Adhesion Behaviour of Organically-Modified Silicate Coatings on Stainless Steel

The mechanical properties of organically modified silicate coatings on stainless steel substrates were investigated, using nano-indentation and simultaneous in situ microtensile testing/optical microscopy. The load-displacement response and fracture behaviour is examined to ascertain the effects of different organic groups on the film properties and adhesion characteristics. The relationship between the morphology and mechanical properties of the films is discussed, and it is demonstrated that the mechanical response of the coatings is significantly influenced by the nature of the organic group attached to the ormocer precursor.     

The activation of MgCl2-supported ziegler-natta catalysts: A structural investigation

A mathematical procedure for the investigation of the lattice disorder by stacking faults in polycrystalline solids has been used in studying samples of MgCl₂ activated by ball milling for various times in the presence of TiCl₄. These samples have been investigated by X-ray diffraction and by measurements of surface area, crystallite dimensions, Ti content after washing and catalytic activity in the polymerization of ethylene.A good relationship has been confirmed between activation time and activity; furthermore, the structural variations introduced by ball milling are mainly associated with rotational disorder of the Cl-Mg-Cl triple layers. Nevertheless, the analysis by X-ray diffraction is not unequivocal about the relationships between structure and activity: other significant parameters, such as the surface area and the porosity, are probably very important.     

Ceramic Micro-Particles Synthesised using Emulsion and Sol–Gel Technology: An Investigation into the Controlled Release of Encapsulants and the Tailoring of Micro-Particle Size

Controlled release technologies have many applications in such diverse fields as the pharmaceutical, agricultural, cosmetic and food industries, where tailored release rates and protection of the active molecule for delivery at a specific site or time are advantageous. Silica microspheres, with controlled diameters of 10–50 m and containing Orange II dye as a model encapsulant, have been synthesised by combining water-in-oil (w/o) emulsion technology with sol–gel chemistry. The average particle size may be controlled by the microemulsion parameters, including the surfactant and solvent concentrations, and by the sol–gel processing parameters, particularly water-to-silicon alkoxide ratio, pH, temperature, ageing and mixing conditions. Physical properties of the SiO₂ microspheres, which modulate the release rates of the encapsulated molecule (including pore size and tortuosity), are also controlled by the sol–gel process parameters.The effect of synthesis parameters, including surfactant concentration, sol–gel solution pH and drying temperature, on the morphology of the SiO₂ microspheres produced will be discussed. The effect of such parameters on the corresponding release rates of the model encapsulants will also be presented.     

A Mild Method for the Preparation of 1,3,4-Oxadiazoles: Triflic Anhydride Promoted Cyclization of Diacylhydrazines

Diacylhydrazines undergo cyclization upon treatment with triflic anhydride and pyridine to form the corresponding 1,3,4-oxadiazoles in yields ranging from 70--95%.     

Cellular automata, quasigroups and symmetries

Summary. We investigate cellular automata (CA) with a local rule f: G² ? G \phi : G^2 \rightarrow G , where the local rule defines a quasigroup structure (Latin square) on the finite set G. If the quasigroup is semisymmetric or totally symmetric, some top-down equilateral triangular subsets of the CA-orbits, the so-called \triangledown \triangledown -configurations, exhibit certain symmetries. The most interesting symmetries are the rotational and the total (dihedral) symmetries, which may be considered in conjunction with certain automorphisms.¶We first explore the conditions for quasigroups to be symmetric (or for local CA-rules to allow symmetric \triangledown \triangledown -configurations), and how to construct symmetric quasigroups by prolongation, i.e., by steadily increasing the order of the quasigroup, thereby conserving the symmetry. Then we study rotationally or totally symmetric \triangledown \triangledown -configurations. We begin with the existence of symmetric \triangledown \triangledown -configurations of arbitrary size N and N o 0,1 mod 3 N \equiv 0,1\,{\rm mod}\,3 , and show that symmetric \triangledown \triangledown -configurations of size N o 2 mod 3 N \equiv 2\,{\rm mod}\,3 exist under mild conditions on J. We present explicit formulas for the number of distinct symmetric \triangledown \triangledown -configurations. By studying the combined group action of the dihedral (or rotational) group and the automorphism group of the quasigroup G on the \triangledown \triangledown -configurations of size N, we are able to classify and count the number of different equivalence classes of \triangledown \triangledown -configurations.     

Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry

Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd.     

Cracking and Decohesion of Sol-Gel Hybrid Coatings on Metallic Substrates

Thin film coatings based on organically modified silanes were synthesized using sol-gel technology. Various mixtures of tetraethoxysilane and glycidoxypropyltrimethoxysilane precursors were used to produce sol-gel coatings on as-received and thermally oxidised copper, aluminium and titanium substrates. The mechanical properties and adhesion behaviour of the coatings were assessed using nano-indentation and microtensile testing, respectively. The relationship between the film structure and its mechanical response is examined. It is shown that the mechanical properties (hardness and Young's modulus) of the coatings are influenced dramatically by the organic substituent and the presence of an oxide layer thermally grown on the substrate material prior to deposition plays an important role on the film/substrate adhesion behaviour.     

Structural studies on some iron 8-oxi-quinolinates using Mössbauer spectroscopy

Using Mössbauer spectroscopy the quinolinates of iron/II/ and iron/III/ have been studied. In iron/II/ quinolinate three sublattices were evidenced, two of them being attributed to Fe²⁺ ions and the third to Fe³⁺ impurities. In the iron/III/ quinolinate five structural sublattices were found, two of them containing Fe³⁺ ions, the other two Fe²⁺ ions and the fifth may be attributed to the interstitial Fe³⁺ ions.