Diopside-fluorapatite-wollastonite based bioactive glasses and glass-ceramics

Bioactive glasses and glass–ceramics are a class of biomaterials which elicit special response on their surface when in contact with biological fluids, leading to strong bonding to living tissue. This particular trait along with good sintering ability and high mechanical strength make them ideal materials for scaffold fabrication. The work presented in this thesis is directed towards understanding the composition-structure-property relationships in potentially bioactive glasses designed in CaOMgOP2O5SiO2F system, in some cases with added Na2O. The main emphasis has been on unearthing the influence of glass composition on molecular structure, sintering ability and bioactivity of phosphosilicate glasses. The parent glass compositions have been designed in the primary crystallization field of the pseudo-ternary system of diopside (CaO•MgO•2SiO2) – fluorapatite (9CaO•3P2O5•CaF2) – wollastonite (CaO•SiO2), followed by studying the impact of compositional variations on the structure-property relationships and sintering ability of these glasses. All the glasses investigated in this work have been synthesized via melt-quenching route and have been characterized for their molecular structure, sintering ability, chemical degradation and bioactivity using wide array of experimental tools and techniques. It has been shown that in all investigated glass compositions the silicate network was mainly dominated by Q2 units while phosphate in all the glasses was found to be coordinated in orthophosphate environment. The glass compositions designed in alkali-free region of diopside – fluorapatite system demonstrated excellent sintering ability and good bioactivity in order to qualify them as potential materials for scaffold fabrication while alkali-rich bioactive glasses not only hinder the densification during sintering but also induce cytotoxicity in vitro, thus, are not ideal candidates for in vitro tissue engineering. One of our bioglass compositions with low sodium content has been tested successfully both in vivo and in preliminary clinical trials. But this work needs to be continued and deepened. The dispersing of fine glass particles in aqueous media or in other suitable solvents, and the study of the most important factors that affect the rheology of the suspensions are essential steps to enable the manufacture of porous structures with tailor-made hierarchical pores by advanced processing techniques such as Robocasting.

Piezoelectricity and ferroelectricity in amino acid glycine

Bioorganic ferroelectrics and piezoelectrics are becoming increasingly important in view of their intrinsic compatibility with biological environment and biofunctionality combined with strong piezoelectric effect and switchable polarization at room temperature. Here we study piezoelectricity and ferroelectricity in the smallest amino acid glycine, representing a broad class of non-centrosymmetric amino acids. Glycine is one of the basic and important elements in biology, as it serves as a building block for proteins. Three polymorphic forms with different physical properties are possible in glycine (α, β and γ), Of special interest for various applications are non-centrosymmetric polymorphs: β-glycine and γ-glycine. The most useful β-polymorph being ferroelectric took much less attention than the other due to its instability under ambient conditions. In this work, we could grow stable microcrystals of β-glycine by the evaporation of aqueous solution on a (111)Pt/Ti/SiO2/Si substrate as a template. The effects of the solution concentration and Pt-assisted nucleation on the crystal growth and phase evolution were characterized by X-ray diffraction analysis and Raman spectroscopy. In addition, spin-coating technique was used for the fabrication of highly aligned nano-islands of β-glycine with regular orientation of the crystallographic axes relative the underlying substrate (Pt). Further we study both as-grown and tip-induced domain structures and polarization switching in the β-glycine molecular systems by Piezoresponse Force Microscopy (PFM) and compare the results with molecular modeling and computer simulations. We show that β-glycine is indeed a room-temperature ferroelectric and polarization can be switched by applying a bias to non-polar cuts via a conducting tip of atomic force microscope (AFM). Dynamics of these in-plane domains is studied as a function of applied voltage and pulse duration. The domain shape is dictated by both internal and external polarization screening mediated by defects and topographic features. Thermodynamic theory is applied to explain the domain propagation induced by the AFM tip. Our findings suggest that β-glycine is a uniaxial ferroelectric with the properties controlled by the charged domain walls which in turn can be manipulated by external bias. Besides, nonlinear optical properties of β-glycine were investigated by a second harmonic generation (SHG) method. SHG method confirmed that the 2-fold symmetry is preserved in as-grown crystals, thus reflecting the expected P21 symmetry of the β-phase. Spontaneous polarization direction is found to be parallel to the monoclinic [010] axis and directed along the crystal length. These data are confirmed by computational molecular modeling. Optical measurements revealed also relatively high values of the nonlinear optical susceptibility (50% greater than in the z-cut quartz). The potential of using stable β-glycine crystals in various applications are discussed in this work.

Alkaline-earth aluminosilicate-based glass and glass-ceramic sealants for functional applications

The planar design of solid oxide fuel cell (SOFC) is the most promising one due to its easier fabrication, improved performance and relatively high power density. In planar SOFCs and other solid-electrolyte devices, gas-tight seals must be formed along the edges of each cell and between the stack and gas manifolds. Glass and glass-ceramic (GC), in particular alkaline-earth alumino silicate based glasses and GCs, are becoming the most promising materials for gas-tight sealing applications in SOFCs. Besides the development of new glass-based materials, new additional concepts are required to overcome the challenges being faced by the currently existing sealant technology. The present work deals with the development of glasses- and GCs-based materials to be used as a sealants for SOFCs and other electrochemical functional applications. In this pursuit, various glasses and GCs in the field of diopside crystalline materials have been synthesized and characterized by a wide array of techniques. All the glasses were prepared by melt-quenching technique while GCs were produced by sintering of glass powder compacts at the temperature ranges from 800−900 ºC for 1−1000 h. Furthermore, the influence of various ionic substitutions, especially SrO for CaO, and Ln2O3 (Ln=La, Nd, Gd, and Yb), for MgO + SiO2 in Al-containing diopside on the structure, sintering and crystallization behaviour of glasses and properties of resultant GCs has been investigated, in relevance with final application as sealants in SOFC. From the results obtained in the study of diopside-based glasses, a bilayered concept of GC sealant is proposed to overcome the challenges being faced by (SOFCs). The systems designated as Gd−0.3 (in mol%: 20.62MgO−18.05CaO−7.74SrO−46.40SiO2−1.29Al2O3 − 2.04 B2O3−3.87Gd2O3) and Sr−0.3 (in mol%: 24.54 MgO−14.73 CaO−7.36 SrO−0.55 BaO−47.73 SiO2−1.23 Al2O3−1.23 La2O3−1.79 B2O3−0.84 NiO) have been utilized to realize the bi-layer concept. Both GCs exhibit similar thermal properties, while differing in their amorphous fractions, revealed excellent thermal stability along a period of 1,000 h. They also bonded well to the metallic interconnect (Crofer22APU) and 8 mol% yttrium stabilized zirconium (8YSZ) ceramic electrolyte without forming undesirable interfacial layers at the joints of SOFC components and GC. Two separated layers composed of glasses (Gd−0.3 and Sr−0.3) were prepared and deposited onto interconnect materials using a tape casting approach. The bi-layered GC showed good wetting and bonding ability to Crofer22APU plate, suitable thermal expansion coefficient (9.7–11.1 × 10–6 K−1), mechanical reliability, high electrical resistivity, and strong adhesion to the SOFC componets. All these features confirm the good suitability of the investigated bi-layered sealant system for SOFC applications.