The tribology of linear tape recording systems

This thesis is devoted to the tribology at the head~to~tape interface of linear tape recording systems, OnStream ADRTM system being used as an experimental platform, Combining experimental characterisation with computer modelling, a comprehensive picture of the mechanisms involved in a tape recording system is drawn. The work is designed to isolate the mechanisms responsible for the physical spacing between head and tape with the aim of minimising spacing losses and errors and optimising signal output. Standard heads-used in ADR current products-and prototype heads- DLC and SPL coated and dummy heads built from a AI203-TiC and alternative single-phase ceramics intended to constitute the head tape-bearing surface-are tested in controlled environment for up to 500 hours (exceptionally 1000 hours), Evidences of wear on the standard head are mainly observable as a preferential wear of the TiC phase of the AI203-TiC ceramic, The TiC grains are believed to delaminate due to a fatigue wear mechanism, a hypothesis further confirmed via modelling, locating the maximum von Mises equivalent stress at a depth equivalent to the TiC recession (20 to 30 nm). Debris of TiC delaminated residues is moreover found trapped within the pole-tip recession, assumed therefore to provide three~body abrasive particles, thus increasing the pole-tip recession. Iron rich stain is found over the cycled standard head surface (preferentially over the pole-tip and to a lesser extent over the TiC grains) at any environment condition except high temperature/humidity, where mainly organic stain was apparent, Temperature (locally or globally) affects staining rate and aspect; stain transfer is generally promoted at high temperature. Humidity affects transfer rate and quantity; low humidity produces, thinner stains at higher rate. Stain generally targets preferentially head materials with high electrical conductivity, i.e. Permalloy and TiC. Stains are found to decrease the friction at the head-to-tape interface, delay the TiC recession hollow-out and act as a protective soft coating reducing the pole-tip recession. This is obviously at the expense of an additional spacing at the head-to-tape interface of the order of 20 nm. Two kinds of wear resistant coating are tested: diamond like carbon (DLC) and superprotective layer (SPL), 10 nm and 20 to 40 nm thick, respectively. DLC coating disappears within 100 hours due possibly to abrasive and fatigue wear. SPL coatings are generally more resistant, particularly at high temperature and low humidity, possibly in relation with stain transfer. 20 nm coatings are found to rely on the substrate wear behaviour whereas 40 nm coatings are found to rely on the adhesive strength at the coating/substrate interface. These observations seem to locate the wear-driving forces 40 nm below the surface, hence indicate that for coatings in the 10 nm thickness range-· i,e. compatible with high-density recording-the substrate resistance must be taken into account. Single-phase ceramic as candidate for wear-resistant tape-bearing surface are tested in form of full-contour dummy-heads. The absence of a second phase eliminates the preferential wear observed at the AI203-TiC surface; very low wear rates and no evidence of brittle fracture are observed.

Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

The geochemistry of radioactive waste disposal

The present study attempted to identify the significant parameters which affect radionuclide migration from a low level radioactive waste disposal site located in a clay deposit. From initial sorption studies on smectite minerals, increased Kd with decreasing initial cation concentration was observed, and three sorption mechanisms were identified. The observation of anion dependent sorption was related to the existence of a mechanism in which an anion-cation pair are bound to the clay surface through the anion. The influence of competing cations, typical of inorganic groundwater constituents, depended on: (1) Ni/Co:Mn+(Mn+ = competing cation) ratio, (2) nature of M^n+, (3) total solution ionic strength. The presence of organic material in groundwater is well documented, but its effect on cation sorption has not been established. An initial qualitative investigation involving addition of simple organic ligands to Ni(Co)-hectorite samples demonstrated the formation of metal complexes in the clay interlayers, although some modified behaviour was observed. Further quantitative examination involving likely groundwater organic constituents and more comprehensive physical investigation confirmed this behaviour and enabled separation of the organic compounds used into two classes, according to their effect on cation sorption; (i) acids, (ii) amine compounds. X-ray photoelectron spectroscopy, scanning electron microscopy and Mossbauer spectroscopy were used to investigate the nature of transition metal ions sorbed onto montmorillonite and hectorite. Evidence strongly favoured the sorption of the hexaaquo cation, although a series of sorption sites of slightly different chemical characteristics were responsible for broadened peak widths observed in XPS and Mossbauer investigations. The surface sensitivity of XPS enabled recognition of the two surface sorption sites proposed in earlier sorption studies. Although thermal treatment of Fe^3+/Fe^2+-hectorite samples left iron atoms bonded to the silicate sheet structure, Mossbauer evidence indicated the presence of both ferric and ferrous iron in all samples.

Interlamellar modification of smectite clays

Clay minerals, both natural and synthetic, have a wide range of applications. Smectite clays are not true insulators, their slight conductivity has been utilized by the paper industry in the development of mildly conducting paper. In particular, the synthetic hectorite clay, laponite, is employed to produce paper which is used in automated drawing offices where electro graphic printing is common. The primary objective of this thesis was to modify smectite clays, particularly laponite, to achieve enhanced conductivity. The primary objective was more readily achieved if the subsidiary objective of understanding the mechanism of conductivity was defined. The cyclic voltammograms of some cobalt complexes were studied in free solution and as clay modified electrodes to investigate the origin of electroactivity in clay modified electrodes. The electroactivity of clay modified electrodes prepared using our method can be attributed to ion pairs sorbed to the surface of the electrode, in excess of the cationic exchange capacity. However, some new observations were made concerning the co-ordination chemistry of the tri-2-pyridylamine complexes used which needed clarification. The a.c. conductivity of pressed discs of laponite RD was studied over the frequency range 12Hz- 100kHz using three electrode systems namely silver-loaded epoxy resin (paste), stainless-steel and aluminium. The a. c. conductivity of laponite consists of two components, reactive (minor) and ionic (major) which can be observed almost independently by utilizing the different electrode systems. When the temperature is increased the conductivity of laponite increases and the activation energy for conductivity can be calculated. Measurement of the conductivity of thin films of laponite RD in two crystal planes shows a degree of anisotropy in the a.c. conductivity. Powder X-ray diffraction and 119Sn Mossbauer spectroscopy studies have shown that attempts to intercalate some phenyltin compounds into laponite RD under ambient conditions result in the formation of tin(IV) oxide pillars. 119Sn Mossbauer data indicate that the order of effectiveness of conversion to pillars is in the order: Ph3SnCl > (Ph3Sn)2O, Ph2SnCl2 The organic product of the pillaring process was identified by 13C m.a.s.n.m.r. spectroscopy as trapped in the pillared lattice. This pillaring reaction is much more rapid when carried out in Teflon containers in a simple domestic microwave oven. These pillared clays are novel materials since the pillaring is achieved via neutral precursors rather than sacrificial reaction of the exchangeable cation. The pillaring reaction depends on electrophilic attack on the aryl tin bond by Brønsted acid sites within the clay. Two methods of interlamellar modification were identified which lead to enhanced conductivity of laponite, namely ion exchange and tin(IV) oxide pillaring. A monoionic potassium exchanged laponite shows a four fold increase in a.c. conductivity compared to sodium exchanged laponite RD. The increased conductivity is due to the appearence of an ionic component. The conductivity is independent of relative humidity and increases with temperature. Tin(IV) oxide pillared laponite RD samples show a significant increase in conductivity. Samples prepared from Ph2SnCl2 show an increase in excess of an order of magnitude. The conductivity of tin(IV) oxide pillared laponite samples is dominated by an ionic component.

Organometallic precursors for pillared clay synthesis

The synthetic hectorite, laponite has been used within the paper industry to produce mildly conducting paper for use in electrographic printing. The aim of this research was to modify laponite in order to improve the electrical conductivity. In a continuation of a previous investigation involving organotin intercalation of laponite, the organotin precursor (p-CH3,OC6H4)4Sn was synthesised and characterised using Mass Spectroscopy, Infrared Spectroscopy and elemental analysis. Results of intercalation with this compound and a range of organobismuth and organoantimony compounds suggested that a halide content within the precursor was necessary for improvement in conductivity to be observed. Organometallic intercalation of a range of organotellurium compounds with laponite provided evidence that a hydrolysis reaction on the clay surface followed by the release of hydrochloric acid was an important first step if a reaction was to occur with the clay. Atomic Absorption Spectroscopy studies have shown that the acid protons underwent exchange with the interlayer sodium ions in the clay to varying degrees. Gas-liquid Chromatography and Infrared Spectroscopy revealed that the carbon-tellurium bond remained intact. Powder X-ray diffraction revealed that there had been no increase in the basal spacing. The a.c. conductivity of the modified clays in the form of pressed discs was studied over a frequency range of 12Hz - 100kHz using two electrode systems, silver paste and stainless steel. The a.c. conductivity consists of two components, ionic and reactive. The conductivity of laponite was increased by intercalation with organometallic compounds. The most impressive increase was gained using the organotellurium precursor (p-CH3OC6H4)2TeCl2. Conductivity investigations using the stainless steel electrode where measurements are made under pressure showed that in the case of laponite, where poor particle-particle contact exists at ambient pressure, there is a two order of magnitude increase in the measured a.c. conductivity. This significant increase was not seen in modified laponites where the particle-particle contact had already been improved upon. Investigations of the clay surface using Scanning Electron Microscopy suggested that the improvement in particle-particle contact is the largest factor in the determination of the conductivity. The other important factor is the nature and the concentration of the interlayer cations. A range of clays were synthesised in order to increase the concentration of sodium interlayer cations. A sol-gel method was employed to carry out these syntheses. A conductivity evaluation showed that increasing the concentration of the sodium cations within the clay led to an increase in the conductivity.

Studies of clay minerals and their decomposition products

Mõssbauer spectroscopy and X-ray diffraction of five coals revealed the presence of pyrite, illite, kaolinite and Quartz, together with other minor phases. Analysis of the coal ashes indicated the formation of hematite and an Fe (3+) paramagnetic phase, the latter resulting from .the dehydroxylation of the clay minerals during ashing at 700 to 750 C. By using a combination of several physicochemical methods, different successive stages of dehydroxylation, structural consolidation, and recrystallisation of illite, montmorillonite and hectorite upon thermal treatment to 1300 C were investigated. Dehydroxylation of the clay minerals occurred between 450 and 750 C, the X-ray crysdallinity of illite and montmorillonite remaining until 800 C. Hectorite gradually recrystallises to enstatite at temperatures above 700°C. At 900 C the crystalline structure of all three clay minerals had totally collapsed. Solid state reactions occurred above 900 C producing such phases as spinel, hematite, enstatite, cristobalite and mullite. Illite and montmorillonite started to melt between 1200 and 1300°C, producing a silicate glass that contained Fe(3+) and Fe(2+) ions. Ortho-pnstatite, clino-enstatite and proto-enstatite were identified in the thermal products of hectorite, their relative proportions varying with temperature. Protoenstatite was stabilised with respect to metastable clinoenstatite upon cooling from 12000 C by the presence of exchanged transition metal cations. Solid state Nuclear Magnetic Resonance spectroscopy of thermally treated transition metal exchanged hectorite indicated the levels at which paramagnetic cations could be loaded on to the clay before spectral resolution is significantly diminished.