24.

Case Hardening
Numerous industrial applications require a hard wear-resistant surface called the case and a

relatively soft, tough inside called the core. There are five principal methods of casehardening. 1.Carburizing 2.Nitriding 3.Cyaniding or carbonitriding 4.Flame Hardening 5.Induction Hardening

The first three methods change the chemical composition, carburizing by the addition of carbon, nitriding by the addition of nitrogen and cyaniding by addition of both carbon and nitrogen. The last two methods do not change the chemical composition of the steel and are essentially shallow-hardening methods. In flame and induction hardening the steel

must be capable of being hardened, therefore, the carbon content must be about 0.30 % or higher. 25. Carburizing: This is the oldest and one of the cheapest methods of case hardening. A low-carbon steel, usually about 0.20 % carbon or lower, is placed in an atmosphere that contains substantial amounts of carbon monoxide. The usual

carburizing temperature is 1700 F. At this temperature, the following reaction takes place:

where represents carbon dissolved in austenite . The maximum amount of carbon that can be dissolved in FeC austenite at 1700 F is indicated on the iron-iron carbide equilibrium diagram at the line. Therefore very quickly, a surface layer of high carbon (about 1.2 %) is built up. Since the core is ofA carbon content, the low carbon atoms trying to reach cm equilibrium will begin to diffuse inward. The rate of diffusion of carbon in austenite, at a given temperature, is dependent upon

Fe  2CO p FeC  CO2
Acm

The diffusion coefficient and the carbon-concentration gradient. Under known and standard operating conditions, with nthe surface at a fixed carbon concentration, the form of the carbon gradient may be predicted, with reasonable accuracy, as a function of elapsed time. After diffusion, has taken for the required amount of time depending upon the case depth desired,

the part is removed from the furnace and cooled.If the part is furnace-cooled and examined microscopically, the carbon gradient will be visiblein the gradual change of the structure. At the surface is the hypereutectoid zone consisting of pearlite with a white cementite network, followed by the eutectoid zone of only pearlite and finally the hypoeutectoid zone

of pearlite and ferrite, with the amount of ferrite increasing until the core is reached. (This is illustrated in Fig: 8-70). Analysis to determine carbon content is made and results can be plotted graphically as in Fig: 8-71. The relation of time and temperature to case depth is shown in Fig: 8-72 and Table: 8-7.

The carburizing equation given previously, Fe  2CO p FeC  CO2 is reversible and may proceed to the left, removing carbon from the surface layer if the steel is heated in an atmosphere containing carbon dioxide. This is called decarburization. Decarburization is a problem primarily with highcarbon steels and tool steels. The surface, depleted of carbon, will not transform to martensite on subsequent hardening, and the

steel will be left with a soft skin . For many tool applications, the stresses to which the part is subjected in service are maximum at or near the surface, so decarburization is harmful. Fig: 8-73 shows decarburization on the surface of a high-carbon steel. Decarburization may be prevented by using an endothermic gas atmosphere

in the furnace to protect the surface of the steel from oxygen, carbon dioxide and water vapour. Commercial carburizing may be accomplished by means of packed carburizing, gas carburizing and liquid carburizing. In packed carburizing, the work is surrounded by a carburizing compound

in a closed container. The container is heated to the proper temperature for the required amount of time and then slowcooled. This is essentially a batch method and does not lend itself to high production. Commercial carburizing compunds usually consist of hardwood charcoal, coke and about 20 % barium carbonate as an energizer. The carburizing compound is in

the form of coarse particles or lumps, so that, when covered is sealed on the container, sufficient air will be trapped inside to form carbon monoxide. The principal advantages of packed carburizing are that it does not require the use of prepared atmosphere and that it is efficient and economical for individual processing of small lots of parts or of large, massive

parts. The disadvantage are that it is not well suited in the production of thin carburized cases that must be controlled to close tolerances. It cannot provide the close control of surface carbon that can be be obtained by gas carburising; parts cannot be direct-quenched from the carburizing temperature; and excessive time is consumed in the heating and cooling the charge. Because of the inherent variation in case depth and cost of packing materials, pack

carburizing is not used on work requiring a case depth of less than 0.03 in., and to tolerances are at least 0.010 in. Gas carburizing may either batch or continuous and lends itself better to production heat treatment. The steel is heated in contact with carbon monoxide and/or a hydrocarbon which is readily decomposed at the carburizing temperature. The hydrocarbon may be methane, propane, natural gas or vapourized fluid

hydrocarbon. Commercial practice is to use a carrier gas, such as obtained from an endothermic generator and enrich it with one of the hydrocarbons. It was mentioned previously that carburized parts will usually have a thin outer layer of high carbon. There are two reasons why it may be desirable to avoid this hypereutectoid layer. First, if the piece is cooled

slowly from the carburizing temperature, a proeutectoid cementite network will form at the grain boundaries. On subsequent hardening, particularly if the steel is heated below the Acm line, some grain boundary cementite will remain in the finished piece and is a frequent cause of failure. Second, the hypereutectoid surfacecarbon content will increase the amount of retain austenite. Therefore, if the steel is highly alloyed, the carbon content of the case should

be no greater than the eutectoid content of 0.80 % carbon. By using a diffusion period , during which the gas is turned off but the temperature maintained, gas carburizing allows the surface carbon to be reduced to any desired value. Use of the diffusion period also produces much cleaner work by dissipation of carbon deposit (soot)

during the time when no gas is flowing. Gas carburizing allows quicker handling by direct quenching, lower cost, cleaner suroundings, closer quality control, and greater flexibility of operation compared to packed carburizing. Liquid carburizing is a method of casehardening steel by placing it in bath of

Molten cyanide so that carbon will diffuse from the bath into the metal and produce a case comparable to one resulting from pack or gas carburizing. Liquid carburizing may be distinguished from cyaniding by the character and composition of the case produced. The cyanide case is higher in nitrogen and lower in carbon; the reverse is true of liquid carburized cases. Cyanide

cases are seldom to depth greater than 0.010 in.; liquid-carburizing baths permit cases as deep as 0.25 in. Low temperature salt baths (light-case) usually contain a cyanide content of 20 %and operate between 1550 and 1650 F. These are best suited for case depths up to 0.030 in. High temperature salt baths (deepcase) usually have a cyanide content of 10

% and operate between between 1650 and 1750 F. High-temperature salt baths are used for producing case depths of 0.030 to 0.120 in., although it is possible to go as high as 0.250 in. In general, liquid carburizing is best suited to small and medium-size parts, since large parts are difficult to process in salt baths. The advantages of liquid carburizing are

1)freedom from oxidation and sooting problems 2)Uniform case depth and carbon content 3)A rapid rate of penetration, and 4)The fact that the bath provides high thermal conductivity, thereby reducing the time required for the steel to reach the carburizing temperature.

Disadvantages include: 1)Parts must be thoroughly washed after treatment to prevent rusting 2)Regular checking and adjustment of the bath composition is necessary to obtain uniform case depth; 3)Some shapes cannot be handled because they either float or will cause excessive

dragout of salt; and 4)Cyanide salts are poisonous and require careful attention to safety. 26. Heat Treatment after Carburizing Since steel is carburized in the austenite region, direct quenching from the carburizing temperature will harden both the case and core if the cooling rate is

greater than the critical cooling rate. Direct quenching of coarse-grain steels often leads to brittleness and distortion, so the treatment should be applied only to finegrain steels. Alloy steels are rarely used in the direct-quenched condition because of large amount of retained austenite in the hardened case. Fig: 8-74 shows a diagrammatic representation of various

hardening treatments for carburized steels together with case and core properties. When a carburized part is hardened, the case will appear as a light martensite zone followed by a darker transition zone (Fig: 8-75). The hard case or effective case is measured from the outer edge to the middle of the dark zone. From the nature of carbon gradient, the hard case contains

the portion of the case above 0.40 % carbon and is approximately equal to twothirds of the total case. Hardness-traverse measurements may also be used to determine the depth of the effective case since the middle of the transition zone is at approximately Rockwell C 50.

28. Nitriding: This is process for case hardening of alloy steel in an atmosphere consisting of a mixture in suitable proportions of ammonia gas and dissociated ammonia. The effectiveness of process depends on the formation of nitrides in the steel by reaction of nitrogen with certain alloying elements. Although at suitable temperatures and with the proper

atmosphere all steels are capable of forming iron nitrides, the best results obtained in those steels that contain one or more of the major nitride-forming alloying elements. These are aluminum, chromium and molybdenum. The nitrogen must be supplied in the atomic or nascent form, molecular nitrogen will not react.

The parts to be nitrided are placed in an airtight container through which the nitriding atmosphere is supplied continuously while the temperature is raised and held between 925 and 1050 F. The nitriding cycle is quite long, depending upon the case depth desired. As shown in Fig: 8-77, a 60-h cycle will give a case depth of ~0.024 in at 975 F.

A nitrided case consists of two distinct zones. In the outer zone the nitrideforming elements, including iron, have been converted to nitrides. This region, which varies in thickness up to a maximum of about 0.002 in., is commonly known as the white layer because of the appearance after the nital etch. In the zone beneath this white layer, alloy

nitrides only have been precipitated. A typical microstructure, illustrated in Fig: 878b, shows the white layer and underlying nitride case. At lower magnification, illustrated in Fig: 8-78a, the lighter core structure can be seen beneath the nitride case. The depth of nitride case is determined by the rate of diffusion of nitrogen from the white layer to the region

beneath. The nitriding medium, therefore, needs to contain only sufficient active nitrogen to maintain the white layer. Any increase beyond this point serves to increase the depth of white layer and does not affect the thickness of the inner layer. The double-stage process, is also known as the Floe process, has the advantage of reducing the thickness of the white nitride

layer. In the first stage of the double-stage process, the ammonia dissociation is held at 20 % for a period of 5 to 10 h at 975 F. During this period the white layer is established and the useful nitride starts to form by diffusion of nitrogen out of it. In the second stage, the ammonia dissociation is increased to 83 to 86 %, and the temperature is usually raised to 1025 to 1050 F.

During the second stage, the gas composition is such that it maintains only a thin white layer on the finished part. A typical structure of the case produced by this method is shown in Fig: 8-79. The white layer is brittle and tends to chip or spall from the surface if it has a thickness in excess of 0.0005 in. Thicker white layers produced by the single-stage

process must be removed by grinding or lapping after nitriding. This very thin white layer obtained by this method, usually from 0.0002 to 0.0004 in., in depth, does not chip or pit, and the frictional characteristics of the surface are excellent. This layer also has good wear-in properties and may be expected to improve corrosion resistance.

Hardest cases ~R/C 70 are obtained with the aluminum alloy steels known as Nitroalloys. These are medium-carbon steels containing also chromium and molybdenum. For some applications where lower hardness is acceptable, medium-carbon standard steels containing chromium and molybdenum (AISI 4100, 4300 series) are used. Nitriding has also

been applied to stainless steels and tool steels for certain applications Some complex parts which cannot be casehardened satisfactorily by carburizing have been nitrided without difficulty. Wear resistance is an outstanding characteristic of the nitrided case and is responsible for it selection in most applications. The hardness of nitrided case is unaffected by

heating to temperatures below the original nitriding temperature. Substantial hardness is retained to at least 1150 F in marked contrast with carburized case, which begins to lose its hardness at relatively low temperatures. Fatigue resistance is also an important advantage. Tool marks and surface scratches have little effect on the fatigue properties of

nitrided steels. Although it is sometimes indicated that nitriding improves the corrosion resistance of a steel, this is true only if the white layer is not removed. Corrosion resistance of stainless steels is reduced considerably by nitriding, a factor which must be taken into account when nitrided stainless steel are used in corrosive atmospheres.

Disadvantages of nitriding include the long cycles usually required, the brittle case, use of special alloy steels if maximum hardness is to be obtained, cost of ammonia atmosphere, and the technical control required. Nitriding is used extensively for aircraft engine parts such as cams, cylinder liners, valve stems, shafts and piston rods.

31. Residual Stresses: These are stresses that remain in the part after force has disappeared. Residual stresses always arise from a nonuniform plastic deformation. In the case of heat treatment, this nonuniform plastic deformation may be caused by a temperature gradient or phase change or usually, a combination of both factors during cooling.

Consider the effect of temperature gradient alone. Under the effect of size and mass, that during quenching the surface is cooled more rapidly than the inside. This results in a temperature gradient across the cross section of the piece or the temperature difference between the surface and the centre. If the stress exceeds the ultimate strength of

the material, cracking will occur. This is what usually happens when glass is subjected to a large temperature difference. In case of steel, however, thermal stresses alone very rarely leading to cracking. If the stress is below the yield strength of the steel, the stress will be borne elastically. Austenite, being f.c.c. (face centred cubic),

is a denser structure than any of its transformation products. Therefore when austenite changes to ferrite, pearlite, bainite and martensite, an expansion occurs. The austenite-to-martensite expansion is the largest and amounts to a volume increase of about 4.6 % . The martensite expansion will be greater the lower the M s temperature. Fig: 8-83 shows
Mf

the changes in length, during cooling of a smalldiameter cylinder as measured in a dilatometer. The piece is austenitic at the elevated temperature, and normal contraction of the austenite takes place until the M s temperature is reached. Between the M s and the M f the transformation of austenite to martensite causes an expansion in length. After the temperature, the martensite undergoes normal contraction.

Let us now consider the combined effect of temperature gradient and phase change for the two possibilities: (1) throughhardened steel and (2) shallow-hardened steel Fig: 8-84 shows the surface and centre cooling curves superimposed on the I-T diagram for the through-hardened steel. Since the centre-cooling rate exceeds the

critical cooling rate, the part will be fully martensitic across its diameter. During the first stage, to time t1 , the stresses present are due to the temperature gradient. The surface, prevented from contracting as much as it should by the centre, will be in tension while the centre will be in compression. During the second stage, between times t and t the surface,
t1 2

having reached the M temperature, transforms to martensite and expands. The centre, however, is undergoing normal contraction due to cooling. The centre contracting will prevent the surface from expanding as much as it should, and the surface will tend to be in compression while the centre will tend to be in tension. After t2 the surface has reached room
s

t2

temperature and will be a hard, brittle, martensitic structure. During the third stage, the centre finally reaches the M temperature and begins to expand, forming martensite. The centre, as it expands, will try to pull the surface along with it, putting the surface in tension. The stress condition in the three stages is summarized below:
s

To initiate and propagate a crack it is necessary for tensile stress to be present. Let us examine the three stages with regard to the danger of cracking. In the first stage, the surface is in tension, however, it is austenitic and if the stress is high enough rather than cracking it will deform plastically, relieving the stress. In the second stage, the centre is in tension

and is austenitic, so that the tendency is to produce plastic deformation rather than cracking. In the last stage the surface is again in tension. Now, however, the surface is hard, unyielding martensite. As the centre expands, there is little likelihood of plastic deformation. It is during this stage that the greatest danger of cracking exists. Depending upon, the difference in

time between the transformation of the surface and centre, the cracking may occur soon after the quench or sometimes many hours later. Fig: 8-85 shows schematically the type of failure that may occur. The crack will take place in the tension layers and will be widest at the surface.

One heat-treating rule which minimizes the danger of cracking is parts should be tempered immediately after hardening. Tempering will give the surface martensite some ductility before the centre transforms. Another very effective method of minimizing distortion and cracking is by martempering or marquenching illustrated in Fig: 8-86. It

is carried out by heating to proper autenitizing temperature, quenching rapidly in liquid-salt bath held just above the M temperature, and holding for a period of time. This allows the surface and centre to reach the same temperature; air cooling to room temperature then follows. Since air cooling from just above the martensite-formation range introduces
s

Ms

very little temperature gradient, the martensite will be formed at nearly the same time throughout the piece. This martempering minimizes residual stresses and greatly reduces the danger of distortion and cracking. The heat treatment is completed by tempering the martensite to the desired hardness.

Fig: 8-87 shows the surface and centre cooling curves superimposed on the I-T diagram for the shallow-hardened steel. During the first stage, up to time t1 , the stresses present are due only to the temperature gradient, and as in the through hardened condition, the surface will be in tension and centre will be in compression. During the second stage,
t2

between times t1 and t 2 both the surface and centre will transform. The surface will transform to martensite while the centre will transform to softer product, like pearlite. The entire piece is expanding, but since the expansion resulting from the formation of martensite is greater than that resulting from the formation of pearlite, the surface tends to expand more than the

centre. This tends to put the centre in tension and the surface is in compression. After t2 the centre will contract on cooling from the transformation temperature to room temperature. The surface, being martensitic and having reached room temperature earlier, will prevent the centre from contracting as much as it should. This will result in higher tensile stresses in

the centre. The stress condition in the three stages are summarized below. Let us examine the three stages with regard to the danger of cracking. In the first stage, the surface is in tension, but being austenitic. If the stress is high enough, it will yield rather than crack. In the second stage, the centre is in tension. However, since both the surface and centre are

expanding, the tensile stress will be small. During the third stage, the surface, as a hard rigid shell of martensite, will prevent the centre from contracting as it cools to room temperature. The tensile stresses in the centre may reach a high value, and since the centre is pearlite of relatively low tensile strength, it is during this stage that the greatest danger of cracking exists.

Fig: 8-88 shows schematically the type of failure that may occur in a shallowhardened steel. The tensile crack is internal and cannot come to the surface because of the compressive stress in the surface layers. Since they are internal, these cracks are difficult to detect. X-ray testing or in some cases Magnaflux inspection may show the presence of

internal fissures. Very often these parts are placed in service without knowledge of internal quenching cracks. As soon as there is the slightest bit of tensile stress in the surface due to the external load, the crack will come through and the part will fail. In many applications, the tensile stress developed by the external force is

maximum at or near the surface. For these applications, shallow-hardened or casehardened parts are preferred, since the surface residual stresses are usually compressive. In order for the surface to be in tension, the residual compressive must first be brought to zero. This effectively increases the strength of the surface. The same beneficial effect and

greatly increased life have been found for leaf springs where residual surface compressive stresses were induced by shot peening before the springs were placed in service.