Kenneth D. Knudsen

Carbon nanocones: wall structure and morphology

Abstract Large-scale production of conical carbon nanostructures is possible through pyrolysis of hydrocarbons in a plasma torch process. The resulting carbon cones occur in five distinctly different forms, and disc-shaped particles are produced as well. The structure and properties of these carbon cones and discs have been relatively little explored until now. Here we characterize the structure of these particles using transmission electron microscopy, synchrotron x-ray and electron diffraction. The carbon nanocones are found to exhibit several interesting structural features; instead of having a uniform cross-section, the walls consist of a relatively thin inner graphite-like layer with a non-crystalline envelope, where the amount of the latter can be modified significantly by annealing. The cones appear with a well-defined faceting along the cone edge, demonstrating strict long-range atomic ordering; they also present occasional examples of symmetry breaking, such as two apexes appearing in the same carbon nanocone.

The charge density of urea from synchrotron diffraction data.

The charge density of urea is studied using very high precision single-crystal synchrotron-radiation diffraction data collected at the Swiss-Norwegian Beam Lines at ESRF. An unprecedented resolution of 1.44 A(-1) in sin theta;/lambda is obtained at 123 K. The optimization of the experiment for charge-density studies is discussed. The high precision of the data allowed the refinement of a multipole model extending to hexadecapoles and quadrupoles on the heavy and H atoms, respectively, as well as a liberal treatment of radial functions. The topological properties of the resulting electron density are analysed and compared with earlier experimental results as well as with periodic Hartree-Fock calculations. The properties of the strongly polarized C-O bond agree with trends derived from previous experimental results while the ab initio calculations differ significantly. The results indicate that the description of the C-O bond requires more flexible basis sets in the theoretical calculations. The calculated integrated atomic charges are much larger than the observed ones. It is suggested that the present experimental results provide new target values for validation of future ab initio calculations. The molecular dipole moment derived from the integrated atomic properties is the same as the one obtained from the multipole model even though the individual atomic contributions differ. Comparison with literature data for urea in solution and the gas phase yields a dipole enhancement in the solid of about 1.5 D. The thermal expansion of urea is determined using synchrotron powder diffraction data. With decreasing temperature, an increasing anisotropic strain is observed.

Effects of temperature and pH on the contraction and aggregation of microgels in aqueous suspensions.

Chemically cross-linked poly(N-isopropylacrylamide) (PNIPAM) microgels and PNIPAM with different amounts of acrylic acid groups (PNIPAM-co-PAA) were synthesized and the temperature-induced aggregation behaviors of aqueous suspensions of these microgels were investigated mainly with the aid of dynamic light scattering (DLS) and turbidimetry. The DLS results show that the particles at all conditions shrink at temperatures up to approximately the lower critical solution temperature (LCST), but the relative contraction effect is larger for the microgels without acid groups or for microgels with added anionic surfactant (SDS). A significant depression of the cloud point is found in suspensions of PNIPAM with very low concentrations of SDS. The compression of the microgels cannot be traced from the turbidity results, but rather the values of the turbidity increase in this temperature interval. This phenomenon is discussed in the framework of a theoretical model. At temperatures above LCST, the size of the microgels without attached charged groups in a very dilute suspension is unaffected by temperature, while the charged particles (pH 7 and 11) continue to collapse with increasing temperature over the entire domain. In this temperature range, low-charged particles of higher concentration and particles containing acrylic acid groups at low pH (pH 2) aggregate, and macroscopic phase separation is approached at higher temperatures. This study demonstrates how the stabilization of microgels can be affected by factors such as polymer concentration, addition of ionic surfactant to particles without charged acid groups, amount of charged groups in the polymer, and pH.

The isotropic-nematic interface in suspensions of Na-fluorohectorite synthetic clay.

Colloidal suspensions of Na-fluorohectorite synthetic clay platelets in saline water exhibit coexisting isotropic and nematic phases, due to gravitational separation of the polydisperse particles. We study the ordering of the platelets at the interfaces between various coexisting phases. Four different experimental techniques are employed: visual observation of birefringence, synchrotron wide angle and small-angle X-ray scattering, and magnetic resonance imaging. We find that at the narrow isotropic sol-nematic sol interface the platelets are lying horizontally, i.e. with their mean platelet normal along the vertical direction. The experiments indicate that the platelets align homeotropically both at the isotropic sol-nematic sol interface and at the nematic sol-wall interface. We further investigate the complex alignment effect of a horizontally applied magnetic field in the nematic sol, and we compare it with the adjacent nematic gel.

Intercalation-enhanced electric polarization and chain formation of nano-layered particles

Microscopy observations show that suspensions of synthetic and natural nano-layered smectite clay particles submitted to a strong external electric field undergo a fast and extended structuring. This structuring results from the interaction between induced electric dipoles, and is only possible for particles with suitable polarization properties. Smectite clay colloids are observed to be particularly suitable, in contrast to similar suspensions of a non-swelling clay. Synchrotron X-ray scattering experiments provide the orientation distributions for the particles. These distributions are understood in terms of competing i) homogenizing entropy and ii) interaction between the particles and the local electric field; they show that clay particles polarize along their silica sheet. Furthermore, a change in the platelet separation inside nano-layered particles occurs under application of the electric field, indicating that intercalated ions and water molecules play a role in their electric polarization. The resulting induced dipole is structurally attached to the particle, and this causes particles to reorient and interact, resulting in the observed macroscopic structuring. The macroscopic properties of these electro-rheological smectite suspensions may be tuned by controlling the nature and quantity of the intercalated species, at the nanoscale.

Rheological and structural aspects on association of hydrophobically modified polysaccharides

This review covers recent rheological and structural advances in the interactions between hydrophobically modified polysaccharides (HMP) and surfactants or cyclodextrin compounds in aqueous media. Depending on the surfactant concentration, mixtures of HMPs and a surfactant can form strong associating complexes or disrupted networks at high levels of surfactant addition. By adding cyclodextrin monomers to semidilute solutions of HMPs, the hydrophobic interactions can be deactivated and a looser network is formed. For HMPs in the presence of cyclodextrin polymers, network structures with intriguing morphological and rheological features can be constructed. These complex fluids are of potential interest in the development of systems for drug delivery formulations. These rheology modifiers are also of current interest in many other technological applications.

Structuring from nanoparticles in oil-based ferrofluids

Abstract.The effect of magnetic field on the structure formation in an oil-based magnetic fluid with various concentrations of magnetite particles was studied. The evaluation of the experimental data obtained from small-angle X-ray scattering and ultrasonic attenuation indicates the formation of chain-like aggregates composed of magnetite particles. The experimental data obtained from ultrasonic spectroscopy fit well with the recent theoretical model by Shliomis, Mond and Morozov but only for a diluted magnetic fluid. In this model it is assumed that a dimer is the main building block of a B -field-induced chain-like structure, thus the estimation of the nematic order parameter does not depend on the actual length of the structure. The scattering method used reveals information about the aggregated structure size and relative changes in the degree of anisotropy in qualitative terms. The coupling constant

Characterization of temperature-induced association in aqueous solutions of charged ABCBA-type pentablock tercopolymers

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Guided self-assembly of nanostructured titanium oxide

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Characterization of polyelectrolyte features in polysaccharide systems and mucin.

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