Design and construction of an ultrasonic probe for use in a Cryo-Magnet NMR Spectrometer

SINNMR (Sonically Induced Narrowing of the Nuclear Magnetic Resonance spectra of solids), is a novel technique that is being developed to enable the routine study of solids by nuclear magnetic resonance spectroscopy. SINNMR aims to narrow the broad resonances that are characteristic of solid state NMR by inducing rapid incoherent motion of solid particles suspended in a support medium, using high frequency ultrasound in the range 2-10 MHz. The width of the normal broad resonances from solids are due to incomplete averaging of several components of the total spin Hamiltonian caused by restrictions placed on molecular motion within a solid. At present Magic Angle Spinning (MAS) NMR is the classical solid state technique used to reduce line broadening, but: this has associated problems, not least of which is the appearance of many spinning side bands which confuse the spectra. It is hoped that SlNNMR will offer a simple alternative, particularly as it does not reveal spinning sidebands The fundamental question concerning whether the use of ultrasound within a cryo-magnet will cause quenching has been investigated with success, as even under the most extreme conditions of power, frequency and irradiator time, the magnet does not quench. The objective of this work is to design and construct a SINNMR probe for use in a super conducting cryo-magnet NMR spectrometer. A cell for such a probe has been constructed and incorporated into an adapted high resolution broadband probe. It has been proved that the cell is capable of causing cavitation, up to 10 MHz, by running a series of ultrasonic reactions within it and observing the reaction products. It was found that the ultrasound was causing the sample to be heated to unacceptable temperatures and this necessitated the incorporation of temperature stabilisation devices. Work has been performed on the investigation of the narrowing of the solid state 23Na spectrum of tri-sodium phosphate using high frequency ultrasound. Work has also been completed on the signal enhancement and T1 reduction of a liquid mixture and a pure compound using ultrasound. Some preliminary "bench" experiments have been completed on a novel ultrasonic device designed to help minimise sample heating. The concept involves passing the ultrasound through a temperature stabilised, liquid filled funnel that has a drum skin on the end that will enable the passage of ultrasound into the sample. Bench experiments have proved that acoustic attenuation is low and that cavitation in the liquid beyond the device is still possible.

Lithium-aluminium casting alloys and their associated metal-mould reactions

Aluminium - lithium alloys are specialist alloys used exclusively by the aerospace industry. They have properties that are favourable to the production of modern military aircraft. The addition of approximately 2.5 percent lithium to aluminium increases the strength characteristics of the new alloys by 10 percent. The same addition has the added advantage of decreasing the density of the resulting alloy by a similar percentage. The disadvantages associated with this alloy are primarily price and castability. The addition of 2.5 weight percent lithium to aluminium results in a price increase of 100% explaining the aerospace exclusivity. The processability of the alloys is restricted to ingot casting and wrought treatment but for complex components precision casting is required. Casting the alloys into sand and investment moulds creates a metal - mould reaction, the consequences of which are intolerable in the production of military hardware. The primary object of this project was to investigate and characterise the reactions occurring between the newly poured metal and surface of the mould and to propose a method of counteracting the metal - mould reaction. The constituents of standard sand and investment moulds were pyrolised with lithium metal in order to simplify the complex in-mould reaction and the products were studied by the solid state techniques of powder X-Ray diffraction and magic angle spinning nuclear magnetic resonance spectroscopy. The results of this study showed that the order of reaction was: Organic reagents> > Silicate reagents> Non silicate reagents Alphaset and Betaset were the two organic binders used to prepare the sand moulds throughout this project. Studies were carried out to characterise these resins in order to determine the factors involved in their reaction with lithium. Analysis revealed that during the curing process the phenolic hydroxide groups are not reacted out and that a redox reaction takes place between these hydroxides and the lithium in the molten alloys. Casting experiments carried out to assess the protection afforded by various hydroxide protecting agents showed that modern effective, protecting chemicals such as bis-trimethyl silyl acetamide and hexamethyldisilazane did not inhibit the metal - mould reaction to a sufficiently high standard and that tri-methylchlorosilane was consistently the best performer. Tri-methyl chlorosilane has a simple functionalizing mechanism compared to other hydroxide protecting reagents and this factor is responsible for its superior inhibiting qualities. Comparative studies of 6Li and 7Li N.M.R. spectra (M.A.S. and `off angle') establish that, for solid state (and even solution) analytical purposes 6Li is the preferred nucleus. 6Li M.A.S.N.M.R. spectra were obtained for thermally treated laponite clay. At temperatures below 800oC both dehydrated and rehydrated samples were considered. The data are consistent with mobility of lithium ions from the trioctahedral clay sites at 600oC. The superior resolution achievable in 6Li M.A.S.N.M.R. is demonstrated in the analysis of a microwave prepared lithium exchanged clay where 6Li spectroscopy revelaed two lithium sites in comparison to 7Li M.A.S.N.M.R. which gave only a single lithium resonance.

High-resolution, wavelength-division-multiplexed in-fibre Bragg grating sensor system

A novel wavelength-division-multiplexed in-fibre Bragg grating sensor system combined with high resolution drift-compensated interferometric wavelength-shift detection is described. This crosstalk-free system is based on the use of an interferometric wavelength scanner and a low resolution spectrometer. A four element system is demonstrated for temperature measurement, and a resolution of ±0.1°C has been achieved.

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.

Transient response in high-resolution Brillouin-based distributed sensing using probe pulses shorter than the acoustic relaxation time

We perform numerical simulations on a model describing a Brillouin-based temperature and strain sensor, testing its response when it is probed with relatively short pulses. Experimental results were recently published [e.g., Opt. Lett. 24, 510 (1999)] that showed a broadening of the Brillouin loss curve when the probe pulse duration is reduced, followed by a sudden and rather surprising reduction of the linewidth when the pulse duration gets shorter than the acoustic relaxation time. Our study reveals the processes responsible for this behavior. We give a clear physical insight into the problem, allowing us to define the best experimental conditions required for one to take the advantage of this effect.

Polarization-independent high-resolution spectral interrogation of FBGs using a BFBG-CCD array for optical sensing applications

Optical fibre strain sensors using Fibre Bragg Gratings (FBGs) are poised to play a major role in structural health monitoring in a variety of application from aerospace to civil engineering. At the heart of technology is the optoelectronic instrumentation required to convert optical signals into measurands. Users are demanding compact, lightweight, rugged and low cost solutions. This paper describes development of a new device based on a blazed FBG and CCD array that can potentially meet the above demands. We have shown that this very low cost technique may be used to interrogate a WDM array of sensor gratings with highly accurate and highly repeatable results unaffected by the polarisation state of the radiation. In this paper, we present results showing that sensors may be interrogated with an RMS error of 1.7pm, drift below 0.12pm and dynamic range of up to 65nm.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO, 30 mol % CaO) for each of the calcium precursors. When CaCl was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.

Use of narrow mass-window, high-resolution extracted product ion chromatograms for the sensitive and selective identification of protein modifications

Protein modifications, including oxidative modifications, glycosylations, and oxidized lipid-protein adducts, are becoming increasingly important as biomarkers and in understanding disease etiology. There has been a great deal of interest in mapping these on Apo B100 from low density lipoprotein (LDL). We have used extracted ion chromatograms of product ions generated using a very narrow mass window from high-resolution tandem mass spectrometric data collected on a rapid scanning quadrupole time-of-flight (QTOF) instrument, to selectively and sensitively detect modified peptides and identify the site and nature of a number of protein modifications in parallel. We have demonstrated the utility of this method by characterizing for the first time oxidized phospholipid adducts to LDL and human serum albumin and for the detection of glycosylation and kynurenin formation from the oxidation of tryptophan residues in LDL. © 2013 American Chemical Society.

High-resolution, wavelength-division-multiplexed in-fibre Bragg grating sensor system

A novel wavelength-division-multiplexed in-fibre Bragg grating sensor system combined with high resolution drift-compensated interferometric wavelength-shift detection is described. This crosstalk-free system is based on the use of an interferometric wavelength scanner and a low resolution spectrometer. A four element system is demonstrated for temperature measurement, and a resolution of ±0.1°C has been achieved.

Polarization-independent high-resolution spectral interrogation of FBGs using a BFBG-CCD array for optical sensing applications

Optical fibre strain sensors using Fibre Bragg Gratings (FBGs) are poised to play a major role in structural health monitoring in a variety of application from aerospace to civil engineering. At the heart of technology is the optoelectronic instrumentation required to convert optical signals into measurands. Users are demanding compact, lightweight, rugged and low cost solutions. This paper describes development of a new device based on a blazed FBG and CCD array that can potentially meet the above demands. We have shown that this very low cost technique may be used to interrogate a WDM array of sensor gratings with highly accurate and highly repeatable results unaffected by the polarisation state of the radiation. In this paper, we present results showing that sensors may be interrogated with an RMS error of 1.7pm, drift below 0.12pm and dynamic range of up to 65nm.

Transient response in high-resolution Brillouin-based distributed sensing using probe pulses shorter than the acoustic relaxation time

We perform numerical simulations on a model describing a Brillouin-based temperature and strain sensor, testing its response when it is probed with relatively short pulses. Experimental results were recently published [e.g., Opt. Lett. 24, 510 (1999)] that showed a broadening of the Brillouin loss curve when the probe pulse duration is reduced, followed by a sudden and rather surprising reduction of the linewidth when the pulse duration gets shorter than the acoustic relaxation time. Our study reveals the processes responsible for this behavior. We give a clear physical insight into the problem, allowing us to define the best experimental conditions required for one to take the advantage of this effect.

High speed and high resolution demodulation system for hybrid WDM/FDM based fiber microstructure sensor network by using Fabry-Perot filter

Hybrid WDM/TDM enabled microstructure based optical fiber sensor network with large capacity is proposed. Assisted by Fabry-Perot filter, the demodulation system with high speed of 500Hz and high wavelength resolution less than 4.91pm is realized. © OSA 2015.

Long-range and high-resolution correlation optical time-domain reflectometry utilizing an all optical chaotic source

A high resolution optical time domain reflectometry (OTDR) based on an all-fiber chaotic source is demonstrated. We analyze the key factors limiting the operational range of such an OTDR, e.g., integral Rayleigh backscattering and the fiber loss, which degrade the optical signal to noise ratio at the receiver side, and then the guideline for counter-act such signal fading is discussed. The experimentally demonstrated correlation OTDR presents ability of 100km sensing range and 8.2cm spatial resolution (1.2 million resolved points), as a verification of the theoretical analysis. To the best of our knowledge, this is the first time that correlation OTDR measurement is performed over such a long distance with such high precision.