Evaluation of the sonically induced narrowing of nuclear magnetic resonance spectra of solids

The Nuclear Magnetic Resonance (NMR) spectra of liquids contain a wealth of quantitative information that may be derived, for instance, from chemical shifts and spin-spin couplings. The available information depends on the incoherent rapid molecular motion that causes complicating effects present in the solid state to average to zero. Whereas liquid state NMR spectra show narrow lines, the corresponding NMR spectra from the solid state are normally composed of exceedingly broad resonance lines due to highly restricted molecular motion. It is, therefore, difficult to obtain directly as detailed information from the spectra of solids as from those derived from the liquid state. Studies on a new technique (SINNMR, the sonically induced narrowing of the NMR spectra of solids) to remove line broadening effects in the NMR spectra of the solid state are reported within this thesis. SINNMR involves narrowing the NMR absorptions from solid particles by irradiating them with ultrasound when they are suspended in a support liquid. It is proposed that ultrasound induces incoherent motion of the suspended particles, producing motional characteristics of the particles similar to those of rather large molecules. The first report of apparently successful experiments involving SINNMR[1] emphasised both the irreproducibility of the technique and the uncertainty regarding its true origin. If SINNMR can be made reproducible and the effect definitively attributed to the sonically induced incoherent motional averaging of particles, the technique could offer a simple alternative to the now classical magic-angle spinning (MAS) NMR[2] and the recently reported dynamic angle spinning (DAS)[3] and double rotation (DOR)[4] techniques. Evidence is presented in this thesis to support the proposal that ultrasound may be used to narrow the NMR spectral resonances from solids by inducing incoherent motion of particles suspended in support liquids and, additionally, for some solids, by inducing rotational motion of molecular constituents in the lattices of solids. Successful SINNMR line narrowing using 20 kHz ultrasound is reported for a variety of samples: including trisodium orthophosphate, polytetrafluoroethylene and aluminium alloys. Investigations of SINNMR line narrowing in trisodium phosphate have revealed the relationship between ultrasonic power, particle size and support liquid density for the production of optimum SINNMR conditions. It is also proposed that the incoherent motion of particles induced by 20 kHz ultrasound can originate from interactions between acoustically induced cavitation microjets and particles.

Nuclear magnetic resonance spectroscopy and ultrasound

The work described in this thesis is directed to the examination of the hypothesis that ultrasound may be used to perturb molecular motion in the liquid phase. These changes can then be detected by nuclear magnetic resonance (NMR) in spin-lattice and spin-spin relaxation times. The objective being to develop a method capable of reducing the pulsed NMR acquisition times of slowly relaxing nuclei. The thesis describes the theoretical principles underlying both NMR spectroscopy and ultrasonics with particular attention being paid to factors that impinge on testing the above hypothesis. Apparatus has been constructed to enable ultrasound at frequencies between 1 and 10 mega-hertz with a variable power up to 100W/cm-2 to be introduced in the NMR sample. A broadband high frequency generator is used to drive PZT piezo-electric transducer via various transducer to liquid coupling arrangements. A commercial instrument of 20 kilo-hertz has also been employed to test the above hypothesis and also to demonstrate the usefulness of ultrasound in sonochemistry. The latter objective being, detection of radical formation in monomer and polymer ultrasonic degradation. The principle features of the results obtained are: Ultrasonic perturbation of T1 is far smaller for pure liquids than is for mixtures. The effects appear to be greater on protons (1H) than on carbon-13 nuclei (13C) relaxation times. The observed effect of ultrasonics is not due to temperature changes in the sample. As the power applied to the transducer is progressively increased T1 decreases to a minimum and then increases. The T1's of the same nuclei in different functional groups are influenced to different extents by ultrasound. Studies of the 14N resonances from an equimolar mixture of N, N-dimethylformamide and deuterated chloroform with ultrasonic frequencies at 1.115, 6, 6.42 and 10 MHz show that as the frequency is increased the NMR signal to noise ratio decreases to zero at the Larmor frequency of 6.42 MHz and then again rises. This reveals the surprising indication that an effect corresponding to nuclear acoustic saturation in the liquid may be observable. Ultrasonic irradiation of acidified ammonium chloride solution at and around 6.42 MHz appears to cause distinctive changes in the proton-nitrogen J coupling resonance at 89.56 MHz. Ultrasonic irradiation of N, N-dimethylacetamide at 2 KHz using the lowest stable power revealed the onset of coalescence in the proton spectrum. The corresponding effect achieved by direct heating required a temperature rise of approximately 30oC. The effects of low frequency (20 KHz) on relaxation times appear to be nil. Detection of radical formation proved difficult but is still regarded as the principle route for monomer and polymer degradation. The initial hypothesis is considered proven with the results showing significant changes in the mega-hertz region and none at 20 KHz.

The PCF and the question of intellectual workers : the crisis of social ideology

The aim of this thesis is to examine the approach of the Parti Communiste Francais (from 1956 to 1982) to the emergence of new strata of salaried `intellectual workers' (technicians, engineers, low to middle managers in industry and commerce, scientific researchers, teachers etc) parallelled by the gradual diminution of the traditional industrial working class which forms the core of the Party's support base. This examination is carried out in the context of the debate in France (initiated in the 1950s by social theorists of the Left) on the class membership and role of these strata. The reason for the emergence of such a debate is that in a society given to both a rapid evolution of its social structure and an increased polarisation between Left and Right, a precise knowledge of the objective and subjective determinations of new strata would enable parties to the Left to make proper distinctions between potential allies and adversaries. The thesis posits the view that the PCF has failed to make correct distinctions between its potential allies and adversaries and has thus pursued unsuccessful alliance strategies. The thesis contributes towards a scientifically-based understanding of one of the reasons governing the PCF's steady decline since the 1950s.

The making of an ideology of the third way:the evolution of christian democracy in Germany (with special reference to 1945-49)

This study investigates the search for the third way in the history of German Christian Democracy. Today, in the United Kingdom, the 'third way' is seen as a new phenomenon, a synthesis of post-war belief in the welfare state and neo-liberal conservatism. Yet it insufficiently acknowledges that the origins of third way thinking, the marriage of social justice with free market economics, of individualism with collective responsibility, are found in the early philosophies of Catholic Social Theory and Protestant Social Ethical Teaching in Germany. This study shows that in the hundred years from the 1840s to the end of the 1940s, there were Catholic and Protestant socio-ethical thinkers and political reformists in Germany who attempted to bridge the philosophical differences between liberalism and socialism, to develop a socio-economic order based on Christian moral values. It will focus on the period 1945-1949, when the CDU was founded as the first interdenominational, Christian party. The study provides the first comprehensive account of the political debates in Christian democratic groups in the Soviet, British, French and American allied occupied zones, also giving equal attention to the contribution from the Protestant wing, alongside the more widely acknowledged role of Catholics in the birth of the CDU. It examines how Christian Democrats envisaged correcting the aberrations of German history, by uniting all social classes and Christian religions in one all-embracing Volkspartei, and transforming party politics from its earlier obsession with sectarian and ideological interests towards a more pragmatic 'third way' programme. The study argues that through the making of its ideology, the CDU modified the nation's understanding of its history, re-interpreted its traditions, and redefined the meaning and perception of established political philosophies. This reveals how the ambiguity of political terminology, and the flexible practice of 'third way' politics, were an invaluable political resource in the CDU's campaign for unity, ideological legitimisation and political power.

Vertical and horizontal scope economies in the regulated US electricity power industry

This paper investigates vertical economies between generation and distribution of electric power, and horizontal economies between different types of power generation in the U.S. electric utility industry. Our quadratic cost function model includes three generation output measures (hydro, nuclear and fossil fuels), which allows us to analyze the effect that generation mix has on vertical economies. Our results provide (sample mean) estimates of vertical economies of 8.1% and horizontal economies of 5.4%. An extensive sensitivity analysis is used to show how the scope measures vary across alternative model specifications and firm types. © 2012 Blackwell Publishing Ltd and the Editorial Board of The Journal of Industrial Economics.

Measuring economies of horizontal and vertical integration in the US electric power industry:how costly is unbundling?

This research employs econometric analysis on a cross section of American electricity companies in order to study the cost implications associated with unbundling the operations of integrated companies into vertically and/or horizontally separated companies. Focusing on the representative sample average firm, we find that complete horizontal and vertical disintegration resulting in the creation of separate nuclear, conventional, and hydro electric generation companies as well as a separate firm distributing power to final consumers, results in a statistically significant 13.5 percent increase in costs. Maintaining a horizontally integrated generator producing nuclear, conventional, and hydro electric generation while imposing vertical separation by creating a stand alone distribution company, results in a lower but still substantial and statistically significant cost penalty amounting to an 8.1 % increase in costs relative to a fully integrated structure. As these results imply that a vertically separated but horizontally integrated generation firm would need to reduce the costs of generation by 11% just to recoup the cost increases associated with vertical separation, even the costs associated with just vertical unbundling are quite substantial. Our paper is also the first academic paper we are aware of that systematically considers the impact of generation mix on vertical, horizontal, and overall scope economies. As a result, we are able to demonstrate that the estimated cost of unbundling in the electricity sector is substantially influenced by generation mix. Thus, for example, we find evidence of strong vertical integration economies between nuclear and conventional generation, but little evidence for vertical integration benefits between hydro generation and the distribution of power. In contrast, we find strong evidence suggesting the presence of substantial horizontal integration economies associated with the joint production of hydro generation with nuclear and/or conventional fossil fuel generation. These results are significant because they indicate that the cost of unbundling the electricity sector will differ substantially in different systems, meaning that a blanket regulatory policy with regard to the appropriateness of vertical and horizontal unbundling is likely to be inappropriate.

Germany at a crossroads:the gathering crisis sharpens

In our book, The Gathering Crisis: The 2005 Federal Election and the Grand Coalition (Miskimmon et al, 2009), we argued that the German political and economic systems faced a number of serious challenges. The resource crunch in public finances has been particularly problematic in a country used to consensus politics- money had previously been used to oil the wheels of German federalism (and European integration). In the light of recent events- the global financial crisis, the Eurozone crisis, the 2009 federal election- we claim that the crisis in the German political economy has sharpened. The task of Angela Merkel and subsequent chancellors will be to navigate the new era, ensuring that Germany remains a leading political and economic power in the European Union and beyond. © 2010 Macmillan Publishers Ltd.

Going it alone? North Korea’s adaptability as a small power in a changing world

This article uses small states scholarship to map North Korea’s evolution from a post-colonial small state to a system-influencing state due to its nuclear weapons programme. The framework allows for contributions to: (1) The DPRK literature which in some parts has suggested the future collapse of the state, (2) The small states literature that suggests they can only survive if they integrate larger political and/or economic units, (3) The mainstream IR literature and its dominant realist streak that considers great powers and their will as the main drivers in contemporary world politics.