Grain size dependence of hardness in nanocrystalline silicon carbide

The response of nanocrystalline silicon carbide (nc-SiC) to nanoindentation is investigated using molecular dynamics (MD) simulation. It is found that the hardness of the nc-SiC decreases with decreasing grain size, showing an inverse Hall-Petch relationship. The behavior is primarily attributed to the reduced number of intact covalent bonds with grain refinement. Dislocation nucleation and growth in nc-SiC are strongly suppressed by the grain boundaries (GBs). In addition to the dislocation region in the grains, the indentation-induced amorphization of nanograins proceeds preferentially from the GBs, leading to grain shrinkage until the grains are fully amorphized. The results provide an improved understanding of the mechanical properties in nc-SiC and other nanostructured covalent materials.     

Radiation and thermal effects on porous and layer structured materials as getters of radionuclides

The long term radiation and thermal effects on porous and layer structured materials that may function as getters for radionuclides have been evaluated using accelerated laboratory experiments including energetic electron, ion or neutron irradiation, as well as high-temperature thermal annealing. The materials studied include: zeolites, layered silicates (mica and smectite clays), open framework structured apatite and crystalline silicotitanate (CST) which is an important synthetic ion-exchange material for the chemical separation of high-level liquid radioactive wastes.In situ transmission electron microscopy during irradiation by energetic electrons and ions has shown that all the studied materials are susceptible to irradiation-induced amorphization. Amorphization can be induced by ionization and/or direct displacement processes. Amorphization may be preceded or accompanied with dehydration, layer spacing reduction and gas bubble formation. In the case of zeolites, CST and some layer silicates, radiation effects are significantly enhanced at higher temperatures. In fact, thermal annealing at high temperatures alone can cause complete amorphization of zeolites. Our experiments have shown that amorphization or even partial amorphization will cause a dramatic reduction (up to 95%) in ion-exchange and sorption/desorption capacities of zeolite for radionuclides, such as Cs and Sr. Because the near-field or chemical processing materials (e.g., zeolites or CST) will receive a substantial radiation dose after they have incorporated radionuclides, our results suggest that radiation effects may, in some cases, retard the release rate of sorbed or ion-exchanged radionuclides.     

On amorphization as a deformation mechanism under high stresses

In this paper we review the work related to amorphization under mechanical stress. Beyond pressure, we highlight the role of deviatoric or shear stresses. We show that the most recent works make amorphization appear as a deformation mechanism in its own right, in particular under extreme conditions (shocks, deformations under high stresses, high strain-rates).     

Effects of Grinding with Microcrystalline Cellulose and Cyclodextrins on the Ketoprofen Physicochemical Properties

Ground mixtures of ketoprofen (KETO) with native crystalline β-cyclodextrin, amorphous statistically substituted methyl-β-cyclodextrin, and microcrystalline cellulose were investigated for both solid phase characterization (differential scanning calorimetry (DSC) powder X-ray diffractometry, and infrared (IR) spectrometry) and dissolution properties (dispersed amount and rotating disk methods) to evaluate the role of the carrier on the performance of the final product. The effects of different grinding conditions, partial sample dehydration, and 1 year storage at room temperature were also investigated. The results pointed out the importance of the carrier nature on the efficiency of the cogrinding process. Both cyclodextrins were much more effective than was microcrystalline cellulose, even though no true inclusion complex formation occurred by mechanochemical activation. The best results were obtained from ground mixtures with methyl-β-cyclodextrin, which showed the best amorphizing and solubilizing power toward the drug and permitted an increase of approximately 100 times its intrinsic dissolution rate constant, in comparison with the approximate 10 times increase obtained from ground mixtures with β-cyclodextrin.     

Amorphization and graphitization of single-crystal diamond — A transmission electron microscopy study

The amorphization and graphitization of single-crystal diamond by ion implantation were explored using transmission electron microscopy (TEM). The effect of ion implantation and annealing on the microstructure was studied in (100) diamond substrates Si⁺ implanted at 1 MeV. At a dose of 1 × 10¹⁵ cm^− 2, implants done at 77 K showed a damage layer that evolves into amorphous pockets upon annealing at 1350 °C for 24 h whereas room temperature implants (303 K) recovered to the original defect free state upon annealing. Increasing the dose to 7 × 10¹⁵ Si⁺/cm² at 303 K created an amorphous-carbon layer 570 ± 20 nm thick. Using a buried marker layer, it was possible to determine that the swelling associated with the amorphization process was 150 nm. From this it was calculated that the layer while obviously less dense than crystalline diamond was still 15% more dense than graphite. Electron diffraction is consistent with the as-implanted structure consisting of amorphous carbon. Upon annealing, further swelling occurs, and full graphitization is achieved between 1 and 24 h at 1350 °C as determined by both the density and electron diffraction analysis. No solid phase epitaxial recrystallization of diamond is observed. The graphite showed a preferred crystal orientation with the (002)g//(022)d. Comparison with Monte Carlo simulations suggests the critical displacement threshold for amorphization of diamond is approximately 6 ± 2 × 10²² vacancies/cm³.     

Structural changes of SiC under electron-beam irradiation: Temperature dependence

Electron-beam-irradiation effects on silicon carbide (SiC) was investigated as a function of the irradiated temperatures. Single crystalline 6H-SiC was irradiated with 300 kV electrons at temperatures ranging from −170 to 250 °C. It was found that amorphous SiC is induced at −170 °C and room temperature, while crystalline Si is formed at 250 °C with a high electron fluence. It is considered that preferential knock-on displacement of C atoms and damage recovery play an important role in the formation of the amorphous SiC and crystalline Si.     

Structural evolution during crystallization in phase separated Ti–Y–Al–Co metallic glass

Structural evolution during heat treatment of melt spun Ti₃₆Y₂₀Al₂₄Co₂₀ alloy was studied using differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. The as-melt spun Ti₃₆Y₂₀Al₂₄Co₂₀ specimen showed a hierarchical complex microstructure consisting of Ti-rich and Y-rich amorphous phases and crystallized with two-step process. Crystallization in the phase separated two phase mixture took place in a confined mode due to different thermal stability and complex microstructure, resulting in various nano-scaled microstructural formation ranging from fine distribution of crystalline particles in amorphous matrix to fine distribution of amorphous particles in crystalline matrix.     

Atomic-scale simulation of displacement cascades and amorphization in β-SiC

Molecular dynamics (MD) methods with a modified Tersoff potential have been used to simulate Si displacement cascades with energies up to 50 keV and to compare clustering behavior for Si and Au recoils in β-SiC (3C). The results show that the lifetime of the thermal spike is very short compared to that in metals, and that the surviving defects are dominated by C interstitials and vacancies for Si displacement cascades. Only 19% of the interstitial population is contained in clusters, with the largest cluster containing only four interstitial atoms for energetic Si recoils. The energy dependence of stable defect formation exhibits a power-law relationship. The high energy Si recoil generates multiple sub-cascades and forms dispersed defect configurations. These results suggest that in-cascade amorphization in SiC does not occur with any high degree of probability during the lifetime of Si cascades. On the other hand, large disordered domains are created in the cascades produced by 10 keV Au recoils. Structure analysis indicates that these highly disordered regions have amorphous characteristics. The data for the cluster spectra have been used to calculate the relative cross-sections for in-cascade amorphization (or clustering) and defect-stimulated amorphization. The ratios of these cross-sections for Si and Au are in excellent agreement with those derived from a fit of the direct-impact/defect-stimulated model to experimental data.