Solid
A solid object is in the states of matter characterized by resistance to deformation and changes of volume. In other words, it has high values both of Young's modulus and of shear modulus; this contrasts e.g. with a liquid, which has a low shear modulus. At the microscopic scale, a solid has these properties :
The atoms or molecules that compose the solid are packed closely together.
These constituent elements have fixed positions in space relative to each other. This accounts for the solid's rigidity. In mineralogy and crystallography, a crystal structure is a unique arrangement of atoms in a crystal. A crystal structure is composed of a unit cell, a set of atoms arranged in a particular way; which is periodically repeated in three dimensions on a lattice. The spacing between unit cells in various directions is called its lattice parameters. The symmetry properties of the crystal are embodied in its space group. A crystal's structure and symmetry play a role in determining many of its properties, such as cleavage, electronic band structure, and optical properties.
If sufficient force is applied, either of these properties can be disrupted, causing permanent deformation.
Because solids have thermal energy, their atoms vibrate. However, this movement is very small, and cannot be observed or detected under ordinary circumstances. In a solid, the particles are vibrating in place. A solid doesn't flow.
The branch of physics that deals with solids is called solid-state physics, and is a type of condensed matter physics. Materials science is primarily concerned with properties of solids such as strength and phase transformations. It overlaps strongly with solid-state physics. Solid-state chemistry overlaps both of these fields, but is especially concerned with the synthesis of novel materials.
The lightest known solids are aerogels. The lightest aerogel produced has a density of 1.9 mg/cm³ or 1.9 kg/m³ (1/530 the density of water.
SOLID BASICS So what is a solid? Solids are usually hard because their molecules have been packed together. The closer your molecules are, the harder you are. Solids also can hold their own shape. A rock will always look like a rock unless something happens to it. The same goes for a diamond. Even when you grind up a solid into a powder, you will see little tiny pieces of that solid under a microscope. Liquids will move and fill up any container. Solids like their shape. In the same way that a solid holds its shape, the atoms inside of a solid are not allowed to move around too much. This is one of the physical characteristics of solids.
Atoms and molecules in liquids and gases are bouncing and floating around, free to move where they want. The molecules in a solid are stuck. The atoms still spin and the electrons fly around, but the entire atom will not change position. Solids can be made up of many things. They can have pure elements or a variety of compounds inside. When you get more than one type of compound in a solid it is called a mixture. Most rocks are mixtures of many different compounds. Concrete is a good example of a manmade mixture.
CRYSTALS On the other end of the spectrum from a mixture is something called a crystal. When a solid is made up of a pure substance and forms slowly, it can become a crystal. Not all pure substances form crystals because it is a delicate process. The atoms are arranged in a regular repeating pattern called a cystal lattice. A crystal lattice is a very exact organization of atoms. A good example is carbon. A diamond is a perfect crystal lattice while the graphite arrangement is more random.
As if the handset didn’t require you to dig deep into your pockets as is, someone out there decided that the handset deserved to etched in gold and thus the very first Solid Gold iPhone 3G was born. Reports have it that the handset took four craftsmen a few long months to build its 22 carat solid gold body by hand. The famous Apple logo on the back is designed with 53 VVS1 diamonds. I feel like it’s costing me a lot of money just writing this.
Image SourceYou’d think that a hand crafted special edition handset like this would at least have a few higher ended features. That’s not the case with this gold edition though. All features remain completely standard. Even the camera still has just a 2 megapixel resolution. But what does a solid gold handset cost? It’s got a hefty price tag of £22,995 which comes to about 1.69588838 million Indian rupees. I’m not sure where the breaks go in that figure. It looks more someone’s cell phone number.
History
Because of its direct relevance to products of commerce, solid state inorganic chemistry has been strongly driven by technology well in advance of atomic-level descriptions or in the academic studies. Applications discovered in the 20th century include zeolite and platinum-based catalysts for petroleum processing in the 1950’s, high-purity silicon as a core component of microelectronic devices in the 1960’s, and “high temperature” superconductivity in the 1980’s. The invention of X-ray crystallograpy in the early 1900s by William Lawrence Bragg enabled further innovation. [1]
Synthetic methods
Given the diversity of solid state compounds, an equally diverse array of methods[2] are used for their preparation. For organic materials, such as charge transfer salts, the methods operate near room temperature and are often similar to the techniques of organic synthesis. Redox reactions are sometimes conducted by electrocrystallisation, as illustrated by the preparation of the Bechgaard salts from tetrathiafulvalene.
Oven techniques
For thermally robust materials, high temperature methods are often employed. For example, bulk solids are prepared using tube furnaces, which allow reactions to be conducted up to ca. 1100 °C. Special equipment e.g. ovens consisting of a tantalum tube through which an electric current is passed can be used for even higher temperatures up to 2000 °C. Such high temperatures are at times required to induce diffusion of the reactants, but this depends strongly on the system studied. Some solid state reactions already proceed at temperatures as low as 100 °C.
Melt methods
One method often employed is to melt the reactants together and then later anneal the solidified melt. If volatile reactants are involved the reactants are often put in an ampoule that is evacuated -often while keeping the reactant mixture cold e.g. by keeping the bottom of the ampoule in liquid nitrogen- and then sealed. The sealed ampoule is then put in an oven and given a certain heat treatment.
Solution methods
It is possible to use solvents to prepare solids by precipitation or by evaporation. At times the solvent is used hydrothermally, i.e. under pressure at temperatures higher than the normal boiling point. A variation on this theme is the use of flux methods, where a salt of relatively low melting point is added to the mixture to act as a high temperature solvent in which the desired reaction can take place.
Gas reactions
Many solids react readily with reactive gas species like chlorine, iodine, oxygen etc. Others form adducts with other gases, e.g. CO or ethylene. Such reactions are often carried out in a tube that is open ended on both sides and through which the gas is passed. A variation of this is to let the reaction take place inside a measuring device such as a TGA. In that case stoechimetric information can be obtained during the reaction, which helps identify the products.
A special case of a gas reaction is a chemical transport reaction. These are often carried out in a sealed ampoule to with a small amount of a transport agent, e.g. iodine is added. The ampoule is then placed in a zone oven. This is essentially two tube ovens attached to each other which allows a temperature grandient to be imposed. Such a method can be used to obtain the product in the form of single crystals suitable for structure determination by X-ray diffraction.
Chemical vapor deposition is a high temperature method that is widely employed for the preparation of coatings and semiconductors from molecular precursors.
Air and moisture sensitive materials
Many solids are hygroscopic and/or oxygen sensitive. Many halides e.g. are very 'thirsty' and can only be studied in their anhydrous form if they are handled in a glove box filled with dry (and/or oxygen-free) gas, usually nitrogen.
Characterization
New phases, phase diagrams, structures
The synthetic methodology and the characterization of the product often go hand in hand in the sense that not one but a series of reaction mixtures are prepared and subjected to heat treatment. The stoichiometry is typically varied in a systematic way to find which stoichiometries will lead to new solid compounds or to solid solutions between known ones. A prime method to characterize the reaction products is powder diffraction, because many solid state reactions will produce polycristalline ingots or powders. Powder diffraction will facilitate the identification of known phases in the mixture. If a pattern is found that is not known in the diffraction data libraries an attempt can be made to index the pattern, i.e. to identify the symmetry and the size of the unit cell. (If the product is not crystalline the characterization is typically much more difficult.)
Once the unit cell of a new phase is known, the next step is to establish the stoichiometry of the phase. This can be done in a number of ways. Sometimes the composition of the original mixture will give a clue, if one finds only one product -a single powder pattern- or if one was trying to make a phase of a certain composition by analogy to known materials but this is rare. Often considerable effort in refining the synthetic methodology is required to obtain a pure sample of the new material. If it is possible to separate the product from the rest of the reaction mixture elemental analysis can be used. Another ways involves SEM and the generation of characteristic X-rays in the electron beam. The easiest way is to solve the structure is by using single crystal X-ray diffraction.
The latter often requires revisiting and refining the preparative procedures and that is linked to the question which phases are stable at what composition and what stoichiometry. In other words what does the phase diagram looks like [3]. An important tool in establishing this is thermal analysis techniques like DSC or DTA and increasingly also, thanks to the advent of synchrotrons temperature-dependent power diffraction. Increased knowledge of the phase relations often leads to further refinement in synthetic procedures in an iterative way. New phases are thus characterized by their melting points and their stoichiometric domains. The latter is important for the many solids that are non-stoichiometric compounds. The cell parameters obtained from XRD are particularly helpful to characterize the homogeneity ranges of the latter.
Further characterization
In many -but certainly not all- cases new solid compounds are further characterized[4] by a variety of techniques that straddle the fine line that (hardly) separates solid-state chemistry from solid-state physics.
Optical properties
For non-metallic materials it is often possible to obtain UV/VIS spectra. In the case of semiconductors that will give an idea of the band gap.
Electrical properties
Four-point (or five-point) probe methods are often applied either to ingots, crystals or pressed pellets to measure resistivity and the size of the Hall-effect. This gives information on whether the compound is an insulator, semiconductor, semimetal or metal and upon the type of doping and the mobility in the delocalized bands (if present). Thus important information is obtained on the chemical bonding in the material.
Magnetic properties
Magnetic susceptibility can be measured as function of temperature to establish whether the material is a para-, ferro- or antiferro- magnet. Again the information obtained pertains to the bonding in the material. This is particularly important for transition metal compounds. In the case of magnetic order neutron diffraction can be used to determine the magnetic structure.
