed, but the transition field (11.5 T) is significantly larger than that in the previous work

The scattering from generalized Cantor fractals

We consider a fractal with a variable fractal dimension, which is a generalization of the well known triadic Cantor set. In contrast with the usual Cantor set, the fractal dimension is controlled using a scaling factor, and can vary from zero to one in one dimension and from zero to three in three dimensions. The intensity profile of small-angle scattering from the generalized Cantor fractal in three dimensions is calculated. The system is generated by a set of iterative rules, each iteration corresponding to a certain fractal generation. Small-angle scattering is considered from monodispersive sets, which are randomly oriented and placed. The scattering intensities represent minima and maxima superimposed on a power law decay, with the exponent equal to the fractal dimension of the scatterer, but the minima and maxima are damped with increasing polydispersity of the fractal sets. It is shown that for a finite generation of the fractal, the exponent changes at sufficiently large wave vectors from the fractal dimension to four, the value given by the usual Porod law. It is shown that the number of particles of which the fractal is composed can be estimated from the value of the boundary between the fractal and Porod regions. The radius of gyration of the fractal is calculated analytically.Comment: 8 pages, 4 figures, accepted for publication in J. Appl. Crys

The use of small angle neutron scattering with contrast matching and variable adsorbate partial pressures in the study of porosity in activated carbons

The porosity of a typical activated carbon is investigated with small angle neutron scattering (SANS), using the contrast matching technique, by changing the hydrogen/deuterium content of the absorbed liquid (toluene) to extract the carbon density at different scattering vector (Q) values and by measuring the p/p0 dependence of the SANS, using fully deuterated toluene. The contrast matching data shows that the apparent density is Q-dependent, either because of pores opening near the carbon surface during the activation processor or changes in D-toluene density in nanoscale pores. For each p/p0 value, evaluation of the Porod Invariant yields the fraction of empty pores. Hence, comparison with the adsorption isotherm shows that the fully dry powder undergoes densification when liquid is added. An algebraic function is developed to fit the SANS signal at each p/p0 value hence yielding the effective Kelvin radii of the liquid surfaces as a function of p/p0. These values, when compared with the Kelvin Equation, show that the resultant surface tension value is accurate for the larger pores but tends to increase for small (nanoscale) pores. The resultant pore size distribution is less model-dependent than for the traditional methods of analyzing the adsorption isotherms

Globally Anisotropic High Porosity Silica Aerogels

We discuss two methods by which high porosity silica aerogels can be engineered to exhibit global anisotropy. First, anisotropy can be introduced with axial strain. In addition, intrinsic anisotropy can result during growth and drying stages and, suitably controlled, it can be correlated with preferential radial shrinkage in cylindrical samples. We have performed small angle X-ray scattering (SAXS) to characterize these two types of anisotropy. We show that global anisotropy originating from either strain or shrinkage leads to optical birefringence and that optical cross-polarization studies are a useful characterization of the uniformity of the imposed global anisotropy.Comment: 18 pages, 14 figures, submitted to Journal of Non-Crystalline Solid

Small Angle Scattering by Fractal Aggregates: A Numerical Investigation of the Crossover Between the Fractal Regime and the Porod Regime

Fractal aggregates are built on a computer using off-lattice cluster-cluster aggregation models. The aggregates are made of spherical particles of different sizes distributed according to a Gaussian-like distribution characterised by a mean $a_0$ and a standard deviation $\sigma$. The wave vector dependent scattered intensity $I(q)$ is computed in order to study the influence of the particle polydispersity on the crossover between the fractal regime and the Porod regime. It is shown that, given $a_0$, the location $q_c$ of the crossover decreases as $\sigma$ increases. The dependence of $q_c$ on $\sigma$ can be understood from the evolution of the shape of the center-to-center interparticle-distance distribution function.Comment: RevTex, 4 pages + 6 postscript figures, compressed using "uufiles", published in Phys. Rev. B 50, 1305 (1994

Anisotropic Aerogels for Studying Superfluid 3^3He

It may be possible to stabilize new superfluid phases of $^{3}$He with anisotropic silica aerogels. We discuss two methods that introduce anisotropy in the aerogel on length scales relevant to superfluid $^{3}$He. First, anisotropy can be induced with uniaxial strain. A second method generates anisotropy during the growth and drying stages. We have grown cylindrical $\sim$98% aerogels with anisotropy indicated by preferential radial shrinkage after supercritical drying and find that this shrinkage correlates with small angle x-ray scattering (SAXS). The growth-induced anisotropy was found to be $\sim90^\circ$ out of phase relative to that induced by strain. This has implications for the possible stabilization of superfluid phases with specific symmetry.Comment: 6 pages, 4 figures, submitted to Quantum Fluids and Solids (QFS) conference 200

Freezing of anisotropic spin clusters in La1.98Sr0.02CuO4

A spin-glass compound, La$_{1.98}$Sr$_{0.02}$CuO$_4$, shows quasi-three-dimensional magnetic ordering below $\sim$40 K. A remarkable feature is that the magnetic correlation length along the orthorhombic $a\rm_{ortho}$ axis is much longer than that along the $b\rm_{ortho}$ axis, suggesting that the spin structure is closely related to the diagonal stripe structure. The spin-glass state can be expressed as a random freezing of quasi-three-dimensional spin clusters with anisotropic spin correlations ($\xi'_a\sim160$ \AA, $\xi'_b\sim25$ \AA, and $\xi'_c\sim4.7$ \AA at 1.6 K). The new magnetic state is important as an intermediate phase between the three-dimensional antiferromagnetic ordered phase in La$_2$CuO$_4$ and the incommensurate phase in La$_{1.95}$Sr$_{0.05}$CuO$_4$ in which the positions of the incommensurate peaks are rotated by 45$^\circ$ in reciprocal space about ($\pi$,$\pi$) from those observed in the superconducting La$_2$CuO$_4$ compounds.Comment: 7 pages, RevTex, 8 PS figures, submitted to Phys. Rev.

Control of silver-polymer aggregation mechanism by primary particle spatial correlations in dynamic fractal-like geometry

Silver nanocrystals have been prepared by reacting silver nitrate with ascorbic acid in aqueous solution containing a low concentration of a commercial polynaphtalene sulphonate polymer (Daxad 19). Various crystalline morphologies have been obtained simply by tuning the reaction temperature. We have investigated the nanoparticle formation mechanism at three different temperatures by in situ and time resolved Small Angle X ray Scattering measurements. By modeling the scattering intensity with interacting spherical particles in a fractal-like polymer-Ag matrix, we found signatures of nucleation, growth and assembly of primary particles of about 15-20 nm. We observed how the time evolution of both spatial correlations between primary particles and the dynamic fractal geometry of the polymer-Ag matrix could influence and determine both the aggregation mechanism and the morphology of forming nanostructures in solution

Magnetic fluctuations in frustrated Laves hydrides R(Mn_{1-x}Al_{x})_{2}H_{y}

By neutron scattering, we have studied the spin correlations and spin fluctuations in frustrated Laves hydrides, where magnetic disorder sets in the topologically frustrated Mn lattice. Below the transition towards short range magnetic order, static spin clusters coexist with fluctuating and alsmost uncorrelated spins. The magnetic response shows a complexe lineshape, connected with the presence of the magnetic inhomogeneities. Its analysis shows the existence of two different processes, relaxation and local excitations, for the spin fluctuations below the transition. The paramagnetic fluctuations are discussed in comparison with classical spin glasses, cluster glasses, and non Fermi liquid itinerant magnets