Small angle neutron scattering study of pore microstructure in ceria compacts

Ceria powders were prepared by gel combustion process using cerium nitrate and hitherto unexplored amino acids such as aspartic acid, arginine and valine as fuels. The powders have been characterized by X-ray and laser diffraction. Cold pressed compacts of these powders have been sintered at 1250°C for 2 h. Internal pore microstructure of the sintered compacts has been investigated by small angle neutron scattering (SANS) over a scattering wave vector q range of 0.003–0.17 nm⁻¹. The SANS profiles indicate surface fractal morphology of the pore space with fractal dimensionality lying between 2.70 and 2.76.      

Sphere-to-rod transition of triblock copolymer micelles at room temperature

A room temperature sphere-to-rod transition of the polyethylene oxide-polypropylene oxide-polyethylene oxide-based triblock copolymer, (PEO)₂₀(PPO)₇₀ (PEO)₂₀ micelles have been observed in aqueous medium under the influence of ethanol and sodium chloride. Addition of 5–10% ethanol induces a high temperature sphere-to-rod transition of the micelles, which is brought to room temperature upon addition of NaCl. The inference about the change in the shape of the micelles has been drawn from small-angle neutron scattering (SANS) and viscosity studies.     

Micellar effects on aromatic nucleophilic substitution by the ANRORC mechanism. Hydrolysis of 2‐chloro‐3,5‐dinitropyridine

The hydrolysis of 2‐chloro‐3,5‐dinitropyridine by sodium hydroxide in the presence of micelles of cetyltrimethylammonium bromide (CTABr), cetyltrimethylammonium chloride (CTACl) and sodium dodecyl sulfate (SDS) has been studied. The reaction follows a consecutive reaction path involving the formation of a long‐lived intermediate 3 and finally giving the product, 3,5‐dinitro 2‐pyridone 2 . The mechanism follows an addition of the nucleophile, ring opening and ring closure (ANRORC) reaction path. The rate constant was observed to be first‐order dependent on [OH^?]. The rate of reaction increased on increasing [CTABr] and, after reaching to the maxima, it started decreasing. The anionic SDS micelles inhibited the rate of hydrolysis. The results of the kinetic experiments were treated with the help of the pseudophase ion exchange model and the Menger–Portnoy model. The added salts, viz. NaBr, Na‐toluene‐4‐sulphonate, and (CH₃)₄NBr on varying [CTACl] and [SDS] inhibited the rate of reaction. The various kinetic parameters in the presence and absence of salts were determined and are reported herewith. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of Nanoparticles by Scattering Techniques

Basic principles and applications of different scattering techniques (including static and dynamic light scattering (SLS and DLS), small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD) and small-angle neutron scattering (SANS)) on the characterization of nanoparticles are reviewed in this paper. By choosing a suitable scattering technique or a combination of different techniques for nanoparticle characterization, the particles' molecular weight, radius of gyration, hydrodynamic radius, size distribution, shape and internal structure as well as interparticle interactions of nanoparticles, can be determined. Examples including some sophisticated colloidal systems are presented.     

Small-angle light scattering studies of dense AOT-water-decane microemulsions

Summary We have performed extensive studies of a three-component microemulsion system composed of AOT-water-decane (AOT=sodium-bis-ethylhexyl-sulfosuccinate is an ionic surfactant) using small-angle light scattering (SALS). The small-angle scattering intensities are measured in the angular interval 0.001–0.1 radians, corresponding to a Bragg wave number range of 0.14 μm⁻¹<Q<<1.4 μm⁻¹. The measurements were made by changing temperature and volume fraction ϕ of the dispersed phase (water + AOT) in the range 0.05<ϕ<0.75. All samples have a fixed water-to-AOT molar ratio,w=[water]/[AOT]=40.8, in order to keep the same average droplet size in the stable one-phase region. With the SALS technique, we have been able to observe all the phase boundaries of a very complex phase diagram with a percolation line and many structural organizations within it. We observe at the percolation transition threshold, a scaling behavior of the intensity data. This behavior is a consequence of a clustering among microemulsion droplets near the percolation threshold. In addition, we describe in detail a structural transition from a droplet microemulsion to a bicontinuous one as suggested by a recent small-angle neutron scattering experiment. The loci of this transition are located several degrees above the percolation temperatures and are coincident with the maxima previously observed in shear viscosity. From the data analysis, we show that both the percolation phenomenon and this novel structural transition are derived from a large-scale aggregation between microemulsion droplets.     

Small angle neutron scattering and small angle X-ray scattering studies of platinum-loaded carbon foams

The morphology of carbon nanofoam samples comprising platinum nanoparticles dispersed in the matrix was characterized by small angle neutron scattering (SANS) and small angle X-ray scattering (SAXS) techniques. Results show that the structure of pores of carbon matrix exhibits a mass (pore) fractal nature and the average radius of the platinum particles is about 2.5 nm. The fractal dimension as well as the size distribution parameters of platinum particles varies markedly with the platinum content and annealing temperature. Transmission electron micrographs of the samples corroborate the SANS and SAXS results.      

Combined SANS and SAXS study of the action of ultrasound on the structure of amorphous zirconia gels

In the present work, we have studied for the first time the combined effect of both sonication and precipitation pH on the structure of amorphous zirconia gels synthesized from zirconium(IV) propoxide. The techniques of small-angle neutron and X-ray scattering (SANS and SAXS) and low temperature nitrogen adsorption provided the integral data on the changes in the microstructure and mesostructure of these materials caused by ultrasonic (US) treatment. Amorphous ZrO₂·xH₂O synthesized under ultrasonic treatment was found to possess a very structured surface, characterized by the surface fractal dimension 2.9–3.0, compared to 2.3–2.5 for the non US-assisted synthesis, and it was also found to possess a higher specific surface area, while the sizes of the primary particles remain unchanged.     

Contrast variation SANS experiments to the study of detergent-induced micellization of block copolymers

PEO—PPO—PEO triblock copolymer P85 [(EO)₂₆(PO)₃₉(EO)₂₆] dissolves as unimers and detergent sodium dodecyl sulfate (SDS) forms micelles in aqueous solution at 20°C. The mixing of detergent with triblock copolymer induces the micellization of triblock copolymers. Contrast variation small-angle neutron scattering measurements show that triblock copolymer forms mixed micelles with detergent and the mixing of two components in the mixed micelles is uniform.     

Small-angle neutron scattering study of temperature vs. salt dependence of clouding in charged micellar system

Clouding is studied by small-angle neutron scattering (SANS) on a charged micellar system of sodium dodecyl sulphate (SDS) and tetrabutylammonium bromide (TBAB) with varying temperature and salt NaCl. We show that the clouding occurs as a result of increase in the attractive potential between the micelles mediated by the dehydrated TBA(+) counterions on increasing temperature and in the presence of salt. Both micelles and clusters coexist at cloud point temperature (CP) and beyond CP. The addition of salt can be used to obtain CP at room temperature (30° C). The relative effect of different salts on clouding has been found in the order CaCl(2) > MgSO(4) > Na(2)SO(4) > NaF > NaCl > KCl > CsCl > NaBr > NaNO(3). This order is explained on the basis of two important roles played by salt ions: i) counterion condensation that increases the size of the micelles and ii) dehydration of TBA(+) counterions by salt ions for bridging the micelles.     

Small-angle neutron scattering study of aggregate structures of multi-headed pyridinium surfactants in aqueous solution

The aggregate structures of a set of novel single-chain surfactants bearing one, two and three pyridinium headgroups have been studied using small-angle neutron scattering (SANS). It is found that the nature of aggregate structures of these cationic surfactants depend on the number of headgroups present in the surfactants. The single-headed pyridinium surfactant forms the lamellar structure, whereas surfactants with double and triple headgroups form micelles in water. The aggregates shrink in size with increase in the number of headgroups in the surfactants. The aggregation number (N) continually decreases and the fractional charge (α) increases with more number of headgroups on the surfactants. The semimajor axis (a) and semiminor axis (b = c) of the micelle also decrease with the increase in the number of headgroups in the surfactants. This indicates that hydrocarbon chains in such micelles prepared from multiheaded surfactants adopt bent conformation and no longer stay in extended conformation.     

Theory of XMCD spectra at the L2,3 absorption edges of mixed valence Ce and Yb compounds in high magnetic fields

We examine the structure of aggregates formed due to DNA interaction with dipalmitoylphosphatidylcholine (DPPC) in presence of Ca²⁺ and Zn²⁺ using small-angle synchrotron X-ray diffraction (SAXD) and neutron scattering (SANS). SAXD shows structural heterogeneity as a function of the cation concentration and temperature: At low cation concentration (∼1 mM), aggregates show two DPPC phases, one with a lateral segregation of DNA and cation, while higher cation concentration improves the DNA packing and the condensed lamellar phase is observed in DNA+DPPC+20mMion²⁺ aggregates. The SANS detected the dissolution of the condensed lamellar phase into unilamellar DPPC+Zn²⁺ vesicles due to gel ↦ liquid-crystal phase transition in DNA+DPPC+20mM Zn²⁺ aggregates with the short fragmented salmon sperm DNA.     

The distribution of counterions around synthetic rod-like polyelectrolytes in solution

An investigation of the radial distribution of the counterions of a synthetic rodlike polyelectrolyte in aqueous solution is presented. The cationic polyelectrolyte used here has a poly(p-phenylene) backbone. For typical molecular weights the macroion comprises approximately one persistence length (ca. 20 nm) and effects of finite stiffness may be disregarded. Each repeating unit bears four charges which leads to a charge parameter of ξ = 6.65. The distribution of the iodide counterions around this highly charged macroion is studied by small-angle X-ray scattering (SAXS) in dilute aqueous solution. These investigations are supplemented by measurements using anomalous small-angle X-ray scattering (ASAXS) that furnishes additional information about the contrast of the macroion. Data taken at high scattering angles give indication for contributions caused by the longitudinal fluctuations of the counterions. After correction for this effect the experimental results are compared to intensities calculated by use of the Poisson-Boltzmann (PB)-cell model. It is found that the PB-cell model describes the corrected data at intermediate and high scattering angles. Deviations at low scattering angle are attributed to the mutual interaction of the rod-like polyelectrolyte that can be described in terms of an effective structure factor. Data taken at lowest scattering angles point to a weak attraction between the rod-like macroions. Received: 27 July 2001 and Received in final form 27 March 2002     

Atomic and superatomic structures of solid solutions of zirconium and calcium oxides

Solid solutions of the ZrO₂-CaO system with 7, 9.6, and 20 mol % of calcium oxide are analyzed by X-ray and neutron diffraction and small-angle neutron scattering. Samples are synthesized by the sol-gel method and annealed at the temperature T = 600°C for 4 h. All samples have a tetragonal structure (P4₂/nmc space group). The size of crystallites is 10–20 nm. Small-angle neutron scattering curves are characterized by a peak near the momentum transfer q = 0.5 nm⁻¹. The existence of the peak is caused by correlation between solid nanoparticles in the samples. Density correlation functions are numerically computed from the experimental small-angle scattering cross-sections by the inverse Fourier transform. Correlation lengths, concentrations of scattering nanoparticles, and specific surface areas of the samples are determined.     

Structural investigation of viscoelastic micellar water/CTAB/NaNO<Subscript>3</Subscript> solutions

A highly viscoelastic worm-like micellar solution is formed in hexadecyltrimethylammonium bromide (CTAB) in the presence of sodium nitrate (NaNO₃). A gradual increase in micellar length with increasing NaNO₃ was assumed from the rheological measurements where the zero-shear viscosity (η ₀) versus NaNO₃ concentration curve exhibits a maximum. However, upon increase in temperature, the viscosity decreases. Changes in the structural parameters of the micelles with addition of NaNO₃ were inferred from small angle neutron scattering measurements (SANS). The intensity of scattered neutrons in the low q region was found to increase with increasing NaNO₃ concentration. This suggests an increase in the size of the micelles and/or decrease of intermicellar interaction with increasing salt concentration. Analysis of the SANS data using prolate ellipsoidal structure and Yukawa form of interaction potential between micelles indicate that addition of NaNO₃ leads to a decrease in the surface charge of the ellipsoidal micelles which induces micellar growth. Cryo-TEM measurements support the presence of thread-like micelles in CTAB and NaNO₃.      

Small-angle neutron scattering studies of sodium butyl benzene sulfonate aggregates in aqueous solution

The aggregation behaviour of a hydrotrope, sodiumn-butyl benzene sulfonate (Na-NBBS), in aqueous solutions is investigated by small-angle neutron scattering (SANS). Nearly ellipsoidal aggregates of Na-NBBS at concentrations well above its minimum hydrotrope concentration were detected by SANS. The hydrotrope seems to form self-assemblies with aggregation number of 36–40 with a substantial charge on the aggregate. This aggregation number is weakly affected by the hydrotrope concentration.     

Temperature variation of the Debye-Waller factors of metal and halide ions in CsCl and CsBr powders by X-ray diffraction. II. Debye-Waller factors of Cs+ and Br− ions in CsBr from room temperature to 78.2°K

The temperature variation of the Debye-Waller factors of Cs⁺ and Br⁻ ions in CsBr powder has been studied using powder X-ray diffraction. The integrated intensities of the Bragg peaks at different temperatures have been obtained. These results have been verified by structure factor least squares refinement program. Theoretical shell model lattice dynamical calculations have been done using a 7-parameter model in the harmonic approximation and the values compared with the present X-ray measurements. The observed intensities have been corrected for first order thermal diffuse scattering.     

Studies on pore morphology of titanium and its oxide by small angle neutron scattering

Titanium metal bodies have been prepared from the sintered powder compacts of TiO₂ by a novel molten salt electrochemical approach, known as FFC Cambridge process. The phase and compositional characterizations of both Ti and TiO₂ have been carried out by X-ray diffraction. The pore morphologies of sintered TiO₂ pellet and the metallic Ti pellet, obtained after electrochemical reduction have been studied by SANS over a scattering wave vector q range of 0.003–3.5 nm⁻¹ using a double crystal diffractometer and a pin-hole collimated SANS instrument. In the case of reduced metal pellet, average pore size was found to be larger than that of the oxide pellet as the voids left behind after the oxygen atoms left the oxide matrix, could not coalesce.      

Macroscopic and microscopic structural integrity in magnetic colloids—cationic micellar solution: Rheology, SANS and magneto-optical study

A stable mixture of two colloid system composed of double surfactant coated aqueous nanomagnetic fluid and aqueous micellar solution of cationic micelles of cetyletrymethyl ammonium bromide (CTABr) is prepared as a function of nanomagnetic fluid concentration. This mixed system is analyzed using three techniques such as zero field and field induced viscosity measurements, Small Angle Neutron Scattering technique and magneto-optical birefringence measurements. In field induced viscosity measurement it is observed that even 20% magnetic fluid concentration in CTABr aqueous solution shows 75% increase in viscosity compared to pure magnetic fluid. This suggests that in presence of CTABr micelles, a novel magneto rheological effect for low concentration of magnetic fluid is observed. From SANS measurements it is observed that aggregation number and a/b ratio increases with magnetic fluid concentration and magnetic birefringence reveals non-superimpose behavior of normalized field induced retardation. Results of these experiments are compared and indicate zero fields and field induced structural integrity between magnetic particles and soft micelles.     

Temperature dependent small-angle neutron scattering of CTABr—magnetic fluid emulsion

Small-angle neutron scattering studies have been carried out to check the structural integrity of citryltrimethylammonium bromide (CTABr) micelles in a magnetic fluid for different magnetic fluid concentrations at two different temperatures 303 and 333 K. It is found that the CTABr micelles grow with increasing magnetic fluid concentration and there is a decrease in the micellar size with increase in temperature.     

Shrinking of anionic polyacrylate coils induced by Ca2+, Sr2+ and Ba2+: A combined light scattering and ASAXS study

Anionic polyacrylate chains (NaPA) form precipitates if alkaline earth cations are added in stoichiometric amounts. Accordingly, precipitation thresholds were established for three different alkaline earth cations Ca²⁺, Sr²⁺ and Ba²⁺. Close to the precipitation threshold, the NaPA chains significantly decrease in size. This shrinking process was followed by means of combined static and dynamic light scattering. Intermediates were generated by varying the ratio [MCl₂]/[NaPA] with M denoting the respective alkaline earth cation. All experiments were performed at an inert salt level of 0.01M NaCl. Similar coil-to-sphere transitions could be observed with all three alkaline earth cations Ca²⁺, Sr²⁺ and Ba²⁺. Based on these findings, supplementary conventional and anomalous small-angle X-ray scattering experiments using selected intermediates close to the precipitation threshold of SrPA were performed. The distribution of Sr counterions around the polyacrylate chains in aqueous solution provided the desired scattering contrast. Energy-dependent scattering experiments enabled successful separation of the pure-resonant terms, which solely stem from the counterions. The Sr²⁺ scattering roughly reflects the monomer distribution of the polyacrylate chains. Different ratios of the concentrations of [ SrCl₂]/[NaPA] revealed dramatic changes in the scattering curves. The scattering curve at the lowest ratio indicated an almost coil-like behaviour, while at the higher ratios the scattering curves supported the model of highly contracted polymer chains. Most of X-ray scattering experiments on intermediate states revealed compact structural elements which were significantly smaller than the respective overall size of the NaPA particles.