Amorphous and bulk amorphous metallic alloys are an intriguing class of structural materials and possess a range of interesting properties, including near theoretical strength, high hardness, extremely low damping characteristics, excellent wear properties, high corrosion resistance, low shrinkage during cooling and almost perfect as-cast surfaces with good potential for forming and shaping. In this study, new Ti-based bulk amorphous alloys are tried to be modeled and synthesized. For that purpose, electronic theory of alloys in the pseudo potential approximation was used as a tool for understanding the theory lying beneath the bulk glass forming ability (BGFA). The results from this approach were evaluated both separately and together with the other theories supposed by our colleagues. Glass forming parameters of ordering energy, &amp / #916 / HM, viscosity, mismatch entropy, Rc was calculated for various Ti-based binary and ternary and the change in these parameters in both cases was evaluated. The results of the theoretical calculations of glass forming parameters has shown good relation with the literature data that the predicted alloying elements, i.e. Mo, Hf, Zr, B, Fe, Sn, and Be, to increase GFA for Ti2Ni binary system were generally used in the production of Ti-based bulk amorphous alloys. In the second part of this thesis, new Ti-based compositions with high GFA were tried to be synthesized with light of these results and encouraging conclusions were drawn. The production of these alloys were made with centrifugal casting method which is relatively a new technique for producing such alloys and the characterization of these alloys were made with metallographic, X-ray and thermal means.

The aim of this study is to form a theoretical model for simulation of glass forming ability of Fe &amp / #65533 / Based bulk amorphous alloys, to synthesize Fe &amp / #65533 / based multicomponent glassy alloys by using the predictions of the theoretical study, and to analyze the influence of crystallization and solidification kinetics on the microstructural features of this amorphous alloys. For this purpose, first, glass forming ability of Fe &amp / #65533 / (Mo, B, Cr, Nb, C) &amp / #65533 / X ( X = various alloying elements, selected from the periodic table) ternary alloy systems were simulated for twenty different alloy compositions by using the electronic theory of alloys in pseudopotential approximation and regular solution theory. Then, by using the results of the theoretical study, systematic casting experiments were performed by using centrifugal casting method. The alloying elements were melted with induction under argon atmosphere in alumina crucibles and casted into copper molds of different shapes. Characterization of the cast specimens were performed by using DSC, XRD, SEM, and optical microscopy. Comparison of equilibrium and nonequilibrium solidification structures of cast specimens were also performed so as to verify the existence of the amorphous phase. Good agreement of the results of experimental work, with the predictions of the theoretical study, and the related literature was obtained.

In recent years, bulk amorphous alloys and nanocrystalline materials have been synthesized in a number of ferrous and non-ferrous based alloys systems, which have gained some applications due to their unique physico-chemical and mechanical properties. In the last decade, Zr-based alloys with a wide supercooled liquid region and excellent glass forming ability have been discovered. These systems have promising application fields due to their mechanical properties / high tensile strength, high fracture toughness, high corrosion resistance and good machinability. In this study, the aim is to model, synthesize and characterize the Zr-based bulk amorphous alloys. Initially, theoretical study on the basis of the semi-empirical rules well known in literature and the electronic theory of alloys in pseudopotential approximation has been provided in order to predict the potential impurity elements that would lead to an increase in the GFA of the selected Zr-Ni, Zr-Fe, Zr-Co and Zr-Al based binary systems. Furthermore, thermodynamic and structural parameters were calculated for mentioned binary and their ternary systems. According to the theoretical study, Zr67Ni33 binary system was selected and its multicomponent alloys were formed by adding its potential impurity elements / Mo, W and Al. Centrifugal casting method was used to produce alloy systems. Structural characterizations were performed by DSC, XRD, SEM and EDS methods. In the near-surface regions of Zr60Ni25Mo10W5 and Zr50Ni20Al15Mo10W5 alloys, amorphous structure has been observed. Experimental studies have shown that Zr-Ni based systems with impurity elements Mo, W and Al, not widely used in literature, might be good candidates for obtaining high GFA.

The aim of this study is to synthesize and characterize new bulk amorphous alloys in the Ni- based systems. Theoretical studies on the basis of semi-empirical rules and the electronic theory of alloys in pseudopotential approximation has been provided in order to predict the impurity elements that will lead to an increase in the glass forming ability of Ni-based alloy systems. Glass forming ability of ten different compositions of alloys of Ni-Nb, Ni-Fe, Ni-B, Ni-Hf and Ni-Cr was simulated by using FORTRAN programs based on pseudopotential theory. In addition to the binary alloys, ternary alloys, which were formed by addition of 1 at% of third element to these systems, were also simulated. Since ordering energy is an indicator of glass forming ability, theoretical studies allowed to predict the effect of various third elements on the formation of amorphous phase. Furthermore, ordering energies were also used to calculate other parameters important for glass forming ability. In the second part of the study, on the basis of theoretical results, a series of casting experiments were done. Different compositions of Ni-Nb, Ni-Nb-Sn and Ni-Nb-Al alloys were cast in the centrifugal casting machine. Alloys were melted in alumina crucibles and cast into the copper moulds. Characterizations of cast alloys were done by the use of Metallography, SEM, XRD and DSC. Fully amorphous Ni52Nb41Al7 alloy was synthesized in bulk form with 0.8 mm thickness.

The aim of this study, which was carried out in two main parts, is to investigate the glass forming ability of Fe-based systems. The first part involves the theoretical modeling to cover the requirement of a predictive model to identify the Fe-based alloy families that have high glass forming ability in the frame of atomistic and thermodynamic approach. The second part involves the experimental investigations to prove the results of the conducted theoretical modeling studies. For this purpose, in the first part, theoretical investigations were performed to identify the third alloying elements that will lead to an increase in the glass forming ability on the base of electronic theory of alloys in pseudopotential approximation for selected Fe- based systems, Fe - (B, Zr, Nb, C, W). In the experimental part, in the frame of the theoretical investigation results, one of the theoretically modeled binary system, and the third alloying elements that were predicted to lead an increase in the glass forming ability of the selected binary system, were determined. As a first step, designated compositions were synthesized by using low grade conventional Fe-B alloy as a raw material by using centrifugal casting technique and copper mold casting method. To compare the results, same compositions were also cast from the high purity elements by using the same technique and method. For the characterization of these cast specimens, DSC, XRD, SEM, EDS and metallographic examination techniques were used. Amorphous structure was successfully obtained in the thin sections of the wedge-cast samples for Fe-B-Nb and Fe-B-W ternary systems.

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Lack of crystalline order and microstructural features such as grain/grain-boundary in metallic glasses results in a suite of remarkable attributes including very high strength, close to theoretical elasticity, high corrosion and wear resistance, and soft magnetic properties. In particular, low coercivity and high permeability of iron and cobalt based metallic glass compositions could potentially lead to extensive commercial use as magnetic heads, transformer cores, circuits and magnetic shields. In the current study, few metallic glass compositions were synthesized by systematically varying the iron and cobalt content. Thermal analysis was done and included the measurement of glass transition temperature, crystallization temperature, and the enthalpies of relaxation and crystallization. Magnetic properties of the alloys were determined including saturation magnetization, coercivity, and Curie temperature. The coercivity was found to decrease and the saturation magnetization was found to increase with the increase in iron content. The trend in thermal stability, thermodynamic properties, and magnetic properties was explained by atomic interactions between the ferromagnetic metals and the metalloids atoms in the amorphous alloys. Mechanical behavior of iron based metallic glasses was evaluated in bulk form as well as in the form of coatings. Iron based amorphous powder was subjected to high power mechanical milling and the structural changes were evaluated as a function of time. Using iron-based amorphous powder precursor, a uniform composite coating was achieved through microwave processing. The hardness, modulus, and wear behavior of the alloys were evaluated using nano-indentation.

The absence of long-range order in glassy chalcogenides provides the convenience of changing the elemental ratios and hence the properties over a wide range. The interesting properties exhibited by chalcogenide glasses make them suitable materials for Phase Change Memories (PCM) and other applications such as infrared optical devices, photo-receptors, sensors, waveguides, etc. One of the most remarkable properties of chalcogenides is their electrical switching behavior. Reversible (threshold type) or irreversible (memory type) switching from a high resistance OFF state to a low resistance ON state in glassy chalcogenides occurs at a critical voltage called the threshold/switching voltage (VT). Investigations on the switching behavior and its composition dependence throw light on the local structural effects of amorphous chalcogenide semiconductors and also help us in identifying suitable samples for PCM applications. Thermal analysis by Differential Scanning Calorimetry (DSC) has been extensively used in glass science, particularly for measurements of thermal parameters such as enthalpy of relaxation, specific heat change, etc., near glass transition. Quite recently, the conventional DSC has been sophisticated by employing a composite temperature profile for heating, resulting in the Temperature Modulated DSC (TMDSC) or Alternating DSC (ADSC). Measurements made using ADSC reveal thermal details with enhanced accuracy and resolution, and this has lead to a better understanding of the nature of glass transition. The thermal parameters obtained using DSC/ADSC are also vital for understanding the electrical switching behavior of glassy chalcogenides. The motivation of this thesis was twofold: The first was to develop a novel, high voltage programmable power supply for electrical switching analysis of samples exhibiting high VT, and second to investigate the thermal and electrical switching behavior of certain Se-Te based glasses with Ge and Sb additives. The thesis contains seven chapters: Chapter 1: This chapter provides an overview of amorphous semiconductors (a-SC) with an emphasis on preparation and properties of glassy chalcogenides. The various structural models and topological thresholds of a-SC are discussed with relations to the glass forming ability of materials. The electronic band models and defect states are also dealt with. The essentials of electrical switching behavior of chalcogenides are discussed suggesting the electronic nature of switching and the role of thermal properties on switching. Chapter 2: The second chapter essentially deals with theory and practice of the experimental techniques adopted in the thesis work. The details of the melt-quenching method of synthesizing glassy samples are provided. Considering the importance, the theory of thermal analysis by DSC & ADSC, are discussed in detail, highlighting the advantages of the latter method adopted in the thesis work. The instrumentation and electronics, developed and used for electrical switching analysis are also introduced at a block diagram level. Finally, the methods used for structural analysis are briefed. Chapter 3: This chapter is dedicated to the design and development details of the programmable High Voltage dc Power Supply (HVPS: 1750 V, 45 mA) undertaken in the thesis work. The guidelines used for power supply topology selection, the specifications and block diagram of the HVPS are provided in that sequence. The operation of the HVPS is discussed using the circuit diagram approach. The details of software control are also given. The performance validations of the HVPS, undertaken through voltage & current regulation tests, step & frequency response tests are discussed. Finally, the sample-test results on the electrical switching behavior of representative Al20As16Te64 and Ge25Te65Se10 samples, obtained using both the current & voltage sweep options of the HVPS developed are illustrated. Chapter 4: Results of the thermally induced transitions governed by structural changes which are driven by network connectivity in the GexSe35-xTe65 (17 ≤ x ≤ 25) glasses, as revealed by ADSC experiments, are discussed in this chapter. It is found that the GexSe35-xTe65 glasses with x ≤ 20 exhibit two crystallization exotherms (Tc1 & Tc2), whereas those with x ≥ 20.5, show a single crystallization reaction upon heating (Tc). The glass transition temperature of GexSe35-xTe65 glasses is found to show a linear, but not-steep increase, indicating a progressive and not an appreciable build-up in network connectivity with Ge addition. The exothermic reaction at Tc1 has been found to correspond to the partial crystallization of the glass into hexagonal Te and the reaction at Tc2 is associated with the additional crystallization of rhombohedral Ge-Te phase. It is also found that the first crystallization temperature Tc1 of GexSe35-xTe65 glasses of lower Ge concentrations (with x ≤ 20), increases progressively with Ge content and eventually merges with Tc2 at x = 20.5 (<r> = 2.41); this behavior has been understood on the basis of the reduction in Te-Te bonds of lower energy and an increase in Ge-Te bonds of higher energy, with increasing Ge content. Chapter 5: This chapter deals with the electrical switching studies on GexSe35-xTe65 (17 ≤ x ≤ 25) glasses, with an emphasis on the role of network connectivity/rigidity on the switching behavior. It is found that the switching voltage (VT) increases with Ge content, exhibiting a sudden jump at x=20, the Rigidity Percolation Threshold (RPT) of the system. In addition, the switching behavior changes from memory to threshold type at the RPT and the threshold switching is found to be repetitive for more than 1500 cycles. Chapter 6: In this chapter, the results of thermal analysis (by ADSC) and electrical switching investigations on SbxSe55-xTe45 (2 ≤ x ≤ 9) are discussed. It is found that the addition of trivalent Sb contributes very meagerly to network growth but directly affects the structural relaxation effects at Tg. Further, SbxSe55-xTe45 glasses exhibit memory type electrical switching, which is understood on the basis of poor thermal stability of the samples. The metallicity factor is observed to outweigh the network factor in the composition dependence of VT of SbxSe55-xTe45 glasses. Chapter 7: The chapter 7 summarizes the results obtained in the thesis work and provides the scope for future work. The references are cited in the text along with the first author’s name and year of publication, and are listed at the end of each chapter in alphabetical order.

The glass-forming composition ranges in Al-La-Ni and Mg-TM (Cu, Zn)-Y alloys were predicted using Miedema’s model. Glass-forming abilities of Al-La-Ni alloys and Mg-Cu-RE alloys were studied in terms of reduced glass transition temperature (Trg), supercooled liquid region (∆Tx) and γ parameters. The glass-forming ability parameters of Mg-Cu-RE (RE: rare-earth) alloys were correlated with Mendeleev number. The Miedema model has been used to determine glass-forming composition range in binary Al-La, Al-Ni and La-Ni alloy systems and the ternary Al-La-Ni system by neglecting the ternary interactions. The glass-forming composition range for Al-La, Al-Ni and La-Ni alloy systems extends from 5 to 90 at% La, 30 to 80 at% Ni and 5 to 95 at% Ni, respectively. In these systems the predicted glass-forming composition range is wider than the experimentally observed range. Miedema model, restricting the difference of enthalpy of formation between the amorphous and solid solution phases to within –10000 J/mole to –55000 J/mole gives rise to better prediction of glass-forming composition range compared to the original models. The concept of mixing enthalpy and mismatch entropy has been used in order to quantify Inoue’s criteria of glass formation. The mixing enthalpy and normalised mismatch entropy of the ternary Al-La-Ni alloys, calculated by the extended regular solution model, vary between –12 to –40 kJ/mol and 0.16 to 0.65, respectively. The enthalpy contour plot has been constructed to distinguish the glass-forming compositions on the basis of the increasing negative enthalpy of the composition. Six Al rich Al-La-Ni alloys with nominal compositions Al89La6Ni5, Al85La10Ni5, Al85La5Ni10, Al82La8Ni10, Al80La10Ni10 and Al60La20Ni20 three La rich Al-La-Ni alloys with nominal compositions Al34La33Ni33, Al40La40Ni20 and Al25La50Ni25 have been chosen from the Al-La-Ni ternary phase diagram, to study the glass-forming ability of Al-La-Ni ternary alloy system and the correlation between La-based and Al-based glasses. All the alloys have been prepared using arc melting unit. All the alloy ribbons have been prepared using single-wheel vacuum melt-spinning unit. Two different wheel speeds of 20 m/s and 40 m/s were used for preparing ribbons of all the nine alloys. All the Al-La-Ni compositions, excluding equi-atomic composition (Al34La33Ni33) and Al60La20Ni20, give rise to amorphous phases. The supercooled liquid region and reduced glass transition temperature of this system increases with a decrease in Al content and an increase in La content. The glass-forming ability of the Al rich Al-La-Ni alloys is lower than that of the La-rich Al-La-Ni alloys. The glass-forming ability has been explained by taking into account the binary heat of mixing and the atomic radius mismatch of the constituent elements. Preferential crystallisation takes place during the heat treatment of glassy ribbons. The crystalline products are partially influenced by composition and binary heat of mixing between elements. Mg65Cu25Y10 alloy is a classical glass former of a family of Mg-based alloys. The partial or complete substitution of Y with other rare earth elements has been introduced to correlate the Mendeleev Number with the glass-forming ability parameters: reduced glass transition temperatures (Trg = Tg/Tl), supercooled liquid regions (∆Tx = Tx – Tg) and γ-criterion (TX/(Tg + Tm)). Mg-Cu-RE alloys with nominal compositions Mg65Cu25Y10, Mg65Cu25Y5Gd5, Mg65Cu25Y5Nd5, Mg65Cu25Gd10 and Mg65Cu25Nd10 were chosen for this work. The high reduced glass transition temperature, wider supercooled liquid region and higher γ value of Mg-Cu-Gd-Y amorphous alloy compared to Mg-Cu-Y and Mg-Cu-Nd-Y systems indicates that Mg-Cu-Gd-Y alloys possess higher glass-forming ability. The devitrification of all Mg-Cu-RE glassy alloys used for this work give rise to Mg2Cu (oF48) phase, which is known as anti-Laves phase. The glass-forming composition range for binary and ternary Mg-Cu-Y systems was calculated using Miedema’s model. The development of accurate methods of prediction of glass-forming ability in metallic systems is an important challenge. Pettifor has pioneered the Structure Mapping approach to binary intermetallics. The Pettifor approach can be adapted to the designing of bulk metallic glasses (BMGs). This method has been used to design Al-based and Mg-based BMG’s. Pettifor introduced an integer parameter to characterize the elements, which he called the Mendeleev Number. Essentially, Pettifor’s scheme orders the elements in a sequence of increasing electronegativity. With respect to Mendeleev Number, the Mg-Cu-RE system can be regarded as a binary system, because of the closeness of Mg and Cu (Mg:73, Cu:72, Y:25, Gd:27 and Nd:30). For this system, Mendeleev Number is a more effective parameter than atomic size (Mg: 1.60 Å, Cu: 1.27 Å), as a predictor of glass-forming ability. The effect of Y and rare earth elements on glass forming ability is similar. The atomic number of Y (39) is away from that of the rare earth elements and the Mendeleev Number of Y (25) comes in between those of the rare earth elements. Mg-Zn-Y system is an interesting system for researchers because of higher strength of these alloys. This system draws the crystallographers’ attention due to its composition-dependent structure variations. The Mg-rich RS/PM Mg-Zn-Y alloys yield superior mechanical properties. Therefore, the Mg-rich Mg-Zn-Y system has been chosen to study the microstructural evolution, even though the theoretical calculations for the glass-forming composition range for the Mg-Zn-Y system shows that this system is not a good glass former. Mg-Zn-Y system with nominal compositions Mg97Zn1Y2, Mg97Zn2Y1, Mg97−xZn1Y2Zrx and Mg92Zn6.5Y1.5 were chosen to study the microstructural evolution of these alloys. A small increase in Zn amount (above 2 at.%) in Mg-rich Mg-Y system results in quasicrystalline particles embedded in the matrix, whereas the addition of Zn up to 2 at.% leads to microstructural changes in the α-Mg solid solution.

Les matériaux moléculaires amorphes, aussi appelés verres moléculaires, sont constitués de molécules organiques de petite taille capables de s’organiser de façon désordonnée. En plus de présenter certaines des propriétés analogues à celles des polymères, ils offrent des avantages supplémentaires, puisqu’ils sont des espèces isomoléculaires dont la synthèse, la purification et la mise en œuvre sont facilitées par leur viscosité relativement faible. Toutefois, la préparation souvent exigeante de ces matériaux et leur durée de vie utile limitée par leur tendance à relaxer vers l’état cristallin demeurent des obstacles à leur utilisation pour certaines applications, e.g. opto-électronique, nanolithographie, pharmaceutique. Le développement de stratégies visant à faciliter la préparation de la phase vitreuse et éviter sa cristallisation est donc essentiel à la conception de matériaux moléculaires amorphes fonctionnels. L’objectif principal de cette thèse est d’établir des relations entre la structure moléculaire des verres moléculaires et leurs propriétés. Pour y arriver, différentes librairies de composés modèles, des dérivés analogues de triazine ayant démontré une excellente capacité à former une phase vitreuse, sont utilisées pour i) déterminer l’influence de la nature et de la position des groupements sur la triazine; ii) explorer l’influence des liaisons hydrogène sur les propriétés des verres lorsque leur structure comporte des groupements fonctionnels reconnus pour faciliter la cristallisation et lorsque leurs conditions de préparation se rapprochent de celles employées en industrie et iii) exploiter la phase amorphe afin d’étudier la photosensibilité des azobenzènes (azo) en vue d’optimiser leur utilisation dans des applications. Tout d’abord, l’influence des différents groupes substituants sur la triazine (groupements de tête, auxiliaires et liants) sur la capacité des composés à former une phase vitreuse (GFA), sur sa stabilité cinétique (GS) et sur sa température de transition vitreuse (Tg) est étudiée. Un système de classification des composés développé à partir de mesures de calorimétrie différentielle à balayage (DSC) et des mesures de spectroscopie infrarouge (IR) à température variable combinées à des analyses chimiométriques facilitent la rationalisation des rôles joués par chaque groupe. L’impact des liaisons hydrogène (H), de la barrière énergétique de rotation et de l’encombrement stérique des groupements est ainsi déterminé, permettant de conclure que le groupe de tête est le plus influent et que la présence de liaisons H n’est pas essentielle au GFA mais qu’elle est importante pour obtenir une Tg élevée. Ensuite, l’influence des liaisons H sur les propriétés des verres se rapprochant de ceux exploités dans l’industrie est explorée. Des mesures de spectroscopie IR à température variable, de DSC et de résolution de structures cristallines ont permis de conclure que les liaisons H réussissent à nuire à la cristallisation des composés et ce, même s’ils sont simultanément fonctionnalisés avec des motifs qui favorisent la cristallisation (empilements π-π entre dérivés stilbènes fluorés et non fluorés). De plus, trois composés analogues fonctionnalisés avec un groupement de tête possédant une capacité décroissante à établir des liaisons H (donneur, accepteur, aucune) ont été déposés en phase vapeur (PVD), une technique employée entre autres dans l’industrie opto-électronique pour évaluer leur capacité à former des verres ultrastables. Les films ainsi préparés présentent tous des propriétés similaires à celles des verres ultrastables précédemment étudiés, telles qu’une plus grande densité et anisotropie, et sont tous plus stables que ceux préparés par refroidissement à partir de l’état liquide. Toutefois, le verre formé du composé avec un groupement de tête donneur de liaisons H est moins stable que les autres d’au moins un ordre de grandeur, suggérant que les liaisons H limitent le niveau de stabilité atteignable par PVD. Finalement, un verre à base de triazine fonctionnalisé avec un groupement azo est employé pour étudier d’un point de vue moléculaire les perturbations provoquées par la photoisomérisation de l’azo. Grâce à une nouvelle méthode de spectroscopie IR, il est possible d’observer un gradient d’environnement moléculaire le long de la molécule lors de la photoisomérisation, permettant de soutenir certaines hypothèses relatives au déplacement macroscopique de la matière qui en résulte. Les mélanges de verres à base de triazine servent aussi de plateforme idéale pour découpler l’influence de la Tg et du contenu en azo sur la photo-orientation de l’azo, mais aussi sur la cinétique d’écriture et l’efficacité des réseaux de diffraction (SRG). Ce travail permet ainsi de déterminer une zone optimale de Tg pour l’inscription de SRG. Ces nouvelles connaissances mèneront à la conception plus rationnelle de nouveaux verres moléculaires, pouvant s’étendre à d’autres matériaux amorphes. / Amorphous molecular materials, also known as molecular glasses, are small organic molecules capable of being organized in a disordered manner. In addition to sharing some of the useful properties of polymers, they offer additional advantages because they are isomolecular species for which synthesis, purification and processing are facilitated by a relatively low viscosity. However, the usually demanding preparation conditions of these materials and their limited functional lifetime due to their tendency to relax to the crystalline state remain obstacles to their use for certain applications, e.g. opto-electronics, nanolithography, pharmaceuticals. The development of strategies to facilitate the preparation of the vitreous phase and avoid its crystallization is therefore essential for the design of functional amorphous molecular materials. The main objective of this thesis is to establish relationships between the molecular structure of molecular glasses and their properties. To achieve it, various libraries of model compounds, analogues of triazine derivatives that have demonstrated excellent glass-forming ability, are used to i) determine the influence of the nature and the position of the groups on the triazine; ii) explore the influence of hydrogen (H) bonds on the properties of glasses when their structure includes functional groups known to facilitate crystallization and when their preparation conditions are similar to those used in industry; and iii) exploit the amorphous phase in order to study the photoresponsiveness of azobenzenes (azo) in order to optimize their use in different applications. The influence of the various substituent groups on the triazine (headgroup, ancillary and linkers) on the glass-forming ability (GFA), the kinetic glass stability (GS) and the glass transition temperature (Tg) of the compounds is first studied. A classification system based on differential scanning calorimetry (DSC) and variable temperature infrared spectroscopy (IR) measurements combined to chemometrics analyses facilitate the rationalization of the roles played by each group. The impact of the H-bonds, the energy of the rotation barrier, and the steric hindrance of the groups is determined, leading to the conclusion that the headgroup is the most influential group and that the presence of H-bonds is not essential to the GFA, but important to obtain a high Tg. The influence of the H-bonds on the properties of glasses approaching those exploited in industry is then explored. Variable temperature IR spectroscopy measurements, DSC studies, and single crystal structure resolution have led to the conclusion that H-bonds impede the crystallization of the compounds even though they are simultaneously functionalized with moieties that promote crystallization (π-π stacking between fluorinated and non-fluorinated stilbene groups). In addition, three similar compounds functionalized with a headgroup presenting a decreasing capability to establish H-bonds (donor, acceptor, none) were vapor-deposited (PVD), a technique used, among others, in the opto-electronic industry, to evaluate their capability to form ultrastable glasses. These PVD glasses all show properties that are similar to those previously reported for ultrastable glasses, including higher density and anisotropy, and are all more kinetically stable than glasses prepared by cooling from the viscous state. However, the PVD glasses prepared with a H-bond donor headgroup are less stable than the others by at least an order of magnitude, suggesting that H-bonds limit the level of kinetic stability achievable by PVD. Finally, a triazine molecular glass functionalized with an azo group is used to study, from a molecular point of view, the perturbations caused by the photoisomerization of the azo. A new IR spectroscopy method was developed to observe a molecular environment gradient along the molecule during photoisomerization, making it possible to support certain hypotheses concerning the resulting macroscopic transport of the material. Triazine-based molecular glass blends are also used as an ideal platform for decoupling the influence of Tg and azo content on the azo photo-orientation, but also on the inscription kinetics and the diffraction efficiency of surface relief gratings (SRGs). This work enables the determination of an optimal Tg range for the inscription of SRGs. Altogether, these new insights will lead to a more rational design of new molecular glasses, which can extend to other amorphous molecular materials.