Structure of liquid and glassy ZnCl2

The method of isotope substitution in neutron diffraction was used to measure the structure of liquid ZnCl2 at 332(5)?°C and glassy ZnCl2 at 25(1)?°C. The partial structure factors were obtained from the measured diffraction patterns by using the method of singular value decomposition and by using the reverse Monte Carlo procedure. The partial structure factors reproduce the diffraction patterns measured by high-energy x-ray diffraction once a correction for the resolution function of the neutron diffractometer has been made. The results show that the predominant structural motif in both phases is the corner sharing ZnCl4 tetrahedron and that there is a small number of edge-sharing configurations, these being more abundant in the liquid. The tetrahedra organize on an intermediate length scale to give a first sharp diffraction peak in the measured diffraction patterns at a scattering vector kFSDP?1 Å-1 that is most prominent for the Zn-Zn correlations. The results support the notion that the relative fragility of tetrahedral glass forming MX2 liquids is related to the occurrence of edge-sharing units.

Sonically induced narrowing of the NMR spectra of solids and other novel NMR techniques

A typical liquid state NMR spectrum is composed of a number of discrete absorptions which can be readily interpreted to yield detailed information about the chemical environment of the nuclei found within the sample. The same cannot be said about the spectra of solid samples. For these the absorptions are typically broad, featureless and yield little information directly. This situation may be further exacerbated by the characteristically long T1 values of nuclei bound within a solid lattice which, consequently, require long inter-sequence delays that necessitate lengthy experiments. This work attempts to address both of these inherent problems. Classically, the resolution of the broad-line spectra of solids into discrete resonances has been achieved by imparting to the sample coherent rotation about specific axes in relation to the polarising magnetic field, as implemented in the magic-angle spinning (MAS) [1], dynamic angle spinning (DAS) [2] and double rotation (DOR) [3] NMR experiments. Recently, an alternative method, sonically induced narrowing of the NMR spectra of solids (SINNMR) [4], has been reported which yields the same well resolved solid-state spectra as the classic solid-state NMR experiments, but which achieves the resolution of the broad-line spectra through the promotion of incoherent motion in a suspension of solid particles. The first part of this work examines SINNMR and, in particular, concentrates on ultrasonically induced evaluation, a phenomenon which is thought to be essential to the incoherent averaging mechanism. The second part of this work extends the principle of incoherent motion, implicit in SINNMR, to a new genre of particulate systems, air fluidized beds, and examines the feasibility of such systems to provide well resolved solid state NMR spectra. Samples of trisodium phosphate dodecahydrate and of aluminium granules are examined using the new method with partially resolved spectra being reported in the case of the latter.

Structure of dysprosium and holmium phosphate glasses by the method of isomorphic substitution in neutron diffraction

The relative distribution of rare-earth ions R3+ (Dy3+ or Ho3+) in the phosphate glass RAl0.30P3.05O9.62 was measured by employing the method of isomorphic substitution in neutron diffraction and, by taking the role of Al into explicit account, a self-consistent model of the glass structure was developed. The glass network is found to be made from corner sharing PO4 tetrahedra in which there are, on average, 2.32(9) terminal oxygen atoms, OT, at 1.50(1) Å and 1.68(9) bridging oxygen atoms, OB, at 1.60(1) Å. The network modifying R3+ ions bind to an average of 6.7(1) OT and are distributed such that 7.9(7) R–R nearest neighbours reside at 5.62(6) Å. The Al3+ ion also has a network modifying role in which it helps to strengthen the glass through the formation of OT–Al–OT linkages. The connectivity of the R-centred coordination polyhedra in (M2O3)x(P2O5)1−x glasses, where M3+ denotes a network modifying cation (R3+ or Al3+), is quantified in terms of a parameter fs. Methods for reducing the clustering of rare-earth ions in these materials are then discussed, based on a reduction of fs via the replacement of R3+ by Al3+ at fixed total modifier content or via a change of x to increase the number of OT available per network modifying M3+ cation.

Structure of lanthanum and cerium phosphate glasses by the method of isomorphic substitution in neutron diffraction

Neutron diffraction was used to measure the total structure factors for several rare-earth ion R3+ (La3+ or Ce3+) phosphate glasses with composition close to RAl0.35P3.24O10.12. By assuming isomorphic structures, difference function methods were employed to separate, essentially, those correlations involving R3+ from the remainder. A self-consistent model of the glass structure was thereby developed in which the Al correlations were taken into explicit account. The glass network was found to be made from interlinked PO4 tetrahedra having 2.2(1) terminal oxygen atoms, OT, at 1.51(1) Angstrom, and 1.8(1) bridging oxygen atoms, OB, at 1.60(1) Angstrom. Rare-earth cations bonded to an average of 7.5(2) OT nearest neighbors in a broad and asymmetric distribution. The Al3+ ion acted as a network modifier and formed OT-A1-OT linkages that helped strengthen the glass. The connectivity of the R-centered coordination polyhedra was quantified in terms of a parameter f(s) and used to develop a model for the dependence on composition of the A1-OT coordination number in R-A1-P-O glasses. By using recent 17 A1 nuclear-magnetic-resonance data, it was shown that this connectivity decreases monotonically with increasing Al content. The chemical durability of the glasses appeared to be at a maximum when the connectivity of the R-centered coordination polyhedra was at a minimum. The relation of f(s) to the glass transition temperature, Tg, was discussed.

A comparison of the vocational training system of Britain and West Germany as experienced by minimum-age school leavers.

The sectoral and occupational structure of Britain and West Germany has increasingly changed over the last fifty years from a manual manufacturing based to a non-manual service sector based one. There has been a trend towards more managerial and less menial type occupations. Britain employs a higher proportion of its population in the service sector than in manufacturing compared to West Germany, except in retailing, where West Germany employs twice as many people as Britain. This is a stable sector of the economy in terms of employment, but the requirements of the workforce have changed in line with changes in the industry in both countries. School leavers in the two countries, faced with the same options (FE, training schemes or employment) have opted for the various options in different proportions: young Germans are staying longer in education before embarking on training and young Britons are now less likely to go straight into employment than ten years ago. Training is becoming more accepted as the normal route into employment with government policy leading the way, but public opinion still slow to respond. This study investigates how vocational training has adapted to the changing requirements of industry, often determined by technological advancements. In some areas e.g. manufacturing industry the changes have been radical, in others such as retailing they have not, but skill requirements, not necessarily influenced by technology have changed. Social-communicative skills, frequently not even considered skills and therefore not included in training are coming to the forefront. Vocational training has adapted differently in the two countries: in West Germany on the basis of an established over-defined system and in Britain on the basis of an out-dated ill-defined and almost non-existent system. In retailing German school leavers opt for two or three year apprenticeships whereas British school leavers are offered employment with or without formalised training. The publicly held view of the occupation of sales assistant is one of low-level skill, low intellectual demands and a job anyone can do. The traditional skills - product knowledge, selling and social-communicative skills have steadily been eroded. In the last five years retailers have recognised that a return to customer service, utilising the traditional skills was going to be needed of their staff to remain competitive. This requires training. The German retail training system responded by adapting its training regulations in a long consultative process, whereas the British experimented with YTS, a formalised training scheme nationwide being a new departure. The thesis evaluates the changes in these regulations. The case studies in four retail outlets demonstrate that it is indeed product knowledge and selling and social-communicative skills which are fundamental to being a successful and content sales assistant in either country. When the skills are recognised and taught well and systematically the foundations for career development in retailing are laid in a labour market which is continually looking for better qualified workers. Training, when planned and conducted professionally is appreciated by staff and customers and of benefit to the company. In retailing not enough systematic training, to recognisable standards is carried out in Britain, whereas in West Germany the training system is nevertheless better prepared to show innovative potential as a structure and is in place on which to build. In Britain the reputation of the individual company has a greater role to play, not ensuring a national provision of good training in retailing.

A linguistic study of interview and conversation

The present thesis focuses on the overall structure of the language of two types of Speech Exchange Systems (SES) : Interview (INT) and Conversation (CON). The linguistic structure of INT and CON are quantitatively investigated on three different but interrelated levels of analysis : Lexis, Syntax and Information Structure. The corpus of data 1n vest1gated for the project consists of eight sessions of pairs of conversants in carefully planned interviews followed by unplanned, surreptitiously recorded conversational encounters of the same pairs of speakers. The data comprise a total of approximately 15.200 words of INT talk and of about 19.200 words in CON. Taking account of the debatable assumption that the language of SES might be complex on certain linguistic levels (e.g. syntax) (Halliday 1979) and might be simple on others (e.g. lexis) in comparison to written discourse, the thesis sets out to investigate this complexity using a statistical approach to the computation of the structures recurrent in the language of INT and CON. The findings indicate clearly the presence of linguistic complexity in both types. They also show the language of INT to be slightly more syntactically and lexically complex than that of CON. Lexical density seems to be relatively high in both types of spoken discourse. The language of INT seems to be more complex than that of CON on the level of information structure too. This is manifested in the greater use of Inferable and other linguistically complex entities of discourse. Halliday's suggestion that the language of SES is syntactically complex is confirmed but not the one that the more casual the conversation is the more syntactically complex it becomes. The results of the analysis point to the general conclusion that the linguistic complexity of types of SES is not only in the high recurrence of syntactic structures, but also in the combination of these features with each other and with other linguistic and extralinguistic features. The linguistic analysis of the language of SES can be useful in understanding and pinpointing the intricacies of spoken discourse in general and will help discourse analysts and applied linguists in exploiting it both for theoretical and pedagogical purposes.

The effect of zinc and titanium on the structure of calcium-sodium phosphate based glass

An array of different structural probes has been used to define the effect of adding Zn and Ti to a sodium-calcium phosphate glass. X-ray absorption spectroscopy at the Zn K-edge suggests that the Zn atoms occupy mixed (4- and 6-fold) sites within the glass matrix. X-ray diffraction reveals a feature at 2.03 angstrom that develops with the addition of Zn and Ti and is consistent with Zn-O and Ti-O near-neighbour distances. Neutron diffraction is used to resolve two distinct P-O distances and highlights the decrease in P center dot center dot center dot P coordination number from 2.0 to 1.7 as the Ti metal concentration rises, which is attributed to the O/P fraction moving away from the metaphosphate value of 3.0 to 3.1 with the addition of Ti. Other correlations, such as those associated with CaO(x) and NaO(x) polyhedra, remain largely unaffected. These results suggest that the network forming P center dot center dot center dot P correlation is most disrupted, with the disorder parameter rising from 0.07 to 0.10 angstrom with the additional modifiers. Zn appears to be introduced into the network as a direct replacement for Ca and causes no structural variation over the composition range studied.

A comparative study of the structure of sodium borophosphates made by sol-gel and melt-quench methods

The atomic scale structure of sodium borophosphates made by the sol-gel method is compared to those made by the melt-quench method. It is found that although the sol-gel generated materials have a higher tendency towards crystallization, they nevertheless show a qualitatively similar crystallization trend with composition to their melt-quench analogues; the progressive introduction of boron oxide into the phosphate network initially inhibits then promotes crystallization. At the composition associated with the most stable amorphous sodium borophosphate (20 mol% boron oxide), it is found that the atomic scale structure of the sol-gel synthesized network glass is almost identical to that of the corresponding melt-quenched one.