Des gels ont été formulés à partir de mélanges de gélatine et de polysaccharides - le guar, le karaya, la xanthane, la maltodextrine et l’amidon - afin de reproduire les propriétés texturales du Camembert et du Coulommiers. La fermeté, le module d’élasticité et le temps de relaxation, mesurés à partir des essais de pénétrométrie et de relaxation, ont été utilisés afin de comparer les gels et les fromages. Les paramètres rhéologiques du mélange de gélatine, de maltodextrine et d’amidon s’approchaient le plus de ceux des fromages. Un plan de mélange à trois composants a été utilisé pour optimiser la concentration des constituants du simulant. Cette approche a permis de développer des modèles mathématiques qui prédisent les effets de chaque composant sur les paramètres texturaux du simulant. Elle a aussi mis en évidence une corrélation linéaire entre ces paramètres et la composition du gel. Des modifications texturales des simulants ont été induites par ajout de Subtilisine Carlsberg afin d’imiter l’évolution de la texture des fromages lors de la maturation. Une différence entre l’évolution des propriétés texturales des simulants et celle du fromage a été notée. La numérisation tridimensionnelle a été utilisée comme nouvel outil pour caractériser la texture. Ces systèmes sont capables de distinguer des gels et des fromages ayant des comportements rhéologiques différents. Les nouveaux paramètres obtenus, corrélés aux propriétés texturales des fromages et simulants, pourraient améliorer les modèles prédisant les mesures sensorielles hédoniques à partir des mesures instrumentales / Various gels formulated from mixtures of gelatin and polysaccharides - guar, karaya gum, xanthan gum, maltodextrin and starch - were elaborated to simulate soft cheeses (Camembert and Coulommiers) texture. Comparisons between gels and cheeses were based on firmness, elasticity modulus and relaxation time constants, obtained from penetrometry and stress relaxation tests. Gels made up of gelatin, maltodextrin and starch were found to imitate best the textural properties of the soft cheeses. A three-component mixture design approach was used to determine the optimum component concentration of the simulants. Mathematical models developed showed linear dependence of the rheological parameters on composition of simulants. Enzyme Subtilisin Carlsberg (Alcalase®) successful induced gradual modifications in rheological parameters of simulants. The rate of change of textural properties occurring in Coulommiers cheese during maturation was however different from that of the simulants. Two optical three-dimensional techniques as new tools for food texture assessment were also investigated. Digital image correlation and the Breuckmann scanning systems were successful in distinguishing between gels and cheeses varying in firmness and viscoelastic properties. New parameters obtained from digital image correlation and Breuckmann scanning systems were related to the textural properties of the cheeses and their simulants. These parameters may be used to develop models predicting accurately the sensory texture of food from instrumental measurements

Scientists have been well aware of the complexity of Martian and lunar regoliths. There are vast unexplored areas on both, the Moon and Mars, as well as uncertainties in our understanding of the physicochemical properties of their regoliths. Lunar and Martian regoliths differ from terrestrial soils in that they appear granular, but are expected to contain some cohesion. As such, cohesion in regolith poses challenges for future space operations, more specifically for landing, settlement, and mobility purposes. The ability to induce prescribed levels of cohesion in regolith simulants and reliably measure it would allow scientists to evaluate space technology limitations under different operational scenarios on Earth prior to a mission. Therefore, the objectives of this research were to (1) develop methods to induce prescribed levels of cohesion in dry granular media, and (2) evaluate accessible and reliable testing methods to measure cohesion. We developed and evaluated several methods to induce cohesion in two types of dry sand, F-75 silica sand and generic play sand. The methods to induce cohesion included play sand mixed with sugar-water, polymeric sand, and nanocellulose fibers, as well as F-75 sand mixed with polydimethylsiloxane, polyvinyl acetate, crystalline silica, agar, zero-valent iron, adhesive spray, and sand surface modification using a plasma gun. Each method was assessed for advantages and disadvantages, and laboratory specimens produced using the most promising methods were tested at different compositions and densities to measure cohesion. The laboratory methods used to measure the cohesion included direct shear test, simple direct shear test, and vertical cut test. The results from these tests were then compared to tensile strength tests, using a split box test. In addition, these tests were also performed on lunar simulants JSC-1A and GRC-3 at different densities. The direct shear apparatus was available, but the other three devices were fabricated as part of this work. Based on the research results, simple methods to potentially induce low levels of cohesion in dry granular media are suggested along with suitability of laboratory methods to measure the added cohesion.

The response of porcine adipose and skeletal muscle tissues to shock compression has been investigated using the plate-impact technique in conjunction with manganin foil pressure gauge diagnostics. This approach has allowed for measurement of the levels of uniaxial stress imparted to both skeletal muscle and rendered adipose tissue by the shock. In addition, the lateral stress component generated within adipose tissue during shock loading has also been investigated. The techniques employed in this study have allowed for equation-of-state relationships to be established for the investigated materials, highlighting non-hydrodynamic behaviour in each type of tissue over the range of investigated impact conditions. While the adipose tissue selected in this work has been shown to strengthen with impact stress in a manner similar to that seen to occur in polymeric materials, the skeletal muscle tissues exhibited a ow strength, or resistance to compression, that was independent of impact stress. Both the response of the adipose material and tested skeletal muscle tissues lie in contrast with the shock response of ballistic gelatin, which has previously been shown to exhibit hydrodynamic behaviour under equivalent loading conditions. Plate-impact experiments have also been used to investigate the shock response of a homogenized variant of one of the investigated muscle tissues. In the homogenized samples, the natural structure of skeletal muscle tissue, i.e. a fibrous and anisotropic composite, was heavily disrupted and the resulting material was milled into a fine paste. Rather than matching the response of the unaltered tissues, the datapoints generated from this type of experiment were seen to collapse back on to the hydrodynamic response predicted for skeletal muscle by its linear equation-of-state (Us = 1.72 + 1.88up). This suggests that the resistance to compression apparent in the data obtained for the virgin tissues was a direct result of the interaction of the shock with the quasi-organized structure of skeletal muscle. A soft-capture system has been developed in order to facilitate post-shock analysis of skeletal muscle tissue and to ascertain the effects of shock loading upon the structure of the material. The system was designed to deliver a one-dimensional, at-topped shock pulse to the sample prior to release. The overall design of the system was aided by use of the non-linear and explicit hydrocode ANSYSR AUTODYN. Following shock compression, sections of tissue were imaged using a transmission electron microscope (TEM). Both an auxetic-like response and large-scale disruption to the I-band/Z-disk regions within the tissue's structure were observed. Notably, these mechanisms have been noted to occur as a result of hydrostatic compression of skeletal muscle within the literature.

AN ABSTRACT OF THE THESIS OFChristopher T. Mandrell, for the Master of Science degree in Physics, presented on April 8, 2020, at Southern Illinois University Carbondale.TITLE: IMPROVING SPECTRAL ANALYSIS WITH THE APPLICATION OF MACHINE LEARNING: STUDY OF LASER-INDUCED BREAKDOWN SPECTROSCOPY (LIBS) AND RAMAN SPECTROSCOPY WITH CLASSIFICATION AND CLUSTERING TECHNIQUESMAJOR PROFESSOR: Dr. Poopalasingam SivakumarAtomic and molecular spectroscopy, in the form of LIBS emissions and Raman scattering, respectively, are tools that provide a vast amount of information with little to no sample preparation. For this reason, these techniques are finding their way into a wide range of fields. However, each spectrum is notoriously complicated to analyze, with many complex interactions at play. Machine learning is the result of work on artificial intelligence. It provides tools to train a computer to look for connections in complex data sets that would likely be missed, or not even looked for, by other analytical methods. The combination of highly informative yet complex data with an analysis that is specifically designed to probe highly complex data for meaningful information is a logical step in the analysis of these spectra. Here we apply statistical analysis and classification algorithms to Raman spectra of pancreatic cancer cells and clustering algorithms to LIBS spectra of Mars Curiosity Rover simulants and Raman spectra of Mars Perseverance Rover simulants. We report here high accuracy in the classification of different types of pancreatic cancer cells, and informative clustering of the two Mars rovers’ simulant data.

This research aims to contribute to the safe methodology for additive manufacturing (AM) of energetic materials. Coating formulation processes were investigated to find a suitable method that may enable selective laser sintering (SLS) as the safe method for fabrication of high explosive (HE) compositions. For safety and convenience reasons, the concept demonstration was conducted using inert explosive simulants with properties quasi-similar to the real HE. Coating processes for simulant RDX-based microparticles by means of PCL and 3,4,5- trimethoxybenzaldehyde (as TNT simulant) are reported. These processes were evaluated for uniformity of coating the HE inert simulant particles with binder materials to facilitate the SLS as the adequate binding and fabrication method. The critical constraints being the coating effectiveness required, spherical particle morphology, micron size range (>20 μm) and a good powder deposition and flow, and performance under SLS to make the method applicable for HEs. Of the coating processes investigated, suspension system and single emulsion methods gave required particle near spherical morphology, size and uniform coating. The suspension process appears to be suitable for the SLS of HE mocks and potential formulation methods for active HE composites. The density was estimated to be comparable with the current HE compositions and plastic bonded explosives (PBXs) such as C4 and PE4, produced from traditional methods. The formulation method developed and the understanding of the science behind the processes paves the way toward safe SLS of the active HE compositions and may open avenues for further research and development of munitions of the future. / Dissertation (MSc (Applied Science:Chemical Technology))--University of Pretoria, 2019. / Chemical Engineering / MSc (Applied Science:Chemical Technology) / Unrestricted

The response of porcine adipose and skeletal muscle tissues to shock compression has been investigated using the plate-impact technique in conjunction with manganin foil pressure gauge diagnostics. This approach has allowed for measurement of the levels of uniaxial stress imparted to both skeletal muscle and rendered adipose tissue by the shock. In addition, the lateral stress component generated within adipose tissue during shock loading has also been investigated. The techniques employed in this study have allowed for equation-of-state relationships to be established for the investigated materials, highlighting non-hydrodynamic behaviour in each type of tissue over the range of investigated impact conditions. While the adipose tissue selected in this work has been shown to strengthen with impact stress in a manner similar to that seen to occur in polymeric materials, the skeletal muscle tissues exhibited a ow strength, or resistance to compression, that was independent of impact stress. Both the response of the adipose material and tested skeletal muscle tissues lie in contrast with the shock response of ballistic gelatin, which has previously been shown to exhibit hydrodynamic behaviour under equivalent loading conditions. Plate-impact experiments have also been used to investigate the shock response of a homogenized variant of one of the investigated muscle tissues. In the homogenized samples, the natural structure of skeletal muscle tissue, i.e. a fibrous and anisotropic composite, was heavily disrupted and the resulting material was milled into a fine paste. Rather than matching the response of the unaltered tissues, the datapoints generated from this type of experiment were seen to collapse back on to the hydrodynamic response predicted for skeletal muscle by its linear equation-of-state (Us = 1.72 + 1.88up). This suggests that the resistance to compression apparent in the data obtained for the virgin tissues was a direct result of the interaction of the shock with the quasi-organized structure of skeletal muscle. A soft-capture system has been developed in order to facilitate post-shock analysis of skeletal muscle tissue and to ascertain the effects of shock loading upon the structure of the material. The system was designed to deliver a one-dimensional, at-topped shock pulse to the sample prior to release. The overall design of the system was aided by use of the non-linear and explicit hydrocode ANSYSR AUTODYN. Following shock compression, sections of tissue were imaged using a transmission electron microscope (TEM). Both an auxetic-like response and large-scale disruption to the I-band/Z-disk regions within the tissue's structure were observed. Notably, these mechanisms have been noted to occur as a result of hydrostatic compression of skeletal muscle within the literature.

Developing a fundamental understanding of the interactions of chemical warfare agents (CWAs) with surfaces is essential for the rational design of new sorbents, sensors, and decontamination strategies. The interactions of chemical warfare agent simulants, molecules which retain many of the same chemical or physical properties of the agent without the toxic effects, with amorphous silica were conducted to investigate how small changes in chemical structure affect the overall chemistry. Experiments investigating the surface chemistry of two classes of CWAs, nerve and blister agents, were performed in ultrahigh vacuum to provide a well-characterized system in the absence of background gases. Transmission infrared spectroscopy and temperature-programmed desorption techniques were used to learn about the adsorption mechanism and to measure the activation energy for desorption for each of the simulant studied. In the organophosphate series, the simulants diisopropyl methylphosphonate (DIMP), dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), dimethyl chlorophosphate (DMCP), and methyl dichlorophosphate (MDCP) were all observed to interact with the silica surface through the formation of a hydrogen bond between the phosphoryl oxygen of the simulant and an isolated hydroxyl group on the surface. In the limit of zero coverage, and after defect effects were excluded, the activation energies for desorption were measured to be 57.9 ± 1, 54.5 ± 0.3, 52.4 ± 0.6, 48.4 ± 1, and 43.0 ± 0.8 kJ/mol for DIMP. DMMP, TMP, DMCP, and MDCP respectively. The adsorption strength was linearly correlated to the magnitude of the frequency shift of the ν(SiO-H) mode upon simulant adsorption. The interaction strength was also linearly correlated to the calculated negative charge on the phosphoryl oxygen, which is affected by the combined inductive effects of the simulants' different substituents. From the structure-function relationship provided by the simulant studies, the CWA, Sarin is predicted to adsorb to isolated hydroxyl groups of the silica surface via the phosphoryl oxygen with a strength of 53 kJ/mol. The interactions of two common mustard simulants, 2-chloroethyl ethyl sulfide (2-CEES) and methyl salicylate (MeS), with amorphous silica were also studied. 2-CEES was observed to adsorb to form two different types of hydrogen bonds with isolated hydroxyl groups, one via the S moiety and another via the Cl moiety. The desorption energy depends strongly on the simulant coverage, suggesting that each 2-CEES adsorbate forms two hydrogen bonds. MeS interacts with the surface via a single hydrogen bond through either its hydroxyl or carbonyl functionality. While the simulant work has allowed us to make predictions agent-surface interactions, actual experiments with the live agents need to be conducted to fully understand this chemistry. To this end, a new surface science instrument specifically designed for agent-surface experiments has been developed, constructed, and tested. The instrument, located at Edgewood Chemical Biological Center, now makes it possible to make direct comparisons between simulants and agents that will aid in choosing which simulants best model live agent chemistry for a given system. These fundamental studies will also contribute to the development of new agent detection and decontamination strategies. / Ph. D.

Reflection absorption infrared spectroscopy was used as the primary analysis technique to study the interfacial chemistry of surfaces relevant to chemical and biological warfare agent defense. Many strategies utilized by the military to detect and decompose chemical and biological warfare agents involve their interaction with surfaces. However, much of the chemistry that occurs at the interface between the agents and surfaces of interest remains unknown. The surface chemistry plays an important role in efficacy of both detection and decontamination technology, and by obtaining a deeper understanding of that chemistry, researchers might be able to develop more sensitive detection devices and more effective decontamination strategies. Our efforts have focused on three different areas of surface chemistry relevant to chemical and biological warfare agent defense: 1) The development of a surface synthesis strategy to create and control the structure of antibacterial self-assembled monolayers (SAMs). Our work demonstrated a successful strategy for creating SAMs that contain long-chain quaternary ammonium groups, which were synthesized and subsequently characterized using RAIRS and X-ray photoelectron spectroscopy (XPS). 2) The determination of the surface conformation, orientation, and relative surface density of immobilized antimicrobial peptides. Our results revealed that the peptides consisted of tilted (50-60°), α-helices on the surface, regardless of solution conditions. 3) The design and construction of a new ultrahigh vacuum surface science instrument that allows for the study of gas-surface reactions with up to three gases simultaneously. 4) The study of the adsorption of chemical warfare agent simulants to silica nanoparticulate films. Our work demonstrated that the adsorbate structure was dependent on the number of hydrogen-bonding groups, and the adsorption consists of a pressure-dependent two part mechanism. The results presented here will help increase the understanding of the surface chemistry of three interfaces relevant to chemical and biological defense. Future researchers may apply the new information to develop more effective detection and decontamination strategies for chemical and biological warfare agents. / Ph. D.

Developing a fundamental understanding of the interactions of chemical warfare agents (CWAs) with surfaces is essential for the rational design of new sorbents, sensors, and decontamination strategies. The interactions of chemical warfare agent simulants, molecules which retain many of the same chemical or physical properties of the agent without the toxic effects, with amorphous silica were conducted to investigate how small changes in chemical structure affect the overall chemistry. Experiments investigating the surface chemistry of two classes of CWAs, nerve and blister agents, were performed in ultrahigh vacuum to provide a well-characterized system in the absence of background gases. Transmission infrared spectroscopy and temperature-programmed desorption techniques were used to learn about the adsorption mechanism and to measure the activation energy for desorption for each of the simulant studied. In the organophosphate series, the simulants diisopropyl methylphosphonate (DIMP), dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), dimethyl chlorophosphate (DMCP), and methyl dichlorophosphate (MDCP) were all observed to interact with the silica surface through the formation of a hydrogen bond between the phosphoryl oxygen of the simulant and an isolated hydroxyl group on the surface. In the limit of zero coverage, and after defect effects were excluded, the activation energies for desorption were measured to be 57.9 ± 1, 54.5 ± 0.3, 52.4 ± 0.6, 48.4 ± 1, and 43.0 ± 0.8 kJ/mol for DIMP. DMMP, TMP, DMCP, and MDCP respectively. The adsorption strength was linearly correlated to the magnitude of the frequency shift of the ν(SiO-H) mode upon simulant adsorption. The interaction strength was also linearly correlated to the calculated negative charge on the phosphoryl oxygen, which is affected by the combined inductive effects of the simulants’ different substituents. From the structure-function relationship provided by the simulant studies, the CWA, Sarin is predicted to adsorb to isolated hydroxyl groups of the silica surface via the phosphoryl oxygen with a strength of 53 kJ/mol. The interactions of two common mustard simulants, 2-chloroethyl ethyl sulfide (2-CEES) and methyl salicylate (MeS), with amorphous silica were also studied. 2-CEES was observed to adsorb to form two different types of hydrogen bonds with isolated hydroxyl groups, one via the S moiety and another via the Cl moiety. The desorption energy depends strongly on the simulant coverage, suggesting that each 2-CEES adsorbate forms two hydrogen bonds. MeS interacts with the surface via a single hydrogen bond through either its hydroxyl or carbonyl functionality. While the simulant work has allowed us to make predictions agent-surface interactions, actual experiments with the live agents need to be conducted to fully understand this chemistry. To this end, a new surface science instrument specifically designed for agent-surface experiments has been developed, constructed, and tested. The instrument, located at Edgewood Chemical Biological Center, now makes it possible to make direct comparisons between simulants and agents that will aid in choosing which simulants best model live agent chemistry for a given system. These fundamental studies will also contribute to the development of new agent detection and decontamination strategies. / Ph. D.