Materials and Nanomaterials Flashcards
In ionic structures are anions or cations bigger?
Anions are MUCH BIGGER!
Which are more mobile in an ionic structure, cations or anions?
Anions are much bigger and cations fill the interstitial sties; cations are much more mobile
TRUE or FALSE? The solid lines in diagrams of solid state structures are the bonds between atoms
FALSE - the lines are coordination not bonds - although many ionic solids show some covalent characteristics
What is the overall charge of a bulk solid
0 - there is no net charge. Charge can be distributed heterogeneously
At what temperature does the perfect ionic crystal exist at?
At absolute zero - 0 K
Above absolute zero, what will every solid contain - why is this thermodynamically favourable?
Solids will contain defects - increased entropy is thermodynamically favourable
What does the number of defects depend on?
The temperature and the energy required to generate the defects
What are the two types of INTRINSIC defects and what is the difference between them?
1) Schottky defects: a missing cation and anion pair
2) Frenkel defects: an ion (usually cation) moves into an interstitial site
What is the equation for calculating the proportion of defects?
n/N = exp(-ΔH / 2 k T)
n = number of defects per unit volume
N = number of anion and cation sites per unit volume
Do higher charge density ions tend to have more or less defects compared to lower charge dense ions?
Higher charge density ions are harder to move and therefore have a larger ΔH. Plugging into the equation shows that there are fewer defects
Name the EXTRINSIC defect and give a brief description
Doping: the introduction of different ions into a structure with the aim to change the properties of the solid.
How does doping with P into an Si lattice increased conductivity?
P has an extra electron (grp 5) than Si (grp 4) leading to a new valence band being introduced closer to the conduction band. The decrease in the band gap means easier excitation of electrons to the conduction band (from the valence band) and greater conductivity
What do defects result in?
Non-stoichiometry and solid solutions
Why is non-stoichiometry common for transition metals?
As transition metals have a range of oxidation states
What is non-stoichiometry?
(Usually of solids) Deviation from the ideal ratio of atoms, usually with as fractions (or d.p.)
What structure is TiOx?
Rock salt
How does the unit cell size change as x increases for TiOx?
As x increases the unit cell volumes decreases
TRUE of FALSE? For TiOx a change in x signifies a change in the number of oxygen atom vacancies?
FALSE - its just a change in the ratio of oxygen:titanium atoms. Could be due to more titanium vacancies
What is a solid solution?
A crystalline solid of 2 or more atoms that repeat to form a structure
What are the two types of solid solutions?
1) Substitutional - where a new atom replaces an existing atom (e.g. by doping)
2) Interstitial - where atoms are added to the structure
Give an example of a substitutional solid solution
Al2O3 + Cr2O3 –> Al(2-x)Cr(x)O3, when x = 0.05 we get ruby (which is used in lasers)
Give an example of an interstitial solid solution
C into Fe –> FeCx. C occupies interstitial sites and gives steel
Above absolute zero, atoms/ions respond to external stimuli . Name 4 different external stimuli
- Electric field
- Magnetic field
- Pressure
- Temperature
What are the components of a rechargeable lithium ion battery?
- 2x Electrodes
- Electrolyte (medium for ions to move)
What is intercalation and why is it important for lithium ion batteries?
The process of inserting an ion into a layered material. Important for the charging/discharging cycle.
What structural features of graphite and LiCoO(2) make for good use in lithium ion batteries?
They have layered structures that allow for intercalation and deintercalation (addition and removal of Li+ ions) and allow for movement of Li+ ions
What is polymorphism?
The solid state equivalent of isomerism - TiO2 can have 3 different structures depending on temperature and pressure
Why should intercalation/deintercalation not result in big structural changes?
Leads to mechanical stress and possible fracture - performance loss
What is the importance of having a secondary layer between the electrolytes and the electrodes?
Very oxidising/reducing environment - stops degradation of electrolyte and growth of dendrites (which could lead to ignition of flammable electrodes
Why, to obtain bulk polarisation, should a material be a non-centrosymmetric crystal?
Otherwise dipoles cancel each other out
What are the 3 types of compounds that respond to external stimuli to give a bulk polarisation? What do each respond to?
- Ferroelectrics: dipoles respond to electric field
- Pyroelectrics: dipoles respond to heat (or photons) and convert heat to electrical energy.
- Piezoelectrics: dipoles respond to pressure and convert kinetic energy to electrical energy
What should 2 qualities should good ferroelectric have?
- A high dielectric strength (not breakdown at high voltages and becoming conducting)
- A low dielectric loss (no loss of electrical energy as heat or as alternating electric field)
What structure is BaTiO(3)?
Perovskite
What happens to the Ti atoms in BaTiO(3) when heated below 120c?
Above 120c the Ti atoms are in Oh geometry (which is centrosymmetric) and so there is no bulk polarisation. Below 120c the Ti atoms are displaced along 1 axis as the TiO(6) octahedra tilt slightly. This leads to a dipole.
Why does a structure distort?
For a compound of containing several elements the ideal preferences of each element is unlikely to be accommodated (e.g. preferred coordination/geometry) which introduces strain. Enough strain and the structure distorts
What is the standard empirical formula for a perovskite structure?
ABO(3)
How can distortion be estimated?
Using a tolerance factor
What is the standard empirical formula for a rock salt structure?
AB (1:1 ratio)
For the ideal structure, what is the tolerance factor (t)?
t = 1
what is the range that the tolerance factor (t) can take for a distorted perovskite structure? And outside of this range what happens to the structure?
0.85 < t < 1.06 - Outside this range a non-perovskite structure is adopted