Applying the Alkali-Activation Method to Encapsulate Silicon Nitride Particles in a Bioactive Matrix for Augmented Strength and Bioactivity.

The development of bioactive ceramics still poses challenges in finding a good compromise between bioactivity and mechanical robustness. Moreover, a facile, low-cost and energy-saving synthesis technique is still needed. This study concerns the synthesis of a bioactive material by growing a bioactive Na-Ca-Mg-Si-based ceramic matrix produced using the alkali-activation method on silicon nitride (Si3N4) particles. This technique simultaneously forms the matrix precursor and functionalizes the Si3N4 particles' surface. The optimal strength-bioactivity compromise was found for the composition containing 60 wt.% Si3N4 and 40 wt.% of the matrix exhibiting good compressive strength of up to 110 MPa and extensive precipitation of hydroxyapatite on the sample surface after 7 days of soaking in simulated body fluid. This innovative approach merging strong non-oxide binary ceramics with the versatile and low-cost alkali-activation method holds great expectations for the future in biomaterials.

Cesium Oxo-fluoro-aluminates in the CsF-Al2O3 System: Synthesis and Structural Characterization.

In an experiment combining various approaches, a precise examination of a portion of the phase diagram of a CsF-Al2O3 system was carried out up to 40 mol% Al2O3. CsF-Al2O3 solidified mixtures have been investigated using high-field solid-state NMR (133Cs, 27Al, and 19F) spectroscopy and X-ray powder diffraction over a broad range of compositions with synchrotron powder diffraction and Rietveld analysis. A new cesium oxo-fluoro-aluminate, Cs2Al2O3F2, was discovered, prepared, and structurally analyzed by synchrotron diffraction analysis. In addition to Cs2Al2O3F2, we have synthesized the following pure compounds in order to aid in the interpretation of NMR spectra of the solidified samples: CsAlF4, Cs3AlF6, and CsAlO2.

Phase Evaluation, Mechanical Properties and Thermal Behavior of Hot-Pressed LC-YSZ Composites for TBC Applications.

In this work, La2Ce2O7-yttria-stabilized zirconia (LC-YSZ) composites with different weight fractions of YSZ (40−70 wt.%) were prepared by hot pressing at 1400 °C and investigated as a material for thermal barrier-coating (TBC) applications. For this purpose, the effect of YSZ addition on the phase composition, microstructure, mechanical performance and thermal behavior was studied. X-ray diffraction analysis showed that the LC-YSZ composites were mainly composed of a cubic ZrO2 and La2O3-CeO2-ZrO2 solid solution with a pyrochlore structure, indicating that the reaction between LC and YSZ took place during hot pressing. Scanning electron microscopy revealed the high microstructural stability of the prepared composites, as the pore formation was significantly controlled and a high relative density (>97%) was obtained. The microstructure of LC-YSZ bulk samples was relatively fine-grained, with an average grain size below or very close to 1 µm. YSZ doping improved the Vickers hardness of the LC-YSZ composites; the highest hardness, with value of 12 ± 0.62 GPa, was achieved for the composite containing 70 wt.% of YSZ. The fracture toughness of LC-YSZ composites was in the range from 2.13 to 2.5 MPa·m1/2. No statistically significant difference in heat capacity or thermal conductivity was found between the composites with different content of YSZ. The results showed that LC-YSZ composites have relatively low thermal conductivities from room temperature (1.5−1.8 W·m−1·K−1) up to 1000 °C (2.5−3.0 W·m−1·K−1). This indicates that the prepared LC-YSZ composite materials are promising candidates for TBC applications.

Determination of water content in raw perlites: Combination of NIR spectroscopy and thermoanalytical methods.

A new approach to determination of water content in raw perlites, an industrially important material, and obsidian was proposed, utilizing diffuse reflectance spectroscopy in the near-IR region. The phase composition of the perlite of the perlite samples was over 94% rhyolitic volcanic glass, with only small admixture of other components. The observed volatile species contents detected from both thermogravimetric analysis (TG) and the loss of ignition method (LOI) varied from 3 to 7%. The samples with the highest content of volatiles released over the temperature interval 30-250 °C (based on thermogravimetric analysis) displayed sharp signals in the 1H MAS NMR spectra, with chemical shifts of 4.6-4.7 ppm attributed to water molecules of high mobility. Using IR spectra taken in the near-infrared region, the water content of perlites was evaluated using the combination mode (ν + δ)H2O near 5240 cm-1. The band area depended on the H2O content, with the highest value found for the sample which displayed the highest mass loss in the thermoanalytical experiments. The samples showed variations in properties depending on the location in the deposit they were taken from. The relationship between water content determined gravimetrically and calculated band areas showed a correlation coefficient of 0.78 and 0.74 for TG and LOI respectively. The correlation was significantly improved by adding internal standards, hexadecyltrimethylammonium bromide salt (HDTMA) or layered hydrosilicate talc, to the perlite samples, and then normalizing the spectra of the mixtures to selected bands of those standards (R2 = 0.89 and 0.88 respectively for TG methods). A better correlation between infrared and TG/LOI results was obtained for HDTMA-Br than for talc. The proposed method using standards could be a reliable way of estimating water content in raw perlites in processing plants.

X-ray Diffraction, NMR Studies, and DFT Calculations of the Room and High Temperature Structures of Rubidium Cryolite, Rb3AlF6.

A crystallographic approach incorporating multinuclear high field solid state NMR (SSNMR), X-ray structure determinations, TEM observation, and density functional theory (DFT) was used to characterize two polymorphs of rubidium cryolite, Rb3AlF6. The room temperature phase was found to be ordered and crystallizes in the Fddd (no. 70) space group with a = 37.26491(1) Å, b = 12.45405(4) Å, and c = 17.68341(6) Å. Comparison of NMR measurements and computational results revealed the dynamic rotations of the AlF6 octahedra. Using in situ variable temperature MAS NMR measurements, the chemical exchange between rubidium sites was observed. The ß-phase, i.e., high temperature polymorph, adopts the ideal cubic double-perovskite structure, space group Fm3m, with a = 8.9930(2) Å at 600 °C. Additionally, a series of polymorphs of K3AlF6 has been further characterized by high field high temperature SSNMR and DFT computation.

Oxo- and Oxofluoroaluminates in the RbF-Al2O3 System: Synthesis and Structural Characterization.

Precise research on the RbF-Al2O3 system was carried out by means of combining X-ray powder diffraction, high-field solid-state NMR spectroscopy, and thermal analysis methods. α-Rb3AlF6, RbAlO2, Rb2Al22O34, and new phase, Rb2Al2O3F2, were identified in the system. The structure of this new rubidium oxofluoroaluminate was determined. It is built up from single layers of oxygen-connected AlO3F tetrahedra, those layers beeing separated by fluorine atoms. This type of structure exhibits a decent ionic conductivity at ambient temperature, 1.74 × 10-6 S cm-1. The similar structural arrangement of O3Al-O-AlO3 and FO2Al-O-AlO2F tetrahedra of the conduction planes in Rb2Al22O34 and Rb2Al2O3F2 were confirmed by 27Al NMR measurements. A thermal analysis of the RbF-Al2O3 system revealed that it can be defined as a pseudobinary subsystem of the more general quaternary RbF-AlF3-Al2O3-Rb2O phase diagram. From a phase analysis of individual phase fields, the mutual metastable behavior of all founded phases can be considered. It was observed that fluoro- and oxoaluminates exist together. Rb2Al2O3F2 is more stable under high temperature. Rubidium fluoro- and oxoaluminates are metastable precursors of the thermodynamically more stable structure of rubidium oxofluoroaluminate.

(Oxo)(Fluoro)-Aluminates in KF-Al2O3 System: Thermal Stability and Structural Correlation.

Precise investigation of part of the phase diagram of KF-Al2O3 system was performed in an experiment combining different techniques. Solidified mixtures of KF-Al2O3 were studied by X-ray powder diffraction and high-field solid-state NMR spectroscopy over a wide range of compositions. To help with the interpretation of the NMR spectra of the solidified samples found as complex admixtures, we synthesized the following pure compounds: KAlO2, K2Al22O34, α-K3AlF6, KAlF4, and K2Al2O3F2. These compounds were then characterized using various solid-state NMR techniques, including MQ-MAS and D-HMQC. NMR parameters of the pure compounds were finally determined using first-principles density functional theory calculations. The phase diagram of KF-Al2O3 with the alumina content up to 30 mol % was determined by means of thermal analysis. Thermal analysis was also used for the description of the thermal stability of one synthesized compound, K2Al2O3F2.