Zugl.: Freiberg (Sachsen), Techn. Univ., Diss., 2007 u.d.T.: Lehnert, Christian: Synthese neuer Silazan- und Borazinverbindungen / Hergestellt on demand

The synthesis of highly porous organic polymers with predefined porosity has attracted considerable attention due to their potential in a wide range of applications. Of particular interest in porous organic polymers is their potential use in automotive applications as well as separation processes whereby advancements could result in a reduction in carbon dioxide emissions and the production of natural gas in a more economically friendly manner. Along these pursuits, seven borazine-linked polymers (BLPs) have been synthesized through the introduction of p-phenylenediamine, 1,3,5-tris-(4-aminophenyl)benzene, benzidine, or tetra-(4-aminophenyl)methane with boron tribromide or boron trichloride followed by the thermolysis reaction of the resulting in situ adduct. All resulting polymers exist as amorphous polymers whose chemical connectivity was confirmed through FT-IR, solid state 11B and 13C NMR, and elemental analysis while thermogravimetric analysis reveals moderate thermal stabilities up to about 200°C. To assess their textural properties, all BLPs were subjected to nitrogen sorption experiments at 77 K. In all cases, the polymers possess high surface areas with chlorinated BLPs exhibiting higher values than their brominated analogues (1174-1569 m2/g versus 503-849 m2/g, respectively). Gas storage capabilities of BLPs for hydrogen, carbon dioxide, and methane were investigated as well. BLPs possess good hydrogen uptakes (0.68-1.75 wt% at 77 K) and zero-coverage isosteric heat of adsorption, Qst, (7.06-7.65 kJ/mol) as calculated by the virial method. The uptakes and heats of adsorption for carbon dioxide (51-141 mg/g at 273 K with Qst: 22.2-31.7 kJ/mol) are also attractive. BLPs do not, however, appear to exhibit significant methane storage capabilities (1.9-15.2 mg/g at 273 K with Qst: 17.1-21.7 kJ/mol). In light of such a difference in storage between carbon dioxide and methane, CO2/CH4 selectivity was calculated for each polymer according to the ideal adsorbed solution theory (IAST). Three of the polymers, BLP-1(Br), BLP-2(Br), and BLP-10(Cl), possess excellent selectivity capabilities over 20 even at low pressures for all molar ratios. Additionally, these selectivity values increase further with increasing pressure. Selectivity was also investigated for benzimidazole-linked polymers. In such systems, the CO2/N2 selectivity values reach 73 at low pressure and exhibit an increasing trend with increasing pressure.

Stuttgart, Univ., Diss., 2006.

Bien que proposant des avantages importants par rapport à d'autres matériaux, les céramiques présentent un défaut récurrent, qui est leur plus ou moins grande fragilité due à des défauts de structure ou à des impuretés dans les réseaux structuraux. On s’affranchit de ces contraintes en améliorant la pureté des matériaux de base, en maîtrisant mieux les processus de fabrication, en les renforçant et en nanostructurant le matériau. C’est ce qui a donné naissance aux méthodes chimiques d’élaboration dites de « Bottom-up » qui reprennent le schéma de principe de la conception de la céramique naturelle en s’adaptant à la démarche des chimistes : des briques élémentaires représentant une architecture moléculaire sont assemblées pour former un composé macromoléculaire dont la composition est contrôlée à l’échelle atomique. Ce composé est mis en forme, durcit pour être transformé par cuisson en une céramique dont la composition est directement liée à la structure moléculaire des briques. Cette démarche est à l’origine de la voie dite des « polymères précéramiques ». Cette voie chimique s’adapte aux exigences des domaines de l’énergie. Notamment et afin d’exploiter et de saisir les opportunités que constituent l’apparition de nouveaux besoins en matériaux et/ou l’établissement de cahiers des charges stricts au regard des propriétés des matériaux dans ce domaine, la présente étude a pour objet d’élaborer des matériaux à base de BN comme les composites à renforts fibreux, les nanocomposites et les mousses.Après une introduction générale, le chapitre 1 décrit l’état de l’art de BN. Il s’intéresse à la littérature sur les propriétés des différentes formes du BN. La voie PDCs est détaillée et son application à l’élaboration du h-BN. Les différents types de précurseurs et de polymères sont décrits et l’accent est mis sur le borazine et le polyborazylène. La dernière partie concerne l’élaboration des composites à renforts fibreux, les nanocomposites et les mousses à base de BN qui sont considérés.Le chapitre 2 s’intéresse à l’élaboration de C/BN composites à partir de polyborazylènes qui est un projet de recherche sur ITER. Après un rappel sur le contexte de CEA, les différentes étapes liées au procédé d’élaboration des composites sont décrites et étudiées à l’aide d’outils de caractérisation comme la RMN solide,TGA, XRD et SEM. Le chapitre 3 s’intéresse à des nanocomposites qui se caractérisent par des phases nanocristallines de nitrure métallique parmi le nitrure de titane, de zirconium et d’hafnium dispersés dans une matrice de BN faiblement cristallisée. L’accent est mis sur la chimie moléculaire et sur la synthèse de polymétalloborazines qui permettent de conduire par pyrolyse à la formation directe de ces nanocomposites par croissance in-situ de la phase nanocristalline dans la matrice BN. Une étude préliminaire sur la possibilité de mettre en forme les polyméres en vue d’élaborer des structures massives nanocomposites est abordée.Le chapitre 4 se consacre à deux procédés de préparation de mousses. Le premier procédé qui combine la voie PDCs à la chimie intégrative vise à élaborer des mousses BN à porosité hiérarchisée. Le second procédé consiste à mélanger PMMA avec polyborazylènes pour subir des étapes de compactage et de pyrolyse générant des mousses. Pour ces deux types de matériaux, des mesures texturales comme BET et la porosimétrie mercure sont entreprises.Une conclusion générale termine le manuscrit. Elle fait un rappel des travaux entrepris dans chacun des trois chapitres et donne des perspectives liées aux trois types de matériau étudiés pendant la thèse. / Energy developments have brought hexagonal boron nitride-based materials increasing interest for future materials and technologies. The objective of this thesis concerns the preparation of BN shapes for energy applications including fiber-reinforced BN composites, BN-based nanocomposites and BN foams. Fiber-reinforced BN composite and BN nanocomposites display potential as tiles for protection limiters for the Ion Cyclotron Range Frequency antennas in fusion nuclear reactors. Porous BN materials have interests as host material for hydrogen storage and as catalyst supports. The Polymer-Derived Ceramics route which offers new preparation opportunities in chemistry and ceramic sciences is applied to manufacture shaped BN-based materials.Firstly, in the context of C/BN composite, polyborazylene vacuum-assisted infiltration and pyrolysis process was successfully introduced. We focused on the design, elaboration and properties of the C/BN composite through the study of the (1) synthesis and polymerization of borazine, (2) the polyborazylene-to-boron nitride conversion, (3) the morphological texture and mechanical properties of derived C/BN composites. We firstly demonstrated that it is possible to obtain dense-derived C/BN composites (density: 1.773 g cm-3, open porosity: 5.09%) by tuning the viscosity of polyborazylene in the infiltration process. SEM observation presented a very strong bonding between fibers and matrix. TGA under air analysis confirmed the improved oxidation resistance property of C/BN composite compared with C fiber.Secondly, we investigated the design, processing, and properties of transition metal-containing boron nitride nanocomposites from polymetalloborazine. With proper choice of boron nitride precursor, and by controlling the B/M ratio (M = Ti, Zr, Hf), a set of representative polymetalloborazines has been prepared as precursors of nanocomposites. In the reaction of BN source with metal precursor leading to polymetalloborazines, two main mechanisms are mainly concerned: N-H and B-H units of BN percursor react with N-alkyl groups presented in metal precursors. After its pyrolysis under ammonia up to 1000 oC then nitrogen from 1000 to 1500oC, the derived nanocomposites reveal the presence of metal nitride nanocrystales with an average diameter of 6.5 nm homogeneously embedded in a poorly crystallized boron nitride matrix. A preliminary study is presented on the preparation of monolith-type nanocomposites from selected polytitanoborazines. Finally, we applied two PDCs route-based strategies to prepare hierarchically porous and micro cellular BN foams. In the first strategy, monolith-type BN foams with a hierarchical porosity were synthesized from polyborazylene using an integrative chemistry combined-based sequence set-up that consists of the impregnation of silica and carbonaceous templates followed by pyrolysis process and elimination of the template. These novel porous BN architectures display hierarchical and high porosity (76 %) with an open-cell interconnected macroporosity and a surface area up to 300 m2g-1. In the second strategy, a sacrificial processing route has been proposed to fabricate micro cellular BN foams with a porosity of 79 % from a mixture of polyborazylene and poly(methylmethacrylate) (PMMA) microbeads by warm-pressing followed by pyrolysis consisting of the burn-out of PMMA while polyborazylene is converted into BN. These novel BN foams display potential as catalyst supports and host material for hydrogen storage.

A new class of porous polymers has been designed and successfully synthesized by thermal dehydrogenation of several polytopic arylamine-borane adducts and has been designated Borazine-Linked Polymers (BLPs). The polymers reported are constructed of linear, triangular, and tetrahedral amine building units to form 2D and 3D frameworks. The boron sites of the pores are aligned with hydrogen atoms contrasted with the recently reported halogenated BLPs which consist of pore channels aligned with bromine or chlorine atoms. One of the reported BLPs, BLP-2(H), was proven to be crystalline by PXRD, matching the experimental pattern to theoretical patterns calculated from modeled structures. BLPs were found to be thermally stable by thermogravimetric analysis, decomposing at temperatures ~450 ºC. Infrared spectroscopy and 11B MAS NMR spectra confirm the formation of borazine as reported in previous borazine-containing polymers and 13C CP MAS spectra confirmed that the structural integrity of the amine building units were maintained and incorporated in the framework of BLPs. Nitrogen isotherms revealed that BLPs exhibit high surface areas ranging from 1132-2866 m2/g (Langmuir) and 400-2200 m2/g (Brunauer-Emett-Teller, BET) with pore sizes from 7-14 Å. Hydrogen, methane, and carbon dioxide measurements were performed at low pressure (up to 1 atm) and were found to be among the best of organic polymers. High pressure isotherms (up to 40 bar) were also taken at various temperatures ranging from 77-298 K. Isosteric heats of adsorption were calculated using the virial method at low pressures. Gas storage performance of BLPs at 40 bar were found to be: 14.7-42.5 mg/g for H2 uptake at 77 K; 348.9-717.4 mg/g for CO2 uptake at 298 K; and 40.8-116.1 mg/g for CH4 uptake at 298 K. The CO2/CH4 selectivity of BLPs at 298 K up to 40 bar was calculated using the Ideal Adsorbed Solution Theory (IAST) to determine their performance as carbon capture and sequestration materials. Additionally, non-borazine containing nanoporous organic polymers (NPOFs) consisting of all carbon and hydrogen atoms were also synthesized and subjected to low pressure hydrogen storage measurements. The results show that though NPOFs generally exhibit higher surface areas (SALang = 2423-4227 m2/g), the H2 storage capacity of BLPs is superior.

Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung neuer Verbindungen in für die Erzeugung nichtoxidischer multinärer Hochleistungskeramiken aussichtsreichen Materialsystemen. Hierzu wurden Reaktionen von Silazanen mit Boran-Donor-Addukten, Tetrakis(dialkylamino)metallaten und Tetrachloriden von Elementen der 4. und 14. Gruppe des PSE sowie Hydroborierungen zwischen N-Trialkylborazinen und Vinylsilanen untersucht. Sowohl in Reaktionen mit Silazanen als auch in denen von Borazinen wurden neue Reaktionswege erschlossen, die vielfältige Optionen für eine Variation der Atomverhältnisse und der molekularen Struktur potenzieller Precursoren für multinäre Keramiken eröffnen. Insbesondere das cyclische Silazan 1,1,3,3,5,5-Hexamethylcyclotrisilazan erwies sich als Quelle zahlreicher neuer Verbindungen. Ausgewählte Moleküle der Elementsysteme SiCNB und SiCNTi wurden durch Hochtemperaturpyrolyse in thermischen Plasmen erstmals erfolgreich in keramische Schichten überführt.

Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung neuer Verbindungen in für die Erzeugung nichtoxidischer multinärer Hochleistungskeramiken aussichtsreichen Materialsystemen. Hierzu wurden Reaktionen von Silazanen mit Boran-Donor-Addukten, Tetrakis(dialkylamino)metallaten und Tetrachloriden von Elementen der 4. und 14. Gruppe des PSE sowie Hydroborierungen zwischen N-Trialkylborazinen und Vinylsilanen untersucht. Sowohl in Reaktionen mit Silazanen als auch in denen von Borazinen wurden neue Reaktionswege erschlossen, die vielfältige Optionen für eine Variation der Atomverhältnisse und der molekularen Struktur potenzieller Precursoren für multinäre Keramiken eröffnen. Insbesondere das cyclische Silazan 1,1,3,3,5,5-Hexamethylcyclotrisilazan erwies sich als Quelle zahlreicher neuer Verbindungen. Ausgewählte Moleküle der Elementsysteme SiCNB und SiCNTi wurden durch Hochtemperaturpyrolyse in thermischen Plasmen erstmals erfolgreich in keramische Schichten überführt.

We present the synthesis and characterisation of novel single organic molecules known as phenoxylene borazines and borazatruxenes. Using temperature-dependant and concentration-dependant 1H NMR, we probe the supramolecular aggregation of these molecules in solution. Finally, we synthesise 2D hybrid material comprised of electron delocalised benzene rings and electron localised borazine rings. Using a combination of solid-state 11B and 13C NMR techniques, Raman spectroscopy and XPS, we confirm the presence of benzene and borazine regions in these novel materials.

No description available.