Basic Engineering Lecture Program

Physical Metallurgy

Definitions
Phase - A phase is a homogenous, physically distinct and mechanically separable portion of the material with a given chemical composition and structure. Phases may exist which are not in the lowest Gibbs Free Energy state at a given temperature and pressure. These phases may be unstable as in the case of a supercooled liquid, or metastable like diamond. Component - A component is a distinct chemical species with its own unique set of chemical properties derived from its own structure. (in the solid state). It can be a pure material or a compound. Constituent - A constituent is a distinct phase or combination of phase that forms on solidification.

Definitions
Solid Solution- A single, solid, homogeneous crystalline phase containing two or more chemical species. Alloy -An alloy is a substance made by melting two or more elements together, at least one of them a metal. An alloy crystallizes upon cooling into a solid solution, mixture, or intermetallic compound. Intermetallic Compound- any solid material, composed of two or more metal atoms in a definite proportion, that has a definite structure which differs from those of its constituent metals Ex; CaSe,Mg2Pb Equilibrium -A system is in equilibrium when it is in lowest Gibbs Free Energy State, more practical is the definition that the system will no longer change with time.

The Gibbs Phase Rule

F=C-P+2
F = # degrees of freedom, or.. The number of intensive parameters that must be specified in order to completely determine the system

What does this MEAN?

The Phase Rule-P & C

F=C-P+2 P = # of phases phases are mechanically separable constituents

C = minimum # of components (the # of chemical constituents that must be specified in order to define all phases)

The Phase Rule-2

F=C-P+2 2 = the number of intensive parameters
Usually = 2 for Temperature and Pressure

Binary Phase Diagrams

Binary phase diagrams are a graphical representation of the temperature and composition limits of phase fields in an alloy system as they actually exist under the specific conditions of heating or cooling.

Isomorphous system
Isomorphous system: complete solid solubility of the two components (both in the liquid and solid phases). Three distinct regions can be identified on the phase diagram: Liquid (L) , solid + liquid ( +L), solid ( ) Liquidus line separates liquid from liquid + solid Solidus line separates solid from liquid + solid

figure 1

The Lever Rule Finding the Amounts of Phases in a Two Phase Region 1. Locate composition and temperature in diagram 2. In two phase region draw the tie line or isotherm 3. Fraction of a phase is determined by taking the length of the tie line to the phase boundary for the other phase, and dividing by the total length of tie line.

The lever principle:

Amount of liquid Amount of solid
ef de

where d = the liquid composition, f = the solid composition and e = the bulk composition

d liquidus
de

D
ef

solidus

Eutectic System

Eutectic Reactions

Eutectic Alloy

Peritectic Reactions
The peritectic reaction also involves three solid in equilibrium, the transition is from a solid + liquid phase to a different solid phase when cooling. The inverse reaction occurs when heating. Solid Phase 1 + liquid Solid Phase 2

Monotectic Reactions
The reversible transition, on cooling, of a liquid to a mixture of a second liquid and a solid: liquid1 liquid2 + solid.

Syntectic Reactions
A reversible reaction that involves the conversion of two liquid phases, l and l , into a solid phase on cooling:

Ex; K-Pb, K-Zn systems

Metatectic Reaction
Metatectic reaction

Ex; Hf-Cu FeB

In this reaction, alloy of composition M, the metatectic composition, precipitate beta a they cool from the liquid phase. This beta content increases until it is all beta. But it is solid only for a short time, for when it reaches point M, it partially remelts. As cooling continues, the alpha phase increases until the solution is all solid and all alpha.

Solid State Reactions

There are three major solid state reactions that arise: The eutectoid: alpha -> beta + gamma

The monotectoid: alpha1 -> beta + alpha2

The peritectoid: alpha + beta -> gamma

Allotropy
The property possessed by certain elements to exist in two or more distinct forms that are chemically identical but have different physical properties. Iron when heated above 910oC the atomic structure changes from BCC to FCC but reverts again when cooled. The allotropy of iron modifies the solubility of carbon, and it is because of this that steel can be hardened.
Cooling curve for pure iron. (Allotropic behavior of pure iron)

Immiscible System There are many combinations of metals which are practically insoluble in each other in liquid and solid states. Ex- Cu-Pb, Cu-Nb , Cu-W

Functions of Binary Diagrams

Phase diagrams are extremely valuable in predicting the microstructure of a material. Although we have focused primarily on metals, such diagrams are available for polymers, ceramics, and even combinations of liquids. Phase diagram predicts what phases will be present at equilibrium. Thus, we can use the phase diagram to predict a materials structure after slow cooling. However to do this, we need to know what phases are present, their compositions, their relative amounts and how they formed.

Functions of Binary Diagrams

Phase diagrams are essential for understanding many industrial processes, especially those used in making liquid and solid materials. Examples are: 1. The distillation of petroleum to make gasoline. Petroleum is a mixture of many different organic compounds and different phases. Gasoline is a single phase containing many different compounds in mutual solution. 2. Heat-treating steel to control its properties. 3. The formation of phases in porcelain for whitewares and dental applications; the starting materials are clay, sand, and felspar, which form many different phases.

Functions of Binary Diagrams

The analysis of problems involving the casting of alloys requires a complex blend of fluid mechanics, heat flow, chemical diffusion and solid mechanics. However, the phase diagram, especially when applied to the character of a material at a given position and time (local equilibrium), provides the basic constitutive relation regarding the physical state of the alloy.

Functions of Binary Diagrams

A major use of phase diagrams comes about in the prediction of the degree of microsegregation and inclusion (or second-phase) formation. Partition coefficients can be read directly from the phase diagram. The solidification path can be calculated and the prediction made of the fraction solid when the liquid can begin formation of second-phase particles, inclusions or eutectics. Such liquid compositions are directly read from phase diagrams.

Functions of Binary Diagrams

The prediction of fraction solid as a function of temperature described above, when coupled with a heat flow analysis of castings, yields the thickness of the mushy zone or liquid-solid region in castings. The thickness of the mushy zone is very important for the prediction and control of microporosity and gas porosity, as well as hot tearing characteristics of castings.

Functions of Binary Diagrams

From the calculated phase diagram, the melting temperature range for solder, the solidification path, as well as the susceptibility to intermetallic formation with various substrates, can be estimated. Extrapolation to higher-component systems In ceramics for development of new materials