Laser-Induced Phosphor Thermometry - Feasibility and Precision in Combustion Applications

Temperature is one of the most fundamental parameters to be measured in many research disciplines. In combustion science, a thorough knowledge of temperature is essential for improving and optimizing combustion processes. Increasingly strict environmental legislation, greater demands for energy, and efforts to reduce dependence upon fossil fuels are forcing the combustion industry to obtain more adequate knowledge of combustion processes generally. Laser Induced Phosphorescence (LIP) can serve as a tool for measuring temperature. It utilizes the temperature-dependent properties of the phosphorescence emitted by inorganic luminescent materials referred to as thermographic phosphors, after these have been illuminated by laser radiation. Either point- or two-dimensional measurements are usually performed by the use of either the temporal or the spectral temperature-dependent properties involved. The technique has many advantages. When used wisely it can be close to non-intrusive, offers remote sensing capabilities, and allows a high degree of temporal resolution, accuracy and precision to be obtained. The phosphor is usually applied to a surface either as a point or covering some area. The phosphorescence is detected using either a point light detector, such as a photomultiplier tube (PMT), or an image detector, such as a CCD camera. By seeding phosphor particles in free flow it is also possible to perform temperature measurements in gaseous media. In the present thesis, temperature measurements using laser-induced phosphorescence will be described and certain limitations of it will be addressed. Since the phosphor is applied to a surface as a very thin layer, the measurements performed are often considered non-intrusive. However, in situations in which the temperature changes very rapidly, such as in a combustion engine, and large temperature gradients are present for short periods of time, a relevant question to ask is whether the temperature of the phosphor agrees with the temperature it is intended to measure. One can also ask whether the phosphor layer acts as an insulator, making the measurements indeed intrusive. These are questions investigated in the thesis. At the same time, the technique is quite susceptible to small systematic errors if measurements of high precision and accuracy are to be performed. The technique also requires highly stable detectors in order for correct temperature values to be obtained. In the thesis, the characteristics of different detectors, both for point- and for 2D measurement, are investigated in terms of non-linear features and saturation effects. Also the precision of the technique, and how this is related to the spatial resolution achieved, are investigated. In addition, the suitability of the technique for measurements in gaseous media is investigated in terms of the laser heating of the phosphor particles and the relaxation time required for thermal equilibrium to be achieved

Planar measurements of spray-induced wall cooling using phosphor thermometry

The wall cooling induced by spray impingement is investigated using phosphor thermometry. Thin coatings of zinc oxide (ZnO) phosphor were applied with a transparent chemical binder onto a steel surface. Instantaneous spatially resolved temperatures were determined using the spectral intensity ratio method directly after the injection of UV-grade hexane onto the surface using a commercial gasoline injector. The investigations showed that 2D temperature measurements with high spatial and shot-to-shot precision of, respectively, 0.5 and 0.6 K can be achieved, allowing the accurate resolution of the cooling induced by the spray. The presence of a liquid film over the phosphor coating during measurements showed no noticeable influence on the measured temperatures. However, in some cases a change in the intensity ratio at the spray impingement area, in the form of a permanent “stain”, could be observed after multiple injections. The formation of this stain was less likely with increasing annealing time of the coating as well as lower plate operating temperatures during the injection experiments. Finally, the experimental results indicate a noticeable influence of the thickness of the phosphor coating on the measured spray-induced wall cooling history. Hence, for quantitative analysis, a compromise between coating thickness and measurement accuracy needs to be considered for similar applications where the heat transfer rates are very high

Development of the gas phase laser induced phosphorscence technique and soot measurements in flame using laser induced incandescence

This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University LondonThermometry measurements were carried out using planar laser induced phosphorescence in conjunction with thermographic phosphors in heated turbulent jets and laminar flames in order to further develop the technique for usage in flames. Two dimensional thermometry measurements are essential to improve the understanding of combustion processes, as temperature governs soot pyrolysis, leading to soot formation. Two particular thermographic phosphors, BAM and YAG:Dy were tested and compared and it was found that they were unsuitable for gas phase flame thermometry measurements. Soot volume fraction measurements were carried out using planar two colour laser induced incandescence in gaseous and liquid fuel flames. The gas fuel flames were diluted with nitrogen, carbon dioxide and hydrogen individually and then with nitrogen and hydrogen together, as well as carbon dioxide and hydrogen together, separately. Results revealed the dilution effects of the gases on the soot formation process, where increasing nitrogen percentage in the flow decreased SVF, carbon dioxide reduced it further and hydrogen showed no marked difference. Biodiesels were compared with each other and with diesel in a wick burner in order to analyse their compositional effects on soot. Biodiesel composition was measured using gas chromatography. The sooting tendencies of the biodiesels were as expected, fuels with a longer average carbon chain length and a higher degree of unsaturation were found to produce more soot than shorter, more saturated fuels. Diesel was sootier than all of the biofuels tested, due to containing aromatics and a lower oxygen content. A pilot study was also done, where the performance and emissions of biofuels and biofuel-diesel blends were tested in a gas turbine engine, in order to relate the investigation to real world situations.Thomas Gerald Gray Charitable Trust,Phosphor Technology Lt

Multimodal Spectroscopy and Imaging of Chabazite Zeolite

Zeolites are a type of crystalline aluminosilicate material that when produced synthetically find use in a variety of contexts, many of which are directly beneficial to society at large. One such application, which is of interest not only from the perspective of commercial profitability but perhaps more pertinently in today’s climate from an environmental point of view, is catalysis. Two important examples of commercialised catalytic reactions are selective catalytic reduction (SCR) and the methanol-to-olefins (MTO) reaction, which, respectively, involve the catalytic conversion of noxious NOx gases to nitrogen & water, and waste methanol to higher value petrochemicals. A central challenge in catalysis is the development of characterisation techniques capable of navigating the structurally and compositionally complex internal landscapes of zeolitic catalysts. While the bulk scale information gleaned through techniques like mass spectroscopy, XRD, and NMR provide an established benchmark against which zeolite behaviour is currently assessed, gaining spatially resolved insight into catalytic activity on a nanometric, single-catalyst length scale is highly desirable in current research efforts focused on optimising and improving existing catalytic systems. Laser-based characterisation, being non-destructive and capable of molecular excitation, is identified here as a viable but underexplored option for studying zeolites in a catalytic chemistry context. Time-resolved photoluminescence spectroscopy (TRPS) and confocal-lifetime microscopy are applied to zeolite systems, providing fresh insight into aspects of the zeolite’s synthesis process. TRPS is further combined with in situ setups to provide new information on zeolite behaviour during an active catalytic reaction as a function of time and temperature. Finally, combined IR spectroscopy and X-ray microscopy studies were conducted on Cu-containing forms of the high silica form (SSZ-13) of the zeolite chabazite (CHA)

Fluorescent conjugated polymer dots for single molecule imaging and sensing applications

While single molecule imaging and sensing hold the promise of providing unprecedented detail about cellular processes, many advanced applications are limited by the lack of appropriate fluorescence probes. In many cases, currently available fluorescent labels are not sufficiently bright and photostable to overcome the background associated with various autofluorescence and scattering processes. This dissertation describes research efforts focused on the development of a novel class of fluorescent nanoparticles called conjugated polymers dots (CPdots) for single molecule fluorescence detection. The CPdots contain highly fluorescent π-conjugated polymers that have been refined over the last decades as the active material in polymer light-emitting devices. Quantitative comparisons of the optical properties of the CPdots indicate their fluorescence brightness is a factor of 102-104 higher than conventional fluorescent dyes, and a factor of 10-103 higher than colloidal quantum dots. Single particle fluorescence imaging and kinetic studies indicate much higher emission rates of the CPdots as compared to quantum dots, with little or no \u27blinking\u27 behavior that is often encountered for fluorescent dyes and quantum dots. In addition, efficient intra-particle energy transfer has been demonstrated in blended CPdots and dye-doped CPdots, which provides a new strategy for improving the fluorescence brightness and photostability of the CPdots, and for designing novel sensitive biosensors based on energy transfer to sensor dyes. These combined features of the CPdots and the demonstration of cellular uptake indicate that CPdots are promising probes for demanding fluorescence-based applications such as single molecule detection and tracking in live cells

New approaches for optical and microoptical diagnostics in IC engines

The development of modern engine concepts like spray-guided spark-ignition direct injection (SG-SIDI) or homogeneous charge compression ignition (HCCI) requires fast, non-invasive in-situ diagnostics methods. Hence, laser-based optical diagnostics are essential for internal combustion (IC) engine research. Within this work, microoptical systems that enable the ap-plication of optical diagnostics methods on unmodified production-line engines or engines with micro-invasive optical access were designed, characterized and realized in a joint project collaborating with the Institut für Technische Optik (ITO) at the University of Stuttgart. These microoptical systems include a fiber-optic spark-plug sensor and an endoscopic UV imaging system. The used optical diagnostics are based on laser-induced fluorescence (LIF) of the fuel tracers toluene and 3-pentanone. The respective total fluorescence signal and its spectral dis-tribution yield information about temperature, pressure and mixture composition (i.e. fuel/air-equivalence ratios). The fiber-optic spark plug is designed to perform LIF measure-ments in a defined small probe volume (~2 mm³) close to the spark gap. Its ignition function is fully maintained. With the spark-plug sensor fuel LIF was measured in a commercial IC en-gine. The hybrid UV endoscope (combining refractive and diffractive optical elements) has an about ten times better light collection efficiency than a commercial UV endoscope with simul-taneous high spatial resolution over a broadband spectral range. Its performance is demon-strated in various experiments. Microoptics for the generation of lightsheets and excitation beam patterns are also presented. For a quantitative application of tracer-LIF diagnostics a comprehensive knowledge of the photophysical properties of the used tracers is essential. As a contribution to this photophysical characterization, within this work, tracer-LIF lifetimes were measured via TCSPC (time-correlated single-photon counting) with unprecedented time resolution. The measured bi-exponential decay for toluene LIF could validate the prevailing model. Before the microoptical systems were finished, two experiments in optical single-cylinder engines were conducted with commercial lenses and a simple commercial fiber-optic spark plug. In an air-guided system the fuel distribution and its temporal evolution close to the spark gap were measured with 3-pentanone-LIF and CN* spark-emission spectroscopy simultaneously. In a spray-guided SIDI engine the interaction between the fuel spray and the spark was measured and the spray induced stretching of the spark was observed

High repetition rate temperature and velocity Imaging in turbulent flows using thermographic phosphors

Turbulent flows involving heat transfer and chemical reactions are prevalent in a huge range of applications such as combustors and engines, boilers, and heating and cooling devices. Directly measuring important variables using laser-based techniques has significantly contributed to our understanding of the underlying flow physics. However, many flows of interest exhibit infrequent or oscillatory behaviour, such as flame extinction or instabilities in thermal boundary layers. Capturing the flow dynamics requires simultaneous, two-dimensional temperature and velocity measurements at sampling rates commensurate with turbulent timescales. Typically this means measuring many thousands of temperature and velocity fields per second, yet there are no high repetition rate diagnostics for temperature imaging in practical, oxygen-containing systems, with the essential capability of simultaneous velocity measurements. This thesis presents a novel laser-based imaging technique based on thermographic phosphor particles. There are a huge variety of thermographic phosphors, which are solid materials with luminescence properties that can be exploited for remote thermometry. Here, phosphor particles are seeded into the flow as a tracer. An appropriate phosphor must be selected, and the particle size chosen so that the particle temperature and velocity rapidly assume that of the surrounding fluid. The particles are probed using high-speed lasers and their luminescence and scattering signals are detected using high-speed cameras to measure the flow temperature and velocity at kHz repetition rates. The development of this method is described in detail. Using the thermographic phosphor BAM:Eu, examples of simultaneous time-resolved measurements are presented in turbulent air flows between 300 and 500 K, consisting of a heated jet (Re = 10,000) and also a flow behind a heated cylinder (Re = 700). The technique permits kHz-rate temperature imaging in oxygen-containing environments. These combined diagnostics currently provide a unique capability for the investigation of transient, coupled heat and mass transfer phenomena in turbulent flows of practical engineering importance. A second objective of this work is to improve the precision of the temperature measurement. The characterisation of a different thermographic phosphor with a high temperature sensitivity, zinc oxide (ZnO), is also reported. Temperature imaging using these tracer particles is demonstrated in a jet (Re = 2,000) heated to 363 K, with a temperature precision of 1%. This extends the capabilities of this versatile technique toward the study of flows with small temperature variations. Also, unlike the majority of phosphors previously investigated for thermometry, this phosphor is a semiconductor. Exploiting the temperature-dependent luminescence of this class of materials presents interesting new opportunities for remote temperature sensing.Open Acces

Utilization of Nanoparticles for Photoacoustic Chemical Imaging

Tumors are known to have unique chemical properties, such as low pH (acidosis), high K+ (hyperkalemia), and low O2 (hypoxia). Tumor acidosis has been known to influence therapeutic activities of chemotherapeutic drugs. Another conventional cancer treatment, radiation therapy, is highly dependent on local oxygen concentrations. Hyperkalemia has been recently reported to suppress the immune response of activated T-cells. It is also believed that the spatial distribution of these analytes and its heterogeneity, are of relevance. Despite the importance of such chemical information on tumors, there are no clinically available tools for “quantitative” pH, K+, or tissue O2 imaging. Here, photoacoustic (PA) imaging is employed to provide chemical imaging of all these target analytes for cancer (pH, O2 and K+). As for pH, we report on an in vivo pH mapping nanotechnology. This subsurface chemical imaging is based on tumor-targeted, pH sensing nanoprobes and multi-wavelength photoacoustic imaging (PAI). The nanotechnology consists of an optical pH indicator, SNARF-5F, 5-(and-6)-Carboxylic Acid, encapsulated into polyacrylamide nanoparticles with surface modification for tumor targeting. Facilitated by multi-wavelength PAI plus a spectral unmixing technique, the accuracy of pH measurement inside the biological environment is not susceptible to the background optical absorption of biomolecules, i.e., hemoglobins. As a result, both the pH levels and the hemodynamic properties across the entire tumor can be quantitatively evaluated with high sensitivity and high spatial resolution in in vivo cancer models. For K+, we extend this technique to ion-selective photoacoustic optodes (ISPAOs) that serve at the same time as fluorescence-based ISOs, and apply it specifically to potassium (K+). However, unfortunately, sensors capable of providing potassium images in vivo are still a future proposition. Here, we prepared an ion-selective potassium nanosensor (NS) aimed at in vivo photoacoustic (PA) chemical imaging of the extracellular environment, while being also capable of fluorescence based intracellular ion-selective imaging. This potassium nanosensor (K+ NS) modulates its optical properties (absorbance and fluorescence) according to the potassium concentration. The K+ NS is capable of measuring potassium, in the range of 1 mM to 100 mM, with high sensitivity and selectivity, by ISPAO based measurements. Also, a near infrared dye surface modified K+ NS allows fluorescence-based potassium sensing in the range of 20 mM to 1 M. The K+ NS serves thus as both PA and fluorescence based nanosensor, with response across the biologically relevant K+ concentrations, from the extracellular 5 mM typical values (through PA imaging) to the intracellular 150 mM typical values (through fluorescence imaging). Lastly, nano-enabled tissue O2 monitoring by PA, called lifetime-based PA (PALT) imaging, was introduced and demonstrated. A known PALT oxygen indicator, Oxyphor G2, is conjugated into polyacrylamide nanoparticles, called G2-PAA NP. The oxygen sensing capability of the G2-PAA NP has been confirmed in vitro and in vivo studies. In an Appendix, we show how to monitor photodynamic therapy (PDT) using the PALT approach to measure the local oxygen depletion as a function of PDT time. Oxygen depletion during PDT is monitored using both oximeter and PALT spectroscopy in vitro. The latter is enabled by theranostic NPs of methylene blue (MB) conjugated PAA, used for both PALT and PDT. This synergistic approach has good potential for personalized medicine.PHDChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttps://deepblue.lib.umich.edu/bitstream/2027.42/143924/1/lechang_1.pd

Quantitative optical imaging platform for studying neurovascular hemodynamics during ischemic stroke

The measurement of cerebral hemodynamics is vital for the study of physiological and pathophysiological conditions in the brain. Preclinical research examining the mechanisms, outcomes, and efficacies of interventions during ischemic stroke require quantitative imaging technologies. This dissertation presents the development of an optical imaging platform capable of chronic in vivo monitoring of cortical hemodynamics during ischemic stroke and the subsequent recovery. The system combines two different imaging techniques, laser speckle contrast imaging (LSCI) and oxygen-dependent quenching of phosphorescence, to measure cerebral blood flow (CBF) and dissolved oxygen tension (pO2) within cortical vasculature. Phosphorescence signal localization is achieved through the use of a spatial light modulator to selectively pattern excitation light in order to overcome the traditional limitations of the imaging modality. The spatial light modulator is also utilized to perform artery-targeted photothrombosis for the induction of highly-localized, reproducible infarcts as an extension of the photothrombotic model of ischemic stroke. The LSCI hardware implements the multi-exposure speckle imaging (MESI) technique for robust estimates of CBF that facilitate day-to-day and between-subject comparisons. The integration of an awake imaging system eliminates the confounding effects of anesthesia upon cerebral hemodynamics. The capabilities of the complete optical imaging platform are demonstrated by monitoring the acute hemodynamic response during targeted photothrombosis and the chronic recovery of the resulting ischemic infarctBiomedical Engineerin