The document discusses solid state reaction or shake 'n bake methods for synthesizing materials. It describes how these reactions are intrinsically slow due to inhomogeneous mixing at the atomic level, requiring diffusion between particles. It also discusses techniques like ball milling to improve mixing, considerations for reactants, containers and heating schedules. Examples of synthesis methods discussed include combustion synthesis, which uses exothermic reactions to achieve rapid synthesis, and mechanosynthesis using high-energy milling.
The document discusses solid state reaction or shake 'n bake methods for synthesizing materials. It describes how these reactions are intrinsically slow due to inhomogeneous mixing at the atomic level, requiring diffusion between particles. It also discusses techniques like ball milling to improve mixing, considerations for reactants, containers and heating schedules. Examples of synthesis methods discussed include combustion synthesis, which uses exothermic reactions to achieve rapid synthesis, and mechanosynthesis using high-energy milling.
The document discusses solid state reaction or shake 'n bake methods for synthesizing materials. It describes how these reactions are intrinsically slow due to inhomogeneous mixing at the atomic level, requiring diffusion between particles. It also discusses techniques like ball milling to improve mixing, considerations for reactants, containers and heating schedules. Examples of synthesis methods discussed include combustion synthesis, which uses exothermic reactions to achieve rapid synthesis, and mechanosynthesis using high-energy milling.
The document discusses solid state reaction or shake 'n bake methods for synthesizing materials. It describes how these reactions are intrinsically slow due to inhomogeneous mixing at the atomic level, requiring diffusion between particles. It also discusses techniques like ball milling to improve mixing, considerations for reactants, containers and heating schedules. Examples of synthesis methods discussed include combustion synthesis, which uses exothermic reactions to achieve rapid synthesis, and mechanosynthesis using high-energy milling.
Materials Synthesis Solid State Reaction or Shake ’n Bake Methods Synthesis of polyanionic cathode with improved electrochemical performance for Na-ion batteries High Tc Superconductors
Almost all of them were made by Solid State
Synthesis! High Tc Superconductors Solid State Reaction or Shake ’n Bake Methods
• The oldest, simplest and still most widely used method to make inorganic solids is to mix together powdered reactants, perhaps press them into pellets or some other shape and then heat in a furnace for prolonged periods. • The method is not sophisticated, hence the use of alternative names such as shake ’n bake or, beat ’n heat!
Solid state reactions are intrinsically slow because, although the reactants may be well mixed at the level of individual particles (e.g. on a scale of 1 μm or 10-3 mm), on the atomic level they are very inhomogeneous. In order to achieve atomic level mixing of reactants, either solid state counterdiffusion of ions between different particles or liquid- or gas-phase transport is necessary to bring together atoms of the different elements, and in the correct ratio, to form the desired product. Solid State Reaction or Shake ’n Bake Methods
• Solid state reactions are intrinsically slow because, although the reactants may be well mixed at the level of individual particles (e.g. on a scale of 1 μm or 10-3 mm), on the atomic level they are very inhomogeneous.
• In order to achieve atomic level mixing of reactants, either solid state counter-diffusion of ions between different particles or liquid- or gas-phase transport is necessary to bring together atoms of the different elements, and in the correct ratio, to form the desired product. Solid State Reaction or Shake ’n Bake Methods
MgO and Al2O3 reacts to form MgAl2O4 spinel structure
Nucleation and growth, epitaxy and topotaxy
The first stage, therefore, is nucleation of small crystals with the spinel stoichiometry and structure. For nuclei to be stable and not to disintegrate spontaneously as soon as they form, they must usually be several tens of angstroms across, i.e. they must be considerably larger than a single unit cell and must therefore contain many tens of atoms.
The critical size of nuclei represents a balance between
the negative free energy of formation of the spinel product and the positive surface energy of the nuclei. Epitaxy and Topotaxy
Oriented nucleation of spinel on an alumina substrate
is still easy but the structural similarity between substrate and nucleus is limited to the 2D interface and is referred to as epitaxy.
In the MgO/spinel case, the structural similarity extends to
3D since there is a common oxygen packing arrangement; this is referred to as topotaxy. When discussing chemical reactions in which major structural features of one of the reactants are preserved in the product, it is common to refer to these as topochemical reactions. In the crossover region, the structure has recognisable features of both fishes and birds but is not completely one or the other. Similar effects may occur at the interfaces between two solids; even if there are no atomic displacements at the interface, the coordination environments of atoms at the interface are different to either side of the interface. In practice, atomic displacements may also occur, further complicating the structural details within the interfacial region. When the reactants are no longer in contact with each other For Electrical neutrality
Right-hand interface should move three times as quickly as the left-hand interface
In cases where reactant and product are of different colour, it may be possible, in carefully designed experiments, to observe visually the displacement of the interfaces; this is known as the Kirkendall effect. Practical considerations and some examples of solid state reactions
• choice of starting materials,
• mixing method, • container and • heat treatment conditions.
Starting materials
• Ideal starting materials should be of accurately known stoichiometry, pure and reactive. • Problems with stoichiometry and purity can arise if the reagents are sensitive to water and/or CO2 in the atmosphere or contain transition elements in uncertain or mixed valence states. • Reagents may need to be dried, at a temperature found by trial and error, and subsequently kept in a desiccator. • evolution of gases during the decomposition can help to mix the solid reactants Mixing of reactants
For solid state reaction, it is essential to bring particles of reactants into contact; this is facilitated by increasing the surface area of the reactants. Samples are therefore mixed and milled. This can be done manually using a mortar and pestle
Ball milling, in which the mixture of reactants is placed inside a rotating container together with a number of balls of, for instance, agate. The container is then rotated for a period of time, e.g. 3–24 h, and the effect of the tumbling motion with the agate balls is to reduce the average particle size of the reactants in addition to achieving an intimate mixture.
High-energy milling is possible in planetary ball mills, which are rotated at very high speed. While the mixing and milling processes are carried out rapidly and effectively, there is a danger of contamination from the milling media. To facilitate mixing, by whatever method, a liquid such as water or an organic liquid is often added and then needs to be removed by drying at the end of the mixing stage. Container
Prime consideration for the container is that it should not react with the sample. Frequently- used inert containers for oxides are boats or crucibles of Firing schedule
The heating schedule should be designed to
(a) cause smooth decomposition of any oxy salt reagents without excessive frothing, melting or leakage of reagent from the container,
(b) avoid melting and in particular volatilisation of one or more of the reagents and
(c) apply temperatures at which the reagents react together on a reasonable timescale (e.g. 12–24 h). Reactions may be carried out in air or, if a tube furnace is available, a range of controlled atmospheres may be used. Alternatively, sealed ampoules of silica glass or precious metals may be used to prevent loss of volatile reagents or atmospheric attack. For known materials, there may be recipes in the literature detailing appropriate reaction conditions, but for the attempted synthesis of new materials, a trial and error approach is usually needed. Examples Combustion synthesis
In complete contrast to solid state reactions that often
require heating for several days at high temperatures to complete a synthesis, controlled explosions in reactions known variously as combustion synthesis, selfpropagating high temperature synthesis, SHS, and solid state metathesis, SSM, can give reaction products in minutes or even seconds
In the SHS technique pioneered by Merzhanov and co-
workers in Russia, starting materials are chosen that react together exothermically. Consequently, once a reaction is initiated, enough heat is generated for high temperatures to be attained and complete reaction occurs rapidly. The starting materials may be classified as either ‘fuels’ or ‘oxidants’. An example of an SHS reaction is the ‘thermite’ process for the extraction of iron: Mechanosynthesis
Solid state reactions are generally high-temperature
methods, but in favourable cases reactions can be carried out simply by grinding together the reagents. High-energy milling is necessary, often for periods of several hours, and there can be a danger of contamination from the milling media. Nevertheless, the method is finding increasing applications as a synthetic method. Lecture 6 – Lattice energy and nucleation On board
188 Lecture 7- Growth and Heterogeneous nucleation- on board
Geochemistry, Geochronology and Metallogeny of Pre-Katangan and Post-Katangan Granitoids of The Greater Lufilian Arc, Zambia and Namibia (Ph.D. Thesis)
Geochemistry, Geochronology and Metallogeny of Pre-Katangan and Post-Katangan Granitoids of The Greater Lufilian Arc, Zambia and Namibia (Ph.D. Thesis)
