In-Situ Fabrication of ZrB2-ZrC-SiCnws Hybrid Nanopowders With Tunable Morphologies of SiCnws

SiC nanowires (SiCnws) with different morphologies have great potential for the reinforcement of ceramic materials. But it is a big challenge in the in-situ synthesis of SiCnws in the ceramic powders which is critical to ensure high reinforcing effects. For the reinforcement of ZrB2-ZrC composites, a simple method is developed to in-situ fabricate SiCnws with various morphologies in nano-sized ZrB2-ZrC powders through pyrolyzing ZrB2-ZrC-SiC gel precursors. The prepared ZrB2-ZrC ceramic powders have mean diameter of about 100 nm with uniformly distributed SiCnw in morphologies of nanocylider, bead-like, bamboo-shape with tunable nodes, chain-like and hexagonal prisms were prepared by optimizing the preparation process. Moreover, the SiCnws were in a diameter of ranging from 100 to 400 nm, while the length was controlled from tens to hundreds of microns. The generation of ZrB2/ZrC can determine the formation of SiCnws with specific morphologies by producing CO gas to affect the local supersaturation of the SiO and CO vapors. The study provides an opportunity for fabricating SiCnw reinforced ceramic materials with enhanced strengthening effect and also overcome its critical fabrication process.

Impact of Surface Roughness on Crystal Nucleation

We examine the effect of rough surfaces on crystal nucleation by means of kinetic Monte Carlo simulations. Our work makes use of three-dimensional kMC models, explicit representation of transport in solution and rough surfaces modeled as randomly varying height fluctuations (roughness) with exponentially decaying correlation length (topology). We use Forward-Flux Sampling to determine the nucleation rate for crystallization for surfaces of different roughness and topology and show that the effect on crystallization is a complex interplay between the two. For surfaces with low roughness, small clusters form on the surface but as clusters become larger they are increasingly likely to be found in the bulk solution while rougher surfaces eventually favor heterogeneous nucleation on the surface. In both cases, the rough surface raises the local supersaturation in the solution thus leading to another mechanism of enhanced nucleation rate.

Transient Evolution of Inclusions during Al and Ti Additions in Fe-20 Mass pct Cr Alloy

The transient evolution of inclusions during Al and Ti additions in a Fe-20 mass pct Cr alloy was investigated using polished cross sections and electrolytic extraction. After Al addition, the evolution of Al2O3-based inclusions based upon the area and particle size passed through the following three main stages with time: Particle agglomeration, inclusion floating, and a slow decrease of the remaining Al2O3-based inclusions. Titanium wire was fed into the steel at the end of the floating stage after Al addition when the Ostwald ripening process was finished. Immediately after Ti addition, the transient phase of Ti oxide was readily generated on the existing Al2O3-based inclusion and disappeared due to Al reduction as time progressed. The formation of the transient TiOx phase was affected by the low disregistry between Al2O3 and TiOx and the local Ti supersaturation, which cannot be predicted by the equilibrium relations of Ti–O–N or Ti–Al–O in the high-Cr-containing melt. Because of the local supersaturation of dissolved [%Ti] and [%N] shortly after Ti addition, TiN associated with existing inclusions and three types of individual TiN including single cubes, twinned inclusions, and clusters were identified. In order to minimize the Ti loss caused by the formation of Ti-rich zones during the transient stages, the removal of large Al2O3-based particles including aggregates, clusters, and flower-shaped inclusions should be promoted by stirring before Ti addition. After Ti addition, Brownian and turbulent were the major factors affecting the collision of particles smaller than the threshold of 2.7 μm. The agglomeration of inclusions larger than this threshold was mainly dominated by turbulent and Stokes’ collisions.

Directed nucleation and growth by balancing local supersaturation and substrate/nucleus lattice mismatch

Controlling nucleation and growth is crucial in biological and artificial mineralization and self-assembly processes. The nucleation barrier is determined by the chemistry of the interfaces at which crystallization occurs and local supersaturation. Although chemically tailored substrates and lattice mismatches are routinely used to modify energy landscape at the substrate/nucleus interface and thereby steer heterogeneous nucleation, strategies to combine this with control over local supersaturations have remained virtually unexplored. Here we demonstrate simultaneous control over both parameters to direct the positioning and growth direction of mineralizing compounds on preselected polymorphic substrates. We exploit the polymorphic nature of calcium carbonate (CaCO3) to locally manipulate the carbonate concentration and lattice mismatch between the nucleus and substrate, such that barium carbonate (BaCO3) and strontium carbonate (SrCO3) nucleate only on specific CaCO3 polymorphs. Based on this approach we position different materials and shapes on predetermined CaCO3 polymorphs in sequential steps, and guide the growth direction using locally created supersaturations. These results shed light on nature’s remarkable mineralization capabilities and outline fabrication strategies for advanced materials, such as ceramics, photonic structures, and semiconductors.

Assembling semiconducting molecules by covalent attachment to a lamellar crystalline polymer substrate

We have investigated the potential of polymers containing precisely spaced side-branches for thin film applications, particularly in the context of organic electronics. Upon crystallization, the side-branches were excluded from the crystalline core of a lamellar crystal. Thus, the surfaces of these crystals were covered by side-branches. By using carboxyl groups as side-branches, which allow for chemical reactions, we could functionalize the crystal with semiconducting molecules. Here, we compare properties of crystals differing in size: small nanocrystals and large single crystals. By assembling nanocrystals on a Langmuir trough, large areas could be covered by monolayers consisting of randomly arranged nanocrystals. Alternatively, we used a method based on local supersaturation to grow large area single crystals of the precisely side-branched polymer from solution. Attachment of the semiconducting molecules to the lamellar surface of large single crystals was possible, however, only after an appropriate annealing procedure. As a function of the duration of the grafting process, the morphology of the resulting layer of semiconducting molecules changed from patchy to compact.

Considerations about mass and energy flow in discontinuous evaporating crystallizers

The massecuite circulates in a loop within the evaporating crystallizing vessel. The massecuite flows upwards through the heating tubes. In the room above the calandria the massecuite flow changes its direction to radial inwards and then to vertical downwards. An impeller in the central tube forces the circulation. Below the calandria the main direction of flow is radially outwards until threads of the massecuite stream enter the heating tubes in upwards direction. Within the tubes heat is transferred to the massecuite. At low temperature differences between heating steam and massecuite and higher levels of the massecuite in the crystallizer vapor bubbles are not found in the tubes. Vapor bubbles can be formed at a massecuite level in the crystallizer where the temperature of the massecuite is higher than the local boiling temperature of water, which depends on the local pressure (including the static pressure of the massecuite at this point) and the boiling point elevation of the mother liquor. The surface tension of the liquid is a resistance against the bubble formation, which has to be overcome by the local superheating i.e. the part of the enthalpy of the massecuite exceeding the local boiling temperature. The formation and the flow of the bubbles change the density of the massecuite/bubbles mixture and has an influence on the massecuite flow. The formation of a vapour bubble is connected with a local drop of the massecuite temperature which changes the local supersaturation. Today the heat transfer into the magma is quite well known but the process of bubble formation is quite unknown. Some basic considerations about the formation of bubbles and its influence on local supersaturation based on calculation of heat and mass balances and models of bubble formation are be given and discussed. Experiments for basic investigations are proposed.

Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid

Hydroxyapatite (HA, Ca 5 (PO 4 ) 3 OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca 2+ and PO 4 3− ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca 2+ and PO 4 3− ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca 2+ and PO 4 3− ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only.

Growth of micro-ikebana on a floating substrate: a method to monitor local supersaturation levels

The growth of biomimetic SrCO3–SiO2 micro-ikebana was conducted by an organic additive-free process to monitor the degree of local supersaturation at the surface of a floating substrate. The obtained crystallization pattern mirrors the level of local concentration which was the basis to derive a mathematical equation for the prediction of local nucleation rates.