Melting, Casting, and Hot Processing
THE PRIMARY PRODUCTION PROCESSES of melting, casting, and hot processing are invisible to the end user. The vast majority of stainless steel is made by arc furnace melting followed by argon oxygen decarburization (AOD) reﬁning and continuous casting. It is not normal, and it is seldom beneﬁcial for the end user to specify processing paths. The end user should, however, be knowledgeable and require the producer to document the process and the producer’s control of it. austenitic alloys, impossible to produce. The advent of AOD, continuous casting, ladle metallurgy, and powerful hot rolling mills has led to stainless steels of much higher quality produced at lower cost. Ironically, the low processing cost of stainless steel has spurred demand and made some of its ingredients, such as molybdenum and nickel, which are relatively scarce and expensive commodities, even more costly, forcing the cost of many alloys to spike even higher than in earlier years.
Melting and Reﬁning
The arc furnace is nearly universally used for the ﬁrst step in the production of stainless steel. The arc furnace is quite ﬂexible in the types of charge materials it can accept. Since the charge materials for stainless steel are typically carbon steel and stainless steel scrap, this ﬂexibility allows scrap of all types to be used. The necessary chromium is added as ferrochromium, whose cost is inversely related to its carbon content. The carbon content of the heat of steel is roughly 1.5 to 2.5% when it is melted and ready to charge into the separate reﬁning vessel. It is this carbon whose removal is the primary focus of reﬁning. In the 1960s, Union Carbide engineers perfected a method, the previously mentioned AOD process, of removing nearly all the carbon from molten stainless steel without signiﬁcant loss of chromium. This process is based on the following chemical reaction:
Cr3O4 (Solid) + yC = yCO (gas) + Cr (Eq 1)
The manner in which stainless steel is made at the producing mill can have a great impact on its ﬁnal properties. These production methods have undergone a major evolution over the last 50 years and are mainly responsible for stainless steels becoming the practical, widespread engineering materials they are today. Traditional carbon and alloy steel-making methods are not suitable for stainless steels. The fundamental difference is that the basic decarburization step, which is common to all steel making, is thermodynamically very difficult in stainless steel because the essential element, chromium, reacts more strongly with the purifying agent, oxygen, than does carbon. Thus, early stainless steel making, done in an arc furnace, was a lengthy process that necessarily involved high chromium losses to the slag as carbon was removed. This process was not only very expensive, the carbon levels that could be achieved were not much below 0.10%, making most of today’s stainless steels, whose carbon levels range from 0.010% in stabilized ferritic alloys to about 0.07% in normal
The equilibrium for this reaction is:
Ln (K ) = −ΔG 4575T (Eq 2)
A typical starting ratio is 3 to 1 oxygen to argon/nitrogen by volume.020% or less in ferritic alloys. Any known process to remove it ﬁrst removes chromium.800 =− + 8. It is possible to use a vacuum system to keep the partial pressure of CO low when reﬁning with injected oxygen. machinability can be improved by calcium additions that produce malleable oxides to replace the deleterious sulﬁdes (see Chapter 15). can be used when required. The thermodynamic activity of aluminum is considerably reduced in iron as chromium levels increase.15%+) for machinability (see Chapter 15). This is the vacuum oxygen decarburization (VOD) process. Phosphorus is an impurity for which no practical removal technology exists in stainless steel. chromium. Once the steel has been deoxidized. is based on cost and ﬁnal nitrogen content desired. but also the mixing of the slag and metal also permits desulfurization. about 0. Sulfur. The injection and the reaction cause extremely thorough mixing. other impurities can be removed from the molten stainless. There are processing methods for which higher levels of sulfur are not necessary that are preferable to the end user while not compromising welding or machining costs. which are
. This is similar in principle to the basic oxygen furnace (BOF) process for carbon steel in which oxygen is injected into molten steel to remove carbon by oxidizing it. it exists in almost all stainless steel at levels close to its normal speciﬁcation limit.76 − 0. which evolves from the melt. is enhanced as a deoxidizer in chromium-iron alloys. arc furnace bath. and consequently small amounts of it are sometimes used as a supplementary deoxidant in alloys even though an alloy speciﬁcation may not call for any. so the more expensive argon must be used. and CO (Ref 1):
Log = %Cr 13. which are beneﬁcial to processors.030% in austenitic alloys and 0. Titanium. and G is the Gibbs free energy. The key to the AOD process. and welding methods. is often deliberately kept at moderate levels (0. This is done at a temperature consistent with economic refractory life. and this excellent purity level is commercially furnished without additional price premium. though. sulfur can be readily removed by contact with a basic slag. The choice of which inert gas to use. producing measurable calcium content in the metal. should be viewed with skepticism by end users. The silicon plus the manganese in the
steel combine to reduce the oxygen content of the steel to around 100 ppm. strong deoxidation with aluminum or titanium can reduce small amounts of calcium from the CaO in the slag. stagnant. Sulfur can be reduced to less than 0. Thus.156 / Stainless Steels for Design Engineers
where K is the equilibrium constant. can be used in many cases to eliminate the need for the weld penetration enhancement of sulfur while increasing welding speeds. is the injection of oxygen and argon into the bath to keep the partial pressure of CO (pCO) very low. Also note that even if no intentional addition of metallic calcium is made.001% in the AOD.925 log p CO T %C (Eq 3)
Thus. The excellent mixing of the slag and metal in the AOD permits this to be done efficiently. after ﬁnal carbon content has been achieved ferrosilicon is added to reduce the chromium in the slag and have it return to the molten steel. although a harmful impurity from a corrosion standpoint. These trade-offs. This mixing not only allows the CO-producing reaction to reach equilibrium. for instance. increasing the temperature works to increase the elimination of carbon as CO. the carbon is selectively oxidized without concurrent chromium oxidation. argon or nitrogen. Working through the thermodynamics yields the relationship that summarizes the important relationship among carbon. Besides carbon and oxygen. whose product integrity is compromised. which would never happen in the ﬂat.008 to 0. oxygen to argon/nitrogen. By increasing the ratio of argon to oxygen in the injected gas as the reﬁning proceeds. The injection is done through tubes called tuyeres in the bottom of the barrelshaped vessel. The ending ratio can be as low as 1 to 9. This could be further reduced by aluminum. Stabilized stainless steels require low carbon and nitrogen levels. such as laser welding. Titanium is believed to reduce hot working defects. For example. More active deoxidants. such as calcium and magnesium. In both processes.015%) for tungsten inert gas (TIG) welding penetration (see Chapter 17) and at high levels (0. on the other hand. but aluminum-based inclusions are generally undesirable. so its role as a deoxidizer is less valuable in stainless steels. The VOD process can achieve slightly lower carbon levels but does not achieve cleaner steel as some believe.
02 –.01 . A high-current direct current (dc) arc is established between the electrode and a starter plate at the bottom of the chamber. nitrogen..01 –.
Some stainless steels and related alloys are remelted to reﬁne composition or ingot structure. Use of VIM is generally limited to high-value. This is a nearly slag-free process. The higher solubility of carbon. which is a risk when using damp or contaminated scrap for coolant. nitrogen. but there are subtle differences because of the difference in the thermodynamics of dilute solutions like carbon steel and highly alloyed..05 . sulfur.Chapter 12: Melting. This oxygen precipitates as oxides in the solid state. –. This can be done very precisely by wire feeding of alloying elements through the slag into the heat.39
. and oxygen
J i Al C Cr Mn Mo N Ni O S Si Ti W
O N S 0
.001 . which can be stirred by argon bubbling via porous plugs..03 –.006
–. Consequently. Heavy metals are eliminated by high-temperature AOD blowing. and oxygen in stainless steels is signiﬁcant. The end of the electrode is melted.13 . The activity coefficient γ varies with the concentration of alloying element x by:
RT lnγ i = RT lnγ i0 +
on interstitial solubility. It should be noted that chromium. VAR parameters are adjusted to maintain a shallow pool.06 –.01 .005 –. Volatile constituents escape from the molten drops.13
. and little reﬁning is possible. as is hydrogen.01 .06
. This technique is very effective for the ﬁnetuning of reactive elements such as titanium.45
–.01 –. which is always present in nondilute quantities. very low carbon levels (less than 50 ppm) are achievable commercially. In VAR.20
. The reﬁning treatments used for carbon steel and stainless steel are very similar.05 –. nondilute solutions like stainless steel. A manganese/silicon deoxidized stainless steel will still have about 100 ppm of dissolved oxygen at the freezing temperature as opposed to the less than 10 ppm of oxygen found in aluminum-killed carbon steel.11 0. Casting.34 . Limited decarburization is possible via injection of oxides such as Fe3O4 or SiO2 to create CO evolution inside the vessel.02 –.. Care must be taken not to reintroduce such impurities after reﬁning. and the puriﬁed drops collect to form a molten pool on top of the starter plate.07 –. and Hot Processing / 157
made from a higher percentage of low-phosphorus carbon steel scrap. Vacuum induction melting (VIM) is another method of melting stainless steels.. Table 1 shows the factors by which additions of various elements to stainless steel (j) alter the thermodynamic activity of other alloying elements (i). Alloy adjustment can be done in the AOD or preferably in a treatment-and-transfer ladle.04 –. This allows the composition to be measured and adjusted before it must be cast. The tapped molten steel generally has excess heat from the highly exothermic reﬁning process. There are two principal remelt processes: vacuum arc remelting (VAR) and electroslag remelting (ESR).6
. The deleterious effects of phosphorus on corrosion are not avoided unless much lower levels are achieved. Melt purity is largely controlled by the purity of the starting material.01 –. The shallowness of the molten pool produces a reﬁned grain
j =1. the material to be remelted is cast into a cylindrical electrode and placed inside a cylindrical water-cooled vacuum chamber.03 –.01 0.05 .14 . and the molten drops fall through the intervening vacuum.08 . or low-tonnage melts.01 –.003 ..05 –.04
δ ln γ i δxj
This calculation is best left to computer programs such as Thermo-Calc that have been perfected for these lengthy procedures.01 –. –. Equation 4 is used to calculate the activity of elements in steel. has a powerful effect
Table 1 Inﬂuence of alloying elements on the thermodynamic activity of carbon.11 –. Using this technique.27 –. its presence is tolerated since it has no differential effect over the range in which it is found. and use of AOD master melt stock for VIM remelting is common.0 . high-purity.53 –.03 . which solidiﬁes in a bottom-up fashion.
however. Elimination of hot rolling could be quite valuable in stainless steel. In a well-executed continuous casting operation. the material to be remelted is cast into an electrode of similar shape. it can cause excessive grain growth. The metal in the tundish is covered with a protective slag cover. replacing the obsolete ingot method. Carbon and molybdenum are examples of alloying elements with this tendency.158 / Stainless Steels for Design Engineers
structure with less solidiﬁcation segregation than found in typical cast product. called the submerged entry nozzle. Typically. which detracts from hot workability. Some end users stipulate that no ﬁrst slabs be applied to their orders. and non-steady-state solidiﬁcation structure. where they defy homogenization. copper alloy mold oscillates in a precise pattern as the solidifying strand of steel is withdrawn from the mold bottom by pinch rolls and sprayed with water to cool it. but these represent a miniscule percentage of stainless production. In ferritic alloys. Reaction of the molten drops with the slag removes sulfur and some other impurities. Slabs are sometimes quenched to avoid precipitation of phases. to prevent ﬂuctuations in level that may entrap slag in the slab surface. The level of the molten metal should be carefully controlled by ultrasonic measurement. This deformation has a crucial. and carbon. and bloom casting have become the standard methods of making stainless steel primary products. which is covered with a consumable protective and lubricating slag cover. and certain alloying elements concentrate at the centerline. More than one heat of steel may be cast sequentially without restarting the process. and the molten drops fall through the slag. the result can be slabs with poor surface quality that must be surface ground. slabs are of sufficient quality that they require no surface conditioning before being hot rolled. A gap between the electrode and a starter plate at the bottom of the mold is ﬁlled with a prepared slag. ESR melting typically is done at a higher rate than VAR. ﬂuxes. which melts in the mold as it is added. It causes a beneﬁcial recrystallization that improves hot working characteristics of austenitic and duplex alloys.). called a mold powder. but slightly smaller than the water-cooled mold. or other methods. In ESR. and ﬂow patterns within the tundish are designed to minimize dead spots and encourage removal of inclusions by impingement with the slag cover. seldom-recognized effect. There are a
. In properly executed continuous casting. There are some alloys that cannot be continuously cast. It is not eliminated. oxidizing potential. Ferritic and martensitic alloys are especially prone to these problems. and the puriﬁed drops collect to form a molten pool on top of the starter plate. they may be held at high enough temperatures prior to hot rolling to stay above the temperature range in which embrittlement can occur or to stay above the temperature at which an embrittled slab can fracture. with commensurate intermediate segregation patterns. whose hot rolling from slab can be both expensive and problematic. into a ceramic tube into the large tundish situated over the caster mold. contains ceramics. however. This is ideal economically and for quality reasons since initial and ﬁnal segments of a casting can contain more inclusions and aberrant structure. the ladle feeds by a slide gate. Additional ingredients control the basicity.
Continuous slab. A high current is used to melt the slag. This deeper pool produces a grain structure between that of VAR and typical cast product. There has been great interest for decades in producing stainless steel coils directly from the melt in so-called strip casters. into the mold. The defective portion must be identiﬁed and scrapped or diverted to low-quality requirement end uses. and the molten pool is deeper. thus removing the costly soaking and slabrolling processes. The strand is bent from an initial slightly curved shape to ﬂat and cut into slabs. ﬂuidity. billet. which in turn melts the end of the electrode. this slag is calcium ﬂuoride-based with high lime (CaO) content. entrapped mold powder. The initial portion of slab cast in a sequence is seldom of adequate quality to be used because of exogenous inclusions. Continuous casting produces slabs directly. Producers generally apply ﬁrst slabs to less-critical uses or discard suspect sections of them. or preferably a stopper rod gate. The mold powder. If casting conditions are not optimal. The pinch rolls apply enough pressure to slightly deform the slab. and other properties of the slag. The metal feeds through another
ceramic tube. Slabs range in thickness from 13 to 63 cm (5 to 15 in. The entire water-cooled. The segregation in continuous casters is less than in ingots because of the smaller section size.
2-in.18-in. singlephase structure at hot rolling temperatures. the reﬁned molten metal is atomized by gas or liquid and made to freeze into small particles. In both cases.06 in. Since their development is only being undertaken by those large stainless steel producers who already have the hot rolling assets that strip casting would replace. which permits energy-saving hot charging of slabs. the transfer band is rolled to ﬁnal gauge on a separate reversing four-high ﬁnishing mill with coil boxes to preserve temperature. Hot rolling characteristics of stainless steels vary greatly.01 in. the hot-rolled band must then be annealed and pickled since the as-rolled hot-rolled band
. The microstructure during hot rolling is the crucial factor. avoiding most of the costly machining steps. This permits the melt shop and caster to be adjacent to the hot mill. such as roll shifting. Some alloys can be cold rolled in the “black band” state at a cost of coarser surface ﬁnish and greater rolling mill roll wear. More impressively.) thickness for 316 stainless. Ferritic stainless steels are extremely easy to hot roll since they have a soft. and lower reductions must be taken than for alloy steels. Casting. powder technology is also used to produce massive components. having been quenched extremely rapidly. the low diffusion rates in austenite slow recrystallization so that the steel does not always soften between stands in tandem mills. the logic applies more to austenitic alloys than to the easily rolled ferritic stainless alloys. For example. which if not countered by roll bending or roll shifting schemes can lead to signiﬁcant variation in thickness across the sheet.25 mm (0. The high separating forces on the hot rolling mill stands also cause greater roll deﬂection and compression. Powerful hot strip tandem
mills that routinely roll carbon steel to 1. Chapter 9 on martensitic alloys discusses these materials. the hot-rolled band carries a heavy. Another method of shortcutting the casting/ ingot step has been perfected: the powder metallurgy approach. Traditional powder metallurgy production methods are used to make small near-net shape components. Hot Steckel mills have become the favored method of hot rolling stainless steel because their throughput better matches stainless steel melt shop production outputs. These particles. and Hot Processing / 159
number of such machines in pilot or limited production.5 mm (0. are quite homogeneous.) thick. it seems unlikely that strip casting will soon become a major factor even if it is perfected technically. They have not had sufficient commercial or technical success to have become a factor in the industry. as much as 0. If normal cold rolling or use as hot-rolled coil is foreseen. This variation as a percentage of thickness is not reduced by cold rolling and is a major cause of tolerance loss in sheet and strip. embedded scale that must be removed from the surface before further processing in most cases.Chapter 12: Melting.). Coil boxes (on reversing mills) address this problem to a degree by permitting the semirolled coil to equalize in temperature. Then. not to have to be duplicated among many stands. typically a fourhigh reversing rougher rolls slabs to about 3-cm (1. This is the same justiﬁcation for using Sendzimir mills to cold roll stainless.5-mm (0. Hot strip tandem mills powerful enough to successfully roll high-quality stainless steel hotrolled bands are massively expensive and are seldom justiﬁed for the tonnage of stainless steel rolling a given melt shop produces. The economy of having only two mill stands makes these mills ideal for typical stainless production quantities and permits the cost of sophisticated mill capabilities. very high carbon/vanadium stainless tool steel components can be made by encapsulating powder in an evacuated canister in which it can be sintered and hot worked to 100% density and virtually complete homogeneity.) can struggle to attain 4.
Hot rolling remains an essential process for the vast majority of stainless steel used. Powder technology methods allow for the design of alloys that would otherwise freeze with too much segregation and too coarse a structure with conventional production methods. In either case. Martensitic stainless steels roll like their carbon and alloy steel counterparts since their microstructure during hot rolling is a moderately alloyed austenite similar to alloy steels. Austenitic stainless steels have high strength at hot rolling temperatures. This increases mill loads. In hot Steckel mills. Furthermore. roll crossing. In powder metallurgy. Hot-rolled bands vary in thickness along the length of the coil because the tail end of the slab is colder and harder to roll. or roll bending. although rolling stainless on hot tandem mills used primarily for carbon steel can be an excellent production method.
Peckner and I. The former has a mixed-phase structure. McGraw-Hill. which facilitates diffusion of sulfur and oxygen to the grain boundaries and also encourages very large grains. p 3–13
. Stainless hot ductility often has a narrow temperature window. gouges. digs. where they form very weak ﬁlms. a skid mark from a slab-heating furnace will remain through the hot rolling.
1. Bernstein. Sometimes. These tendencies are fought by low oxygen and sulfur levels and minimal slab-reheating temperatures and times. This is true of all hot mill scratches.M.” which can require grinding of the entire hot band surface. Rolling stainless requires a different mindset than rolling carbon steel. which argues against the beneﬁts of rolling stainless on a mill built and primarily used for carbon steel. residual cold work and hardness variations. Edge cracks are simply a lack of ductility at the colder strip edge. as well as a heavy oxide layer. But. They arise from many causes and are manifest prima-
rily as edge cracks and slivers. Handbook of Stainless Steels. 1977. and the phases can exhibit mechanical incompatibility at certain temperatures. The most inherently challenging alloys for hot working are the duplex alloys and the alloys that solidify in the fully austenitic state. The latter alloys reject sulfur and oxygen during solidiﬁcation and slab reheating to the grain boundaries. They do have repercussions on delivery. annealing. poor mechanical properties. even alloys such as 304 and 316 can have very poor hot ductility if they contain much sulfur and oxygen or if they are reheated for long times or at temperatures above 1250 °C (2280 °F). Hot ductility defects are more subtle. and cold rolling processes. Inclusion-related defects are all essentially avoidable by using state-of-the-art technology.
Stainless steel hot-rolled bands can contain many types of defects.160 / Stainless Steels for Design Engineers
has poor corrosion resistance. The major categories are: • Hot mill defects • Inclusion-related defects • Hot ductility-related defects Stainless steel is less forgiving of hot mill faults because its surface is not removed by oxidation to the degree carbon steel’s surface is. Thus. and many factors can affect the size of that window depending on alloy type. D. very poor hot working alloys are given a single hot reduction pass on a hot mill to produce a full recrystallization that disperses grain boundary-weakening elements on subsequent reheat. Protecting metal from reoxidation and keeping precise mold-level control in the continuous caster prevents all inclusions of a size that can produce a defect. These are seldom seen by the end user because they are removed when they are not prevented. This poor hot ductility manifests itself as “slivers. etc. as well as slab surface working in the caster pinch rolls.