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Novel thermal and electron-beam approaches for the fabrication of boron-rich nanowiresGonzalez Martinez, Ignacio Guillermo 01 November 2016 (has links)
Pursuing the development and implementation of novel synthesis techniques to produce nanostructures with an interesting set of properties is a goal that advances the frontiers of nanotechnology. Also of fundamental importance is to revisit well-established synthesis techniques employing a new set of materials as precursors, substrates and catalysts. Fundamental breakthroughs in the field of nanotechnology can be achieved by developing new synthesis procedures as well as by adapting known procedures to new materials. This thesis focuses on both kinds of experiments.
A variant of chemical vapor deposition (CVD) has been used to produce Al5BO9 nanowires out of sapphire wafers without the need of a catalyst material. The novelty of the work relies on the formation mechanism of the Al5BO9 nanowires. Essentially, the process can be described as a large-scale topological transformation taking place on the substrate’s surface as its chemical composition changes due to the arrival of precursor molecules. Dense mats of Al5BO9 nanowires cover large areas of the substrate that were previously relatively flat. The process is enhanced by a high temperature and the presence of pre-existing superficial defects (cracks, terraces, etc.) on the substrates. Al5BO9 nanowires as well as B/BOX nanowires and BOX nanotubes were also produced via a novel in-situ electron beam-induced synthesis technique. The process was carried out at room temperature and inside a transmission electron microscope. Au nanoparticles were used as catalyst for the case of B/BOX nanowires and BOX nanotubes, while the Al5BO9 nanowires were synthesized without the need of a catalyst material. The formation and growth of the nanostructures is solely driven by the electron beam. The growth mechanism of the B/BOX nanowires and BOX nanotubes relies on interplay between electrostatic charging of the precursor material (to produce and transport feedstock material) and electron stimulated desorption of oxygen which is able to activate the catalytic properties of the Au nanoparticles. For the case Al5BO9 nanowires a nucleation process based on massive atomic rearrangement in the precursor is instigated by the e-beam, afterwards, the length of some of the nanowires can be extended by a mechanism analogous to that of the growth of the B/BOX nanowires.
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Growth and properties of GdCa4O(BO3)3 single crystalsMöckel, Robert 29 June 2012 (has links)
In der vorliegenden Arbeit wird die Einkristallzüchtung nach dem Czochralskiverfahren von GdCa4O(BO3)3 (GdCOB) beschrieben. Aus insgesamt 18 Zuchtversuchen, bei denen auch die Ziehgeschwindigkeit zwischen 1 und 3mm/h variiert wurde, wurden erfolgreich nahezu perfekte Einkristalle gewonnen. In einigen Kristallen traten jedoch auch Risse oder Einschlüsse auf. Diese enthielten neben Iridium vom Tiegelmaterial auch andere Phasen des Gd2O3–B2O3–CaO-Systems, sowie P und Yb, deren Herkunft unklar ist. Als Hauptziehrichtung wurde die kristallographische b-Achse gewählt, ergänzt durch einige Experimente in der c-Richtung.
In den drei kristallographischen Hauptrichtungen wurden die thermischen Ausdehnungskoeffizienten von GdCOB bestimmt. Diese können in zwei nahezu lineare Bereiche unterteilt werden: von Zimmertemperatur bis etwa 850° C und von 850 bis 1200° C, wobei die Koeffizienten im Hochtemperaturbereich deutlich höher sind (unter 850° C: alpha_a=11.1, alpha_b=8.6, alpha_c=13.3 10^-6/K, oberhalb 850° C: alpha_a=14.1, alpha_b=11.7, alpha_c=17.8 10^-6/K). Daraus ergibt sich, dass ein Phasenübergang höherer Ordnung vorliegen muss. Als mögliche Ursache wurde mittels HT-Raman Spektroskopie ein Ordnungs-Unordnungs-Übergang identifiziert, während dessen die BO3-Gruppen in der Struktur leicht rotieren. Weitere Untersuchungen mittels thermodynamischer Methoden führten zu schwachen, aber eindeutigen Signalen, die diesem Effekt ebenfalls zuzuordnen sind.
Obwohl das Material ein vielversprechender Kandidat für piezoelektrische Anwendungen im Hochtemperaturbereich ist, wurde dieser Effekt bisher unzureichend beschrieben. Dieses Verhalten, kombiniert mit den anisotropen thermischen Ausdehnungskoeffizienten, könnte eine der Ursachen für das Vorkommen von Rissen in den Kristallen während der Synthese darstellen.
Spektroskopische Untersuchungen ergaben einen großen Transparenzbereich von 340 bis 2500nm (29 400–4000 cm^-1), was für optische Anwendungen von großer Bedeutung ist. / In a series of 18 growth experiments, GdCa4O(BO3)3 (GdCOB) single crystals were successfully grown by the Czochralski method. They have a well-ordered structure, as revealed by single crystal structure analysis. Although the main growth direction was along the crystallographic b-axis, some experiments were conducted using the cdirection. Pulling velocities were varied between 1 and 3mm/h. Except for a few crystals with cracks or elongated "silk-like" inclusions consisting of multiphase impurities, most of the obtained crystals are of good quality. Those inclusions contain iridium, deriving from the crucible, P and Yb with unclear source, and other phases from the system Gd2O3–B2O3–CaO.
Thermal expansion coefficients of GdCOB were determined in the directions of the crystallographic axes and found to be approximately linear in two temperature ranges: from 25° C to around 850° C, and from 850 to 1200° C, with the latter range showing significantly higher coefficients (below 850° C: alpha_a=11.1, alpha_b=8.6, alpha_c=13.3 10^-6/K, and above 850° C: alpha_a=14.1, alpha_b=11.7, alpha_c=17.8 x10^-6/K). This sudden increase of thermal expansion coefficients indicates a phase transition of higher order. An order-disorder transition in form of the rotation of BO3-triangles in the structure was made tentatively responsible for this transition, as revealed by HT-Raman spectroscopy. This transition was also detected by DSC-methods but appeared to result in very weak effects.
Although the material is thought to represent a promising candidate for high temperature piezoelectric applications (noncentrosymmetric space group Cm), this effect of change in specification has not been described and it is unknown whether it has influence on the piezoelectric properties. Furthermore, this characteristic behaviour in combination with anisotropic coefficients may be the reason for the development of cracks during cooling of crystals, making the growth difficult. Spectroscopic investigation revealed a wide transparency range from 340 to 2500nm (29 400–4000 cm^-1) of GdCOB, which is a very important property for optical applications.
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Vývoj elektroforetické metody stanovení fosfátů a borátů v nemrznoucích směsích / Development of the electrophoretic method for determination of phosphates and borates in cooling mixturesListakhava, Iryna January 2021 (has links)
In this diploma thesis, a method of routine analysis of commercial coolants was developed, focused on the simultaneous determination of inorganic anions - phosphates and borates - as corrosion inhibitors in fresh mixtures and the markers of recycling quality. The method was developed for the instrumental technique of capillary zone electrophoresis with indirect detection at 254 nm. The following were optimized: background electrolyte (its composition, concentration, pH), measured samples (coolant dilution, suitable internal standard) and measurement conditions (capillary length, sample dosing). The influence of the sample matrix on the measurement results, the robustness of the calibration line (or the agreement of the response with the actual analyte concentration) and also the repeatability of the method were tested. Optimizations and tests resulted in a method based on a standard addition with the following parameters: background electrolyte of pH = 11.50 containing sodium chromate at 10 mmol l-1 concentration and CTAB at 1 mmol l-1 concentration; dilution of the coolant sample 20-50×, addition of internal standard MES at 0,1 mmol l-1 concentration, electrokinetic sample injection at -5 kV for 10 s, capillary length 50.0 cm, inner diameter 75 μm. The repeatability of the method expressed as a...
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Effect of Co-Ion and Counterion on Self-Assembly of MacroionJiahui, Chen 30 October 2020 (has links)
No description available.
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Mechanical And Physical Properties Of Preservative-Treated StrandboardKirkpatrick, John Warren 10 December 2005 (has links)
The purpose of this research was to quantify properties of strandboard panels manufactured with various preservatives at loading levels effective against native termites. Panels were manufactured using nine different formulations. The method of preservative addition was also examined for some preservative formulations, increasing the total number of preservative treatments to twelve. Panels were manufactured with one target retention for each preservative treatment. An effective preservative loading relative to termites was established by previous studies or referencing current standards. Mechanical testing performed included static bending and internal bond. Physical testing included water absorption, thickness swell, and linear expansion. Few treatments met the Canadian standards for strandboard, but several preservatives performed well. Copper naphthenate, bifenthrin, and copper betaine each deserve further investigation to optimize manufacturing variables to meet required mechanical and physical properties.
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Borophosphate der Haupt- und Nebengruppenmetalle: Synthese, Charakterisierung und Strukturchemische KlassifizierungEwald, Bastian 05 December 2006 (has links) (PDF)
Es werden neue Erkenntnisse über Borphosphat und Borophosphate der Haupt- und Nebengruppenmetalle vorgestellt. Neben Hydrothermalsynthesen und Feststoffreationen, die üblicherweise zur Synthese von Borophosphaten angewendet werden, haben insbesondere die solvothermalen Experimente mit Alkoholen bzw. Alkohol-Wasser-Mischungen zu neuen Ergebnissen geführt. Es wurden neue Borophosphate und Borat-Phosphate in den Systemen MxOy–B2O3–P2O5(–H2O) (M = K+, Rb+, Mg2+, Sc3+, Pr3+, Sm3+, In3+) dargestellt, weitere Verbindungen enthalten neben Mg2+ weitere Kationen der Haupt- und Nebengruppenmetalle (Ca, Sr, Ba, Mn, Fe, Co, Zn). Darüberhinaus gelang die Darstellung bislang unbekannter Scandium- und Lanthanphosphate(III) sowie von sauren Alkalimetall-Scandiumphosphaten(V). Aus Synthesen in Gegenwart von Ethylendiamin und Diazabizyklooktan wurden ferner zwei neue templatierte Scandiumphosphate mit porösen Gerüststrukturen erhalten. Die Kristallstrukturen aller Verbindungem wurden rötgenographisch anhand von Einkristallaufnahmen oder Pulverdaten aufgeklärt. Die Charakterisierung der Präparate erfolgte mit Röntgenpulverdiffraktometrie, EDX- und Elementaranalysen sowie durch Schwingungsspektroskopie und thermische Stabilitätsuntersuchungen. Zur Klassifizierung von (Metallo)borophosphaten wird eine Struktursystematik vorgeschlagen, welche Borophosphate und Metalloborophosphate entsprechend ihrer anionischen Teilstrukturen hierarchisch klassifiziert und in Analogie zur Terminologie der Silikate (nach Liebau) beschreibt. In Anlehnung an bestehende Konzepte für Boratminerale geht das Klassifizierungsschema dabei von einfachen Oligomeren aus. In einer struktursystematischen Übersicht wurden alle bis dato bekannten (Metallo)Borophosphate hierarchisch klassifiziert und sind in einer Übersicht vorgestellt. Beobachtete Verknüpfungsregeln und der Einfluss der Zusammensetzung B:P auf die Dimensionalität und die Verknüpfungsmuster der anionischen Teilstruktur werden diskutiert.
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Borophosphate der Haupt- und Nebengruppenmetalle: Synthese, Charakterisierung und Strukturchemische KlassifizierungEwald, Bastian 02 November 2006 (has links)
Es werden neue Erkenntnisse über Borphosphat und Borophosphate der Haupt- und Nebengruppenmetalle vorgestellt. Neben Hydrothermalsynthesen und Feststoffreationen, die üblicherweise zur Synthese von Borophosphaten angewendet werden, haben insbesondere die solvothermalen Experimente mit Alkoholen bzw. Alkohol-Wasser-Mischungen zu neuen Ergebnissen geführt. Es wurden neue Borophosphate und Borat-Phosphate in den Systemen MxOy–B2O3–P2O5(–H2O) (M = K+, Rb+, Mg2+, Sc3+, Pr3+, Sm3+, In3+) dargestellt, weitere Verbindungen enthalten neben Mg2+ weitere Kationen der Haupt- und Nebengruppenmetalle (Ca, Sr, Ba, Mn, Fe, Co, Zn). Darüberhinaus gelang die Darstellung bislang unbekannter Scandium- und Lanthanphosphate(III) sowie von sauren Alkalimetall-Scandiumphosphaten(V). Aus Synthesen in Gegenwart von Ethylendiamin und Diazabizyklooktan wurden ferner zwei neue templatierte Scandiumphosphate mit porösen Gerüststrukturen erhalten. Die Kristallstrukturen aller Verbindungem wurden rötgenographisch anhand von Einkristallaufnahmen oder Pulverdaten aufgeklärt. Die Charakterisierung der Präparate erfolgte mit Röntgenpulverdiffraktometrie, EDX- und Elementaranalysen sowie durch Schwingungsspektroskopie und thermische Stabilitätsuntersuchungen. Zur Klassifizierung von (Metallo)borophosphaten wird eine Struktursystematik vorgeschlagen, welche Borophosphate und Metalloborophosphate entsprechend ihrer anionischen Teilstrukturen hierarchisch klassifiziert und in Analogie zur Terminologie der Silikate (nach Liebau) beschreibt. In Anlehnung an bestehende Konzepte für Boratminerale geht das Klassifizierungsschema dabei von einfachen Oligomeren aus. In einer struktursystematischen Übersicht wurden alle bis dato bekannten (Metallo)Borophosphate hierarchisch klassifiziert und sind in einer Übersicht vorgestellt. Beobachtete Verknüpfungsregeln und der Einfluss der Zusammensetzung B:P auf die Dimensionalität und die Verknüpfungsmuster der anionischen Teilstruktur werden diskutiert.
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Multifunctionalities Of Telllurite And Borate Based Glasses Comprising Nano/Micro Crystals Of Tetragonal Tungsten Bronze-Type Ferroelectric OxidesAhamad, M Niyaz 10 1900 (has links)
Transparent glasses embedded with TTB structured ferroelectric nano/micro crystals (K3Li2Nb5O15, Ba5Li2Ti2Nb8O30) were fabricated in various tellurite and borate based glass matrices and characterized for their physical properties.
Nanocrystals of K3Li2Nb5O15 were successfully grown inside tellurite glass matrix via conventional heat-treatment route. Eventhough, tellurite glasses preferentially crystallize only on the surface, bulk uniform crystallization was achieved in the (100-x) TeO2 - x(1.5K2O-Li2O-2.5Nb2O5) system. Heat capacity studies revealed them to be thermodynamically less fragile than any other tellurite glasses ever reported in the literature. Pyroelectric and ferroelectric effects as well as second harmonic generation were demonstrated for the heat treated (glass nanocrystal composites) samples in this system.
The conventional method of melt-quenching of constituent oxides could not yield Ba5Li2Ti2Nb8O30 crystallites. So, Ba5Li2Ti2Nb8O30 microcrystals were successfully formed in tellurite glass matrix by mixing pre-reacted Ba5Li2Ti2Nb8O30 ceramic powders with TeO2. The glass transition temperature was found to be the highest ever reported and this system was kinetically strong based on the fragility parameter. Dielectric studies revealed a frequency and temperature independent nature of the dielectric constant and very low dielectric loss. The SHG measurement which was carried out as a function of temperature demonstrated the incidence of blue second harmonic generation in the microcrystals present in the glass matrix.
Ba5Li2Ti2Nb8O30 nanocrystals were successfully crystallized in the transparent glass system (100-x)Li2B4O7 – x(Ba5Li2Ti2Nb8O30). Dielectric constant increased while the dielectric loss decreased with the increase in Ba5Li2Ti2Nb8O30 content. Nuclear magnetic resonance spectroscopic studies were carried out to have an insight into the structure of this system. Transmission studies and refractive index measurements were performed and various optical parameters were calculated.
Dielectric and transport properties were studied for the glasses and glass nano/microcrystal composites of all the systems reported in this thesis. Li+ ion was found to be responsible for conduction in all these systems.
Evolution of self-organized nanopatterns of K3Li2Nb5O15 crystals has been demonstrated in the glass system (100-x) TeO2 - x(1.5K2O-Li2O-2.5Nb2O5) by excimer laser irradiation. The second harmonic signal observed by the Maker fringe technique has been attributed to the presence of well-aligned nano-sized grating structures in the glass system. Glasses belonging to the systems TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30 and V2Te2O9 undergo spinodal decomposition on exposing to KrF pulsed excimer laser. The spinodally phase separated structures were observed on all the surfaces of the samples. Ring shaped patterns were observed on several locations of the samples at higher frequency of laser pulses probably owing to the shock waves produced by the high intense laser beam. Line shaped patterns were found to originate on the sample surfaces when irradiated for longer periods.
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Growth And Physical Properties Of Nonlinear Optical Crystals CsH(C4H4O5)H2O, CsLiB6O10 And Near-Stoichiometric LiNbO3Reddy, Babu J N 05 1900 (has links)
NLO materials have been researched for nearly five decades from the point of view of understanding the basic mechanisms and also in the pursuit of new materials possessing improved properties. Materials satisfying a set of physico-chemical properties such as wide transmission range, good mechanical hardness, high po-larizablity, noncentric crystal structure, good chemical stability, etc are the ones which are sought after. Several organic and inorganic molecules have been synthe-sized with the hope of finding materials that possess the desired NLO properties. Most of the organic materials are known to possess high figure of merit. However, their poor mechanical strength and needle like growth habit are hindrances to practical applications. Inorganic NLO materials have better mechanical properties but many of them possess small deff and laser induced damage threshold. Semi-organic NLO materials are intended to have the merits of both organic and inorganic counterparts. In this investigation, three important NLO crystals, viz cesium hydrogen L-malate monohydrate (CsLM, CsH[C4H4O5]H2O), cesium lithium borate(CLBO,CsLiB6O10)and near stoichiometric lithium niobate codoped with Nd and Zn (Nd:Zn:LiNbO3)are chosen for detailed study.
The thesis is organized into 6 chapters. First chapter contains the theoretical background of the physical and chemical phenomena including a review of nonlin-ear optics, second harmonic generation, multiphoton absorption & refraction con-cepts, single crystal growth, principles of ferroelectricity and the scope of the work involved. For better connectivity, a brief review of the earlier work carried out on the chosen materials is given in the beginning of each chapter. The second chapter discusses the methodology of work and experimental details used in the present study.
The third chapter deals with studies on CsLM, the new organometallic NLO crystal. Its structure, electro-optical properties and dielectric properties in FIR region are reported very recently. This material is also reported to show a phase transition at 50 0C though not much is understood about its nature. Further details of crystal growth conditions, nonlinear optical properties and laser damage thresholds are little known on this newly discovered NLO material. In this chapter detailed crystal growth studies and investigations of physical properties are presented. During growth, CsLM crystals manifest in platy and prismatic morphologies depending on level of super saturation invoked. The maximum dimensions of the grown crystal are 20 x15 x35 mm3. It has very good transmission in the range, 250-1300 nm and dislocation density of ≈104/cm2 . The dc conductivity measurements place this crystal between an ionic conductor and a dielectric. Dielectric properties show considerable frequency dispersion and axial anisotropy with є′ being the highest along the polar b axis. Maker fringes experiment reveals that CsLM possesses good second harmonic generation efficiency, an order of magnitude higher than KDP. It also has high laser damage threshold for fundamental and second harmonic wavelengths of Nd:YAG pulsed laser. TGA/DTA experiments are performed on the crystals grown below and above the reported transition temperature(labelled as CsLM and Anhydrous-CsLM respectively). The present investigations on Anhydrous-CsLM show that it crystallizes in a structure different from that of CsLM and the nature of the reported ′phase transition ′is driven by sluggish hydration and dehydration processes.
Recently UV transparent nonlinear optical materials were evaluated for the fab-rication of all solid state UVlasers and CLBO is one such NLO material. It crystal-lizes in non-centrosymmetric tetragonal space group, I42d. It is highly transparent in the wide range of wavelengths from 180 to 2500 nm and has good deff. It pos-sesses very good angular and spectral bandwidth tolerances compared to its contemporaries such as lithium triborate(LBO) and beta barium borate(β-BBO). There is, however, a problem associated with this material that it cracks when exposed to atmosphere due to its hygroscopic nature. This chapter details the fabrication of the required instrumentation to grow single crystals of this material and the study of possible solutions to avoid cracking problem besides its new nonlinear properties. Since the melts of borate materials are known to be highly viscous, the crystal growth apparatus should have the options for tuning the parameters like seed and crucible rotation rates, temperature isotherms, slow pulling rate, etc. Keeping the above in mind, a high temperature top seeded solution growth unit was designed and fabricated inhouse. Highly transparent single crystals of CLBO were grown using the above unit which were characterized for the defects/dislocations using X-ray topography. The average dislocation density estimated is ≈103/cm2. The nonlinear optical absorption(NLA) and refraction(NLR) properties are studied. Z-scan experiments reveal that five photon absorption(5PA )is responsible for nonlinear absorption when the wavelength and pulse width are 800 nm and 110 fs respectively. For 532 nm and 6 ns pulses, dielectric breakdown occurs before NLA could occur due to high pulse influence. CLBO is found to show negative nonlinear refraction under high intensities. Hygroscopicity of CLBO is attributed to the entry of water through the channels that are present along a and b axes, which in turn, cause cracking. Doping, is expected to modify the size of the channels. Since certain dopants are found to improve the stability of CLBO, substitution of Cs site with Zn and Gd is carried out to reduce the size of channels. As there was no significant improvement with doping experiments, an alternate approach is attempted by coating with SiO2 thin films on the optical elements to prevent the water molecules from entering lattice through the channels. The results and discussion of the above studies are presented in the chapter 4.
Lithium niobate is the most widely used single crystal for fabricating optical modulators, waveguides, SAW devices and optical parametric oscillators. Although single crystals of this ferroelectric material were grown way back in 1965 by Ball-man and Fedulov independently, most of the work till the beginning of 90’s was concentrated on crystals with congruent composition(CLN) because there were no suitable methods available for growing homogeneous single crystals of stoichiomet-ric lithium niobate(SLN). Recently, Double Crucible Czochralski method with au-tomatic powder feeding technique and top seeded solution growth technique with
Li2O and K2O fluxes are shown to produce SLN crystals. In this work, top seeded solution growth technique with58.6 mol% Li2O composition(self flux) is adopted to grow SLN crystals and the details of the growth and investigations are presented in chapter 5. Initially, crystal growth of SLN, and Zn & Nd codoped SLN are de-scribed. The maximum dimesions of the SLN crystals are 20 mm diameter and 35 mm length. CLN crystals(30mm diameter and 70 mm length) are also grown for comparison. The growth rate for SLN crystals is approximately 25 times lower than that for CLN. The maximum amount of Zn added to the melt is 2.5 mol%. For Nd codoping, four concentrations (0.2, 0.5, 0.9, 1.5 mol%) have been chosen with Zn concentration in the melt fixed at 2.5 mol%. Addition of Zn is to enhance the pho-torefractive damage threshold and Nd to use SLN as laser host. Structural studies on the grown crystals using powder X-ray diffraction show no additional phases. The domain structure analysis by chemical etching studies reveal that it is sensitive to doping and temperature gradient above the melt surface. The grown crystals possess good transmission in the UV-Vis-NIR region. Apparent increase in the dielectric constant found in doped crystals is attributed to space charge effect. In Nd:Zn codoped SLN, the parameters corresponding to lasing (Judd-Ofelt parameters, radiative transition probabilities, branching ratios) have been evaluated and found to be better than those obtained for codoped CLN. Surface laser damage and photorefractive damage thresholds are enhanced by 2 and 4 orders of magnitude respectively for the crystals grown with 2.5 mol% Zn in the melt. Nonlinear absorption and refraction studies using femtosecond Z-scan experiments reveal a correlation between the nonstoichiometric defects and nonlinear absorption & refraction coefficients. Polarization switching studies carried out on pure and Zn doped samples indicate an enhancement in switching rate at elevated temperatures.
In the sixth and final chapter, a comprehensive summary of the present work and the scope for further investigations related to this work are given.
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New Anions In The Assembly Of The Open-Framework Compounds : Synthesis, Structure And PropertiesPaul, Avijit Kumar 07 1900 (has links) (PDF)
Open-framework inorganic materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. After the discovery of nanoporous aluminium phosphates (AlPOs) by Flanigen et al in 1982, there has been a tremendous growth in the area of porous solids that are based on phosphates. Apart from phosphates, phosphites, arsenates, sulfates, sulfites, selenates, selenites etc. have also been investigated. In addition to the different anions, the framework compounds now encompass almost all the elements of the periodic table. The compounds exhibit wide variety and structural diversity. New building units, such as thiosulfate and borate have also been explored as a network builder in the formation of framework structures. In this thesis, the results of the investigations on open-framework metal thiosulfates, metal borates and metal sulfates are presented. The studies are aimed not only at the synthesis of the new compounds based on the new anions, but also their possible applications.
In Chapter 1 of the thesis an overview of inorganic open-framework materials with different anions is presented. In Chapter 2 (Part A), the synthesis, structure and transformation of inorganic-organic hybrid open-framework cadmium thiosulfate are presented. The lack of stability of the thiosulfate ion in solution prompted the exploration of new approaches such as low temperature solvothermal methods, use of rigid linkers etc. The transformations of lower to higher dimensional structures have been accomplished. The possible mechanisms for such transformations were investigated. In Part B, the physical and chemical properties of the hybrid cadmium thiosulfate frameworks are presented. The studies indicate that the anionic dyes selectively adsorb on the compounds in the water medium and also desorb reasonably in alcoholic medium. The cadmium thiosulfate compounds appear to be reasonable photocalysts for the photodecomposition of the cationic dyes under UV irradiation as well as under sunlight with good recyclability. The compounds also exhibit heterogeneous catalytic behavior (Lewis acidity) for the cyanosilylation of the imines.
In Chapter 3, a new family of organically templated open-framework borate materials is presented. The zinc and aluminoborate structures, prepared in the present study, are rationalized using the HSAB theory. The [B4O9H2] units polymerize differently to form different zinc borate structures. The amine molecules act as a ligand by binding with the metal. The nature of the amine appears to control the dimensionality of the final zinc borate structures. The zinc borate compounds exhibit absorption of UV-light (λ = 365 nm) suggesting that the zinc borate compounds could be exploited for UV-blocking applications. Organically templated aluminoborates have connectivities between the Al3+ ions and the [B5O10] cyclic pentaborate units. The aluminoborate structures exhibit graphite layer and three-dimensional diamond structure. Detailed studies and comparison of the various amine templated open-framework aluminoborate structures reveals subtle relationships between the organic amines (shape and length of the amines) and the final framework structures.
In Chapter 3, the synthesis, structure and catalytic studies of a variety of cadmium sulfate phases have been carried out. Polyazaheterocyclic ligands were employed to study their possible role in the formation of such structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The connectivity between the Cd2+ and (SO4)2− ions form one-, two-and three-dimensionally extended cadmium sulfate phases, though the starting source is cadmium sulfate (CdSO4.8/3H2O) in all the cases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one-and two-dimensional structures. The interconnectivity between the two units gives rise to the final observed structure. As part of the study, a variety of properties i.e. adsorption-desorption, photocatalytic degradation and cyanosilylation reaction, exhibited by the cadmium sulfate compounds have been investigated and the properties are comparable to the cadmium thiosulfate phases.
AlPOs are well known for their many important properties. The wide varieties in their structures and heterogeneous catalytic properties have been extensively investigated. The photocatalytic behaviors, on the contrary, have not been investigated in detail. The photocatalytic properties of the metal-doped AlPOs, for the photodegrdation of organic dyes have been investigated in the Chapter 5. The metal ions (Mg2+, Zn2+ and Co2+) have been substituted in place of Al3+ and Ti4+ in place of both the Al3+ and P5+ in a variety in AlPO structures and the synthesized phases are characterized by a variety of techniques. Photodecomposition studies of organic dye molecules under UV-light were carried out in aqueous medium. The studies suggest that the photocatalytic activity is reasonable and appears to depend on the dopant concentration. Ti-substituted phase exhibits the maximum catalytic activity.
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