Identification and characterization of shallow impurity states in gallium arsenide and indium phosphide using photothermal ionization spectroscopy

A model of far infrared (FIR) dielectric response of shallow impurity states in a semiconductor has been developed and is presented for the specific case of the shallow donor transitions in high purity epitaxial GaAs. The model is quite general, however, and should be applicable with slight modification, not only to shallow donors in other materials such as InP, but also to shallow acceptors and excitons. The effects of the enormous dielectric response of shallow donors on the FIR optical properties of reflectance, transmittance, and absorptance, and photoconductive response of high purity epitaxial GaAs films are predicted and compared with experimental photothermal ionization spectra. The model accounts for many of the peculiar features that are frequently observed in these spectra, one of which was the cause of erroneous donor identifications in the early doping experiments. The model also corrects some commonly held misconceptions concerning photo-thermal ionization peak widths and amplitudes and their relationships to donor and acceptor concentrations. These corrections are of particular relevance to the proper interpretation of photothermal ionization spectra in the study of impurity incorporation in high purity epitaxial material. The model also suggests that the technique of FIR reflectance, although it has not been widely employed, should be useful in the study of shallow impurities in semiconductors.

Diamond Surface Modification to Enhance Interfacial Thermal Conductivity in Al/Diamond Composites

Diamond/metal composites are very attractive materials for electronics because their excellent thermal properties make them suitable for use as heat sink elements in multifunctional electronic packaging systems. To enlarge the potential applications of these composites, current efforts are mainly focused on investigating different ways to improve the contact between metal and diamond. In the present work, a theoretical study has been carried out to determine the differences between the interfacial thermal conductance of aluminum/diamond and aluminum/graphite interfaces. Additionally, diamond particles were surface modified with oxygen to observe how it affects the quality of the diamond surface. The characterization of the surface of diamonds has been performed using different surface analysis techniques, especially x-ray photoelectron spectroscopy and temperature-programmed desorption.

Structural characterization and comparative analysis of human and piscine cartilage acidic protein (CRTAC1/CRTAC2)

Dissertação de mestrado, Biotecnologia, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2014

Characterization and age determination of Quaternary volcanism in the southern Ankaratra region (central Madagascar) through novel approaches in luminescence dating

This work introduces two novel approaches for the application of luminescence dating techniques to Quaternary volcanic eruptions: crystalline xenoliths from lava flows are demonstrated to be basically suitable for luminescence dating, and a set of phreatic explosion deposits from the Late Quaternary Vakinankaratra volcanic field in central Madagascar is successfully dated with infrared stimulated luminescence (IRSL). Using a numerical model approach and experimental verification, the potential for thermal resetting of luminescence signals of xenoliths in lava flows is demonstrated. As microdosimetry is an important aspect when using sample material extracted from crystalline whole rocks, autoradiography using image plates is introduced to the field of luminescence dating as a method for detection and assessment of spatially resolved radiation inhomogeneities. Determinations of fading rates of feldspar samples have been observed to result in aberrant g-values if the pause between preheat and measurement in the delayed measurements was kept short. A systematic investigation reveals that the phenomenon is caused by the presence of three signal components with differing individual fading behaviour. As this is restricted to short pauses, it is possible to determine a minimal required delay between preheating and measurement after which the aberrant behaviour disappears. This is applied in the measuring of 12 samples from phreatic explosion deposits from the Antsirabe – Betafo region in the Late Quaternary Vakinankaratra volcanic field. The samples were taken from stratigraphically correlatable sections and appear to represent at least three phreatic events, one of which created the Lac Andraikiba maar near Antsirabe. The obtained ages indicate that the eruptive activity in the region started in the Late Pleistocene between 113.9 and 99.6 ka. A second layer in the Betafo area is dated at approximately 73 ka and the Lac Andraikiba deposits give an age between 63.9 and 50.7 ka. The youngest phreatic layer is dated between 33.7 and 20.7 ka. These ages are the first recorded direct ages of such volcanic deposits, as well as the first and only direct ages for the Late Quaternary volcanism in the Vakinankaratra volcanic field. This illustrates the huge potential of this new method for volcanology and geochronology, as it enables direct numerical dating of a type of volcanic deposit which has not been successfully directly dated by any other method so far.

Multifunctional Nanoparticles in Cancer: in vitro Characterization, in vivo Distribution

A novel biocompatible and biodegradable polymer, termed poly(Glycerol malate co-dodecanedioate) (PGMD), was prepared by thermal condensation method and used for fabrication of nanoparticles (NPs). PGMD NPs were prepared using the single oil emulsion technique and loaded with an imaging/hyperthermia agent (IR820) and a chemotherapeutic agent (doxorubicin, DOX). The size of the void PGMD NPs, IR820-PGMD NPs and DOX-IR820-PGMD NPs were approximately 90 nm, 110 nm, and 125 nm respectively. An acidic environment (pH=5.0) induced higher DOX and IR820 release compared to pH=7.4. DOX release was also enhanced by exposure to laser, which increased the temperature to 42°C. Cytotoxicity of DOX-IR820-PGMD NPs was comparable in MES-SA but was higher in Dx5 cells compared to free DOX plus IR820 (pIn vivomouse studies showed that NP formulation significantly improved the plasma half-life of IR820 after tail vein injection. Significant lower IR820 content was observed in kidney in DOX-IR820-PGMD NP treatment as compared to free IR820 treatment in our biodistribution studies (p

Fast Detection and Chemical Characterization of Gunshot Residues by CMV-GC-MS and LIBS

Gunshot residue (GSR) is the term used to describe the particles originating from different parts of the firearm and ammunition during the discharge. A fast and practical field tool to detect the presence of GSR can assist law enforcement in the accurate identification of subjects. A novel field sampling device is presented for the first time for the fast detection and quantitation of volatile organic compounds (VOCs). The capillary microextraction of volatiles (CMV) is a headspace sampling technique that provides fast results (< 2 min. sampling time) and is reported as a versatile and high-efficiency sampling tool. The CMV device can be coupled to a Gas Chromatography-Mass Spectrometry (GC-MS) instrument by installation of a thermal separation probe in the injection port of the GC. An analytical method using the CMV device was developed for the detection of 17 compounds commonly found in polluted environments. The acceptability of the CMV as a field sampling method for the detection of VOCs is demonstrated by following the criteria established by the Environmental Protection Agency (EPA) compendium method TO-17. The CMV device was used, for the first time, for the detection of VOCs on swabs from the hands of shooters, and non-shooters and spent cartridges from different types of ammunition (i.e., pistol, rifle, and shotgun). The proposed method consists in the headspace extraction of VOCs in smokeless powders present in the propellant of ammunition. The sensitivity of this method was demonstrated with method detection limits (MDLs) 4-26 ng for diphenylamine (DPA), nitroglycerine (NG), 2,4-dinitrotoluene (2,4-DNT), and ethyl centralite (EC). In addition, a fast method was developed for the detection of the inorganic components (i.e., Ba, Pb, and Sb) characteristic of GSR presence by Laser Induced Breakdown Spectroscopy (LIBS). Advantages of LIBS include fast analysis (~ 12 seconds per sample) and good sensitivity, with expected MDLs in the range of 0.1-20 ng for target elements. Statistical analysis of the results using both techniques was performed to determine any correlation between the variables analyzed. This work demonstrates that the information collected from the analysis of organic components has the potential to improve the detection of GSR.

Synthesis and Characterization of Photochromic Copolymers Containing 3-Indolylfulgides/Indolylfulgimides

Fulgides and fulgimides are important organic photochromic compounds and can switch between the open forms and the closed forms with light. The 3-indolylfulgides and 3-indolylfulgimides exhibit promising photochromic properties and have great potential in optical memory devices, optical switches and biosensors. Copolymers containing 3-indolylfulgides/indolylfulgimides synthesized via free radical polymerizations increase conformation changes and allow the photochromic compounds to be uniformly distributed in the polymer matrix. A trifluoromethyl 3-indolylfulgide and two trifluoromethyl 3-indolylfulgimides with one or two polymerizable N-stryryl group(s) were prepared. Copolymerization with methyl methacrylate provided two linear copolymers or a cross-linked copolymer. The properties of the monomeric fulgide/fulgimides and copolymers in toluene or as thin films were characterized. In general, the photochromic monomers and copolymers revealed similar photochromic properties and exhibited good thermal and photochemical stability. All compounds absorb visible light in both open forms and closed forms. The closed form copolymers were more stable than the open form copolymers and showed little or no degradation after 400 h. The photochemical degradation rate was less than 0.03% per cycle. In films, conformational restrictions were observed for the open forms suggesting that the preparation of films from the closed forms is advantageous. Two novel methyl 3-indolylfulgimides with one or two polymerizable N-stryryl group(s) were prepared. Copolymerization of acrylamide with the methyl indolylfulgimides or the trifluoromethyl indolylfulgimides yielded two aqueous soluble linear copolymers and two photochromic hydrogels. The closed form copolymers containing trifluoromethyl indolylfulgimides were hydrolyzed in aqueous solution by replacing the trifluoromethyl group with a carboxylic acid group. The resulting carboxylic copolymers were also photochromic. The copolymers containing methyl fulgimides were stable in aqueous solutions and did not hydrolyze. Both methyl and carboxylic copolymers exhibited good stability in aqueous solutions. In general, the open form copolymers were more stable than the closed form copolymers, and the copolymers revealed better stability in acidic solution than neutral solution. The linear copolymers displayed better photochemical stability in neutral solution and degraded up to 22% after 105 cycles. In contrast, the hydrogels showed enhanced fatigue resistance in acidic condition and underwent up to 60 cycles before degrading 24%.

Modeling, Simulation, and Characterization of Space Debris in low-Earth Orbit

Every space launch increases the overall amount of space debris. Satellites have limited awareness of nearby objects that might pose a collision hazard. Astrometric, radiometric, and thermal models for the study of space debris in low-Earth orbit have been developed. This modeled approach proposes analysis methods that provide increased Local Area Awareness for satellites in low-Earth and geostationary orbit. Local Area Awareness is defined as the ability to detect, characterize, and extract useful information regarding resident space objects as they move through the space environment surrounding a spacecraft. The study of space debris is of critical importance to all space-faring nations. Characterization efforts are proposed using long-wave infrared sensors for space-based observations of debris objects in low-Earth orbit. Long-wave infrared sensors are commercially available and do not require solar illumination to be observed, as their received signal is temperature dependent. The characterization of debris objects through means of passive imaging techniques allows for further studies into the origination, specifications, and future trajectory of debris objects. Conclusions are made regarding the aforementioned thermal analysis as a function of debris orbit, geometry, orientation with respect to time, and material properties. Development of a thermal model permits the characterization of debris objects based upon their received long-wave infrared signals. Information regarding the material type, size, and tumble-rate of the observed debris objects are extracted. This investigation proposes the utilization of long-wave infrared radiometric models of typical debris to develop techniques for the detection and characterization of debris objects via signal analysis of unresolved imagery. Knowledge regarding the orbital type and semi-major axis of the observed debris object are extracted via astrometric analysis. This knowledge may aid in the constraint of the admissible region for the initial orbit determination process. The resultant orbital information is then fused with the radiometric characterization analysis enabling further characterization efforts of the observed debris object. This fused analysis, yielding orbital, material, and thermal properties, significantly increases a satellite’s Local Area Awareness via an intimate understanding of the debris environment surrounding the spacecraft.

FABRICATION, CHARACTERIZATION, AND IRRADIATION OF AN AUSTENITIC OXIDE DISPERSION STRENGTHENED STEEL SUITED FOR NEXT GENERATION NUCLEAR APPLICATIONS

As nuclear energy systems become more advanced, the materials encompassing them need to perform at higher temperatures for longer periods of time. In this Master’s thesis we experiment with an oxide dispersion strengthened (ODS) austenitic steel that has been recently developed. ODS materials have a small concentration of nano oxide particles dispersed in their matrix, and typically have higher strength and better extreme temperature creep resistance characteristics than ordinary steels. However, no ODS materials have ever been installed in a commercial power reactor to date. Being a newer research material, there are many unanswered phenomena that need to be addressed regarding the performance under irradiation. Furthermore, due to the ODS material traditionally needing to follow a powder metallurgy fabrication route, there are many processing parameters that need to be optimized before achieving a nuclear grade material specification. In this Master’s thesis we explore the development of a novel ODS processing technology conducted in Beijing, China, to produce solutionized bulk ODS samples with ~97% theoretical density. This is done using relatively low temperatures and ultra high pressure (UHP) equipment, to compact the mechanically alloyed (MA) steel powder into bulk samples without any thermal phase change influence or oxide precipitation. By having solutionized bulk ODS samples, transmission electron microscopy (TEM) observation of nano oxide precipitation within the steel material can be studied by applying post heat treatments. These types of samples will be very useful to the science and engineering community, to answer questions regarding material powder compacting, oxide synthesis, and performance. Subsequent analysis performed at Queen’s University included X-ray diffraction (XRD) and inductively coupled plasma optical emission spectrometry (ICP-OES). Additional TEM in-situ 1MeV Kr2+ irradiation experiments coupled with energy dispersive X-ray (EDX) techniques, were also performed on large (200nm+) non-stoichiometric oxides embedded within the austenite steel grains, in an attempt to quantify the elemental compositional changes during high temperature (520oC) heavy ion irradiation.

New bio-based polymers: from synthesis to characterization

The environmental problems caused by human activity are one of the main themes of debate of the last Century. As regard plastics, the use of non-renewable sources together with the accumulation of waste in natural habitats are causing serious pollution problems. For this reason, a continuously growing interest is recorded around sustainable materials, potential candidate for the replacement of traditional recalcitrant plastics. Promising results have been obtained with biopolymers, in particular with the class of biopolyesters. Their potential biodegradability and biobased nature is particularly interesting mainly for food packaging, where the multilayer systems normally used and the contamination by organic matter create severe recycling limits. In this framework, the present research has been conducted with the aim of synthetizing, modifying and characterizing biopolymers for food packaging application. New bioplastics based on monomers derived from renewable resources were successfully synthetized by two-step melt polycondensation and chain extension reaction following the “Green chemistry” principles. Moreover, well-known biopolyesters have been modified by blending or copolymerization, both resulting effective techniques to ad hoc tune the polymer final characteristics. The materials obtained have been processed and characterized from the chemical, structural, thermal and mechanical point of view; more specific characterizations as compostability tests, surface hydrophilicity film evaluation and barrier property measurements were conducted.

Preparation and characterization of multifunctional bio-based polymers exhibiting enhanced properties

Driven by environmental reasons and the expected depletion of crude oil, bio-based polymers are currently undergoing a renaissance in the attempt to replace fossil-based ones. The present work aims at contributing in the development of the steps that start from biomass and move to new polymeric multifunctional materials. The study focuses on two bio-based building blocks (itaconic and vanillic acids) characterized by exploitable functionalities, i.e. a lateral double bond and a substituted aromatic ring respectively, able to confer interesting properties to the final polymers. The lateral double bond of dimethyl itaconate was functionalized via thia-Michael addition reaction obtaining a thermo-stable building block that can undergo polycondensation under classical conditions of reaction. The addition of a long lateral chain allows the polymer to express antimicrobial activity against Staphylococcus aureus making it attractive for packaging and targeting antimicrobial applications. Moreover, the architecture of the homopolymer was modified by means of copolymerization with dimethyl 2,5-furandicarboxylate thus improving the rigidity and obtaining a thermo-processable material. Potential applications as thermoset or thermoplastic material have been discussed. As concerns vanillic acid, the presence of aromatic rings on the polymer backbone imparts high thermal stability, but brittle behaviour in the homopolymer. Therefore, the architecture of the polyester was successfully tuned by means of copolymerization with a flexible bio-based comonomer, i.e. ω-pentadecalactone, providing processable random copolymers. An in depth investigation of water transport mechanism has been undertaken on the synthesized polyesters. Since the copolymers present a succession of aromatic and aliphatic units, as a consequence of the chemical structure water vapor permeability interposes between polyethylene and poly(ethylene terephthalate) proving that the copolyesters are suitable for packaging applications. Moving towards a sustainable model of development, novel sustainable synthetic pathways for the eco-design of new bio-based polymeric structures with high value functionalities and different potential applications have been successfully developed.

Development and Characterization of Biopolymers

Development and characterization of biopolymers was done in AIJU’s laboratories. AIJU, Technological Institute for children’s products and leisure is based in Spain. The work has the aim to study qualities and characteristics of bioplastics’ blends, in order to design where improvements can be executed. Biopolymers represent a sector with great development possibilities because they combine high technical potential and eco-sustainability. Nowadays, plastic pollution has becoming increasingly concerning, particularly in terms of management of waste. Bioplastics provide an alternative for the disposal of products, reducing the volume of waste and enhancing the end of life recovery. Despite the growing interest in biopolymers there is some gaps that need be filled. The main objective on this work, is the optimization of bioplastics mechanical properties, to find suitable substitutes, as similar as possible to conventional plastics. Firstly, investigations on processability of biomaterials has been deepen since the project deals with toy manufacturing’s sector. Thus, starting from laboratory scale the work aspires to expand industrially. By working with traditional machines, it was notable that, with some limited modifications, the equipment can perform the same functions. Therefore, operational processes do not emerge as an obstacle to the production chain. Secondly, after processing bio-blends, they are characterized by thermal tests (melt flow index, differential scanning calorimetry-DSC, thermogravimetry-TGA) and mechanical tests (traction and flexural tests, Charpy impact, SHORE D hardness and density). While the compatibility does not show relevant results, mechanical improvements has been visualized with addition of more ductile materials. The study was developed by inclusion of sustainable additive VINNEX® to blends. The thesis has highlighted that integration of more flexible materials provides elasticity without compromising bioplastics’ properties.

Synthesis, Characterization, and Applications of a Novel Cu(II)-MOF Based on a Propargylcarbamate-Functionalized Isophthalate Ligand

This work describes the synthesis of a propargylcarbamate-functionalized isophthalate ligand and its use in the solvothermal preparation of a new copper(II)-based metal organic framework named [Cu(1,3-YBDC)]ˑxH2O (also abbreviated as Cu-MOF. The characterization of this compound was performed using several complementary techniques such as infrared (ATR-FTIR) and Raman spectroscopy, X-ray powder diffraction spectroscopy (PXRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS) as well as thermal and surface area measurements. Synchrotron X-ray diffraction analysis revealed that this MOF contains a complex network of 5-substituted isophthalate anions bound to Cu(II) centers, arranged in pairs within paddlewheel (or “Chinese lantern”) structure with a short Cu…Cu distance of 2.633 Å. Quite unexpectedly, the apical atom in the paddlewheel structure belongs to the carbamate carbonyl oxygen atom. Such extra coordination by the propargylcarbamate groups drastically reduces the MOF porosity, a feature that was also confirmed by BET measurements. Indeed, its surface area was determined to be low (14.5 ± 0.8 m2/g) as its total pore volume (46 mm3/g). Successively the Cu-MOF was treated with HAuCl4 with the aim of studying the ability of the propargylcarbamate functionality to capture the Au(III) ion and reduce it to Au(0) to give gold nanoparticles (AuNPs). The overall amount of gold retained by the Cu-MOF/Au was determined by AAS while the amount of gold and its oxidation state on the surface of the MOF was studied by XPS. A glassy carbon (GC) electrode was drop-casted with a Cu-MOF suspension to electrochemically characterize the material through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The performance of the modified electrodes towards nitrite oxidation was tested by CV and chronoamperometry.

Production and characterization of novel thermoplastic (nano)composite materials for additive manufacturing applications

The increasing environmental global regulations have directed scientific research towards more sustainable materials, even in the field of composite materials for additive manufacturing. In this context, the presented research is devoted to the development of thermoplastic composites for FDM application with a low environmental impact, focusing on the possibility to use wastes from different industrial processes as filler for the production of composite filaments for FDM 3D printing. In particular carbon fibers recycled by pyro-gasification process of CFRP scraps were used as reinforcing agent for PLA, a biobased polymeric matrix. Since the high value of CFs, the ability to re-use recycled CFs, replacing virgin ones, seems to be a promising option in terms of sustainability and circular economy. Moreover, wastes from different agricultural industries, i.e. wheat and rice production processes, were valorised and used as biofillers for the production of PLA-biocomposites. The integration of these agricultural wastes into PLA bioplastic allowed to obtain biocomposites with improved eco-sustainability, biodegradability, lightweight, and lower cost. Finally, the study of novel composites for FDM was extended towards elastomeric nanocomposite materials, in particular TPU reinforced with graphene. The research procedure of all projects involves the optimization of production methods of composite filaments with a particular attention on the possible degradation of polymeric matrices. Then, main thermal properties of 3D printed object are evaluated by TGA, DSC characterization. Additionally, specific heat capacity (CP) and Coefficient of Linear Thermal Expansion (CLTE) measurements are useful to estimate the attitude of composites for the prevention of typical FDM issues, i.e. shrinkage and warping. Finally, the mechanical properties of 3D printed composites and their anisotropy are investigated by tensile test using distinct kinds of specimens with different printing angles with respect to the testing direction.

Design and characterization of wideband Hall current sensors in BCD technology for smart power and metering applications

Power electronic circuits are moving towards higher switching frequencies, exploiting the capabilities of novel devices to shrink the dimension of passive components. This trend demands sensors capable enough to operate at such high frequencies. This thesis aims to demonstrate through experimental characterization, the broadband capability of a fully integrated CMOS X-Hall current sensor in current mode interfaced with a transimpedance amplifier (TIA), chip CH09, realized in CMOS technology for power electronics applications such as power converters. The system exploits a common-mode control system to operate the dual supply system, 5-V for the X-Hall probe and 1.2-V for the readout. The developed prototype achieves a maximum acquisition bandwidth of 12 MHz, a power consumption of 11.46 mW, resolution of 39 mArms, a sensitivity of 8 % /T, and a FoM of 569-MHz/A2mW, significantly higher than current state-of-the-art. Further enhancements were proposed to CH09 as a new chip CH100, aiming for accuracy levels prerequisite for a real-time power electronic application. The TIA was optimized for a wider bandwidth of 26.7 MHz with nearly 30% reduction of the integrated input referred noise of 26.69 nArms at the probe-AFE interface in the frequency band of DC-30 MHz, and a 10% improvement in the dynamic range. The expected input range is 5-A. The chip incorporates a dual sensing chain for differential sensing to overcome common mode interferences. A novel offset cancellation technique is proposed that would require switching of polarity of bias currents. Thermal gain drift was improved by a factor of 8 and will be digitally calibrated utilizing a new built-in temperature sensor with a post calibration measurement accuracy greater than 1%. The estimated power consumption of the entire system is 55.6 mW. Both prototypes have been implemented through a 90-nm microelectronic process from STMicroelectronics and occupy a silicon area of 2.4 mm2.