In this thesis, geometry is used as a basis for conducting experiments aimed at growing
and arranging inorganic minerals on curved interfaces. Mineralisation is directed using
crystalline and liquid-crystalline metallic soaps and surfactant/water systems as
templates.¶
A review of the history, syntheses, structure and liquid crystallinity of metallic soaps
and other amphiphiles is presented as a foundation to understanding the interfacial
architectures in mesostructured template systems in general.¶
In this study, a range of metallic soaps of varying chain length and cation type are
synthesised and characterised to find potentially useful templates for mineral growth.
These include alkaline-earth, transition metal, heavy metal and lanthanide soaps. These
are systematically characterised using a variety of analytical techniques, including
chemical analyses, x-ray diffraction (XRD) infrared spectroscopy (IR) and differential
scanning calorimetry (DSC). Their molecular and crystal structures are studied using
transmission electron microscopy (TEM), cryo-TEM, electron diffraction (ED), electron
paramagnetic spin resonance (EPR), absorption spectroscopy (UV-VIS), high resolution
laser spectroscopy, atomic force microscopy (AFM), nuclear magnetic resonance
spectroscopy, scanning electron microscopy (SEM), electron dispersive x-ray analysis
(EDXA), thermal gravimetric analysis (TGA) and magnetic measurements. Models for
the molecular and crystal structures of metallic soaps are proposed. The soaps are
predominantly lamellar crystalline or liquid crystalline lamellar rotor phases with tilted
and/or untilted molecular constituents. These display evidence of varying degrees of
headgroup organisation, including superstructuring and polymerisation. A single crystal
structure is presented for a complex of pyridine with cobalt soap. Simple models for
their structure are discussed in terms of their swelling properties in water and oils.
Experiments are also presented to demonstrate the sorbent properties of aluminium
soaps on oil spills.¶
The thermotropic liquid crystallinity of alkaline earth, transition metal, heavy metal and
lanthanide soaps is investigated in detail. This is done to assess their suitability as
templates, and to document their novel thermotropic behaviour, particularly the
relatively unknown lanthanide soaps. Liquid crystalline behaviours are studied using
high-temperature XRD (HTXRD), hot-stage optical microscopy and DSC. Models for a
liquid crystalline phase progression from crystals to anisotropic liquids are discussed in
terms of theories of self-assembly and interfacial curvature. The terminology required
for this is drawn from various nomenclature systems for amphiphilic crystals and liquid
crystals. General agreement with previous studies is reported for known soaps, while
liquid crystallinity is demonstrated in the lanthanide and some non-lanthanide soaps for
the first time. A general phase progression of crystalline lamellar through liquid
crystalline lamellar to non-lamellar liquid crystalline is discussed in terms of models
concerned with the molecular and crystal structures of the soaps and their phase
transitions via headgroup and chain re-arrangements.¶
Experiments aimed at guiding growth of metal sulfides using metallic soaps as
templates are described, and a model for this growth is discussed. Metal sulfides have
been successfully grown by reacting crystalline and liquid crystalline transition metal
and heavy metal soaps with H2S gas at room temperature and at elevated temperature.
These have been characterised using XRD, TEM, ED and IR. Sulfide growth is
demonstrated to be restricted and guided by the reacting soap template architecture.
Zinc, cadmium, indium and lead soaps formed confined nanoparticles within the matrix
of their reacting soap template. In contrast, curved and flat sheet-like structures, some
resembling sponges were found in the products of sulfided iron, cobalt, nickel, copper,
tin and bismuth soaps. A model to explain this behaviour is developed in terms of the
crystal and liquid crystal structures of the soaps and the crystal structures of the metal
sulfide particles.¶
Liquid crystalline iron soaps have been subjected to controlled thermal degradation
yielding magnetic iron oxide nanoparticles. Some XRD and TEM evidence has been
found for formation of magnetic mesostructures in heat-treated iron soaps. Models for
the molecular and liquid crystalline structure of iron soaps, their thermotropic phase
progression and eventual conversion to these magnetic products are discussed.
Systematic syntheses of mesoporous silicates from sheeted clays are discussed.¶The
templates that have been used are cationic surfactants and small, organic molecular
salts. Experiments are reported where a cooperative self-assembly of
surfactant/water/kanemite plus or minus salt and oils yields 'folded sheet materials'
(FSM'S). Templating of kanemite has also been achieved using cobalt cage surfactants.
A theoretical prediction of the specific surface areas and specific volumes of
homologous sets of FSM's gave excellent agreement with measured values. The
geometry and topology of the mesostructures are discussed. A theoretical model is also
discussed regarding the curvature found in the sheets of natural clays , and results of
templating clays and silica using metallic soaps are presented. Experiments and a model for low temperature nucleation and growth of microporous silicalite-1 are described in
terms of silica templating by water clathrates.¶
Finally, the problem of finding minimal surface descriptions of crystal networks is
addressed. Combinatoric methods are used to disprove the existence of possible
embeddings of type I and II clathrate networks in non-self intersecting periodic minimal
surfaces. The crystal network of the clathrate silicate, melanophlogite is successfully
embedded in the WI-10 self-intersecting surface. Details of a previously unreported,
genus-25 periodic surface with symmetry Im3m are discussed.
| Identifer | oai:union.ndltd.org:ADTP/216867 |
| Date | January 1998 |
| Creators | Corkery, Robert, robert.corkery@anu.edu.au |
| Publisher | The Australian National University. Research School of Physical Sciences and Engineering |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | http://www.anu.edu.au/legal/copyrit.html), Copyright Robert Corkery |
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