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The Fe-C diagram in Fig. 1 is of experimental origin. The knowledge of the thermodynamic principles and modern thermodynamic data now permits very accurate calculations of this diagram.
If alloying elements are added to the iron-carbon alloy (steel), the position of the A1, A3, and Acm boundaries and the eutectoid composition are changed (1) all important alloying elements decrease the eutectoid carbon content, (2) the austenite-stabilizing elements manganese and nickel decrease A1 (3) the ferrite-stabilizing elements chromium, silicon, molybdenum, and tungsten increase A1.
Characteristics
bcc
bcc
fcc
Cementite (Fe3C)
Complex orthorhombic
Graphite
Hexagonal
Pearlite
Martensite bct (supersaturated solution of carbon in ferrite) Hard metastable phase; lath morphology when <0.6 wt% C; plate morphology when >1.0 wt% C and mixture of those in between
Bainite
... Hard metastable microconstituent; nonlamellar mixture of ferrite and cementite on an extremely fine scale; upper bainite formed at higher temperatures has a feathery appearance; lower bainite formed at lower temperatures has an acicular appearance. The hardness of bainite increases with decreasing temperature of formation.
Accm. In hypereutectoid steel, the temperature at which the solution of cementite in austenite is completed during heating. Ac1. The temperature at which austenite begins to form during heating, with the c being derived from the French chauffant. Ac3. The temperature at which transformation of ferrite to austenite is completed during heating.
Arcm. In hypereutectoid steel, the temperature at which precipitation of cementite starts during cooling, with the r being derived from the French refroidissant. Ar1. The temperature at which transformation of austenite to ferrite or to ferrite plus cementite is completed during cooling. Ar3. The temperature at which austenite begins to transform to ferrite during cooling.
Ar4. The temperature at which delta ferrite transforms to austenite during cooling. (or Ar''). The temperature at which transformation of austenite to martensite starts during cooling. Mf. The temperature at which martensite formation finishes during cooling.
Ms
One can conveniently describe what is happening during transformation with transformation diagrams. Four different types of such diagrams can be distinguished. These include: Isothermal transformation diagrams describing the formation of austenite, which will be referred to as IT diagrams Isothermal transformation (IT) diagrams, also referred to as time-temperature-transformation (TTT) diagrams, describing the decomposition of austenite Continuous heating transformation (CHT) diagrams Continuous cooling transformation (CCT) diagrams
ITh Diagrams (Formation of Austenite). During the formation of austenite from an original microstructure of ferrite and pearlite or tempered martensite, the volume (and hence the length) decreases with the formation of the dense austenite phase (see Fig. 3). From the elongation curves, the start and finish times for austenite formation, usually defined as 1% and 99% transformation, respectively, can be derived.
Fig. 3 The procedure for determining isothermal heating (ITh) diagrams. Line 1: Temperature versus time. Line 2: Elongation versus time. S represents the start and F the finish of the transformation of the original microstructure to austenite transformation, respectively.
(Fig. 4). Below Ac1 no austenite can form, and between Ac1 and Ac3
the end product is a mixture of ferrite and austenite
Transformation
Austenite-martensite
4.64-0.53 (%C)
Austenite-lower bainite
4.64-1.43 (%C)
Austenite-upper bainite
4.64-2.21 (%C)
Hardenability Concepts The goal of heat treatment of steel is very often to attain a satisfactory hardness. The important microstructural phase is then normally martensite The hardness of martensite is primarily dependent on its carbon content as is shown in Fig In practical heat treatment, it is important to achieve full hardness to a certain minimum depth after cooling, that is, to obtain a fully martensitic microstructure to a certain minimum depth, which also represents a critical cooling rate. CCT diagrams constructed according to Atkins or Thelning can serve this purpose if one knows the cooling rate at the minimum depth
Successful hardening usually means achieving the required microstructure, hardness, strength, or toughness while minimizing residual stress, distortion, and the possibility of cracking. The selection of a quenchant medium depends on the hardenability of the particular alloy, the section thickness and shape involved, and the cooling rates needed to achieve the desired microstructure. The most common quenchant media are either liquids or gases. The liquid quenchants commonly used include: Oil that may contain a variety of additives Water Aqueous polymer solutions Water that may contain salt or caustic additives The most common gaseous quenchants are inert gases including helium, argon, and nitrogen. These quenchants are sometimes used after austenitizing in a vacuum.
Fig. Calculated hardness (dashed line) and reported hardness (solid line) from a Jominy test of AISI 4130 steel.
TEMPERING OF STEEL
is a process in which previously hardened or normalized steel is usually heated to a temperature below the lower critical temperature and cooled at a suitable rate, primarily to increase ductility and toughness, but also to increase the grain size of the matrix. Steels are tempered by reheating after hardening to obtain specific values of mechanical properties and also to relieve quenching stresses and to ensure dimensional stability. Tempering usually follows quenching from above the upper critical temperature; however, tempering is also used to relieve the stresses and reduce the hardness developed during welding and to relieve stresses induced by forming and machining. Principal Variables Variables associated with tempering that affect the microstructure and the mechanical properties of a tempered steel include: Tempering temperature Time at temperature Cooling rate from the tempering temperature Composition of the steel, including carbon content, alloy content, and residual elements
Fig. Tempering curves for some current steels. The steel 42CrMo4 is equivalent to AISI 4142 and C45 to AISI 1045.
Temper embrittlement The toughness of a steel increases with decreasing hardness. However, when certain impurities such as arsenic, phosphorus, antimony, and tin are present, a toughness minimum "temper embrittlement" may occur in the temperature range 350 to 600 C due to segregation of impurities to grain boundaries. Temper embrittlement is a problem when parts are exposed to temperatures in the critical range for rather long times and is a concern for parts exposed to these temperatures while in service or when heat treating very massive parts which require long times to heat and cool. It is not a concern, even for susceptible alloys, if small parts are exposed to these temperatures for an hour or so during heat treatment, then used at ambient temperatures. Nuts and bolts, for example, made of various types of steels, are tempered in this temperature range with no problems as long as they are used at lower temperatures. The time for embrittlement to occur at differing tempering temperatures shows a C-shaped curve behavior . Temper embrittlement can be removed by reheating the steel above 600 C (1110 F) followed by rapid cooling, for example, water quenching.
Martensite embrittlement
Another type of embrittlement that affects high-strength alloy steels is tempered martensite embrittlement (also known as 350 C, or 500 F, embrittlement), which occurs upon tempering in the range of 205 to 370 C (400 to 700 F). It differs from temper embrittlement in the strength of the material and the temperature exposure range. In temper embrittlement, the steel is usually tempered at a relatively high temperature, producing lower strength and hardness, and embrittlement occurs upon slow cooling after tempering and during service at temperatures within the embrittlement range. In tempered martensite embrittlement, the steel is tempered within the embrittlement range, and service exposure is usually at room temperature. Therefore, temper embrittlement is often called two-step temper embrittlement, while tempered martensite embrittlement is often called one-step temper embrittlement
MARTEMPERING
is a term used to describe an interrupted quench from the austenitizing temperature of certain alloy, cast, tool, and stainless steels. The purpose is to delay the cooling just above the martensitic transformation for a length of time to equalize the temperature throughout the piece. This will minimize the distortion, cracking, and residual stress. The term martempering is somewhat misleading and is better described as marquenching. The microstructure after martempering is essentially primary martensitic that is untempered and brittle. Figure 1(a and b) shows the significant difference between conventional quenching and martempering. Martempering of steel (and of cast iron) consists of: Quenching from the austenitizing temperature into a hot fluid medium (hot oil, molten salt, molten metal, or a fluidized particle bed) at a temperature usually above the martensite range (Ms point) Holding in the quenching medium until the temperature throughout the steel is substantially uniform Cooling (usually in air) at a moderate rate to prevent large differences in temperature between the outside and the center of the section
Time temperature transformation diagrams with superimposed cooling curves showing quenching and tempering. (a) Conventional process. (b) Martempering. (c) Modified martempering
The advantage of martempering lies in the reduced thermal gradient between surface and center as the part is quenched to the isothermal temperature and then is air cooled to room temperature.
Heat treatment of steel, is usually accompanied by the large residual stresses, that is, stresses that exist without any external load on the part considered. Causes for such stresses include: 1. Thermal expansion or contraction of a homogeneous material in a temperature gradient field 2. Different thermal expansion coefficients of the various phases in a multiphase material 3. Density changes due to phase transformations in the metal 4. Growth stresses of reaction products formed on the surface or as precipitates, for example, external and internal oxidation
Formation of residual stress on cooling considering thermal expansion and the austenite to martensite transformation. The dashed line is the yield stress, s, at the surface.
HARDENABILITY STEELS H-steels, offer a wide range of mechanical properties that depend on the development of tempered martensite after quenching and tempering. Typical room-temperature properties of quenched and tempered steels can vary as follows: Hardness values of 130 to 700 HV (30 kgf load) Tensile strengths of 400 to 2000 MPa (58 to 290 ksi) Yield strengths of 300 to 1800 MPa (43 to 261 ksi) Elongation of 8 to 28% in 50 mm (2 in.)
Carbon, % Rockwell C hardness (HRC) with martensite contents of: 50% 0.18 0.23 0.28 31 34 36.5 80% 35 37.5 40.5 90% 37.5 40.5 43 95% 39 42 44.5 99.9% 43 46 49
0.33
0.38 0.43 0.48
39
42 44 46.5
43.5
46 48 52
46.5
49 51 54
48.5
51 53.5 57
52
54 57 60
Relationship of CCT (heavy lines) and IT (light lines) diagrams of eutectoid steel. Four cooling rates from different positions on a Jominy end-quench specimen are superimposed on the CCT diagram
Comparison of IT diagram for steel with German designation 42 CrMo 4 (0.38% C, 0.99% Cr, and 0.16% Mo) determined by dilatometry
Stress-relief heat treating is the uniform heating of a structure, or portion, to a suitable temperature below the transformation range (Ac1 for ferritic steels), holding at this temperature for a predetermined period of time, followed by uniform cooling. Care must be taken to ensure uniform cooling, particularly when a component is composed of variable section sizes. If the rate of cooling is not constant and uniform, new residual stresses can result that are equal to or greater than those that the heat-treating process was intended to relieve. Stress-relief heat treating can reduce distortion and high stresses from welding that can affect service performance. The presence of residual stresses can lead to stress-corrosion cracking (SCC) near welds and in regions of a component that has been cold strained during processing. Residual stresses in a ferritic steel cause significant reduction in resistance to brittle fracture
Examples of the causes of residual stresses: (a) Thermal distortion in a structure due to heating by solar radiation. (b) Residual stresses due to welding. (c) Residual stresses due to grinding.
Relationship between time and temperature in the relief of residual stresses in steel.
Typical stress-relief temperatures for low-alloy ferritic steels are between 595 and 675 C (1100 and 1250 F). For high-alloy steels, these temperatures may range from 900 to 1065 C (1650 to 1950 F). For high-alloy steels, such as the austenitic stainless steels, stress relieving is sometimes done at temperatures as low as 400 C (750 F). However, at these temperatures, only modest decreases in residual stress are achieved. Residual stresses can be significantly reduced by stress-relief heat treating those austenitic materials in the temperature range from 480 to 925 C (900 to 1700 F). At the higher end of this range, nearly 85% of the residual stresses may be relieved. Stress-relief heat treating in this range, however, may result in sensitizing susceptible material. This metallurgical effect can lead to SCC in service. Frequently, solution-annealing temperatures of about 1065 C (1950 F) are used to achieve a reduction of residual stresses to acceptably low values.
NORMALIZING OF STEEL
NORMALIZING OF STEEL is a heattreating process that is often considered from both thermal and microstructural standpoints. Normalizing is an austenitizing heating cycle followed by cooling in still or slightly agitated air. Typically, the work is heated to a temperature about 55 C (100 F) above the upper critical line of the iron-iron carbide phase diagram, as shown in Fig. that is, above Ac3 for hypoeutectoid steels and above Acm for hypereutectoid steels. To be properly classed as a normalizing treatment, the heating portion of the process must produce a homogeneous austenitic phase (face-centered cubic, or fcc, crystal structure) prior to cooling. Typical normalizing temperatures for many standard steels are given in Table 1.
Table 1 Typical normalizing temperatures for standard carbon and alloy steels
Grade Temperature(a) Grade Temperature(a) Grade Temperature(a) Grade Temperature(a)
1090
830
1525
3310
925
1700
4140
870
1600
1015
915
1675
1095
845
1550
4027
900
1650
4142
870
1600
1020
915
1675
1117
900
1650
4028
900
1650
4145
870
1600
1022
915
1675
1137
885
1625
4032
900
1650
4147
870
1600
1025
900
1650
1141
860
1575
4037
870
1600
4150
870
1600
1030
900
1650
1144
860
1575
4042
870
1600
4320
925
1700
1035
885
1625
4047
870
1600
4337
870
1600
1040
860
1575
1330
900
1650
4063
870
1600
4340
870
1600
1045
860
1575
1335
870
1600
4118
925
1700
4520
925
1700
1050
860
1575
1340
870
1600
4130
900
1650
4620
925
1700
1060
830
1525
3135
870
1600
4135
870
1600
4621
925
1700
1080
830
1525
3140
870
1600
4137
870
1600
4718
925
1700
Grade
Temperature(a)
Grade
Temperature(a)
Grade
Temperature(a)
Grade
Temperature(a)
4720
925
1700
5155
870
1600
8642
870
1600
9840
870
1600
4815
925
1700
5160
870
1600
8645
870
1600
9850
870
1600
4817
925
1700
6118
925
1700
8650
870
1600
50B40
870
1600
4820
925
1700
6120
925
1700
8655
870
1600
50B44
870
1600
5046
870
1600
6150
900
1650
8660
870
1600
50B46
870
1600
5120
925
1700
8617
925
1700
8720
925
1700
50B50
870
1600
5130
900
1650
8620
925
1700
8740
925
1700
60B60
870
1600
5132
900
1650
8622
925
1700
8742
870
1600
81B45
870
1600
5135
870
1600
8625
900
1650
8822
925
1700
86B45
870
1600
5140
870
1600
8627
900
1650
9255
900
1650
94B15
925
1700
5145
870
1600
8630
900
1650
9260
900
1650
94B17
925
1700
5147
870
1600
8637
870
1600
9262
900
1650
94B30
900
1650
5150
870
1600
8640
870
1600
9310
925
1700
94B40
900
1650
Comparison of time-temperature cycles for normalizing and full annealing. The slower cooling of annealing results in higher temperature transformation to ferrite and pearlite and coarser microstructures than does normalizing.
All of the standard low-carbon, medium-carbon, and high-carbon wrought steels can be normalized, as well as many castings. Many steel weldments are normalized to refine the structure within the weld-affected area. Austenitic steels, stainless steels, and maraging steels either cannot be normalized or are not usually normalized. Tool steels are generally annealed by the steel supplier.
Normalization may increase or decrease the strength and hardness of a given steel in a given product form, depending on the thermal and mechanical history of the product. Actually, the functions of normalizing may overlap with or be confused with those of annealing, hardening, and stress relieving. Improved machinability, grain refinement, homogenization, and modification of residual stresses are among the reasons normalizing is done.
in.) 25 in
NiCrMo
Tensile strength, 620 MPa (90 ksi); 0.2% yield strength, 415 MPa (60 ksi); elongation in 50 mm, or 2 in., 20%; reduction in area, 40%
Forged flange
4137
Valve-bonnet forging
4140
Annealing of Steel
ANNEALING is a generic term denoting a treatment that consists of heating and holding at a suitable temperature followed by cooling at an appropriate rate, primarily for the softening of metallic materials.
Generally, in plain carbon steels, annealing produces a ferrite-pearlite microstructure. Steels may be annealed to facilitate cold working or machining, to improve mechanical or electrical properties, or to promote dimensional stability. The following equations will give an approximate critical temperature for a hypoeutectoid steel
Ac1(C) = 723 - 20.7(% Mn) - 16.9(%Ni) + 9.1(%Si) - 16.9(%Cr) Standard deviation = 11.5 C Ac3(C) = 910 - 203 %C - 15.2(% Ni) + 44.7(% Si) + 104(% V) + 31.5(% Mo) Standard deviation = 16.7 C
Annealing Cycles
In practice, specific thermal cycles of an almost infinite variety are used to achieve the various goals of annealing. These cycles fall into several broad categories that can be classified according to the temperature to which the steel is heated and the method of cooling used. The maximum temperature may be below the lower critical temperature, A1 (subcritical annealing); above A1 but below the upper critical temperature, A3 in hypoeutectoid steels, or Acm in hypereutectoid steels (intercritical annealing); or above A3 (full annealing).
Subcritical Annealing
Subcritical annealing does not involve formation of austenite. The prior condition of the steel is modified by such thermally activated processes as recovery, recrystallization, grain growth, and agglomeration of carbides. In as-rolled or forged hypoeutectoid steels containing ferrite and pearlite, subcritical annealing can adjust the hardness of both constituents, but excessively long times at temperature may be required for substantial softening. The subcritical treatment is most effective when applied to hardened or cold-worked steels, which recrystallize readily to form new ferrite grains. The rate of softening increases rapidly as the annealing temperature approaches A1. Cooling practice from the subcritical annealing temperature has very little effect on the established microstructure and resultant properties.
lntercritical Annealing
Austenite begins to form when the temperature of the steel exceeds A1. The solubility of carbon increases abruptly (nearly1%) near the A1 temperature. In hypoeutectoid steels, the equilibrium structure in the intercritical range between A1 and A3 consists of ferrite and austenite, and above A3 the structure becomes completely austenitic.
In hypereutectoid steels, carbide and austenite coexist in the intercritical range between A1 and Acm; and the homogeneity of the austenite depends on time and temperature. The degree of homogeneity in the structure at the austenitizing temperature is an important consideration in the development of annealed structures and properties. The more homogeneous structures developed at higher austenitizing temperatures tend to promote lamellar carbide structures on cooling, whereas lower austenitizing temperatures in the intercritical range result in less homogeneous austenite, which promotes formation of spheroidal carbides.
A common annealing practice is to heat hypoeutectoid steels above the upper critical temperature (A3) to attain full austenitization. The process is called full annealing.
4047
4063 4130 4135 4137 4140 4145 4147 4150
790-845
790-845 790-845 790-845 790-845 790-845 790-845 790-845 790-845
1450-1550
1450-1550 1450-1550 1450-1550 1450-1550 1450-1550 1450-1550 1450-1550 1450-1550
201
223 174 ... 192 197 207 ... 212
4161
790-84
1450-155
...
AISI
4337 4340 AISI
Temp
790-84 790-84 Temp 1450-155 1450-155 Hardness
Hardness
... 223
50B40
50B44 5046 50B46 50B50 50B60
815-870
815-870 815-870 815-870 815-870 815-870
1500-1600
1500-1600 1500-1600 1500-1600 1500-1600 1500-1600
187
197 192 192 201 217
5130
5132
790-845
790-845
1450-1550
1450-1550
170
170
AISI
5132 5135 5140
Temp
790-845 815-870 815-870 1450-1550 1500-1600 1500-1600
Hardness
170 174 187
5145 5147
5150 5155 5160 51B60 50100
815-870 815-870
815-870 815-870 815-870 815-870 730-790
1500-1600 1500-1600
1500-1600 1500-1600 1500-1600 1500-1600 1350-1450
197 197
201 217 223 223 197
51100
730-790
1350-1450
197
8637
815-870
1500-1600
192
8655
8660 8740 8742 9260 94B30 94B40
815-870
815-870 815-870 815-870 815-870 790-845 790-845
1500-1600
1500-1600 1500-1600 1500-1600 1500-1600 1450-1550 1450-1550
223
229 202 ... 229 174 192
Process Annealing
As the hardness of steel increases during cold working, ductility decreases and additional cold reduction becomes so difficult that the material must be annealed to restore its ductility. Such annealing between processing steps is referred to as in-process or simply process annealing. It may consist of any appropriate treatment. In most instances, however, a subcritical treatment is adequate and least costly, and the term "process annealing" without further qualification usually refers to an in-process subcritical anneal. is often necessary to specify process annealing for parts that are cold formed by stamping, heading, or extrusion. Hot worked high-carbon and alloy steels also are process annealed to prevent them from cracking and to soften them for shearing, turning, or straightening.
Types of Furnaces
Types of Furnaces Furnaces for annealing are of two basic types: 1. Batch furnaces and 2. Continuous furnaces. Batch-type furnaces are necessary for large parts such as heavy forgings and often are preferred for small lots of a given part or grade of steel and for the more complex alloy grades requiring long cycles. Specific types of batch furnaces include car-bottom, box, bell, and pit furnaces. Annealing in bell furnaces can produce the greatest degree of spheroidization (up to 100%). However, the spheroidizing cycles in bell furnaces are long and last from 24 to 48 h depending on the grade of material being annealed and the size of the load.
Continuous furnaces such as roller-hearth, rotary-hearth, and pusher types are ideal for isothermal annealing of large quantities of parts of the same grade of steel. These furnaces can be designed with various individual zones, allowing the work to be consecutively brought to temperature, held at temperature, and cooled at the desired rate. Continuous furnaces are not able to give complete spheroidization and should not be used for products that require severe cold forming..
A low-carbon sheet steel in the (a) as-cold-rolled unannealed condition, (b) partially recrystallized annealed condition, and (c) fully recrystallized annealed condition. Marshall's etch. 1000
(a) In the as-received hot-rolled condition, microstructure is blocky pearlite. Hardness is 87 to 88HRB. (b) In the partially spheroidized condition following annealing in a continuous furnace. Hardness is 81 to 82 HRB. (c) In the nearly fully spheroidized condition following annealing in a bell furnace. Hardness is 77 to 78 HRB.