Material Science

Lecture 1 Cooling Curves

Most substances can exist as a solid, liquid and gas. For example water, if it is sufficient hot it is steam and if it is sufficiently cold it is ice. Between these two temperatures it is obviously a liquid. If water is brought to above its boiling temperature and then allowed slowly to cool, the change in temperature against time can be plotted and a cooling curve can be constructed. This is shown in figure 1.

Figure 1 Cooling curve of pure water

It can be seen that where a change of state occurs i.e. a change in phase, there is a short pause in the cooling process. This pause is referred to as an arrest point and it is the result of the water giving up latent heat energy. Latent heat is the heat energy required to produce a change in state in a substance at a constant temperature. Thus a physical change in state during cooling or heating is always accompanied by an arrest point in the cooling or heating curve. The cooling curve of water is typical of all pure substances and applies equally to pure metals. Alloys, however, consist of two or more components and to understand their behaviour we will consider a solution of water and salt.

Figure 2 Cooling curve for salt solution

It can be seen that the salt-water solution has two arrest points and that both of these are below the freezing point of pure water. As cooling continues below 0C droplets of pure water separate out from solution and immediately turn into ice particles. This occurs at the upper arrest point, which is usually not too well defined. This process of separation continues as the temperature falls therefore, more and more water separates out causing the concentration of the salt water to increase. When the lower arrest point is reached,

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even the concentrated salt solution freezes and no liquid phase is left. The solid formed consists of a mixture of fine crystals of pure water and fine crystals of salt. If the experiment is repeated several times using stronger and weaker solutions a family of cooling curves can be plotted.

Figure 3 Cooling curves for salt solutions of different concentrations

Four important observations can be made:

Since the amount of salt which can be held in solution with water varies with temperature, water separates out as ice crystals between the arrest points of hypo-eutectic solutions as the temperature falls, and salt crystals separate out between the arrest points of hyper-eutectic solutions as the temperature falls, therefore the remaining solution is always of a constant concentration and therefore, has a constant arrest point temperature. This concentration is the eutectic composition. The fact that excess water or salt is rejected from solution means that the eutectic balance or equilibrium is always ultimately achieved. When a family of cooling curves is plotted in this way it is referred to as a phase equilibrium diagram. Summary Questions Lecture 1 1. What is latent heat? 2. Differentiate between a saturated and a super saturated solution. 3. Explain why impure substances have a less defined freezing/melting point. 4. Why is salt spread onto the roads in icy conditions? 5. What would be the ideal salt concentration for reducing the risk of ice?

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Lecture 2 Phases in solidified alloys

Until now weve understood the term phase to describe whether a material is a solid, liquid or gaseous state. Let us now consider it in more detail and define it as: A portion of a system, which is of uniform composition and texture throughout, and, which is separated from the other phases by clearly defined surfaces. Thus for the salt solution considered last lecture there are four possible phases:

Each of these four phases is uniform composition and is separated from adjacent phases by definite boundaries. It is necessary to distinguish between crystals (or grains) and phases. The ice phase may appear as separate lumps with each lump containing many single-phase water crystals and similarly the single-phase crystalline sodium chloride may appear as lumps of salt containing many separate crystals. Extending this argument to metal alloys, when a liquid solution of two metals (a binary alloy) solidifies, one of the following conditions will occur. Simple eutectic type - Metals that are soluble in the liquid state, become totally insoluble in the solid state and they separate out as grains of two pure metals. In practice this is rare since there is usually some solubility of one metal in another. Solid solution type - If the alloying elements have similar chemical properties, and their atoms are of similar size they will form a solid solution, that is, they remain totally soluble in the solid state.

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Combination type - they remain just partially soluble in the solid state

Intermetallic Compound - In a situation where atoms with sufficiently different chemical properties attract each other the two metals react together to form an intermetallic compound. Upon cooling a single phase consisting of many grains of the same composition will be present. In general, intermetallic compounds tend to be hard and brittle and are thus less useful for engineering alloys than the tough and ductile solid solutions. The exceptions being some bearing metals where they form hard, wear resistant pads with a low coefficient of friction, set in a matrix of tough, ductile solid solution. The individual grains found in any of these phases may vary considerably in size. Some are large enough to see with the unaided eye, whilst others are so small that a highpowered microscope is required. Note that although the phases found in alloys, as described above, are formed from two metals, they may equally be formed between a metal and a non-metal. For example, austenite is a solid solution of carbon in iron, whilst cementite is the compound iron carbide. Well consider these in a lot more detail in future lectures. Summary Questions Lecture 2 1. How many phases are present in the solid form of salt water? 2. Which of the four solid compositions (as discussed above) would best describe the solid form of salt water? 3. State two metals that are insoluble in each other in their molten form. 4. Define a solid solution. 5. What factors determines which solid composition an alloy will exhibit?

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Lecture 3 Phase Equilibrium Diagrams (eutectic type)

In the next couple of lectures we will continue to consider binary alloys and the three main ways in which they solidify, namely; eutectic, solid solution and combination type. Eutectic type Figure 1 shows a eutectic-type phase equilibrium diagram and it can be seen that it is very similar to the diagram produced for a sodium chloride and water solution. That is, total solubility of the salt in water in the liquid state and total insoluble in the solid state. In figure 1 the two components are referred to as metal A and metal B. although they are mutually soluble in the liquid state, both components retain their identities of crystal A and crystal B in the solid state.

Figure 1 - Phase equilibrium diagram (eutectic type)

This type of equilibrium diagram gets its name from the fact that at one particular composition (E), the temperature at which solidification commences is a minimum for the alloying elements present. With this composition the liquidus and the solidus coincide at the same temperature, i.e. crystals of A and B form instantaneously at the same temperature. In practice, few metal alloys form simple eutectic type equilibrium diagrams. The diagram can be used to further categorise the alloys into two groups; hypo-eutectic and hyper-eutectic. Hypo-eutectic simply means that it is to the left of the eutectic point and hyper-eutectic is to the right. Consider 25%A, 75%B alloy. Firstly, this is a hypo-eutectic alloy as it is to the left of the eutectic point. Let us consider what happens as this alloy cools. To begin with it is a molten mixture of A and B. Solidification commences as it cools at the liquidus line. The first crystals to precipitate out are crystals of B (as this is in excess). As crystals of B fall out of solution the proportion of A in the remaining solution increases. At the solidus line the concentration of the remaining solution is the same as the eutectic composition and on reaching the eutectic temperature crystals of A and B precipitate out simultaneously to form lamellar eutectic crystals (see figure 3). Therefore, the solid alloy is made up of two phases; B phase and a A+B phase (eutectic phase).

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Example Alloys of cadmium and bismuth are an example of the simple eutectic type. The phase diagram is shown below.

Figure 2 Cadmium-bismuth phase equilibrium diagram

Figure 3 Lamellar structure of eutectic composition

Figure 4 Solid compositions a)20% Cd, 80% Bi; b)40% Cd, 60% Bi; c)80% Cd, 20% Bi

Summary Questions Lecture 3 Referring to figure 1; 1. What is the name of the line joining the points where solidification begins? 2. What is the line joining the points where solidification is complete? 3. What is name given to the point where the liquidus and the solidus coincide? 4. What is the temperature it occurs at called? 5. What is the composition at this point called? 6. State the range of both hypo and hyper-eutectic alloys. Referring to figure 2; 7. State the eutectic composition and temperature. 8. Consider alloy 80% cadmium and 20% bismuth. Is it a hypo or a hyper-eutectic alloy? 9. Describe what is happening, in terms of crystal growth, as the liquid cools from above the liquidus temperature to below the solidus temperature. 10. What are alloys of Cadmium and Bismuth commonly used for?

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Lecture 4 Phase Equilibrium Diagrams (solid solution and combination types)

Solid Solution Copper and Nickel are an example of solid solution type binary alloy, that is, not only are they mutually soluble in the liquid state, they are also mutually soluble in the solid state. The phase diagram for copper-nickel is shown in figure 1. Again, the line marked liquidus joins the points where solidification commences, whilst the solidus joins the points where solidification is complete. This time there is no eutectic composition.

Figure 1 Phase diagram for copper-nickel alloy

The following points can be made; Pure copper

Pure nickel

At the solidus

At the liquidus

Between the liquidus and solidus

Below the solidus

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Combination Type Many metals and non-metals are neither completely insoluble nor are they completely soluble. Therefore, they form a phase diagram of the type shown in figure 2.

Figure 2 Combination type phase diagram

Greek symbols are used and are defined as follows;

Tin-lead alloys are a typical example of the combination type of phase diagram.

Figure 3 Combination type phase diagram for Tin and Lead

Summary Questions Lecture 4 1. What are alloys of tin and lead commonly used for? Referring to figure 3; 2. Define the solvus line 3. What is the composition of the and the phase at the eutectic temperature? 4. Describe the solidification of an alloy of composition 10% tin and 90% lead. 5. Describe the solidification of an alloy of composition 30% tin and 70% lead.

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Lecture 5 Plain Carbon Steels

Ferrous Metals Ferrous metals and alloys are based upon the element iron (Fe). Iron is a soft, grey metal and rarely found in its pure state. When iron is alloyed with carbon it forms solid solutions and the compound iron carbide. The carbon content is carried over from the smelting process during which iron is extracted from its ore. Table 1 shows the relationship between the amount of carbon present and the resulting ferrous metal.

Table 1 Ferrous metals

Figure 1 shows the iron-carbon phase equilibrium diagram.

Figure 1 Iron-carbon phase equilibrium diagram

You should recognize it as a combination type, that it, the elements are only partially soluble in each other in the solid state. It is different and more complex than the example last lecture due to the fact that iron is allotropic, that is, it can exist in more than one form. However, we will only be concerned with the solid phases of the diagram, conventionally known as the steel section. This is drawn in figure 2 and will be the focus for the next few lectures.

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Steels can be defined as Those alloys of iron and carbon in which the entire carbon content is combined with the iron in solid solution or as iron carbide (or both) and that no free carbon is present.

Figure 2 Iron-carbon phase equilibrium diagram (steel section)

Eutectoid The steel section of the iron-carbon phase equilibrium diagram is very similar to the combination type of phase diagram. In the combination type diagram there was one eutectic composition at which both alloying elements crystallized out simultaneously at the same temperature to form lamellar structure. However, in the steel section of the ironcarbon phase diagram such transformations occur in the solid state and the point at which ferrite and cementite precipitate out from the solid solution of austenite is called the eutectoid point. Thus, the eutectoid point is similar to the eutectic point but occur in the solid state. There are only three important phases in the steel portion of the equilibrium diagram: Ferrite ( phase)

Austenite ( phase)

Cementite (iron-carbide phase)

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Eutectoid Steel Steel with the eutectoid composition (i.e. with a carbon content of 0.83%) at room temperature consists entirely of pearlite. A wholly pearlitic structure gives steel maximum toughness. Similarly to previous eutectic type binary alloys previously discussed, the resulting structure is lamellar i.e. alternating layers of ferrite and cementite.

Figure 3(a) Structure of pearlite

Summary Questions Lecture 5 1. Differentiate between the eutectic point and the eutectoid point. 2. By referring to figure 1, state the following; the eutectic temperature, the eutectoid temperature, the eutectic composition and the eutectoid composition. 3. State the carbon content range of hypo-eutectoid steels and a hyper-eutectoid steels 4. Is there such a thing as a hyper-eutectic steel? 5. Differentiate between steel and cast iron. 6. Define toughness.

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Lecture 6 Cooling Transformations

Cooling transformation for a steel with eutectoid composition At T1

At T2
Cementite

At T3 Final structure crystals of pearlite. Cooling transformation for a steel with hyper-eutectoid composition

Final structure crystals of pearlite surrounded by bands of primary cementite at crystal boundaries.

At T1 At T2 At T3

At T4

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Cooling transformation for a steel with hypo-eutectoid composition

Final Structure crystals of ferrite and crystals of pearlite

At T1 At T2 At T3

At T4 At T5

Summary Questions Lecture 6 1. By referring to both table 1 in lecture 5 and the steel section of the phase diagram suggest how the proportion of ferrite, pearlite and cementite in the final composition of a steel affects the use of the steel. 2. Explain why eutectoid steel is used for chisels and springs.

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Lecture 7 The Lever Rule

Composition of phases The phase diagram for a binary alloy shows single-phase fields and two-phase fields (e.g. liquid plus A). The fields are separated by phase boundaries. When a phase boundary is crossed, a phase change starts, or finishes, or both.

When a single point lies in a single-phase region, the alloy consists of a single, homogeneous, phase. Its composition must be that of the alloy. Therefore, we can say that the phase composition and the alloy composition coincide in single-phase fields. When a single point lies in a two-phase field the alloy breaks up into two phases that do not have the same composition as the alloy (e.g. + ). The composition of each phase is then given by constructing a tie line (the isotherm spanning the two-phase region, terminating at the nearest phase boundary on either side). The ends of the tie line define the composition of each phase. Any alloy that lies on the tie line breaks into the same two phases at its end. The proportions of each phase depend on the alloy composition.

Example 1 Consider the alloy 60% Pb and 40% Sn (refer to fig.1) a) Name the phases present at 250 C b) Name the phases present at 200 C What is the composition of phase 1? What is the composition of phase 2? c) Name the phases present at 150 C What is the composition of phase 1? What is the composition of phase 2?

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Proportion of phase in two-phase alloys You can get relative amounts of each phase in a two-phase alloy from the phase diagram. The weight fraction of phase is W and that of phase is W . In a binary alloy, W +W =1 The weight fractions of each phase, W + W , are fixed by the requirement that matter is conserved. Then the weight fraction of -phase in the alloy is W = a/l And the weight fraction of the -phase is W = b/l This is the lever rule. The easiest way to understand this result is to notice that, if the point coincides with the left-hand end of the tie line the alloy is all -phase and if it coincides with the right-hand end it is all -phase. Or if the point is closer to the left-hand end -phase is the dominant phase, if the point is closer to the right-hand end -phase is the dominant phase. Example 2 Consider a lead-tin alloy with composition 80% Pb and 20% Sn. a) At 280 C which is the dominant phase? b) At 200 C which is the dominant phase? c) At 200 C what are the approximate composition of the phases and the proportions by weight of each phase? d) At 150 C what are the approximate composition of the phases and the proportions by weight of each phase?

Temp Solid L+ Solid + L+

Figure 1 Tin-Lead phase equilibrium diagram

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