t INTRODUCTION TO METALLURGY

USE OF MATERIALS COURSE INTRODUCTION TO METALLURGY LECTURE NOTES

INDEX Page 1. Introduction.................................................................................................... 4 1.1 1.2 1.3 1.4 Metals ........ ................................................................................... 4 Alloys ......... ................................................................................... 7 Solid Solutions............................................................................... 7 Phase Mixtures.............................................................................. 8

2.

Equilibrium Diagrams ................................................................................. 10 2.1 2.2 2.3 2.4 Iron - Carbon Diagram................................................................. 10 Slowly Cooled Structures ............................................................ 12 Quenched Structures .................................................................. 13 Critical Temperatures .................................................................. 15

3.

Hot and Cold Working................................................................................. 17 3.1 3.2 3.3 Stress Relief ................................................................................ 17 Recrystallisation .......................................................................... 17 Grain Growth ............................................................................... 18

4.

Hardness and Strength............................................................................... 19 4.1 4.2 4.3 Influence of Grain Size ................................................................ 20 The effects of Structural Changes............................................... 20 Hardenability................................................................................ 21

5.

Heat Treatment.......... .................................................................................. 24 5.1 Hardening Mechanisms .............................................................. 24 5.1.1 5.1.2 5.1.3 5.1.4 Solid Solution Hardening........................................... 24 Precipitation Hardening............................................. 25 Work Hardening ........................................................ 26 Strain Ageing............................................................. 28 1

5.2

Isothermal Transformations ........................................................ 29 5.2.1 5.2.2 5.2.3 TTT Curves ............................................................... 29 Continuous Cooling Transformation Curves............. 30 Effects of Alloys on Transformations ........................ 30

5.3 5.4 5.5 5.6 5.7

Normalising.................................................................................. 31 Full Annealing.............................................................................. 31 Quenching and Tempering.......................................................... 34 Importance of Grain Size............................................................. 35 Grain Size Determination ............................................................ 37

6.

Alloying......................................................................................................... 39 6.1 Alloying Elements in Steel........................................................... 39 6.1.1 6.1.2 6.1.3 6.1.4 6.2 Carbide Formers ....................................................... 40 Crystal Growth........................................................... 41 Corrosion Resistance................................................ 42 Strength ..................................................................... 42

Effects of Alloying on Steel.......................................................... 42 6.2.1 6.2.2 6.2.3 6.2.4 6.2.5 6.2.6 6.2.7 6.2.8 6.2.9 6.2.10 6.2.11 Carbon....................................................................... 42 Manganese................................................................ 42 Chromium.................................................................. 43 Nickel......................................................................... 43 Molybdenum.............................................................. 44 Niobium ..................................................................... 44 Vanadium .................................................................. 45 Aluminium.................................................................. 45 Sulphur ...................................................................... 45 Phosphorus ............................................................... 46 Silicon ........................................................................ 47

6.3

Alloy Addition in Steel - Summary............................................... 47

7.

Microstructures in Steel Arc Welds .......................................................... 49 7.1 7.2 7.3 7.4 Weld Metal................................................................................... 49 Heat Affected Zone ..................................................................... 51 Welding Heating Cycle ................................................................ 52 Carbon Equivalent....................................................................... 53

8.

Structure of Ingots.... .................................................................................. 54 8.1 8.2 8.3 Pipe.............................................................................................. 54 Segregation ................................................................................. 55 Steel Types.................................................................................. 56 8.3.1 8.3.2 8.3.3 Rimming Steel ........................................................... 56 Semi-killed Steel........................................................ 57 Killed Steel................................................................. 57

1. 1.1

INTRODUCTION Metals Metals are chemical elements or alloys, which in general exhibit the following properties: Good conductivity of heat and electricity Relatively hard, yet possess properties of malleability and ductility Solid at normal temperatures - except Mercury High densities Low specific heats Reflect light and are generally white in colour -except Gold and Copper Difficult to penetrate with X-rays Magnetic to some degree but only Iron, Nickel and Cobalt are ferro magnetic

However, it is the properties of strength, ductility and toughness which dictate their principal uses. All metals have a crystalline structure of which there are three common types: Body-centred cubic Face-centred cubic Hexagonal close-packed Body-centred cubic - Iron (ferrite) Vanadium Tungsten Chromium Face-centred cubic - Iron (austenite) Copper Silver Gold Aluminium Lead Nickel Platinum Hexagonal close packed Magnesium Titanium Zinc Cadmium

The most economical packing arrangements for the metal atoms are the hexagonal close packed and face centred cubic, followed the body centred cubic structure, which occupies a larger volume (Fig 1).

Fig 1 The three Principal Types of Structure in which metallic elements crystallise

Fig 2

Volume changes in Iron with Temperature

Fig 3

The Early Stages in the Growth of a Metallic Dendrite

The importance of different packing densities is illustrated by the fact that the metal iron is allotropic, that is it adopts different crystal structures according to its temperature. Up to a temperature of 910C it has a body-centred cubic form, from 910C to 1400C it is face centred cubic, and above 1400C it reverts to body centred cubic until it melts at about 1535C. Heating the metal will not only produce an increase in volume by thermal expansion, but also, volume changes will be caused by alterations in crystal structure. The diagram (Fig 2) demonstrates the volume effects of different atomic packing arrangements resulting from the allotropic changes from body centred cubic structure to face centred cubic structure and back to body centred cubic structure. When a metal alloy solidifies, each crystal begins to form independently from a nucleus or centre of crystallisation. The nucleus will be a simple unit of appropriate crystal lattice, and from this the crystal will grow. It develops by the addition of atoms according to the lattice pattern and rapidly begins to assume visible proportions in what is called a dendrite. (Dendritic-tree-like). A metallic crystal grows in this way because heat is dissipated more quickly from a point, leading to the formation of a rather elongated skeleton (Fig 3). The dendrite arms continue to grow and meet neighbouring dendrites which will be orientated differently owing to their independent formation; that is, their lattices will meet at odd angles. Hence the independent formation of each crystal leads to the irregular overall shape of crystals and to the characteristic grain structure of metals when in the as cast condition.

1.2

Alloys An alloy is essentially a mixture of two or more elements, the principal component being a metallic element (the 'parent metal' or 'solvent'), so that the resultant mixture exhibits metallic properties. A wide variety of mechanical and physical properties may be obtained by alloying, so that alloys, rather than pure metals, are of the greatest importance for engineering. If the constituent metallic atoms are chemically similar to one another, they will crystallise as a single set of crystals, since all the atoms will behave as if they belonged to the same species. A single-phase solid solution is then said to form, and its microstructure is often indistinguishable from that of a pure metal. However, there may be a tendency for the elements to crystallise separately to form distinct and different crystals joined at mutual grain boundaries. Such a structure is an example of a phase mixture, which can usually be distinguished from a single-phase solid by metallographic examination. Note that this could include the formation of an intermetallic compound. These compounds are in themselves of little practical value, since they tend to be hard and brittle, but they can be important as constituents of alloy systems.

1.3

Solid Solutions Initially when a solid solution is formed the crystal structure is the same as that of the parent metal - the atoms of the solute or alloying element are distributed throughout each crystal, and a range of composition is possible. The solution may be formed in two ways: (a) In substitutional solid solutions the atoms share a single common array of atomic sites (Fig 4a). In some systems the parent metal will dissolve any proportion of the solute and retain its original crystal structure. However, in many cases there is a limited solubility and in order to accommodate a larger proportion of the added alloying element a change in the initial crystal structure becomes necessary to form a different solid solution, that is, another phase. In this way two solid solutions may exist together over a range of composition. (b) In interstitial solid solutions the atoms of the solute element are small enough to fit into the spaces between the parent metal atoms, as illustrated (Fig 4b).

(a)

substitutional

(b)

interstitial

Fig 4 The formation of solid solutions Because of the atom size limitation, interstitial solid solutions are less common than substitutional solutions, although Carbon atoms can dissolve in iron crystals in this way in steel. Similarly Nitrogen can dissolve in steel and this is the basis of the Nitriding surface hardening process. The very small atoms of Hydrogen will dissolve interstitially in ferrous alloys, usually producing brittleness. 1.4 Phase Mixtures A phase, present in an alloy as a separate entity, can be pure metal, a solid solution or an intermetallic compound. Any mixtures of two or more of these can occur. In binary systems, that is those of two elements, generally not more than two phases can exist together.

2.

EQUILIBRIUM DIAGRAMS Thermal equilibrium (also known as Phase or Constitutional) diagrams are of great importance in metallurgy for with their aid it is possible to determine exactly the structure of a particular alloy at any given temperature, provided the alloy has been allowed to reach a state of equilibrium. Thus the phases present, their quantities and the chemical composition of each phase can be shown with precision. The diagrams are constructed principally by thermal analysis but also with microscopic studies, the examination of volume changes, X-ray diffraction and other techniques. Equilibrium can be considered as a state of balance ultimately arrived at by the components at the temperature of the system concerned. However, in some cases such a state would take a very long time to be reached while in others it may never be reached at the temperature in question. For example, if an alloy is rapidly cooled by quenching to room temperature, chemical and physical changes may be suppressed such that they will never take place unless the alloy is reheated to allow them to occur. Very slow cooling must then follow.

2.1

Iron-Carbon Equilibrium Diagram (Fig 5) Steel may be defined as an alloy of Iron and Carbon (up to about 1.7%C). Here it may be helpful to recall the allotropic nature of iron and that up to 910C it has a body centred cubic crystalline form known as alpha Iron, from 910C-1400C a face centred cubic structure, gamma Iron, reverting to body centred cubic delta . Iron above that temperature. These terms are modified in steel to Ferrite, Austenite and Ferrite. Other phases in the equilibrium structure are Cementite the inter-metallic compound Fe3C, and, Pearlite a phase mixture known as a Eutectoid consisting in this case of alternate layers of Cementite and Ferrite. Pearlite contains about 0.83%C. Ferrite and Ferrite, the body centred cubic structures dissolve only very small amounts of carbon: less than 0.01% at room temperature. The face centred cubic Austenite however, is capable of dissolving up to nearly 2%C at 1150C although this structure will change on reaching the Lower Critical Temperature 723C below which the Eutectoid reaction will be complete. (Fig 6)

Fig 5

The Iron-Carbon phase diagram

10

Fig 6

Part of the Iron-Carbon Thermal-equilibrium diagram

Note that the Lower Critical Temperature 723C below which all Austenite has been converted to Ferrite and Cementite is commonly known as the A1 temperature. The temperature above which the structure will be wholly Austenite, the Upper Critical Temperature, is known as the A3 temperature. Also the temperature above which the steel reverts to a wholly body centred cubic ferrite is known as the A4 temperature. 2.2 Slowly Cooled Structures The most important reaction in steel is the decomposition of austenite on cooling. Consider the slow cooling of a steel of 0.83%C content (i.e. of the eutectoid composition) (Fig 7a); at 723C the structure will transform to an eutectoid mixture consisting of alternate lamellae or plates of ferrite and cementite. A steel of higher carbon content (known as a 'hyper-eutectoid' steel) (Fig 7b), 1.20%C, will remain austenitic down to the temperature around, say, 870C at which the solvus line is crossed, so that Fe3C will start to be precipitated at the austenite grain boundaries. Continued cooling and precipitation of cementite Fe3C will reduce the carbon content of the austenite until it reaches that of the eutectoid 0.83%C. When the temperature falls to below 723C, this residual austenite will transform to pearlite, and the final microstructure will be cementite plus pearlite.

11

A lower carbon steel (i.e. a 'hypoeutectoid steel) of 0.4%C (Fig 7c) will begin to transform when the temperature falls below the solvus line by the precipitation of ferrite at the austenite grain boundaries. Continued cooling and precipitation of ferrite will increase the carbon content of the austenite until it reaches that of the eutectoid 0.83%C. At 723C this remaining austenite will transform to pearlite resulting in a final structure of ferrite plus pearlite. 2.3 Quenched Structures The previous microstructures form in plain carbon steels which have been moderately slowly cooled (e.g. by cooling in air) from temperatures within the austenitic phase field, say from 50C above the lower boundary line CED. This is called a 'normalising' heat treatment, but medium and high-carbon steels are very commonly subjected to more complex treatments in order fully to exploit their properties. These treatments involve, first, heating the alloy into the austenite phase field, as before, but then quenching it in water or brine which suppresses diffusion and thus the formation of ferrite and cementite. Under these conditions the austenite transforms by a process not involving diffusion into a metastable distorted form of body-centred iron known as 'Martensite' (Fig 7d). This process is extremely rapid and the transformation may be completed in a few microseconds.

Fig 7a

Structure of Eutectoid Steel (1000X) (Pearlite)

Fig 7b

Structure of Hypereutectoid Steel (1000X) 12

Fig 7c

Structure of Hypoeutectoid Steel (1000X)

Fig 7d

Martensite (2000X)

All the carbon originally dissolved in the Austenite at high temperature remains after quenching in interstitial solution in the Martensite crystals. This has the effect of distorting the lattice from cubic to tetragonal symmetry. This lattice distortion by the dissolved carbon has the effect of hardening the structure and the resulting steels will not only be hard but brittle, for which there is little practical application. A second heat treatment called tempering is therefore required and this will reduce hardness and brittleness. If Martensitic steel is reheated to the temperature range 200-600C (below the Austenite forming temperature) it rapidly decomposes to form body centred cubic ferrite and particles of Cementite. This structure is on an extremely fine scale, the size of the carbide particles being dependent on the time and temperature of the treatment. The higher the temperature and the longer the time, the softer and less brittle the product.

13

2.4

Critical Temperatures There has been reference to the A1 lower critical temperature, the A3 upper critical temperature and the A4 temperature above which austenite reverts to ferrite. Examination of the Iron-Carbon equilibrium diagram shows that the latter change will not occur when the carbon content approaches and exceeds 0.5%C. In such cases liquid steel will solidify directly to austenite. Concern may be felt regarding the non-appearance of an A2 temperature and also the absence of a beta phase in the equilibrium diagram. Originally the designation A2 was given to the temperature 769C, the Curie point, at which iron ceases to be magnetic, a fact that was expected to be accompanied by a phase change. This proved not to be the case and the A2 has no structural significance. It cannot be emphasised too strongly that the structural changes in the diagram and the temperatures at which they occur refer to conditions of equilibrium. In practice it is found that, on heating, it is necessary to exceed the equilibrium temperatures to achieve the expected structural changes. Such temperatures would normally be about 50C above the A1 and A3 and can be determined with reasonable accuracy for particular conditions of heating. Here the lower critical point is termed the Ac1 and the upper critical point the Ac3 temperature. The suffix C has been derived from the French chauffage meaning heating. In a similar way it may be expected that on cooling it is necessary to reach temperatures lower than those of the equilibrium diagram to obtain the appropriate structural changes. Thus, for example, in hot rolling operations, which are accompanied by continuous cooling, temperatures of 100-150C below equilibrium become necessary for the expected structural changes. In such cases AR1 and AR3 temperatures are referred to, the suffix R again being French, derived from Refroidissement, cooling. The Effect of Heating Rates on Lower and Upper Critical Temperatures Steel AISI 1045 (0.45%C) Equilibrium Temperature HEATING RATES C/SEC FROM 700-1000C 3 Ac1 Ac3 723 770 780 820 30 790 830 300 800 860 1400 840 935

14

3.

HOT AND COLD WORKING In a process such as rolling, the crystals making up a metal are deformed in the direction of rolling. If the temperature of the operation is such that the deformation is accompanied by simultaneous recrystallisation the process is Hot Working. Here relatively minor ductility changes can be expected and these can be attributed largely to improved crystal structures and better dispersion of non-metallic inclusions. On the other hand if there is no recrystallisation and the crystals become progressively more deformed on working then the process is Cold Working. In this case major property changes arise with a loss of ductility and marked increases in hardness and strength. A cold-worked metal is in a state of considerable mechanical stress, resulting from elastic strains internally balanced. These elastic strains are largely due to inhomogeneous deformation having taken place during cold-working. If the metal is heated to a sufficiently high temperature the strains will be removed; at the same time the tensile strength and hardness of the metal will fall to approximately their original values and the capacity for cold-work return. This form of heat-treatment is known as annealing, and is employed when the metal is required for use in a soft but tough state or, alternatively, when it is to undergo further cold deformation. Annealing takes place in three stages as follows:

3.1

Stage 1 - Stress Relief This occurs at relatively low temperatures at which dislocations are able to move to equilibrium positions in the crystal lattice (see Heat treatment section for an explanation of dislocations). Such small movements can reduce internal mechanical stress without, however, producing any visible alteration in the distorted shape of the cold-worked crystals. Moreover, hardness and tensile strength will remain at the high value produced by cold-work and may even increase.

3.2

Stage II - Recrystallisation As mentioned previously, a low-temperature anneal to relieve internal stress may sometimes be used, but generally annealing involves a definite and observable alteration in the crystal structure of the metal. If the annealing temperature is increased a point is reached when new crystals begin to grow from nuclei produced in the deformed metal. These nuclei are formed at points of high energy, such as crystal boundaries. The crystals so formed are at first small, but grow gradually until they absorb the entire distorted structure produced originally by cold-work. The new crystals are equi-axed in form, that is, they do not show any directional elongation, as did the distorted coldworked crystals which they replace. This phenomenon is known as recrystallisation, and it is a method employed, in conjunction with cold-work, of course, to produce a fine-grained structure in non-ferrous metals and alloys. Only in some cases - notably in steels and 15

aluminium bronze, where certain structural changes take place in the solid state - is it possible to refine the grain size by heat-treatment alone. 3.3 Stage III - Grain Growth The temperature at which recrystallisation will take place is called the recrystallisation temperature and if the annealing temperature is above this, the crystals will continue to grow until the structure is relatively coarse grained. The amount of grain growth is governed to a large extent by the annealing temperature, the duration of annealing and the degree of previous cold-work. A high annealing temperature or a long annealing time will encourage grain growth. Heavy deformation will lead to a small grain size, light deformation will give rise to a larger grain size on annealing since there will be fewer nuclei for crystal growth.

16

4.

HARDNESS AND STRENGTH Although hardness is a property difficult to describe precisely, tests have been devised which are quick and easy to apply. Such tests are non-destructive, unlike tensile and impact determinations, and they are therefore attractive means of assessing the mechanical properties of metals. In practice, routine hardness tests on manufactured parts will be applied over limited property ranges and reliable correlations between hardness, ultimate tensile strength, yield strength, elongation and reduction of area can be established. As such they will provide excellent guides to the acceptability of the items concerned (and possibly their chemical compositions), the suitability of the manufacturing processes and heat treatment to which they have been subjected. Increases in hardness values (which results from an increase in C content) will usually be associated with increases in ultimate tensile and yield strength, but there will be reductions in ductility (elongation) expressed as reduction of area and elongation (Fig 8). Note that an increase in C content will also be accompanied by a reduction in impact (Charpy) toughness.

Fig 8 Diagram showing the Relationship between Carbon Content, Mechanical Properties, Microstructure and Uses of Plain Carbon Steels in the Normalised Condition

17

4.1

Influence of Grain Size on Hardness Usually in metals a smaller grain size will lead to some increase in hardness and tensile strength. This strengthening effect is due not only to the complex intersecting slip process in the various grains but also to the grain boundaries which are themselves obstacles to the movement of slip planes which therefore cannot propagate freely from grain to grain. In structural steels, processing for optimum properties is aimed at producing very small sized relatively soft grains. In this way Yield Strength is enhanced and the Impact properties markedly improved especially at low temperatures.

4.2

The Effects of Structural Changes on the Hardness of Steels It must be emphasised that in steels the most profound changes in mechanical properties occur as a result of changes in microstructure. These are illustrated in the table below relating to the different structures obtained in a plain carbon eutectoid steel (0.83%) which has been subjected to isothermal transformations. (See later section). Structure/Hardness HARDNESS STRUCTURE BHN Coarse pearlite Fine pearlite Feathery bainite (upper) Acicular bainite (lower) Bainite & Martensite Martensite 170 293 388 401 415 555 578 601 682 HARDNESS ROCKWELL C 5 31 41 42 44 56 58 60 66 TEMPERATURE OF TRANSFORMATION C 720 660 580 500 400 280 230 175 RT

18

4.3

Hardenability Hardenability is a measure of the depth a steel will harden on quenching. The uniform rapid cooling of a heavy steel section is impossible even with drastic quenching. Such a section will not harden completely to its core whereas a thin section would be wholly martensitic. This difficulty can however be overcome by the addition to the steel of alloying elements which will in general increase the time available to begin and complete transformation. Thus a martensitic structure becomes possible with the lower cooling rates found in heavier sections. This is one of the most important functions of alloying and to ensure the correct application of such steels, from both the technical and economic aspects, some measure of hardenability becomes necessary. To determine this, tests have been devised to estimate the maximum diameter at which the required structures can be produced by quenching. If this diameter is exceeded, hardening at the core will be incomplete resulting in non-uniform properties. The Jominy end-quench test (Fig 9) is widely used in evaluating the hardenability of steel. Here a standard test piece is heated to its austenitic region, dropped into a frame and quenched, at one end only, by a measured jet of water at 25C. Thus different rates of cooling are obtained along the length of the bar and the resulting hardness values can be determined. The drawings illustrate the test and the graphs show typical hardness values from the tests of three steels of differing compositions (Fig 10). It will be noted that the depth of hardening increases markedly with growing alloy content even though the proportion of carbon at 0.45% is the same in each case. Using the Jominy test results as a basis it is possible, for a particular steel, to calculate a maximum diameter at which uniform properties can be obtained. Such a measure is known as the ideal diameter or ruling section. The ideal diameter here represents the section at which a structure of 50% martensite is achieved.

19

(A)

The standard form of test piece used

(B)

Diagrammatic representation of the apparatus used in the test

Fig 9

The Jominy End-Quench Test

20

Fig 10 The Depth of Hardening of Three Different Steels as indicated by the Jominy Test

21

5. 5.1

HEAT TREATMENT Hardening Mechanisms It has been calculated that the theoretical strengths of pure metals should be much greater than those observed. These differences have been convincingly explained by dislocation theory. This theory has been likened to a situation where one carpet lying on top of another is very difficult to move by pulling at one end. However a ruck in the upper carpet will move across it very easily. This ruck represents the dislocation moving between slip planes in a metal giving rise to plastic deformation, which otherwise could not occur. Calculations confirm that the stress required to make the dislocation lines move is in good agreement with the measured yield stress so that such faults can account for the weakness of metals. The dislocation lines finish only when they reach a metal surface or grain boundary. If dislocation motion is impeded, for example by interaction with other dislocations, there will usually be an increase in hardness and strength. It should be emphasised that dislocation theory is much more complex than this grossly over-simplified version (Fig 11).

Fig 11 5.1.1

The Movement of a Dislocation During Slip

Solid Solution Hardening The most common reason for alloying is to increase the yield strength of a metal. This requires the movement of dislocations to be impeded by making alterations to the structure on an atomic scale. The effectiveness of foreign atoms as barriers to the movement of dislocations depends first upon the size difference between the solute atoms and those of the parent metal and second upon the proportion of foreign atoms present in the crystal. Elastic strain fields will be set up around the misfitting atoms making dislocation motion more difficult. Interstitial solute atoms such as carbon and nitrogen in body centred cubic crystals provide an important example of solute hardening alloys. Thus carbon 22

or nitrogen dissolved in iron produces a local strain which causes a very steep rise in yield strength with increasing solute. If only a very small quantity of such a solute is present one effect of this high local strain is that the solute element will tend to migrate to the space provided along the dislocations present rather than being uniformly distributed in solution in each crystal. This has the effect of pinning (holding) the dislocations in place, a phenomenon which is revealed by the presence of a Yield Point when plastic flow sets in during a tensile test. Substitutional solute addition is the commonest way of solution-hardening a metal. Brass (copper-zinc) and bronze (copper-tin) are two familiar materials which make use of this hardening effect. 5.1.2 Precipitation Hardening Thermal treatment can be used to control the size and distribution of second phase particles in any alloy which undergoes a phase transformation in the solid state. Alloy systems which have a phase diagram showing a decreasing solid solubility limit with decreasing temperature are particularly appropriate for such treatments and particles of the second phase can often be made to precipitate in a very finely dispersed form. In Figure 12, an alloy C exists as a single phase solid solution () at high temperatures but on slow cooling it becomes supersaturated with respect to the second phase, which therefore separates out. The distribution of the phase may be controlled as follows. The alloy is first solution heat-treated at the high temperature and then rapidly cooled by quenching into water or other cooling fluid. Solid-state diffusion is suppressed in this way, so that the phase cannot separate and the alloy exists at the low temperature in an unstable supersaturated state. If the temperature is now increased, so that diffusion can take place at a measurable rate, the second phase will nucleate and grow. In alloys of relatively low melting-point, there will be an appreciable diffusion rate of solute atoms at room temperature, so that over a sufficient length of time, the second phase will precipitate out. This effect is known as 'ageing', but in most alloys the temperature has to be raised in order to cause precipitation to occur and the material is said to be 'artificially aged'. The rate of growth of the precipitate is controlled by the rate of atomic diffusion, so that the precipitation increases with increasing ageing temperature. The size of the precipitate becomes coarser as the ageing temperature is increased, as shown schematically in Fig 12. If, at any temperature, the time of heat treatment is very prolonged, coagulation or coarsening of the particles occurs; the small ones tend to redissolve and the large ones to grow at their expense.

23

Precipitation hardening is the term now used to describe ageing. Just as heating will accelerate precipitation hardening, refrigeration will impede the process.

Fig 12

Variation of precipitate size with ageing temperature

24

5.1.3

Work Hardening Owing to the interaction of dislocations within the grains, plastic deformation will progressively harden a metal. The dislocations will multiply with strain and their density will continually rise with increasing deformation and thus the number of interactions per unit volume will rise as the strain continues. When a polycrystalline metal is stressed, each grain is deformed into a shape that is dictated by the deformation of its neighbours which requires the operation of several slip systems. The following graphs given in Figs 13, 14 and 15 show the effects of cold work on mechanical properties. Ultimate tensile strength can be increased by up to 1040 N/mm2 by reducing the cross-section by cold working by 90%. A reduction in cross-section by 10% will reduce percentage elongation from about 30% to 4%. Thereafter there will be little decrease to about 2%.

Fig 13 Stress-strain curves for metal subsequent to varying degrees of prior cold-working. It will be observed that cold working brings about an increase in tensile and yield strengths and a decrease in elongation prior to fracture.

25

Fig 14 Effect of cold deformation on the strength and hardness of metal. It will be seen that the spread between the yield strength and tensile strength curves becomes less with greater amounts of deformation and a consequent reduction in ductility.

Fig 15 Stress-strain curves for metal subsequent to varying degrees of prior cold-working. It will be observed that cold working brings about an increase in tensile and yield strengths and a decrease in elongation prior to fracture.

26

Gain in UTS (N/mm2) % Reduction in Cross-Section 30 50 80 0.20%C 140 280 450 0.80%C 200 350 700

5.1.4

Strain Ageing Strain ageing is observed when low carbon steel has been subjected to a small amount of deformation and then allowed to age for a period. This results in an increase in hardness and strength with reduced ductility and a drastic reduction of toughness as measured by impact tests. Even less than 1% cold reduction can produce such ageing which can be attributed largely to the movement of nitrogen atoms in the steel to sites which allow dislocations to be pinned in place. The maximum effect is with about 15% reduction. Such ageing proceeds very slowly at room temperatures and may take several months to reach a peak. Temperature increases will however rapidly increase the rate of hardening and at 300C this will reach the maximum value in a few seconds.

5.2

Isothermal Transformations So far consideration has been given to very slow cooling, when conditions will approach equilibrium, or very fast cooling to ambient temperatures. Variations in cooling rates between these extremes are possible and the results can be shown in isothermal transformation curves, also known as S curves, or timetemperature-transformation (TTT) curves. These are constructed by taking a number of specimens of the steel in question, heating them into the austenitic range and then quenching them in baths of different temperatures. At predetermined time intervals individual specimens are taken from their baths and quenched in water. They are then examined microscopically to evaluate the extent of the transformation that has occurred.

5.2.1

TTT Curves for Steel Figure 16 shows TTT Curves for a eutectoid plain carbon steel i.e. 0.83%C. First to be noted is the horizontal broken line at 723C which is the temperature above which a eutectoid steel will be wholly stable austenite. Below this line the austenite is unstable and the two C shaped curves indicate the times necessary for the transformation of this austenite to ferrite plus cementite to begin and go to completion following quenching to a particular temperature. The horizontal lines at the foot of the TTT diagram, strictly speaking, are not part of the TTT curves but represent the temperatures at which the formation of martensite will begin MS, and end MF, during the cooling of unstable austenite through this range. Unlike the formation of pearlite and bainite the transformation of unstable austenite to martensite is not dependent on time as it occurs almost instantly. The degree to which this change takes place is 27

determined simply by the temperature to which the steel is cooled. Once a transformation has gone to completion a steel will usually be water quenched with no further change in its constitution.

Fig 16 Time - Temperature - Transformation (TTT) Curves for a Plain Carbon Steel of Eutectoid Composition 5.2.2 Continuous Cooling Transformation Curves The TTT curves indicate structures which are produced by transformations which take place at a fixed temperature and specify a given incubation period before the transformation begins. It is important to realise that there can be no direct connection between such isothermal transformations and those which take place under continuous cooling at a constant rate from 723C to room temperature. Therefore it is not possible to super-impose curves which represent continuous cooling onto a TTT diagram. However, modified TTT curves which are related to continuous cooling can be produced. They are of a similar shape to the TTT curves but are displaced to the right.

28

5.2.3

The Effects of Alloy Additions on Isothermal Transformations With the exception of the metal cobalt, all alloy additions to steel will increase both the incubation period and the time necessary for transformations at specific temperatures. In effect this will increase hardenability. These changes are illustrated in the attached series of TTT diagrams (Fig 17). It should be noted that alterations in composition will be accompanied by variations in the temperatures A1, A3 and A4 and also those of MS and MF. Attention is drawn to the fact that the diagrams are based on a logarithmic scale so that even apparently minor movements of the TTT curves to the right will result in major increases in incubation and transformation periods. These will be reflected in the continuous cooling transformation diagrams appropriate to these alloys.

5.3

Normalising The process refers only to steel and consists of heating the metal to a temperature about 50C above its Upper Critical Point (Ac3 temperature) or austenitising temperature and having given adequate time for full conversion to Austenite allowing it to cool in still air. On heating, the change from body centred to face centred cubic structure will result in small austenite crystals whose sizes will determine those of the body centred cubic crystals formed on cooling. The process is therefore important in producing a refined grain size. If too high a temperature is employed, grain growth of the austenite will occur which will be reflected in the final cooled structure.

5.4

Full Annealing This process is also applicable only to steel and consists of heating the material to the appropriate normalising temperature and then cooling it very slowly (Fig 18), usually in the furnace. The resulting structure, as with normalised steel, will consist of ferrite or cementite with grains of pearlite but full annealed steel will be expected to have a somewhat larger grain size. More important is the effect of slow cooling on the structure of pearlite and this will become more coarsely lamellar with decreasing cooling rate which may even lead to very coarse lamellae balling up into coalesced particles of cementite in a groundmass of ferrite. Steel subjected to full annealing treatment will have lower tensile strength, impact strength and yield point but higher elongation values than those of normalised steel.

29

Fig 17 TTT-curves for alloy steels (after US Steel Corp)

30

Fig 18 (A) (B) (C) (D) Normalised Fully Annealed Water-quenched Water-quenched and tempered

31

5.5

Quenching and Tempering If a plain carbon steel is sufficiently rapidly cooled from above its upper critical temperature, i.e. within the wholly austenitic area, martensite will be formed. This phase becomes harder and more brittle as the carbon content increases up to the eutectoid value, 0.83%C. The hardness so attained will vary somewhat with the rate of cooling. The upper set of values shown in Fig 19 are the result of rapid cooling while those below are of average rates.

Fig 19 The effect of carbon content on hardness of martensite Occasionally such high martensitic hardnesses are useful for applications requiring good wear resistance but more often they are the essential starting points for tempered structures. Thus a steel may be hardened by heating it to 30-50 degrees C above its upper critical temperature and quenching it in some medium to produce the desired rate of cooling. In this condition, a tool steel for example, will be hard and brittle and some treatment to relieve internal stresses and to reduce brittleness is needed. Tempering will cause martensite to transform and the higher the temperature the nearer will the structure revert to the stable pearlitic type appropriate to that temperature. Tempering is always carried out below the lower critical level and when the desired temperature is reached may be followed by an immediate water quench, if the alloy is susceptible to temper embrittlement. Rate of cooling from the tempering temperature has little other effect. Up to 200C tempering will provide only some stress relief but from 230-400C the martensite will change to form a new constituent consisting of a very finely dispersed granular mixture of ferrite and cementite. This phase is much tougher than martensite and somewhat softer and less brittle. Toughness may be defined as the resistance to fracture by impact. Increasing tempering temperatures causes coalescence of the cementite particles until at about 32

400C they become visible at magnifications of about 500 times. Subsequent increases of tempering temperature to above 550C will cause strength to fall away with no rise in ductility. The importance of the fact that steels can be heat treated to give marked changes in properties cannot be over-emphasised. Thus it is possible by correct treatment to produce a relatively soft and ductile material that can be cold worked and machined to the desired shape and size and then to change its properties, drastically increasing its hardness and strength, making it far more suitable for its eventual service life. Compared with the pearlitic and bainitic structures of the same hardness, tempered martensites will have higher yield, tensile and impact strengths compatible with a high level of ductility. For most purposes therefore they are the most desirable structures. Tempering and Water Quench 0.40%C Steel Hardness HV Tensile N/mm2 Elongation % Charpy Impact (J) As Quenched 670 1850 5 11 200C 620 1700 12 19 350C 440 1420 14 14 450C 370 1200 16 30 600C 220 880 24 75

5.6

The importance of grain size As steel is heated through the critical range it is recrystallised with the formation of fine grains (Fig 20).

Fig 20 Schematic representation of the effect of temperature and grainrefining elements on grain size

33

These grains tend to grow as the temperature is raised, but the growth is more or less abrupt at a characteristic temperature - with the formation of first some coarse and some fine grains and finally all coarse grains, as indicated above. Prolonged heating also tends to increase the grain size. Each steel has a characteristic coarsening-temperature range and if that temperature is below the maximum commonly used for hardening, the steel is classed as coarse grained. If the steel is treated with effective amounts of aluminium, niobium, vanadium or titanium, or a combination of these elements, it does not coarsen at the usual hardening temperatures and is classed as fine grained. Coarse-grained steels (ASTM grain size 1-5) have some advantages in easier machining, higher creep strength at elevated temperatures, greater hardenability, and possibly less notch sensitivity in fatigue, but they have lower notched-bar impact strength and the impact resistance falls off rapidly at subnormal temperatures. Fine-grained steels (ASTM grain size 5-8 plus) have much better toughness, and virtually all heat-treating alloy steels used in machine construction are treated during melting so that they will be fine grained. Steels that develop a mixture of coarse and fine grains tend to give erratic properties, and are unlikely to be used. The grain-coarsening temperature of fine-grained steels varies somewhat but can be expected to be in the neighbourhood of 980C for aluminium-treated steel. This temperature may, however, vary widely with the composition and prior treatment. The coarsening temperature of high-carbon steels tends to be relatively low but grain growth may be restrained by undissolved carbides. 5.7 Grain Size Determination Grain size is commonly measured according to ASTM Standard Method E 112, Determining The Average Grain Size. In materials having two or more constituents, the grain size usually refers to that of the matrix. Minor constituent phases, inclusions, and additives are not normally considered. It is important in using these methods to recognise that the measurement of grain size is not precise, but an estimate. A metal grain is a three-dimensional shape of varying sizes. The grain cross section produced by a random plane (surface of observation) is dependent upon where the plane cuts each individual grain. Thus, no two fields of observation can be exactly equal.

34

Of the three methods listed in the standard, the comparison procedure is most popular since it takes the least time to carry out. This method involves viewing grains in a microscope and comparing them at the same magnification, 75X or 100X, to charts defined in ASTM E112, with two examples shown in Figure 21. The ASTM Grain Size Number corresponds to a certain number of grains/in2 according to Table below: ASTM No 0 1 2 Grains/in 0.5 1 2 2 3 4 4 8 5 16 6 32 7 64 8 128 9 256 10 512

The relationship between the Grain Size Number and the number of grains/in2 is given by the expression: Where: N = ASTM Grain Size Number n = 2 (N 1) n = number of grains/in2 at the specified magnification

Fig.21 Examples of ASTME E 112 Comparison procedure grain size charts for No. 5 and 8 Thus they may be added to improve mechanical properties. They may be used to enhance resistance to corrosion or high temperature oxidation. Further, they may be present to develop special characteristics such as those of an electrical or magnetic nature, strength at high temperatures or for the steel to remain austenitic at room temperatures.

35

6. 6.1

ALLOYING Alloying Elements in Steel The principal function of alloying elements in steel is to improve its properties. Thus they may be added to improve mechanical properties. They may be used to enhance resistance to corrosion or high temperature oxidation. Further, they may be present to develop special characteristics such as those of an electrical or magnetic nature, strength at high temperatures or for the steel to remain austenitic at room temperatures. The alloying elements added may either simply dissolve in the ferrite or they may combine with some of the carbon, forming carbides. The principal effects which these alloying elements have on the microstructure and properties of a steel include those on the allotropic transformation temperatures. Some elements, notably nickel, manganese, cobalt and copper, raise the A4 temperature and lower the A3 temperature, as shown in Figure 22 (A). In this way these elements, when added to a carbon steel, tend to stabilise austenite and increase the range of temperature over which austenite can exist as a stable phase. Other elements, the most important of which include chromium, tungsten, vanadium, molybdenum, aluminium and silicon, have the reverse effect, in that they tend to stabilise ferrite by raising the A3 temperature and lowering the A4, as indicated in Figure 22 (B). Such elements restrict the field over which austenite may exist, and thus form what is often called a loop. The elements of the -stabilising group generally have a face-centred cubic lattice. Since this is the same as austenite, these elements will retard the transformation of austenite to ferrite. At the same time these elements retard the precipitation of carbides, and again this has the effect of stabilising austenite. The a-stabilising elements are usually those with a body-centred cubic lattice. These will dissolve more readily in ferrite than in austenite, and at the same time diminish the solubility of carbon in austenite. In this way they stabilise ferrite. As shown in Figure B, progressive increase in one or more of the -stabilising elements will cause a point to be reached beyond the confines of the -loop, where the austenite cannot exist at any temperature.

36

Fig 22 Relative effects of the addition of an alloying element on the allotropic transformation temperature at A3 and A4 (A) Tending to stabilise (B) Tending to stabilise

6.1.1

Carbide or Graphite Formers (Fig 23) Some alloying elements form very stable carbides when added to a plain carbon steel. This generally has as hardening effect especially when the carbides formed are harder than iron carbide. Such elements include chromium, tungsten, molybdenum, titanium and manganese. When one or more of these elements is present, a structure containing complex carbides is often formed.

37

Fig 23 The condition in which alloying elements are present in steel Other elements have a graphitising effect on the iron carbide; that is, they tend to make it unstable so that it breaks up, releasing free graphitic carbon. This effect is more evident if no carbide stabilisers are present. Elements which tend to cause graphitisation include silicon, nickel and aluminium. Therefore, if it is necessary to add appreciable amounts of them to a steel, it can be done only when the carbon content is extremely low. Alternatively, if the carbon content needs to be high, one or more of the elements of the first group, namely the carbide stabilisers, must be added in order to counteract the effects of the graphitising element. 6.1.2. Crystal Growth The rate of crystal growth is accelerated, particularly at high temperatures, by the presence of some alloy additions, notably chromium. Care must therefore be taken that steels containing elements in this category are not overheated or, indeed, kept for too long at an elevated temperature, or brittleness, which is usually associated with a coarse grain size, will result. Fortunately, grain growth is retarded by other elements, notably niobium and vanadium, whose presence thus produce a steel which is less sensitive to the temperature conditions of heat-treatment.

38

6.1.3

Corrosion Resistance The corrosion-resistance of steels is substantially improved by the addition of aluminium, silicon and chromium. These metals form thin but dense and adherent oxide films which protect the surface of the steel from further attack. Of the elements mentioned chromium is the most useful when mechanical properties have to be considered. When nickel also is added in sufficient quantities, the austenitic structure is maintained at room temperature.

6.1.4

Strength One of the main reasons for alloying is to effect improvements in the mechanical properties of steel. These improvements are generally the result of physical changes already referred to. For example, hardness is increased by stabilising the carbides; strength is increased when alloying elements dissolve in the ferrite; and toughness is improved by refinement of the grain size.

6.2 6.2.1

The Effects of Alloying on Steel Strength and Hardenability Carbon It has been shown that increasing carbon content in plain carbon steels will lead to increases in hardness and, up to the eutectoid composition (0.83%C) increases the tensile and yield strengths. Corresponding to these changes will be decreases in ductility, malleability and impact strength. Increasing the carbon content of martensitic steels may be expected to show increases in hardness up to the eutectoid point. Tempered martensitic structures will show increases in hardness and brittleness up to about 1.4%C. Hardenability in plain carbon steels is at a maximum at the eutectoid composition. Increasing or decreasing the carbon content from the eutectoid composition will lead to lower hardenability, i.e. it becomes increasingly more difficult to obtain martensitic structures, and increasingly rapid quenching is required.

6.2.2

Manganese Some manganese is present in nearly all steels. It is usually below 1% and it is only when this amount is exceeded that it is regarded as a deliberately added alloying element. Like nickel, manganese stabilises austenite but unlike nickel it also has the effect of stabilising the carbides, by itself forming Mn3C. It has a considerable strengthening effect on ferrite and increases hardenability.

39

6.2.3

Chromium Very small amounts of chromium when added to carbon steel will cause a considerable increase in hardness. At the same time strength is raised with some loss of ductility which is not apparent with less than 1.0%Cr. The increase in hardness is mainly due to the fact that chromium is a carbide stabiliser forming hard carbides itself or double carbides with Fe3C. Chromium is a ferrite stabiliser and austenite may be eliminated entirely when more than 11%Cr is added to pure iron. The main disadvantages in the use of chromium as an alloying element is its tendency to promote grain growth, with its attendant brittleness. Care must therefore be taken to avoid overheating or holding for too long at the normal heat-treatment temperature. Steels containing small amounts of chromium and up to 0.45% carbon are used for axle shafts, connecting-rods and gears; whilst those containing more than 1.0% carbon are extremely hard and are useful for the manufacture of ball-bearings, drawing dies and parts for grinding machines. Chromium is also added in larger amounts - up to 21% - and has a pronounced effect in improving corrosion-resistance, due to the protective layer of oxide formed. This oxide layer is extremely thin, and these steels take a very high polish. They contain little or no carbon and are therefore completely ferritic and non-hardening (except by cold-work). Stainless steels which have only chromium as the main alloying element and have C levels that exceed 0.1% are of the martensitic type, the structure being obtained by rapid cooling. If these steels are allowed to cool slowly, carbides will be precipitated, with consequent loss in corrosion-resistance (sensitisation).

6.2.4

Nickel The addition of nickel to a plain carbon steel tends to stabilise the austenite phase. For example, the addition of 25% nickel to pure iron renders it austenitic, and so non-magnetic, even after slow cooling to room temperature. Nickel makes the carbides unstable and tends to cause them to decompose to graphite. It is therefore inadvisable to add nickel by itself to high carbon steels and most nickel steels are of the low carbon type. Generally the 3.5% nickel steels are the most widely employed, those with about 0.12%C being used mainly for case hardening, while the 0.30%C types are used for structural purposes and in engines for shafting and axles etc. Nickel also has a grain refining effect enabling the alloys to be employed in case hardening as grain growth will be limited during prolonged treatment at about 900C.

40

Nickel was one of the first elements added to plain carbon steels, its main advantage being to increase tensile strengths without adversely affecting ductility. Its effect of lowering critical temperatures for heat treatment is also an advantage in cost reduction. Nickel in moderate amounts also increases hardenability allowing slower quench rates than in plain carbon steels. 6.2.5 Molybdenum Molybdenum is a strong carbide stabiliser and relatively small amounts will markedly enhance the properties of plain carbon steels. Usually it is added in quantities ranging from 0.12-0.65% depending on the intended application of the steel. More often it is used in combination with manganese, nickel and/or chromium to give a noticeable improvement in properties. Hardenability is increased especially when used in conjunction with chromium. One of the metal's advantages is that it will reduce the tendency to temper brittleness in low nickel low chromium steels when heat treated at 250-400C. In general NiCr-Mo alloy steels possess the best all-round combination of properties, especially when high tensile strength and good ductility are required in large components. Such steels are relatively free from the mass effects of heat treatment, the transformation rates of the Ni-Cr steels being even further reduced by the presence of molybdenum which contributes considerably to hardenability. Its presence will also raise the high temperature strength and creep resistance of high temperature alloys and it is added to stainless steels in proportions of up to 3.0% to improve corrosion resistance especially in chlorides and acids. The disadvantages of molybdenum steels are that they require higher tempering temperatures to obtain properties comparable to plain carbon steels and they need a longer holding period at quenching and normalising temperature to ensure complete solid solution of the molybdenum iron carbide. 6.2.6 Niobium (US Columbium) Plain low carbon steels for structural purposes benefit greatly from small additions of niobium and quantities as low as 0.02-0.04% will increase Yield Point by 62-110N/mm2 and Ultimate Tensile Strength 54-85N/mm2. This will give a higher Yield to Ultimate Tensile Strength ratio than in plain carbon steels. Above 0.04%Nb this strengthening effect falls away rapidly. Niobium is a strong carbide former but its effect on low carbon steels is thought to be mainly by precipitation hardening. It has a marked grain refining function sometimes reinforced by aluminium and/or vanadium additions. Such refined grain structures give high impact values. Niobium as a very strong carbide stabiliser, is also added to some stainless corrosion resisting steels (type 347) of the 18/8 chromium-nickel variety to prevent weld decay sensitivity.

41

6.2.7 Vanadium Plain vanadium steels are manufactured to a very limited extent, but chromium-vanadium steels containing up to 0.2% vanadium are widely used for small and medium sections. The mechanical properties resemble those of nickel-chromium steels, but usually show an advantage in respect of the limit of proportionality and percentage reduction in area. Chromium-vanadium steels are also easier to forge, stamp and machine, but are more susceptible to mass effects of heat-treatment than the corresponding nickel-chromium steels. Vanadium has a strong carbide-forming tendency. It also stabilises martensite and low temperature tempered martensite on heat-treatment and increases hardenability. Like nickel, it restrains grain growth of the austenite. One of the most important effects of vanadium is that it induces resistance to softening at high temperatures provided that the steel is first heat-treated to absorb some of the vanadium carbide into solid solution. Consequently vanadium steels are used for hot-forging dies, extrusion dies, die-casting dies and other tools operating at elevated temperatures. 6.2.8 Aluminium The presence of aluminium in plain carbon and low alloy steels will tend to stabilise ferrite but as it will normally be in very low concentrations (<0.050%) its direct effect on hardenability will be negligible. It can however act as a strong grain refiner (levels >0.015%) which may reduce hardenability somewhat although improving tensile and impact strengths. It is widely used as a deoxidant in low carbon mild steels where ductility is the principal quality. In such steels the presence of small amounts of nitrogen introduced during steel making will cause strain ageing to the detriment of their properties. A small amount, up to about 0.08%, of residual aluminium by forming aluminium nitride will suppress this phenomenon in cold rolled annealed tempered grades. In offshore structures a Al to N ratio of at least 2:1 is sometimes specified to overcome strain ageing during welding. 6.2.9 Sulphur The element sulphur will tend to decrease hardenability somewhat, but as, with a few exceptions, considerable efforts are made to eliminate it from plain carbon and alloy steels, it is usually present only in small amounts and its effect in this respect may be neglected. It is the most deleterious impurity commonly present in steel. If precautions are not taken to render it harmless it will form the brittle sulphide, FeS. This is soluble in molten steel, but when solidification takes place the solid solubility falls to an equivalent of 0.03% sulphur. If the effects of extensive coring are also taken into account amounts as low as 0.01% sulphur may cause precipitation of the sulphide at the grain boundaries. In this way the austenite grains will become virtually coated with brittle films of ferrous sulphide. Since this sulphide has a fairly low melting point, the steel will tend to crumble during hot-working. Being brittle at ordinary temperatures, ferrous sulphide will also 42

render steel unsuitable for cold-working processes, or, indeed, for subsequent service of any type. The sulphur is rendered harmless by the presence of manganese with which it combines preferentially to form manganese sulphide MnS. This MnS is insoluble in molten steel and some will be lost in the slag while the rest will be present as globules distributed throughout the steel and not associated with the structure when solidification takes place. These globules are plastic at hot working temperatures and the tendency of the steel to crumble is thus removed while the globules will be rolled out as threads in subsequent operations. With modern steel making practices levels of <0.01%S and 0.02%P are commonly achieved. The demand for high grade weldable steels for stringent applications such as off-shore pipelines has led to the availability of grades with less than 0.01%S and 0.01%P. These have become possible largely by the selection of high-grade raw materials which themselves have low proportions of these elements and the introduction of new steelmaking techniques the most notable being vacuum degassing. With such steels MnS will also be low which will reduce the extent of non-metallic inclusions with consequent benefits to weldable steels for critical structural applications. Free cutting steels are made with a deliberately high level of sulphur, from 0.15-0.25%S in plain carbon steels, with about five times the manganese content to ensure its presence a globular MnS. This sulphide is widely distributed so that on machining the cutting tool forms small chips which are easily handled. 6.2.10 Phosphorus In the same way as sulphur, phosphorus is almost always considered an undesirable element in steel and its proportion is usually kept to a minimum. It will increase hardenability but as it is present in such a small amount its effect and that of sulphur are generally thought to cancel each other out. Phosphorus forms the brittle phosphide Fe3P, which is soluble in ferrite. In solution, it has a considerable hardening effect but it must be rigidly controlled to amounts in the region of 0.05% or less because of the brittleness also introduced, particularly if Fe3P should appear as a separate constituent in the microstructure. Nowadays 0.02% is commonly produced and high grade materials with 0.01%P are available.

43

6.2.11

Silicon Silicon is widely used as a deoxidant in steelmaking and it is often present in quantities of 0.2-0.5%. Like nickel it encourages graphite formation and it must therefore be kept low in high carbon steels. It dissolves in ferrite where it has a substantial strengthening effect. Hardenability is only moderately affected by the element. Silicon is included in some heat resisting steels in amounts up to 1.5% as it aids high temperature resistance to oxidation.

6.3

Alloying Additions in Steel - Summary The effects of individual alloying elements are shown in tabular form below: Effect on Effect in Effect on Strengthening Forming Transformation Ferrite Carbides Temperatures Manganese Strong Weak Lowers Silicon Strong None Raises Phosphorus Strong None Lowers Nickel Moderate None Lowers Chromium Weak Moderate * Copper Moderate None Lowers Molybdenum Strong Strong Raises Vanadium Weak Strong Raises Tungsten Moderate Strong Raises * Raises or lowers depending on carbon content 1. 2. Alloying Element Effect on Hardenability Strong Moderate Moderate Moderate Strong Weak Strong Mild Moderate

Elements which tend to form carbides - Cr, W, Ti, V, Nb, Mo, Mn. Elements which tend to graphitise the carbide - Si, Co, Al, Ni. Elements from category 1. should be present to avoid graphitisation when small additions of the above are exceeded. Elements which tend to stabilise the Austenite - Mn, Ni, Co, Cu. Elements which tend to stabilise the Ferrite - Cr, W, Mo, V, Si.

3. 4.

The Austenite phase may disappear when a closed loop is formed. If no carbon is present in the alloy the loop will disappear when the following elements are present in these approximate percentages. Cr 12.8%, S 2.0%, W 6.0%, P 0.5%, Al 1.1%, Ti 0.75%, Mo 4.0%

44

7. 7.1

MICROSTRUCTURES IN STEEL ARC WELDS Weld Metal The large number of variables inherent in welding such as the welding process itself, the final composition of the melt, welding speed and thermal cycle make it unrealistic even to attempt to predict with any precision the microstructures that can arise. Nevertheless, some general points can be made. In the welding operation itself a pool of molten metal is retained within the work piece. This may be likened to molten metal within an ingot mould, and on freezing, large columnar crystals will form and since the weld pool is small, and in the case of a single arc weld, solidification rapid, they will usually occupy the complete crosssection of weld metal. This metal has a characteristic cellular-dendritic structure of cast metal consisting of the rather coarse columnar austenitic grains which curve into the weld centre line and a fine cellular network within the grains. The transformation products resulting from the decomposition of these grains is dependant mainly on the rate of cooling of the weld metal. Although it has been pointed out that accurate predictions of weld metal structure are not possible a schematic CCT (Continuous Cooling Time) (Fig 24) in which general changes arising with differing cooling rates and the effects of heat input, alloying elements and slag inclusions are related in a qualitative way. Thus C, N, Mn etc tend to move the diagram to the right to give more time for transformations. If cooling curves are superimposed on such a diagram it will be clear that rapid cooling rate curves will approach the vertical whereas slow cooling rate curves will approach the horizontal. All phases intersected by such curves will be present in the final structure. It may be expected that the strength and hardness of welds would be generally high as rapid cooling rates tend to promote lower temperatures of transformation and there are usually large quantities of impurities and alloying elements. On the other hand the impact properties and toughness of such steel welds can be impaired especially at the weld centre line which is the area of maximum segregation where the columnar crystals meet. To this must be added the deleterious effects of the coarse columnar structure with mixtures of transformation products which may result in the precipitation of carbides which on impact tend to rupture to produce brittle fractures of the pro-eutectoid ferrite.

45

Fig 24 Continuous Cooling Time. Schematic CCT diagram for steel weld metal, summarising the possible effect of microstructure and alloying on the transformation products for a given weld cooling time In a plain carbon steel of 0.15-0.20%C with slow cooling and small under-cooling below A3, a structure of blocky ferrite with pearlite will be formed. A mediumslow cooling rate with larger undercooling below A3 will result in a form of ferrite known as Pro-eutectoid ferrite and on further cooling the production of ferrite needles known as Widmanstatten side plates and the remaining austenite at even lower temperatures transforming into pearlite and cementite. Another possible phase in such weld metals at undercooling near A1 is Acicular Ferrite the transformation to which is enhanced by the presence of strong carbide formers such as Mo or Cr. The presence of acicular ferrite gives improved toughness to such welds. The acicular ferrite is formed intragranularly resulting in randomly orientated short ferrite needles with a basket weave feature. This interlocking nature together with the fine grain size provides maximum resistance to crack propagation by cleavage. Notch toughness increases with increasing volume fraction of acicular ferrite in the weld metal. The formation of either grain boundary ferrite, ferrite side plates or upper bainite is detrimental to weld metal toughness since these microstructures provide easy crack propagation paths. Medium high cooling rates result in the transformation occurring below A1 with a fast initial ferrite growth resulting in rapid carbide concentration at the austeniteferrite interface causing the precipitation of cementite which is again followed by very rapid ferrite growth with the same consequences. This is known as the Periodic Pearlite reaction. A fast cooling rate results in the formation of the phase Upper Bainite, while a very fast cooling rate may produce Lower Bainite or Lath martensite.

46

7.2.

Heat Affected Zone (HAZ) To be satisfactory, dilution of a weld metal must occur by melting part of the base metal which in the region of the melt will be exposed to similar high temperatures. Subsequently, conditions of rapid cooling under conditions of severe restraint will be imposed and as a result of this thermal cycle the original microstructure and properties of the metal close to the weld will be changed. This region is normally referred to as the HAZ. The HAZ can be conveniently divided into a series of sub-zones and illustrated in fig 25 are those of a 0.15%C transformable steel.

Fig 25 Various regions of the HAZ in a single pass weld Changes taking place in the Solid-liquid transition zone depend largely on the composition of the metal and whether the austenite melts directly or is transformed to delta ferrite. In the latter case boundary segregation will result in reduced grain growth and a layer of small crystals, but in the former there will be no such changes. In the grain-coarsened HAZ pro-eutectoid ferrite networks feature prominently for lower carbon equivalent x 2 grades but with higher steels this will be reduced in favour of lower temperature transformation products such as Widmanstatten side plates with possibly some martensite mainly in the midgrains. In the grain refined HAZ the structure tends to be fine grained ferritepearlite. The intercritical HAZ can yield a wide range of probable structures, depending on the cooling rate, and may be pearlite, upper bainite, autotempered martensite or high carbon martensite. The subcritical HAZ produces its most notable change in the degradation of pearlite to spheroidal particles of cementite. The zone of unaffected base material at lower temperatures may result in embrittlement of the structure caused by dynamic strain ageing. The production of high strength structural materials is mainly based on developing a product with as small a grain size as possible but the severity of the weld thermal cycle is such that the structure is completely modified near the weld. In high energy processing such as submerged arc it is not uncommon for the grain size to be increased tenfold or more in the zone closest to the fusion line. In steels of high Carbon equivalent (above 0.40) it is likely that the grain growth zone will contain martensite. Thus the microstructure of the grain growth zone more than other zones in the HAZ will determine the properties of the weld.

47

The thermal cycle that is to say the heating time, the time at temperatures or dwell time, and the cooling time are important and must be considered together with the presence of precipitates and their solubility at high temperatures. Moreover the previous thermal and mechanical history is also important. Thus for example the original steel may have been in the cold rolled condition, it may have been annealed or normalised or subjected to other treatments. With these aspects in mind the sub-zones may be considered separately since each one will have a different type of microstructure with appropriately different properties. Notwithstanding the complexities involved such structure can be predicted with greater certainty then those arising in the weld metal. 7.3 Welding Heating Cycle The importance of the welding heating cycle is not always fully recognised. The temperature increases can be 200-300C/sec and thus to transformations will be above that of equilibrium and the phase will be substantially superheated before the change occurs. The degree of superheating will be affected by the welding process and the thermal cycle is such that in most metals some grain growth will occur in the HAZ which not only affects strength and toughness but also influences grain size in the weld metal. In most steels the presence of carbide or nitride particles tends to hinder grain growth and it has been shown that such growth occurs predominantly at temperatures above the equilibriumsolubility limits of such particles. Also it has been observed that most grain growth occurs during the heating part of the thermal cycle and in some steels experiments indicate that only about 20% of growth occurs in the cooling cycle. In general some degree of grain growth control can be exerted either by limiting the duration of the weld thermal cycle or by precipitate pinning, that is, mainly by Carbides and Nitrides in steels. The best way to control grain size is to use large quantities of very small precipitates but this is not always easy to achieve. The employment of multi-run welds will result in a refinement of microstructure and improvements in toughness with reductions in residual stress when compared with a single run of the same cross-section.

48

7.4

Carbon Equivalent (Ceq) Weldable structural steels are normally capable of being welded without the need for any pre-heat because the fectors which cause high hardness and the likely presence of martensite would be absent in such welds. These characteristics are usually expressed by reference to the Carbon Equivalent value. This is assessed in terms of how the alloying elements affect the transformation characteristics including the martensite start temperature Ms of the steel. An empirical formula has been devised for Carbon Equivalent (CE) and adopted by the International Institute of Welding as follows:

A weldable structural steel will normally have a CE value not greater than 0.40%. Other formulae such as PCM used in Japan are also available. It should be realised that such formulae and the values calculated from them are principally guides and circumstances may arise when departures from them are justified. Essentially a Carbon Equivalent is a measure of the hardenability of a steel.

49

8.

STRUCTURE OF INGOTS When molten metal is poured into a metal ingot mould, solidification will usually begin with the formation of small chill crystals at the mould-metal interface (Fig 26). These are followed by long columnar crystals growing at right angles to the mould surface. The size of these crystals will depend on the rate of solidification and they will be small if this is rapid, increasing in size with slower rates. With very slow solidification, as with a sand mould for example, the columnar and chill crystals will not generally form but dendrites will develop into irregular equi-axed grains. Where columnar crystals have formed, planes of weakness can be expected at sharp corners and in extreme cases even at the ingot centre.

Fig 26 Ingot Solidification 8.1 Pipe As a layer of cooled metal forms around the ingot walls, contraction occurs resulting in a fall of the level of liquid. Successive layers of solid form, each accompanied by a fall in the liquid level, the fall increasing as the volume of liquid decreases. In this manner a central cavity is formed, known as Primary Pipe. With the ingot mould designed narrow end up (Fig 27) a conical volume of metal still remains liquid after the top portion of the ingot is solid. Solidification of this metal will give rise to further cavities known as Secondary Pipe.

50

Fig 27 Effects of Ingot Taper and Hot Top/Feeder Head This can be prevented by using a mould wide end up when shrinkage will be counteracted by molten metal feeding down from the top. The primary pipe can also be reduced by using a brick-lined top on the mould - called a hot top or feeder head, in which the metal will remain molten for a prolonged period acting as a reservoir of molten metal, which will consequently feed the ingot. 8.2 Segregation (fig.28) Molten steel contains soluble impurities - sulphur and phosphorus - and soluble alloying elements together with insoluble impurities or slag particles in suspension. The first crystals to separate contain less impurity than the average composition and those elements which lower the freezing point, such as sulphur, phosphorus, carbon, silicon and manganese collect in the last portions to solidify. This phenomenon is known as segregation and in the case of steel ingots means that there is a concentration of sulphur, phosphorus and carbon in the centre and upper portions of the ingot. Associated with the pipe they are largely removed when it is discarded. Segregation also occurs as the microscopic scale. Impurities and soluble alloying elements are rejected by the solidifying crystal with the result that an alloy rich area surrounds each crystal. This can be clearly seen in carbon steel castings, the original crystal lower in alloy content tends to be ferritic whilst the more highly alloyed crystal surround is pearlitic.

51

Fig 28 Segregation in Steel 8.3 Steel Types Steel, manufactured from impure pig-iron or scrap, is first purified to a great extent by a process of oxidation which inevitably leaves the molten material with excessive oxygen which must be reduced to render it suitable for casting to an ingot. The steel type is defined by the degree of deoxidation. 8.3.1 Rimming Steel (Fig 29) The structure of this type of ingot is characterised by an outer envelope or rim of solid, comparatively pure steel, with the inner core of less solid or pure character. Such ingots are made from steel of an effervescing nature, i.e. steel in which deoxidation either in the ladle or in the mould has been intentionally limited with the result that a free evolution of gas progressively takes place during freezing. The evolution of gas towards the centre of the ingot produces globular blowholes which counteract cooling and solidification shrinkage and are subsequently welded together during rolling. The thickness of the rim and the proportion of blowholes will both decrease with increasing carbon content. This type of steel improves the yield of ingot to finished product and will provide rolled material of good surface finish especially important in applications for low carbon grades such as cold rolled sheets and strip. Rimming steel is not usually available with carbon contents exceeding 0.35% and is not acceptable for critical structural applications.

52

Fig 29 Rimming Steel 8.3.2 Balanced or Semi-killed steel A balanced steel is a non-piping steel in which no observable gas evolution takes place but where sufficient gas is formed during solidification to balance or offset normal shrinkage. Numerous blow-holes are produced so the central shrinkage cavity or pipe is prevented or considerably reduced in extent. Balanced steels are only partially deoxidised and small additions of aluminium are made to the moulds, if necessary, to reduce the oxygen content to that amount which will give an ingot with a flat or slightly bulging top. 8.3.3 Killed steel Killed steel is steel that has been completely deoxidised by additions of manganese, silicon and sometimes aluminium, before casting, so that there is practically no evolution of gas during solidification and sound ingots are obtained. The shrinkage cavity or pipe is limited to upper portions of the ingot or in the feeder head with which such ingots are usually provided. Steel used for continuous casting is always fully killed.

53