Solidification involves phase transformation from liquid to solid states. Nucleation begins the process, where small crystal nuclei form either homogeneously within the melt or heterogeneously on foreign substrates. Growth then occurs as more atoms attach to the solid nuclei. Cooling curves can show the temperature changes that occur during phase transformations in pure metals and binary alloys. Phase diagrams map the equilibrium phases that exist at different compositions and temperatures, indicating solubility limits and eutectic reactions.
Solidification involves phase transformation from liquid to solid states. Nucleation begins the process, where small crystal nuclei form either homogeneously within the melt or heterogeneously on foreign substrates. Growth then occurs as more atoms attach to the solid nuclei. Cooling curves can show the temperature changes that occur during phase transformations in pure metals and binary alloys. Phase diagrams map the equilibrium phases that exist at different compositions and temperatures, indicating solubility limits and eutectic reactions.
Solidification involves phase transformation from liquid to solid states. Nucleation begins the process, where small crystal nuclei form either homogeneously within the melt or heterogeneously on foreign substrates. Growth then occurs as more atoms attach to the solid nuclei. Cooling curves can show the temperature changes that occur during phase transformations in pure metals and binary alloys. Phase diagrams map the equilibrium phases that exist at different compositions and temperatures, indicating solubility limits and eutectic reactions.
Solidification involves phase transformation from liquid to solid states. Nucleation begins the process, where small crystal nuclei form either homogeneously within the melt or heterogeneously on foreign substrates. Growth then occurs as more atoms attach to the solid nuclei. Cooling curves can show the temperature changes that occur during phase transformations in pure metals and binary alloys. Phase diagrams map the equilibrium phases that exist at different compositions and temperatures, indicating solubility limits and eutectic reactions.
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Solidification, Phase
Diagrams and Phase
Transformation Solidification Solidification is the process of phase transformation of metals and alloys from the liquid to the solid state. During this process, the atoms arrange themselves in an orderly three dimensional pattern. The mechanism of solidification proceeds by the formation of stable nuclei in the liquid metal followed by the growth of nuclei into the crystal with the formation of grain structure. Nucleation Nucleation is the beginning of phase transformation and is indicated by the appearance of a small cluster of atoms or molecules to form the basic crystal structure or small solids called nuclei. The formation of small crystals in molten metal takes place in two mechanisms- homogeneous and heterogeneous nucleation. Homogeneous or self nucleation: The formation of nuclei within its own melt without the aid of impurity or foreign particles is called homogeneous or self nucleation. This nucleation occurs in perfectly homogeneous materials such as pure(aluminium, copper, etc) molten metals. During the nucleation, the molten metal must be cooled below its freezing temperature. Nucleation occurring at any part of liquid or molten metal is identical and group of atoms form small zones. The atoms in a molten liquid bond together to form a small crystal called embryo. This embryo grows into a nucleus with the addition of atoms. In pure metals, this takes place by super cooling and the nucleation of super cooled grain is governed by the following two factors: 1. The free energy available from the solidification process, which depends on the volume of the particle formed 2. The energy required forming a solid-liquid interface, which is dependent on the surface area of the particle Heterogeneous nucleation: the formation of nuclei within its own melt with the help of foreign substances or substrates is known as heterogeneous nucleation. The phase transformation takes place with the help of impurities, which lower the free energy. since large amount of under-cooling does not takes place in industrial casting process, nucleation should be heterogeneous and not homogeneous. In molten metal, usually impure particles will reduce the liquid-solid interface energy and helps in nucleation and thereby reduce the amount of super-cooling. If the metal is to solidify on a foreign substrate, it is essential that the surface of the substract should be wet by a liquid metal. Once this condition is satisfied, next the liquids solidify easily on the substract. When angle of contact θ is small, interface between solid and substrate has a low surface energy. Hence, the total free energy for formation of stable nucleus is also decreased and critical radius of the nucleus will be smaller. Growth Mechanism Once the solid nuclei of a phase form (in a liquid or another solid phase), growth begins to occur as more atoms become attached to the solid surface. The nature of the growth of the solid nuclei depends on how heat is removed from the molten material. In the solidification process, two types of heat must be removed: the specific heat of the liquid and the latent heat of fusion. The specific heat must be removed first, either by radiation into the surrounding atmosphere or by conduction into the surrounding mold, until the liquid cools to its freezing temperature. Therefore, when solid crystals form from a liquid, heat is generated! This type of heat is called the latent heat of fusion. The latent heat of fusion must be removed from the solid- liquid interface before solidification is completed. The manner in which we remove the latent heat of fusion determines the material’s growth mechanism and final structure of a casting. Planer growth: When a well-inoculated liquid (i.e., a liquid containing nucleating agents) cools under equilibrium conditions, there is no need for undercooling since heterogeneous nucleation can occur. Therefore, the temperature of the liquid ahead of the solidification front (i.e., solid-liquid interface) is greater than the freezing temperature. The temperature of the solid is at or below the freezing temperature. During solidification, the latent heat of fusion is removed by conduction from the solid liquid interface. Any small protuberance that begins to grow on the interface is surrounded by liquid above the freezing temperature (Figure). The growth of the protuberance then stops until the remainder of the interface catches up. This growth mechanism, known as planar growth, occurs by the movement of a smooth solid-liquid interface into the liquid. Dendritic Growth : When the liquid is not inoculated and the nucleation is poor, the liquid has to be undercooled before the solid forms (Figure). Under these conditions, a small solid protuberance called a dendrite, which forms at the interface, is encouraged to grow since the liquid ahead of the solidification front is undercooled As the solid dendrite grows, the latent heat of fusion is conducted into the undercooled liquid, raising the temperature of the liquid toward the freezing temperature. Cooling curves The phase diagrams are usually constructed from the data of cooling curve obtained by plotting falling temperature versus time for small selected alloys, which are allowed to cool under equilibrium condition. If a plot is drawn between temperature and time at a constant composition, the resulting cooling curve shows a change of slope when a phase change occurs. Cooling curve for pure metals: The pure metals melt and solidify at the same temperature which may be termed as melting point or freezing point. These metals are cooled under equilibrium conditions from the molten state till they solidify. In second graph, the horizontal line corresponds to the solidifying or melting temperature of a single component system at a constant pressure. In real systems, a certain amount of under cooling occurs before the solidification starts. That is the melt is maintained in a metastable state at a temperature below the freezing point. Cooling curve for binary alloy: In binary system, during the freezing period, temperature does not remain constant, rather it drops along the line till the whole mass is solid and cool to room temperature as shown in first graph. At the room temperature, the alloy is homogeneous in the solid state similar to in the liquid state. In some binary alloy system(second graph), the liquid metal cools along the curve AB until the temperature reaches point B. at point B, one component in excess will crystallize and the temperature will drop along BC as indicated in graph. At C , the residue liquid reaches eutectic composition and the two components crystallize simultaneously from the eutectic mixture. The temperature remains same until the whole mass is solid between points C and D. from D to E metal cools to room temperature. Phase Diagrams Phase diagrams are an important tool in the armory of an materials scientist In the simplest sense a phase diagram demarcates regions of existence of various phases. Phase diagrams are also referred to as “Equilibrium Phase Diagrams” Solubility Limit: For many alloy systems and at some specific temperature, there is a maximum concentration of solute atoms that may dissolve in the solvent to form a solid solution; this is called a solubility limit. The addition of solute in excess of this solubility limit results in the formation of another solid solution or compound that has a distinctly different composition. Example: sugar and water phase Physically distinct, chemically homogenous and mechanically separable region of a system (e.g. gas, crystal, amorphous...). Gases Gaseous state always a single phase → mixed at atomic or molecular level. Liquid 1. Liquid solution is a single phase → e.g. NaCl in H2O. 2. Liquid mixture consists of two or more phases → e.g. Oil in water (no mixing at the atomic/molecular level) Solids In general due to several compositions and crystals structures many phases are possible. For the same composition different crystal structures represent different phases. E.g. Fe (BCC) and Fe (FCC) are different phases. For the same crystal structure different compositions represent different phases. E.g. in Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases. Gibbs Phase Rule The phase rule connects the Degrees of Freedom, the number of Components in a system and the number of Phases present in a system via a simple equation. To understand the phase rule one must understand the variables in the system along with the degrees of freedom. We start with a general definition of the phrase: “degrees of freedom”. Degrees of Freedom: A general definition In response to a stimulus the ways in which the system can respond, corresponds to the degrees of freedom of the system. F – Degrees of Freedom C – Number of Components For a system in equilibrium : F = C P + 2 P – Number of Phases The ‘2’ comes from– Pressure & T One-Component phase diagrams The simplest and easiest type of phase diagram to understand is that for a one- component system, in which composition is held constant this means that pressure and temperature are the variables. This one-component phase diagram (or unary phase diagram) [sometimes also called a pressure–temperature (or P–T) diagram] is represented as a two-dimensional plot of pressure versus temperature. This type of phase diagram and demonstrate its interpretation using as an example the one for H2O Binary Isomorphous Systems A binary phase is a two component system. Binary phase diagrams are most commonly used in alloy designing. The simplest binary system is the Cu-Ni which exhibits complete solubility in liquid and solid state. The line above which the alloy is liquid is called the liquidus line. At temperature just below this line crystals of α solid solution start forming. The line below which solidification completes is called solidus line. Hence, only α solid solution exists at any temperature below the solidus line. The intermediate region between liquidus and solidus lines is the two-phase region where liquid and solid coexist. It can be noted that the two metals are soluble in each other in the entire range of compositions in both liquid and solid state. This kind of system is known as ‘Isomorphous’ system. Interpretation of Phase Diagrams For a binary system of known composition and temperature that is at equilibrium, at least three kinds of information are available:(1) the phases that are present,(2) the compositions of these phases,and (3) the percentages or fractions of the phases. The procedures for making these determinations will be demonstrated using the copper–nickel system using graphs in last slide. Phase present: one just locates the temperature –composition point on the diagram and notes the phases with which the corresponding phase field is labeld. Determination of phase composition: The first step in the determination of phase compositions is to locate the temperature–composition point on the phase diagram. Different methods are used for single- and two-phase regions. If only one phase is present, the procedure is trivial: the composition of this phase is simply the same as the overall composition of the alloy. For an alloy having composition and temperature located in a two-phase region, the situation is more complicated. In all two-phase regions, one may imagine a series of horizontal lines, one at every temperature; each of these is known as a tie line, or sometimes as an isotherm These tie lines extend across the two-phase region and terminate at the phase boundary lines on either side. To compute the equilibrium concentrations of the two phases, the following procedure is used: 1. A tie line is constructed across the two-phase region at the temperature of the alloy. 2. The intersections of the tie line and the phase boundaries on either side are noted. 3. Perpendiculars are dropped from these intersections to the horizontal composition axis, from which the composition of each of the respective phases is read. Determination of Phase Amounts: The relative amounts (as fraction or as percentage) of the phases present at equilibrium may also be computed with the aid of phase diagrams. Again,the single- and two-phase situations must be treated separately. The solution is obvious in the single phase region: Since only one phase is present, the alloy is composed entirely of that phase; that is, the phase fraction is 1.0 or, alternatively, the percentage is 100%. If the composition and temperature position is located within a two-phase region, things are more complex. The tie line must be utilized in conjunction with a procedure that is often called the lever rule which is applied as follows: 1. The tie line is constructed across the two-phase region at the temperature of the alloy. 2. The overall alloy composition is located on the tie line. 3. The fraction of one phase is computed by taking the length of tie line from the overall alloy composition to the phase boundary for the other phase, and dividing by the total tie line length. 4. The fraction of the other phase is determined in the same manner. 5.If phase percentages are desired, each phase fraction is multiplied by 100. When the composition axis is scaled in weight percent, the phase fractions computed using the lever rule are mass fractions—the mass (or weight) of a specific phase divided by the total alloy mass (or weight).The mass of each phase is computed from the product of each phase fraction and the total alloy mass. Lever rule: For example, fraction solid, fs is given by
Similarly fraction liquid, fl
Development of microstructure in isomorphous alloys Equilibrium Cooling:
At this point it is instructive to examine the
development of microstructure that occurs for isomorphous alloys during solidification.We first treat the situation in which the cooling occurs very slowly, in that phase equilibrium is continuously maintained. Nonequilibrium Cooling:
The reason for this is that with changes in
temperature, there must be readjustments in the compositions of the liquid and solid phases in accordance with the phase diagram. These readjustments are accomplished by diffusional processes—that is,diffusion in both solid and liquid phases and also across the solid–liquid interface. In asmuch as diffusion is a time-dependent phenomenon , to maintain equilibrium during cooling, sufficient time must be allowed at each temperature for the appropriate compositional readjustments Diffusion rates are especially low for the solid phase and, for both phases, decrease with diminishing temperature. In virtually all practical solidification situations, cooling rates are much too rapid to allow these compositional readjustments and maintenance of equilibrium; consequently, microstructures other than those previously described. Mechanical Properties of Isomorphous Alloys Iron-carbon Phase Diagrams A portion of the iron–carbon phase diagram is presented in Figure. Pure iron, upon heating, experiences two changes in crystal structure before it melts. At room temperature the stable form, called ferrite, has a BCC crystal structure. Ferrite experiences a polymorphic transformation to FCC austenite at 912°C. This austenite persists to 1394°C, at which temperature the FCC austenite reverts back to a BCC phase known as δ ferrite, which finally melts at 1538°C. All these changes are apparent along the left vertical axis of the phase diagram. The composition axis in Figure, extends only to 6.70 wt% C;at this concentration the intermediate compound iron carbide,or cementite(Fe3C),is formed,which is represented by a vertical line on the phase diagram. Development of microstructure in iron-carbon alloy Phase Transformation Metastable Versus Equilibrium States • The rate of approach to equilibrium for solid systems is so slow. • Equilibrium conditions are maintained only if heating or cooling is carried out at extremely slow and unpractical rates. • For other than equilibrium cooling, transformations are shifted to lower temperatures than indicated by the phase diagram.(super cooling) • For heating, the shift is to higher temperature(super heating) • For many technologically important alloys, the preferred state or microstructure is a metastable one • Intermediate between the initial and equilibrium states • It thus becomes imperative to investigate the influence of time on phase transformations. Austenite to pearlite In interpreting this diagram, note first that the eutectoid temperature is indicated by a horizontal line; at temperatures above the eutectoid and for all times, only austenite will exist, as indicated in the figure. The austenite-to-pearlite transformation will occur only if an alloy is supercooled to below the eutectoid; as indicated by the curves, the time necessary for the transformation to begin and then end depends on temperature. The start and finish curves are nearly parallel, and they approach the eutectoid line asymptotically. To the left of the transformation start curve, only austenite (which is unstable) will be present, whereas to the right of the finish curve, only pearlite will exist. In between, the austenite is in the process of transforming to pearlite, and thus both microconstituents will be present. Isothermal Transformation Diagrams(TTT Diagram) With superimposed isothermal heat treatment curve