Binary Peritectic Systems

Like the eutectic system, the peritectic reaction is found in systems with complete
liquid solubility but limited solid solubility
In the peritectic reaction the liquid (L) reacts with one solid (α) to produce
another solid (β)
L+α=β

solid β forms at the interface between the L and the α, further reaction is
dependent on solid state diffusion. Needless to say this becomes the rate limiting
step and hence it is difficult to ‘equilibrate’ Peritectic reactions (as compared to
say eutectic reactions)
In some peritectic reactions (e.g. the Pt-Ag system-next page), the (pure) β phase is not
stable below the peritectic temperature (TP = 1186C for Pt-Ag system) and splits into a
mixture of (α+β) just below T
Cu-Zn Phase diagram
Peritectic in Fe-Fe3C
Peritectic reactions in ceramic system

Peritectic reaction:
enstatite = forsterite + SiO2

Forsterite-Silica at 0.1 MPa.

Binary Peritectic in Iridium-Osmium system
 Intermediate Phases and Compounds

Terminal phases: Phases occur at the end of the phase diagrams

Intermediate Phases : occur inside the phase diagrams
Intermediate phases may be stoichiometric (then compounds) or
nonstoichiometric
In Al2O3-SiO2 –mullite (3Al2O3.2SiO2): nonstoichiometric
Non-Stoichiometric: MgN2i Stoichiometric: Mg2Ni
 Types of intermediate compounds

Depending on the two elements involved compounds can be of different types

1. Chemical compounds:
-also called as valency compounds
- When 2 dissimilar elements have greater affinity for each other
- Mixing of electropositive elements, like Na, K, Al, Mg, etc. with
electronegative elements like Sn, Pd, As, Sb, Se, S, etc into compounds
like Mg3As2, Mg2Sn, MgSe, Cu2Se, etc.
- Generally, ionic or covalent bonds
- Nonmetallic in properties
- Hard, brittle, and poor conductors with high MP
 Types of intermediate compounds –contd…

2. Intermetallic compounds
- Unlike chemical comounds, intermetallic ocmpunds rarely obey the laws of
chemical valency
-complex lattice structures and are characterised by high hardness, brittleness
and MP
-ex: Cu3Sn, Cu3Sn4, CuAl2. SnSb, etc.
- Have metallic bonding and valence electrons are free to move in lattice giving
characteristic metallic properties to them.
 Types of intermediate compounds –contd…

3. Interstitial compounds
-sometimes considered as special case of intermetallic compounds (size)
Formed when the extent of interstitail solutes exceeds the solubility limit
-atoms of elements like O, H, C, B , N have smaller radii and occuppy interstitial
space btn other atoms
Base metal is generally transition elements like Sc, Ti, Ta, W, Fe, etc.
They do not obey the laws of valency rules
Interstitial compounds are extremely hard, metallic in nature and have high MP &
BP
Hardness is utilised in dispersion strengthening and high speed cutting tips
Ex: TiC, Fe4N, W2C, TiH, Fe3C
 Types of intermediate compounds –contd…

4. Electron compounds
-again they do not obey the normal valence rules
-Formed in metals with similar electron chemical properties and a favourable size
factor but different no of valence electrons
-Can be characterized by a definite ratio of valence electrons to the no of atms
(3/2, 21/13, 7/4) with a particular crystal lattice corresponding to each ratio.

Formed by 2 metals from the following groups

Group 1: Cu, Ag, Au, Fe, Co, Ni, Pd, Pt
Group 2: Be, Zn, Cu, Al, Sn, Si
Ex: Cu-Zn (CuZn, Cu5Zn8, CuZn3), Ag-Cd (AgCd, Ag5Cd8, AgCd3), Cu-Sn, Cu-Al, Cu-
Si
 Types of intermediate compounds –contd…

5. Lave’s phases
When the difference btn that radii of 2 elements is about 20-30%, ratio
observed btn two atoms is 1: 1.2
General formula AB2
MgCu2, MgZn2, MgNi