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6: Heat Treating of Alloy Steels1, 2

Topics: 1. What are Alloy Steels? 2. Effects of Alloying Elements 3. Hardenability of Alloy Steels 4. Heat Treating Procedures 5. Austempering and Martempering Treatments 1. WHAT ARE ALLOY STEELS? Alloy steels contain alloying elements other than carbon Alloy steels contain elements exceed the limits: Mn: 1.65%, Si: 0.60%, Cu: 0.60% Other elements are contained in alloy steels, such as: Al, B, Cr, Co, Mo, Ni, Ti, V, and Zr Alloy steels also are identified by AISI coding system The first two digits indicate the different grades of alloy steel, as shown in Table 1 The last two digits indicate the middle range of carbon content A prefix of letter E is used to indicate that the steel is made in the basic electric furnace Steels w/o prefix are manufactured by the basic open hearth or basic oxygen process Steels containing 5 wt % total noncarbon additions are called low-alloy steels, while those having 5 wt % total noncarbon additions are called high-alloy steels When B or Pb is specified, a letter B or L is inserted; such as, 41B30 or 41L30 Alloy steels have specified applications. Steel 52100 is extensively used in antifriction bearings, and 9200 series for springs and application where shock resistance is a factor Table 1. Numerical Designation of Alloy Steels


Practical Heat Treating, J. L. Dossett and H. E. Boyer, 2nd Ed., Mat. Park, OH, USA: ASM Intl, 2006 2 Steel Heat Treatment: Metallurgy and Technologies, Edited by George E. Totten, CRC Press 2007
H. Kandil Lect 6: Heat Treatment of Alloy Steels (MDE 355) 1/10

H-Steels Steels carrying the suffix letter H, e.g. 4140H, meet standard hardenability requirements AISI-SAE Compositions Approx. 64 standard compositions of alloy steels are listed by AISI-SAE Composition of some alloy steels are listed in Table 2, p. 124 Free-Machining Alloy Steels Free-machining additives; e.g. Pb and S, lower steel quality However, most alloy steels are available with addition of lead or sulfur by special order

2. EFFECT OF ALLOYING ELEMENTS Alloy steels include Mn, Si, Ni, Cr, Mo, and V Hardenability controls the mechanical properties that can be obtained by heat treatment Manganese (Mn) Mn is a carbide former It slows the transformation, thus increasing hardenability It has the ability to counter hot shortness, that is, the tendency to tear when hot formed Mn combines preferentially with sulfur forming MnS which eliminates hot shortness

Silicon (Si) Si slightly retards critical cooling rate, thereby increasing hardenability Si-steels have considerable structure applications Si improves shock resistance and is used where impact is a problem It is also used as an alloy in spring steels (9260)

Nickel (Ni) Ni shifts the nose of the TTT diagram to the right, thus increasing hardenability It lowers the transformation temperature to the point that steel may become austenitic at RT when large amounts of Ni is used It toughens ferritic-pearlitic steels, esp. at low temp., and gives good fatigue resistance Ni greatly increases corrosion and oxidation resistance Chromium (Cr) It has a marked effect in slowing the rate of austenite transformation, i.e., increases the hardenability of any steel It greatly increases oxidation and corrosion resistance when added in large amount
H. Kandil Lect 6: Heat Treatment of Alloy Steels (MDE 355) 2/10

Molybdenum (Mo) Like Cr, greatly slows the transformation, thus increasing hardenability Vanadium (V) V is a strong deoxidizing agent that promotes fine grain size It is a powerful carbide former that slows the transformation It is specified only in the 61XX steels Effect of alloying elements on eutectoid temperature The influence of the most important alloying elements on the position of eutectoid temperature is illustrated in Figure 1

Fig. 1 Effect of alloying elements on the eutectoid transformation temp.

Effect of alloying elements on austenite transformations Alloying elements are divided into two groups according to their distribution in steel: 1. Elements that do not form carbides in steel, such as Ni, Si, Co, Al, Cu, and N 2. Elements that form stable carbides in steel, such as Cr, Mn, Mo, W, V, Ti, Zr, and Nb Alloying elements that dissolve only in ferrite and cementite without the formation of special carbides have a quantitative effect on the transformation processes (Fig. 2). Cobalt speeds up a transformation but the majority of elements, including Ni, Si, Cu, Al, etc., slow it down.

Fig. 2 Austenite transformation diagrams. (a) C-steel and steel alloyed with noncarbide-forming elements; (b) C-steel and steel alloyed with carbide-forming elements

H. Kandil

Lect 6: Heat Treatment of Alloy Steels (MDE 355)


Carbide-forming elements produce both quantitative and qualitative changes in the kinetics of isothermal transformations Steels alloyed with carbide-forming elements (Cr, Mo, Mn, W, V, etc.) have two maxima of the austenite isothermal precipitation rate separated by a region of relative stability of undercooled austenite (Figure 2). The isothermal precipitation of austenite has two clearly defined intervals of transformation to a: (1) Lamellar structure (pearlite transformation) and (2) Needle-like structure (bainite transformation) Effect of alloying elements on martensite transformation As in carbon steels, the martensite transformation in alloy steels takes place under rapid cooling from temperatures higher than the equilibrium temperature of the transformation (A1) Co and Al elevate the martensite start temperature, Si has little if any effect, and all the other elements decrease Ms (Fig.3)

Fig. 3 The influence of the content of (a) carbon and (b) alloying elements at 1% C on the martensite point position.

The quantitative influence of alloying elements is approx. as follows (per 1 wt% of alloying element):

The martensite start temperature Ms of medium-carbon alloy steels can be estimated using empirical formula: MH (oC) = 520 -320 (%C) 50 (%Mn) 30 (%Cr) 20 [%( Ni+Mo)] 5 [%( Cu+Si)], where % C, % Mn, etc. are the contents of the corresponding elements in wt %
H. Kandil Lect 6: Heat Treatment of Alloy Steels (MDE 355) 4/10

Effect of alloying elements on retained austenite The transformation of austenite to martensite is never complete The end of transformation corresponds to the temperature Mf . At this temperature a certain amount of austenite is still left (retained austenite) Alloying elements that lower and raise the martensite start point increase and decrease the amount of retained austenite, respectively (Figure 4)

Fig. 4 The influence of alloying elements on the amount of retained austenite in quenched steel (1% C).

The largest amount of retained austenite is precipitated due to Mn, Cr, and Ni Similar influence is obtained of these elements on the martensite range(Fig. 5)

Fig. 5 The influence of alloying elements on the martensite range

The influence of carbon on the amount of retained austenite is much stronger than that of alloying elements An increase in the C content of CrNi steel from 0.4 to 0.6% increases the amount of retained austenite to ~8.5% after quenching An increase in the Ni content of the same steel from 1 to 4% brings the amount of retained austenite to ~6% only Carbon promotes the greatest retention of austenite during quenching and is especially unfavorable for low-alloy tool steels.

H. Kandil

Lect 6: Heat Treatment of Alloy Steels (MDE 355)


Effect of alloying elements transformation diagrams There are 6 basic diagrams of -transformation, depending on alloying of steel (Fig. 6.) In carbon steels and some low-alloy steels containing basically noncarbide-forming elements such as Ni, Si, and Cu, the isothermal precipitation is characterized by C-shaped curves with one maximum (Fig. 6a) The pearlite and intermediate stages are not separated When these steels are subjected to continuous cooling, three types of structures martensite, martensite and a ferritecarbide mixture, and only a ferritecarbide mixturecan be formed depending on the cooling rate.

Fig. 6 (a) Carbon and low-alloy steels containing no carbide-forming elements; (b)

alloy steels (up to 0.40.35% C) containing carbide-forming elements; (c) steels alloyed with Cr, Ni, Mo, and Wand having a low content of carbon (up to 0.20.25% C); (d) alloy steels containing carbide-forming elements (over 0.40.5% C); (e) high-alloy steels with a high content of Cr; (f) high-alloy austenitic steels.
1 1

2 Transformation finish Transformation start 3 Start of formation of a ferritecarbon mixture 4 Start of formation of the intermediate transformation products 5 Start of carbide precipitation.

H. Kandil

Lect 6: Heat Treatment of Alloy Steels (MDE 355)


3. HARDENABILITY OF ALLOY STEEL Small amounts of two or more elements is more effective than large amounts of a single element For example, Cr is generally used with Ni and Mo Alloy steels are used for their greater hardenability However, carbon steels are better used in some applications Hardenability bands for three widely used alloy steels are presented in Fig. 7

Fig. 7 Effect of total content on hardenability of three alloy steels

4037H steel has Mo of 0.2-0.3 wt% (Fig. 7a), 4140H steel has Cr addition (Fig. 7b), and 4340H steel (Fig. 7c) has three alloys; Ni, Cr, and Mo Boron effect on hardenability The marked effect of B on hardenability of 5160H steel is shown in Fig. 8 The boron-treated alloy steel offers greater hardenability without using the more highly alloyed and more expensive grades of steels

Fig. 8 Effect of born on hardenability of 5160H alloy steels H. Kandil Lect 6: Heat Treatment of Alloy Steels (MDE 355) 7/10

4. HEAT TREATING PROCEDURES Techniques used for heat treating alloy steels are not much different from those used for carbon steels Alloy steels containing 0.25 wt% C are heat treated by one of case hardening processes Alloy steels having higher C content are austenitized by heating above the upper transformation temp., followed by quenching to near RT, and finally tempered to desired hardness level Major differences in heat treating alloy steels compared with carbon steels are: 1. Temperatures used for normalizing, annealing, and austenitizing are 12-42 oC higher than for carbon steels 2. As alloy content increases, annealing temperature must be much slower 3. Severe quench mediums are rarely used for alloy steels due to their high hardenability. Alloy steels are also more susceptible to cracking from severe quenching Recommended heat treating practice Various heat treatments, such as, normalizing, annealing, hardening, and tempering for 4037/4037H, 4140/4140H,4340/4340H, and E52100 steels are discussed on p. 129-33 Effects of tempering The decrease in hardness due to tempering at higher temp. is more appreciable in alloy steels than in carbon steels The hardness of asquenched alloy steels is a function of carbon content, Fig. 9 High hardness value of 65 HRC is reported for E52100 steel (Fig. 9d)

Fig. 9 Effect of tempering temperature on hardness of four alloy steels. H. Kandil Lect 6: Heat Treatment of Alloy Steels (MDE 355) 8/10

5. AUSTEMPERING AND MARTEMPERING TREATMENTS Austempering Austempering treatment is more suitable for many grades of alloy steels than C-steels The thicker sections of alloy steels can be successfully austempered Martempering Martempering treatment describes an elevated temperature quenching procedure aimed at reducing cracks, distortion, or residual stresses and the proper term is marquenching Martempering of steels consists of: 1. Quenching from the austenitizing temp. into a hot fluid medium at a temp. above Ms 2. Holding in quenching medium 3. Cooling (usually in air) to RT Formation of martensite occurs throughout the steel during cooling to RT The steel is then tempered, as the microstructure after martempering is brittle Fig. 10 shows both the conventional quenching (a) and martempering (b)

Fig. 10 Time-temperature-transformation diagrams with superimposed curves showing quenching and tempering. (a) Conventional process. (b) Martempering. (c) Modified martempering.

The advantage of martempering is the reduced thermal gradient bet. surface & center Residual stresses developed during martempering is much less than in conv. Quenching Steels of sufficient hardenability to harden by oil quench can be successfully martempered

H. Kandil

Lect 6: Heat Treatment of Alloy Steels (MDE 355)


Modified Martempering Modified martempering differs from standard martempering only in that quenching takes place below Ms temperature (Fig. 10c) The lower quench temperature increases the severity of quenching This treatment is important for steels of lower hardenability that requires faster cooling to harden to sufficient depth, or when Ms is high and some bainite is not required Modified martempering is applicable to a greater range of steel compositions than is the standard process Hot oil and molten nitrate-nitrite salts are used for modified martempering at 175 oC _______________________________________________________________________________________________________________ IMPORTANT NOTES1: 1. Steels have one or more of 3 elements Cr, Mo, or Ni, total of 5 wt% are called Low-alloy steels. There are three groups: Mo-steels (4XXX), Cr-steels (5XXX), and triple-alloyed steels (8XXX) 2. Mn is present in all steels to overcome problems with S embrittlement. S cannot be economically removed. Fe + S FeS precipitates at grain boundary causing brittle grain fracture during hot deformation (hot shortness). Mn replaces FeS with MnS which overcomes hot shortness. 3. Addition of Mn, Cr, Mo, and NI changes the position of A3, A1, and Acm transformation lines, as shown in Fig. 11.
Fig. 11 Alloying elements such as Mo, Cr, or Ni cause the A3 and Acm lines to shift and the A1 to split into A1 (L) and A1 (U).

4. The majority of elements, including Ni, Si, Cu, Al, etc., slows down the austenite transformation, while Cobalt speeds it up. 5. Co and Al elevate the martensite start temperature, Si has little if any effect, and all the other elements decrease Ms

_______________________________________________________________________________________ 1 John D. Verhoeven, Steel Metallurgy for the Non-Metallurgist, ASM Intl, 2007.

H. Kandil

Lect 6: Heat Treatment of Alloy Steels (MDE 355)