Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Part One. X-ray crystallography has benefited from the synthetic introduction of selenium to different positions within nucleic acids by easing the solving of the phase problem. Interestingly, its addition to the 2' position of the ribose ring also significantly enhances crystal formation. This phenomenon was investigated to describe the effect of selenium-based and other 2' modifications to the ribose ring of nucleosides in solution, as well as the incorporation of the selenium-modified nucleotides into a helical structure. This work correlates the difference in conformation propensity between the selenium containing nucleosides and oligomers towards a rationale behind the enhanced crystal forming behavior. Part Two. Recombinant protein production is a critical tool in laboratories and industries, and inducing extracellular transport of these products to the culture medium shows potential for improving cases where the yields are not sufficient in quality or quantity. This review incorporates current practices and systems with future perspectives.

The main focus of this work was to investigate substitution effects on the chemical bonding in compounds of AlB 2 -type and related structure types. Delocalization indices within the QTAIM approach and the topological analysis of the ELI functionals were used as tools to describe the bonding situation in digallides and diborides. Digallides of AlB 2 -type were found only within group I and II; for CaGa 2 (meta-stable phase), SrGa 2 , BaGa 2 , YGa 2 and LaGa 2 compounds. Within these compounds, QTAIM analysis showed similar trend as previously found in diborides. That is, along the period in the Periodic Table, metal-triel interactions increase at the expense of in-plane (triel-triel) ab interactions (Tr=triel). However, transition metal diborides adopt the AlB 2 -type up to group VI. To understand this difference, we simulated transition metal (TM) digallides and diborides up to group VI in the AlB 2 -type. Additionally, the puckered variants diborides ReB 2 and OsB 2 were also simulated in the AlB 2 -type. With filling of d shell, there is a delicate balance between increase of TM–Tr and decrease of in-plane (Tr–Tr) ab electron sharing. This balance is maintained as long as interlayer interactions in the c direction (Tr–Tr ) c and (TM–TM ) c are not relatively too high in comparison to in-plane electron sharing. In contrast to TM B 2 of AlB 2 -type, digallides in the same structure type build up strong interlayer interactions for early transition metal elements. Our results showed that within digallides, a relatively strong increase in interlayer electron sharing (Ga–Ga) c and (TM–TM ) c takes place. Such increase occurs already for ScGa 2 and TiGa 2 . On the other hand, diborides show a steady increase in electron sharing of TM –B and (TM–TM ) c , but not of (B–B) c . Therefore, it is reasonable to suggest that diborides will tend to adopt a 3D network composed of boron and transition metal atoms (ReB 2 and RuB 2 types). The additional high (Ga–Ga) c interlayer interactions indicate a tendency for digallides to form 3D networks composed only by gallium atoms, characteristic of CaGa 2 (CaIn 2 -type) and ScGa 2 (KHg 2 -type). The counterbalancing bonding effects of in-plane and out-of-plane interactions that give the chemical flexibility of the AlB 2 -type in diborides is thus disrupted in AlB 2 -type digallides by a further enhanced degree of interlayer interactions (Ga–Ga) c and (TM –TM ) c . This results in a smaller number of digallides than that of diborides in AlB 2 -type. The most conspicuous difference between diborides and digallides of AlB 2 -type is in the representation of the B – B and Ga – Ga bonds revealed by the ELI- D topology. Whereas AlB 2 -type diborides exhibit one ELI-D attractor at the B – B midpoint, AlB 2 -type digallides exhibit two ELI-D attractors symmetrically opposite around the Ga – Ga bond midpoint. We utilized the E 2 H 4 (E=triel, tetrel ) molecular series in the D 2h point group symmetry as model systems for solid state calculations. In particular, we addressed the appearance of ELI- D double maxima for Ga – Ga, by using orbital decomposition within the ELI framework. The ELI-D topology changes along the 13th group T r 2 H 4 series. Whereas B 2 H 4 and Al 2 H 4 exhibit one ELI-D attractor representing the Tr–Tr bond, Ga 2 H 4 and In 2 H 4 give rise to two ELI-D attractors. Partial ELI-D allows the orbital decomposition of the electron density. Partial ELI-q gives access to the decomposition of a two-particle property, which is given by the Fermi-hole curvature. We have found that the d-orbitals enable the formation of the two ELI-D attractors through pairing contributions. This has a net effect of lowering electron localizability at the Ga – Ga bond midpoint. Namely, the different ELI-D topology of Ga – Ga and B – B bonds stems from the contributions of d-orbitals to orbital pairing. We have also investigated the bonding situation in transition metal diborides of ReB 2 -type (MnB 2 , TcB 2 , ReB 2) and RuB 2 -type (OsB 2 , RuB 2). One can consider these two structure types as an extension of the trend found in TM B 2 of AlB 2 -type: an increase in TM –B interactions and an enhanced three-center bonding. The change in the structure type results in a puckered layer of boron atoms with electrons equally shared between B – B and TM –B. However, TM –B bonds exhibit a high three-center character. The ELI-D/QTAIM intersection technique also revealed a high participation of TM in the B – B bonding basin population. Moreover, ELI-D topology in the ReB 2 -type also discloses a seemingly important Re 3 three-center interaction along the flat layer of Re atoms. Such basin is absent in MnB 2 , which coincides with the fact that MnB 2 was only observed in the AlB 2 -type. In this regard, we concluded that the 3D network consists not only of covalent B – B bonds, but also of TM –B bonds.

The main focus of this work was to investigate substitution effects on the chemical bonding in compounds of AlB 2 -type and related structure types. Delocalization indices within the QTAIM approach and the topological analysis of the ELI functionals were used as tools to describe the bonding situation in digallides and diborides. Digallides of AlB 2 -type were found only within group I and II; for CaGa 2 (meta-stable phase), SrGa 2 , BaGa 2 , YGa 2 and LaGa 2 compounds. Within these compounds, QTAIM analysis showed similar trend as previously found in diborides. That is, along the period in the Periodic Table, metal-triel interactions increase at the expense of in-plane (triel-triel) ab interactions (Tr=triel). However, transition metal diborides adopt the AlB 2 -type up to group VI. To understand this difference, we simulated transition metal (TM) digallides and diborides up to group VI in the AlB 2 -type. Additionally, the puckered variants diborides ReB 2 and OsB 2 were also simulated in the AlB 2 -type. With filling of d shell, there is a delicate balance between increase of TM–Tr and decrease of in-plane (Tr–Tr) ab electron sharing. This balance is maintained as long as interlayer interactions in the c direction (Tr–Tr ) c and (TM–TM ) c are not relatively too high in comparison to in-plane electron sharing. In contrast to TM B 2 of AlB 2 -type, digallides in the same structure type build up strong interlayer interactions for early transition metal elements. Our results showed that within digallides, a relatively strong increase in interlayer electron sharing (Ga–Ga) c and (TM–TM ) c takes place. Such increase occurs already for ScGa 2 and TiGa 2 . On the other hand, diborides show a steady increase in electron sharing of TM –B and (TM–TM ) c , but not of (B–B) c . Therefore, it is reasonable to suggest that diborides will tend to adopt a 3D network composed of boron and transition metal atoms (ReB 2 and RuB 2 types). The additional high (Ga–Ga) c interlayer interactions indicate a tendency for digallides to form 3D networks composed only by gallium atoms, characteristic of CaGa 2 (CaIn 2 -type) and ScGa 2 (KHg 2 -type). The counterbalancing bonding effects of in-plane and out-of-plane interactions that give the chemical flexibility of the AlB 2 -type in diborides is thus disrupted in AlB 2 -type digallides by a further enhanced degree of interlayer interactions (Ga–Ga) c and (TM –TM ) c . This results in a smaller number of digallides than that of diborides in AlB 2 -type. The most conspicuous difference between diborides and digallides of AlB 2 -type is in the representation of the B – B and Ga – Ga bonds revealed by the ELI- D topology. Whereas AlB 2 -type diborides exhibit one ELI-D attractor at the B – B midpoint, AlB 2 -type digallides exhibit two ELI-D attractors symmetrically opposite around the Ga – Ga bond midpoint. We utilized the E 2 H 4 (E=triel, tetrel ) molecular series in the D 2h point group symmetry as model systems for solid state calculations. In particular, we addressed the appearance of ELI- D double maxima for Ga – Ga, by using orbital decomposition within the ELI framework. The ELI-D topology changes along the 13th group T r 2 H 4 series. Whereas B 2 H 4 and Al 2 H 4 exhibit one ELI-D attractor representing the Tr–Tr bond, Ga 2 H 4 and In 2 H 4 give rise to two ELI-D attractors. Partial ELI-D allows the orbital decomposition of the electron density. Partial ELI-q gives access to the decomposition of a two-particle property, which is given by the Fermi-hole curvature. We have found that the d-orbitals enable the formation of the two ELI-D attractors through pairing contributions. This has a net effect of lowering electron localizability at the Ga – Ga bond midpoint. Namely, the different ELI-D topology of Ga – Ga and B – B bonds stems from the contributions of d-orbitals to orbital pairing. We have also investigated the bonding situation in transition metal diborides of ReB 2 -type (MnB 2 , TcB 2 , ReB 2) and RuB 2 -type (OsB 2 , RuB 2). One can consider these two structure types as an extension of the trend found in TM B 2 of AlB 2 -type: an increase in TM –B interactions and an enhanced three-center bonding. The change in the structure type results in a puckered layer of boron atoms with electrons equally shared between B – B and TM –B. However, TM –B bonds exhibit a high three-center character. The ELI-D/QTAIM intersection technique also revealed a high participation of TM in the B – B bonding basin population. Moreover, ELI-D topology in the ReB 2 -type also discloses a seemingly important Re 3 three-center interaction along the flat layer of Re atoms. Such basin is absent in MnB 2 , which coincides with the fact that MnB 2 was only observed in the AlB 2 -type. In this regard, we concluded that the 3D network consists not only of covalent B – B bonds, but also of TM –B bonds.

The knowledge of solid-state second phase heterogeneous nucleation process is limited due to the experimental difficulty, such as tiny length scale, short time period, and high temperature condition. In recent years, some significant breakthroughs in nucleation studies have been achieved by aid of computational techniques. In this study, we apply molecular dynamics (MD) simulations to perform with heterogeneous nucleation occurring at grain boundaries (GB) during the austenite (FCC) phase to ferrite (BCC) phase transformation in a pure Fe polycrystalline system. A neighbor vector analysis (NVA) method has been introduced and it is shown how the NVA can be used to determine the misorientation of grain or interphase boundaries, which allow a further investigation of the boundary structure correlated to interfacial energy and mobility during the nucleation and early grain growth stage. Meanwhile, benefited from the MD technique, the bulk energy, grain boundary energy, and interfacial energy can be individually captured during the simulations, which allow a detail analyze of the shape, critical size and nucleation energy of specific nuclei, through the classical nucleation theory (CNT) and according to a faceted-spherical cap geometric model (FSC). In addition, we also compared the results from the classical approach with a new algorithm that combination of the multi-phase field model (MPFM) and the nudged elastic band (NEB) method to demonstrate the CNT in the solid-state conduction. Finally, we extend our simulation method to a more complex triple GB junction nucleation event, and investigate the non-classical barrier-free nucleation behaviors. The results support the critical informations to clarify the initial state of austenite to ferrite transition, and improve our knowledge of the heterogeneous nucleation process, which help to bridge the gap between the experimental measurements and the theoretical calculations. The simulation method also provided a new approach for studying the complicate heterogeneous nucleation phenomenon in solid-state for a wide variety of polycrystalline material systems. / Thesis / Doctor of Philosophy (PhD)

Στα πλαίσια της διατριβής μελετήθηκε αρχικά το πρόβλημα της εύρεσης της θέσης του υφάσματος επάνω στην τράπεζα εργασίας με μεθόδους ψηφιακής ανάλυσης σημάτων βίντεο, παρουσία φαινομένων παραμόρφωσης και μερικής επικάλυψης του υφάσματος. Οι νέες μέθοδοι εντοπισμού που αναπτύχθηκαν αξιολογήθηκαν πειραματικά παρουσιάζοντας ικανοποιητική ακρίβεια εντοπισμού και ανοχή του συστήματος σε μερικές επικαλύψεις και παραμορφώσεις. Μετά την ολοκλήρωση της ραφής του υφάσματος πραγματοποιείται αυτόματος εντοπισμός της θέσης της ραφής από ψηφιακές φωτογραφίες. Αναπτύχθηκαν τρείς πρωτότυπες μέθοδοι εντοπισμού της θέσης της ραφής οι οποίες διαφοροποιούνται στο στάδιο της προεπεξεργασίας. Η πειραματική αξιολόγηση γίνεται σε βάση δεδομένων που περιέχει 118 εικόνες έτοιμων ενδυμάτων. Προτού πραγματοποιηθεί ποιοτικός έλεγχος ραφής, οι εικόνες κανονικοποιούνται ως προς τη θέση και τον προσανατολισμό της ραφής χρησιμοποιώντας τις παραπάνω μεθόδους αυτόματου εντοπισμού της θέσης της ραφής. Αναπτύχθηκαν και αξιολογήθηκαν τρείς διαφορετικές μέθοδοι αυτόματης αναγνώρισης της ποιότητας σε δείγματα ραφής οι οποίες εξάγουν τρία διαφορετικά σύνολα χαρακτηριστικών. Η πρώτη μέθοδος βασίζεται σε φασματικά χαρακτηριστικά, η δεύτερη στην επιβολή αυτό-σκίασης, ενώ η τρίτη βασίζεται στην εκτίμηση της ανομοιομορφίας της επιφάνειας των δειγμάτων ραφής. Η πειραματική αξιολόγηση γίνεται σε βάση δεδομένων δειγμάτων ραφής που περιλαμβάνει 325 ραφές. Η εκτίμηση της ποιότητας ραφής πραγματοποιείται με ταξινόμηση σε πέντε διατεταγμένους βαθμούς ποιότητας. Σε αυτήν την κατεύθυνση, προτείνονται και συγκρίνονται τέσσερις μέθοδοι αναγνώρισης προτύπων διατεταγμένων κατηγοριών. Η πρώτη μέθοδος χρησιμοποιεί για την ταξινόμηση μοντέλο σύμμετρων αναλογιών πιθανότητας. Η δεύτερη μέθοδος κάνει αναγνώριση με χρήση γραμμικού μοντέλου. Οι άλλες δύο μέθοδοι είναι πρωτότυπες και επίσης χρησιμοποιούν γραμμικό μοντέλο για την ταξινόμηση. Η διαφοροποίησή τους από τη δεύτερη μέθοδο είναι ότι η επιλογή των αριθμητικών τιμών των διατεταγμένων κατηγορίων δεν γίνεται αυθαίρετα., αλλά προκύπτει ως λύση προβλημάτων ελαχιστοποίησης.. Η πειραματική αξιολόγηση και σύγκριση των μεθόδων στο πρόβλημα του ποιοτικού ελέγχου ραφών οδηγεί στην επιλογή του μοντέλου σύμμετρων αναλογιών πιθανότητας σε περίπτωση που υπάρχει ικανός αριθμός παραδειγμάτων εκπαίδευσης, ενώ σε αντίθετη περίπτωση μπορεί να προτιμηθεί το γραμμικό μοντέλο αφού προηγηθεί βελτιστοποίηση με χρήση κάποιας εκ των δύο προτεινόμενων μεθόδων επιλογής αριθμητικών τιμών. / One of the problems studied in the present dissertation is that of the detection of the fabrics’ position on the working area. The proposed detection methods are based on image processing and analysis techniques and take into consideration both partial occlusion and fabric deformation. The methods have been experimentally evaluated and the results indicate sufficient detection accuracy and robustness regarding partial occlusion and fabric deformation. After sewing the fabric, the position and orientation of the seam is automatically detected. Three novel seam detection methods have been developed using different pre-processing techniques. The experimental evaluation of the three detection methods is made on a database containing 118 images of ready sewn garments. Before performing seam quality control the seam images are normalized with respect to the seam position and orientation, using the aforementioned seam detection methods. Feature selection has been studied next, extracting three different sets of features and assessing seam quality using three different methods. The first method uses spectral features; the second method is based on the detection of self-shadows onto the seam specimens, while the third method is based on the estimation of the surface roughness of the specimens. The experimental evaluation of the proposed methods is made on a database containing 325 images of seam specimens. Seam quality control is performed by classifying the seam specimens into five ordinal grades of quality. In this direction, four classification methods are proposed and evaluated, taking into account the ordered arrangement of the classes. The first method uses the proportional odds model; while the second method uses a linear model. The other two methods are novel and also employ a linear model. The difference between these two methods and the second method is that the numerical values they are assigning to the ordered categories are not arbitrary like in the case of the second method. The experimental evaluation of these four methods indicates that in case of a large number of training data, the first method which is based on the proportional odds model is more efficient, while in case of an insufficient number of training data the linear model optimized by one of the two novel methods should be selected.