Chapter 7.

Non-equilibrium solid phase transformations

129

Chapter 7. NON-EQUILIBRIUM SOLID PHASE TRANSFORMATIONS

7.1 Introduction

The purpose for strengthening metallic materials is to extend the elastic range and raise their yield and ultimate strength. The underlying mechanism responsible is the generation of more dislocation while restricting their movement. However, complete pile up of dislocations must be prevented, because it may result into brittle fracture. Six techniques are recognised to give rise to strengthening in metallic materials. (i) Workhardening: Strengthening due to creation of dislocations during cold working, while distorting the lattice. (ii) Solid solution hardening: Introduction of substitutional or interstitial solid solute atoms that result in lattice distortion which restricts dislocation movement, thus strengthening the metal. (iii) Grain size: Fine grain size raises the grain boundary area hence the dislocation density. Hence fine grain size is associated with high strength and density. (iv) Dispersion hardening: When particles of a second phase are dispersed in the matrix of a metallic phase, they may form a coherent matrix lattice with some degree of lattice distortion. Such a situation inhibits dislocation movement, thus strengthening the material. (v) Transformation hardening: The transformation of the crystalline structure during heat treatment may result into formation of a structure with fewer slip planes and distortions. Martensitic transformation in steels is an example of such mechanism which results into considerable hardening of steels. (vi) Irradiation hardening: X-ray or Gamma radiations can produce vacancies or lattice defects. However this technique is not commercially applied.

In this chapter, we cover two basic strengthening mechanisms resulting from non-equilibrium phase transformations in metallic materials, namely precipitation hardening and martensitic transformations.

Chapter 7. Non-equilibrium solid phase transformations

7.2 Dispersion (Precipitation) Hardening PRECIPITATION is the decomposition of a solid solution into two solid phases of different composition, the precipitate and the solid solution.

130

'

(7.1)

PRECIPITATION HARDENING is the process whereby hardening of an alloy is caused by the precipitation of a constituent from a supersaturated solid solution by heating to some elevated temperature. AGE HARDENING is a form of precipitation hardening in which there is a spontaneous increase of hardness at room temperature with lapse of time, on a supersaturated solid solution. The phenomena of precipitation hardening can occur ONLY in those alloys in which there is a decrease of solid solubility with decreasing temperature resulting in formation of a supersaturated solid solution upon fast cooling of the alloy from above the solvus line. This phenomena occurs in certain types of aluminium alloys (e.g. Al-Ag, Al-Mg) and in Cu-Be alloys. The process of precipitation hardening has three important steps as illustrated in Fig. 7.1: (a) Solution treatment: The alloy is first heated to a temperature above the solvus temperature and held until a homogeneous solid solution is produced. This step dissolves the precipitate and reduces any segregation present in the original alloy. (b) Quench: The solid solution which contains the solid solution only, is then rapidly cooled or quenched. The atoms do not have enough time to diffuse to potential nucleation sites and allow the phase to form. After the quench, the structure contains , the supersaturated solid solution of . (c) Age: Finally, the supersaturated is heated to a temperature below the solvus temperature. At this aging temperature the atoms are able to diffuse short distances. Because the supersaturated solid is unstable, extra solute atoms diffuse to numerous nucleation sites and a precipitate forms and grows. If we were to hold the alloy for a sufficient time at the aging temperature, the equilibrium and structure is produced. The first stage in the precipitation reaction is the formation of nuclei of the precipitating phase, followed by the growth of the nuclei to larger particles. This results into lattice distortion which is

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131

responsible for the hardening of the alloys. The actual cause of age hardening however, is the obstruction to the motion of dislocations set up by the fine transition precipitate particles and the strains produced by the mismatch of the transition products with the matrix. If an alloy is held for a long period of time at the treatment temperature, coagulation of the particles is observed and this intermediate phase becomes stable. This phenomena is called overaging. Other changes that are observed to accompany precipitation are: 1. 2. 3. Increase in electrical conductivity (except in Al-Cu alloys) Increase in hardness, passing through a max. and then decreasing. Increase in strength with hardness, decrease in ductility.

700 L 600
+L

548

500
Quench
+

400
+

300

3
' '

Age

200

2
5.65

'

Weight percent Copper

Fig 7.1: Steps in the heat treatment of an Al-Cu precipitation hardening alloy During the aging of Al-Cu alloys, a series of precipitates form before the equilibrium is produced. At the start of aging, the copper atoms concentrate on {100} planes in the matrix and produce very thin clusters of copper atoms called GUINIER-PRESTON, or GP-I, zones. As aging continues, more copper atoms diffuse to the precipitate and the GP-I zones grow into thin disks, or GP-II zones. Later, the GP-II zones dissolve and , which is similar to the stable , forms. Finally, dissolves and the stable phase precipitates.

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132

The non-equilibrium precipitates - GP-I, GP-II and the - are coherent precipitates (Fig. 7.2). The strength of the alloy increases with aging time as these coherent phases grow in size during the initial stages of heat treatment. When these coherent precipitates are present, the alloy is in the aged condition.

Fig. 7.2: A coherent precipitate

Fig. 7.3: A non coherent precipitate phase

When the stable non-coherent

phase precipitates, the strength of the alloy decreases. Now the

alloy is in the overaged condition, as illustrated by Fig. 7.3. Aging at room temperature is called natural aging. Aging at higher temperatures is called artificial aging, because the alloy is heated to produce precipitation.

Chapter 7. Non-equilibrium solid phase transformations

REQUIREMENTS FOR AGE HARDENING Four conditions must be satisfied: 1 2

133

The phase diagram must display decreasing solid solubility with decreasing temperature. The matrix should be relatively soft and ductile and the precipitate should be hard and brittle.

3 4

The alloy must be quenchable, rapidly enough to suppress formation of the second phase. The precipitate that forms must be coherent with the matrix structure in order to develop the maximum strength and hardness.

7.3

Non-equilibrium solid phase transformations of Austenite

7.3.1 Introduction When steel is quenched rapidly from high temperatures, there is no time for the austenite (-Fe) to transform to the lamellar structure called pearlite. Pearlite consists of alternate plates of a-iron (ferrite) and iron carbide (cementite, Fe3C). During fast cooling, the separate ferrite and cementite particles cannot form. When the - phase is quenched below a certain temperature called Ms (Martensite starts temperature), a new phase called martensite begins to form. Martensite has a body centred tetragonal structure. The c/a ratio is proportional to the carbon content of the steel. On the other hand, martensite can be regarded as a BCC crystal structure which has been distorted along one axis as a result of the presence of carbon atoms. The atoms of martensite are less densely packed than austenite, hence an expansion occurs during the transformation giving rise to evolution of internal stresses. The martensitic transformation is diffusionless and usually results in the formation of platelets which form by a shearing mechanism at velocities above one third the velocity of sound in the material.

Chapter 7. Non-equilibrium solid phase transformations

Below a temperature called Mf (martensite finish temp.) no more austenite is transformed to martensite. There is usually some retained austenite. Ms and Mf vary with carbon content in

134

carbon steel, as illustrated in Fig.7.4. The temperature Ms is further affected by the alloy content: Ms = 561-474 (%C)-33(%Mn) - 17 (%Ni)-17 (%Cr)-21 (%Mo) Mf is about 215 C below Ms The structure martensite is very hard and strong. Dislocations move only with great difficulty. The strength and hardness of martensite increase with carbon content, as shown in Fig. 7.5.

600 500 Temperature, C 400 300 200 100 0 -100 0 -200 Carbon w t % 0.2 0.4 0.6 0.8 1 1.2 1.4 Ms C Mf C

Fig. 7.4. Effect of carbon content on Ms and Mf Temperatures.

70 60 Hardness, HRC 50 40 30 20 10 0 1 2 3 4 5 6 7 8 Carbon, w t %

100% Martensite

50% Martensite

Fig. 7.5. The effect of carbon content on Martensite hardness

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135

7.3.2. Decomposition of Austenite In alloys, the structural changes are preferably documented in equilibrium phase diagrams. Equilibrium means that they have been established for conditions where the properties of the system do not change with time and infinitum. In reality, equilibrium conditions are rarely encountered; i.e. the cooling (or heating) rates are not slow enough to allow the continual phase adjustments (diffusion) to occur. Under these conditions, data from equilibrium diagrams are no longer directly applicable but serve only as an estimate. Under equilibrium conditions, austenite, a solid solution of carbon in iron, is decomposed to pearlite after precipitating ferrite in hypo-eutectoid steels, or cementite in hyper-eutectoid steels, as shown in Fig. 7.6.

910 C

Austenite ( )
+ Fe 3 C

723 C

-Fe

Pearlite + Ferrite

Pearlite + Fe 3C Fe 3C

0.035

0.8

Carbon, wt % Fig. 7.6. The steel part of the iron carbon phase diagram Mechanism of Pearlite Formation The pearlite transformation of supercooled austenite is a diffusion mechanism. Austenite decomposes with the formation of ferrite (almost pure iron) and cementite containing 6.67 % carbon. The carbide appears first as its nuclei are formed at the boundaries of the austenite grains. (Fig. 7.7). As a result, the adjacent volumes of austenite Are depleted of carbon, become less stable, and undergo the allotropic transformation from austenite to ferrite. Thus small crystals of ferrite are formed adjacent to the cementite (iron carbide). Subsequent diffusion leads to formation of more platelets of iron carbide with simultaneous formation of ferrite plates, to form a mixture or colony, called pearlite. The structure of pearlite is characteristically lamellar. The greater the degree of supercooling, the finer the ferrite-cementite structure obtained.

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136

Fe 3C

Grain Boundary

(a)

(b)

(c)

Fig. 7.7. Development of pearlite structure Transient cooling The effect of cooling rate on the decomposition of Austenite in a eutectoid steel is illustrated in Fig. 7.8. A r1
Beginning of decomposition A to F+Fe3 C (Pearlite) End of decomposition to P

A rz A+T F + Fe 3C M Mf T+M+A M+ A ret

Ms

Cooling rate, v
Lower critical cooling rate

Upper critical cooling rate

Fig. 7.8. Effect of cooling rate on the transformation of austenite As we increase the cooling rate, the temperature at which the austenite transforms to Pearlite is lowered. The higher the cooling rate, the lower the decomposition temperature, the more dispersed (finer) the ferrite - cementite structure obtained. At higher cooling rates, the pearlite occurs as a very fine structure often called Sorbite or Troostite (T) . At some high cooling rates, below the temperature Arz, a new modified structure called Bainite occurs. Bainite consists of ferrite with finely dispersed cementite globules. When the cooling rate exceeds a critical cooling rate, at a lower temperature, Ms, martensite begins to form. This transformation continues until a

Chapter 7. Non-equilibrium solid phase transformations

temperature Mf is reached. Any untransformed austenite remains in the structure as retained austenite (Aret). 7.3.3. Kinetics of Martensitic Transformation

137

Baines and Davenproof studied the isothermal decomposition of austenite. Small specimen were heated above the upper critical temperature, Ac3, to form austenite. Subsequently they were quenched in a suitable bath at a certain temperature. After holding at that temperature for different periods of time, the specimen were withdrawn and quenched in water. By so doing, the microstructure transformed so far is kept and the remaining austenite is converted to martensite. From the microsection, the amount of transformed austenite can be assessed. If the procedure is executed for different halting temperatures a series of s-shaped curves is obtained. These can then be summarized on a Time-Temperature-Transformation (TTT) diagram.

Temp T halt

A3

3 time

to P at GB

100

T halt

80

P
60

40

20

0 Holding Time (s)

100% Pearlite

Fig. 7.9. Isothermal transformation of austenite Fig. 7.9 shows how the S-curve is produced, and Fig. 7.10 shows how the TTT diagram is produced. Three ranges are distinct on the TTT diagram: (a) PEARLITIC: Down to temperatures of about 550 C, pearlite is formed. At higher temperatures the pearlite is coarse, and at lower temperatures it is fine.

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(b)

BAINITE: Between 550 and 350 C, Bainite is formed. Bainite consists of cementite, finely dispersed particles in ferrite. It is hard but reasonably ductile. Upper Bainite is coarse, and its microstructure can be resolved in an optical microscope. Lower Bainite is very fine, and can only be resolved by an electron microscope. MARTENSITE: This range exists at temperatures below Ms. The formation of martensite is diffusionless and is therefore independent of time.

(c)

T halt (C)
100 650 500 350

50

800 700 600 500 400 300 200 100 0 -100 M

A3 A1 Coarse PEARLITE Fine Coarse PEARLITE

Fine

Fig. 7.10. Development of the TTT diagram from the isothermal transformation of Austenite.

7.3.4 TTT Diagrams for Continuous Cooling In the foregoing section, the kinetics of austenite transformation were established for the case of isothermal cooling. A more realistic approach is achieved by studying the behaviour while cooling continuously. Consider the TTT diagram shown in Fig. 7.11, showing various cooling curves super - posed on the diagram.

Chapter 7. Non-equilibrium solid phase transformations

800

139

A3

700

A1
3

P
4

600

500

400

300

200

100

II Log (time)

III

IV

Transformations 1. Ferrite s tarts 2. Ferrite ends , Pearlite s tarts 3. Pearlite ends 4. Bainite s tarts 5. Bainite ends

C omposition of microstructure I : Pure Martens ite II: Fine pearlite, coars e bainite III: Ferrite, Fine pearlite, Bainite IV: Ferrite, Pearlite

Fig. 7.11: TTT diagram of a carbon steel for continuous cooling (CCT) Alloying of steels alters the form and shape of the TTT diagram.

7.3.5 Hardenability Curves CCT and TTT diagrams are not available for all steels, and it is not easy to accurately determine the cooling rates. Instead, a JOMINY TEST is used to cmpare the hardenability of steels. A bar 100 mm long and 25 mm in diameter is austenitized, placed in afixture , and sprayed at one end with water. This procedure produces a wide range of cooling curves - very fast at the quenched end, and almost air cooling at the opposite end. Fig. 7.12 illustrates the set up of the Jominy test.

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140

Support

Hardenability index

Water splash

50 HRC

Hardness

Fig. 7.12 The Jominy Test After the quenching, hardness measurements are made along the length of the specimen and plotted as shown to produce a hardenability curve. The distance from the quenched end which gives a minimum hardness of 50 HRC is called the hardenability index. This represents the region that full underwent martensitic transformation. The hardenability index therefore represents the depth to which a particular steel can be hardened, and increases accordingly with alloy additions. Refer to notes in the Practical handbook. 7.3.6. Tempering of Martensite Martensite is extremely brittle, and its transformation give rise to high internal stresses which may cause cracking. A subsequent heat treatment, called tempering, may relieve the stresses and/or alter the microstructure to produce a better material. For stages of martensite tempering are distinguished: 80-150 C The specimen contracts, C atoms can move to a certain extent and the tetragonal distortion is reduced. Slowly the so called cubic martensite is formed. Fine carbide precipitates are precipitated (-carbide). Specimen expands (0-1) % elongation, the tetragonal lattice is transformed to the cubic lattice, fine carbides are precipitated, retained austenite transformed into cubic martensite. Specimen contracts again, all carbon is precipitated Carbide coagulate, globules can be seen in an optical microscope. Above 400 TABLE 7.1 EFFECT OF TEMPERING TEMPERATURE ON THE HARDNESS OF A CARBON STEEL, C=1.3% Tempering Temp. (C) HRC 20 63 100 63 200 59 300 55 400 48 500 41 600 34 700 25

150-290 C

290-400 C

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TABLE 7.2 EFFECT OF TEMPERING TEMPERATURE ON THE MECHANICAL PROPERTIES OF A CARBON STEEL, C= 0.45 % Tempering Temp. (C) 300 400 500 600 700 Hardness HBN 320 285 250 220 200 Tensile strength (MPa) 1050 1000 900 800 700 Yield strength (MPa) 750 700 620 520 430 Elongation (%) 10 15 20 25 30 Reduction in Area (%) 30 40 50 55 60

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142