Phase Disgeams—Unlerstanding the Basi FC. Campbell, editor ah APPENDIX B Copyright © 2012 ASM leet All igh reserved ‘wor atinternaional org Fundamentals of Solidification ALMOST ALL METALS AND ALLOYS are produced from liquids by solidification, Sometimes, the liquid metal is poured ina mold with a shape that is close to the desired final shape, a process called casting. The cast part then requires little or no final machining prior to use. On the other hand, simple castings called ingots are initially cast and then shaped by combinations of hot and cold working into wrought product forms, such as plate, sheet, or bar stock. For both castings and wrought products, the solidification process has a major influence on both the microstructure and mechanical properties of the final product. B.1 The Liquid State The liquid state is intermediate between a gas and a crystalline solid Liquids possess neither the long-range order of solids nor the complete disorder of gases. Liquids do, however, possess short-range order. In fact, the structure of liquid metals is very close to the solid that freezes from it, For close-packed metals with the face-centered cubic (Fee) and hex- ‘agonal close-packed (hep) crystalline structures, melting causes a volume decrease of only 3.5 10 6% and even less in the more loosely packed body- centered cubic (bcc) metals, which usually exhibit a volume decrease of only | 103% on freezing, Some elements with even looser atomic packing, such as silicon, actually expand on freezing. In addition, the latent heat of fusion is only approximately 3 10 4% of the corresponding latent heat of vaporization, The small amount of volume change and the relatively small fatent heats of fusion are evidence that the atomic bonding in liquids and solids is very similar. X-ray diffraction studies of liquid metals indicate that the atoms in liquids are arranged in an orderly manner over short distances, but lack long-range ‘order. This is probably due to the presence of increased amounts of defects nos 20‘930.7 Phase Diagrams—Understanding the Basics Such as vacancies, interstitials, and dislocations. This large population of Gefects is believed to be responsible for the much higher rates of diffusion in liquid metals. The higher diffusion rates leads to a picture of liquid met- als in which the structure is continuously changing. Atoms form clusters With a high degree of short-range order that may exist for a moment and then fall apart to appear again in another location. As the liquid is cooled towards its freezing point, the degree of shortrang. the ordered clusters become larger and more stable. order increases and B.2 Solidification Interfaces ‘The solidifying solid-iquid interface can exhibit one of three types of interfacial growth in the liquid: planar, celular, or dendritic. Ac shown 12 Fig. Bul, the type of growth is controlled by the manner in which heat inert tffom the system. When the liquid ahead of the solid-liquid fratrace has a positive temperature gradient, heat is removed from the Tiquid by conduction through the growing solid, Be radient is linear and uniform perpendicul Wrgzitee is maintained and the growths planar into the liquid (Fig. lgn, When there is a temperature inversion and the temperature decregeog anti of the Solid-iguid interface, then ether cellular or dendritic ronth will occur (Fig. B.lb, c). The difference between the two is a mney or rae eal undereoolings will end to produce cellular growth, while Jatge uneercoolings will tend to produce dendfiic growth, In pure nee “undercooling can result from thermal SUpercooling, While in alloys. it can Fesull from a combination of thermal and Go cause the temperature lar to the interface, a smooth tional supercool Thermal supercooling, Cellular growth, as illustrated in Fig, B2, ‘Cccurs when the advancing planar solid-liquid interface becomes unstable and a small spike appears on the interface that then grows into acellular type structure. The planar surface becomes unstable be of the interface that grows ahead of the remainder enters 1 liquid that is at a lower tempe use any part on in the ture. The initial spikes that form remain isolate at fist, because as they grow by solifaton they release tei Jatent heat of fusion into the adjae in the temperature. Consequently advance into the liquid Dendritic growth isa further ma liquid, causing a localized increase parallel spikes of almost equal spacing ation of cellular growth the spikes develop side protrusions, ALstil higher undercoling and higher growth velocities, the cells grow info rapilly advancing projections sores ‘Times of complex geometry Their rele forms (Fig. ave gen to the name dendrites, aftr the Greek word dendros for tee. The secondary arms of dendrites develop perpendicular to the primary arms becatve, 4 the primary arm solidifies and gives off its latent heat of reaction theAppendix: Fundamentals of Solidification / 431 Front Temperate Sido Piane Grown | Sold) aug @ as \ - GP PSP ap ee ceed = Ceee wine | [Spdhdp dt © Fig. BA. secs of unecooing on clicaion structures Source Re. as pulshedin Re 2 temperature immediately adjacent to the primary arm increases. This cre- ates another temperature inversion in the liquid between the primary arms, So secondary arms shoot out in that direction. A similar argument can be made for the formation ofthe tertiary arms. The spacing of the secondary | arms is proportional to the rate at which heat is removed from the casting during solidification, with faster cooling rates producing smaller dendrite arm spacings. Dendrites start as long thin crystals that grow into the liquid and thicken, The change in interface morphology of a succinonitrile-4% acetone solution with increasing solidification velocity (Fig. B.) demon. strates the evolution of a dendritic structure, sa.en8 8.013.008 1$32.7 Phase Dingrams—Understanding the Basics Fig, B.2_ Transition rom planar o cellar growth, Source: Re 8.2 Fig, B.3_bendvite formation. Source: Ref 8.3 as published in Re 8.2 Constitutional Supercooling. While dendrites can form to a lim- ited extent in pure metals due to temperature inversions, they are more prevalent in alloys because of the additional undercooling due to consti: tutional supercooling. Constitutional supercooling arises because of the Ss42_e08 8 6stinad 432 gare 23500 9uUST ECOm eres. tae Fundamentals of Solidification / 435 Dee lished in Ref B.2 : : : segregation of alloying elements ahead of the solid-liquid front, The extra ‘concentration of alloying elements reduces the melting point of the liquid. If this reduction i sufficient to reduce the melting point to betow the actual temperature at that point, then the liquid is said to be locally constitut ally supercooled; that is, itis effectively undercooled because of a change in the constitution of the liquid B.3 Solidification Structures ‘A metal cast into a mold can have up to two or three distinet zones: a chill zone, zone containing columnar grains, and a centerequiaxed grain zone (Fig. B.5). It should be noted that all three zones do not always occur. For example, pure metals can exhibit a chill zone and a columnar zone but do not contain a center-equiaxed zone, gave vasscaru34.7 Phase Dingrams—Understanding the Basics Cokin Grane eet Lu Noel cht Gains Egulaed / oaine Fig. B.5 Freezing sequence foran alloy casting Source: Rel 8.3 a5 publish in Rt 8.2 Chill Zone. Because the mold is cooler than the metal, nucleation will ‘occur over the interior surface of the mold, Because the mold wall is much cooler than the liquid metal, the nucleation rate is high and thus the average grain size is small. Each nucleation event produces an individual erystal or grain, tha ows dendritically in a direction roughly perpendicular to the mold wall until it impinges on other grains, As a large amount of latent heat of fusion is released from the solidifying grains, and as the superheat Of the liquid is dissipated, the rate of growth decreases. The chill zone grains are oriented randomly with respect to the mold; that is, the major ixis of each grain is randomly oriented‘Appendix B: Fundamentals of Solidification / 435 Center-Equiaxed Zone. A third region at the center of some alloy Castings consists of smaller grains that are randomly oriented and nearly equiaxed. As freezing progresses, the thermal gradient decreases, and this Causes the dendrites to become very long. Breakdown of columnar growth may Occuras a result of fracturing of the very long dendrite grains by con. ection currents in the melt. These broken arms (Fig. B.7) can theirserve as nuclei for new grains. Another possibility is that new grains nucleate as 4 result of alow thermal gradient and segregation that is occurring during freezing. At low casting temperatures, the entire the casting may solidify with an equiaxed structure. Chit Grains on ‘Morirted Grins Favorably Ovented Mold Wall Crowded Out ‘Coumnar Grains / I Tne {growth from mold wall. Source: Ret 8.1 as published in | Fig. B.6 pera 5a n86.8.811 988 498“36-7 Phase Diggrams— Understanding the Basis over E Fig, B.7_ Formation of equaned zone inalloy cating Source Ref 49s published in Ref B2 53.188 0111in00 498 The amount of the final cast structure that is columnar or equiaxed depends on the alloy composition and on the thermal gradient atthe fig. Uid-solid interface during solidification, thermal gradient is most easily Controlled by controlling the rate of heat extraction from the casting, + the cooling rate. Alloys that have a wide spread between the liquidus and the solidus temperatures solidify with a mostly equiaxed grain structure at normal cooling rates, whereas alloys with small differences in solidus and ius temperatures solidify with a mostly colummnarstructure High Cooling rates encourage columnar solidification because they estublich Tigh thermal gradients at the liquid-solid interface. Low thermal gradients ‘Encourage equiaxed solidification, B.4 Segregation Segregation may be defined as any departure from a uniform distribution of the chemical elements in the alloy. Because of the way in which alloys sane 1235106ix B: Fundamentals of Solidification / 437 Apps deere oh freezing it follows that all castings ae segregated to different ‘Brees. Alloys can exhibit several types of segregation, and more than one {ype can be present in any given casting. Normal Segregation. Normal segregation is the result of rejection of the alloy solute at an. advancing interface because it is more soluble in the liquid than the solid, As freezing progresses, there is a buildup of the sol- Ute in the liquid that freezes last, such as at the center of the casting. Such long range variations in composition are called macrosegregation. Normal Segregation frequently occurs when the direction of growth is inward, as in columnar growth. ‘An examination of the relevant portion ofa phase diagram (Fig. B8) can be used to show the effects of segregation during freezing. The original melt of composition C, starts to freeze at the liquidus temperature, 7) The first solid to appear has the composition & C,, where k is known as the partition coefficient. The partition coefficient usually has a value less than 1. For example, for k= 0.5, the first solid has only 50% of the concentration of alloying element compared to the original melt; the first metal to appear is therefore usually rather pure. In general, k defines how the solute alloy partitions between the solid and liquid phases. Thus: k= CIC (Eq B.D, ‘where C; is the solute fraction by weight in solid and C, is the solute frac~ tion by weight in liquid For solidus and liquidus lines that are straight, &is constant for all com- positions. However, even where they are curved, the relative matching of the curvatures often means that & is still reasonably constant over wide ranges of composition. When k is close to I, the close spacing of the liqui dus and solidus lines indicates little tendency toward segregation. When k is small, then the wide spacing of the liquidus and solidus lines indicates a strongly partitioning alloying element and a tendency to segregate on solidification. ‘On forming the solid that contains only k C, amount of alloying element, the alloying element remaining in the liquid has to be rejected ahead of the advancing front. Thus, although the liquid ahead of the front was initially cof composition C,, after an advance of approximately a millimeter or so, the composition ahead of the front builds up to a peak value of C, /k Gravity Segregation, Gravity segregation is another type of macrosee- regation that occurs due to differences in density in the liquid melt, Denser ‘constituents tend to sink toward the bottom, while lighter ones float toward the top, Microsegregation, As the dendrite grows into the melt,and as second- ary arms spread from the main dendrite stem, solute i rejected, effectively | szone.s eins 37 sas can pigs498 / Phase Diagram+—Understanding the Basics Freezng Pot olMen Etecive Undercacied Regen CComposiion t Solue-ion zone bul up shea oy advancing Woot as a fesut ot gaa Distance From Freezing Pont Fig. B.B. constiutionalsupercoolng Source: Ref 81 a5 pushed in Rel 82 being pushed aside to concentrate in the tiny regions enclosed by the sec- ondary dendrite arms. This gradation of composition from the inside to the outside of the dendrite is called coring, because on etching a polished section of such dendrites, the progressive change in composition appears as onionlike layers around a central core, ate oe 8 91ihn09 48 aa ane]alc creating a suc- ; on be the ingot San) Foeeanectt HAC PUTls The Soluie-ennieher ee Iquidl toward the surface Another coher mechanisms that large Amount of gas evolv ou 2 at the end of ay c-enriched Tiquid through the dendritic chan= rd the surface: Albay ngs. While ingot homogenizat effective in smoothing out microsegres ion treatments can be ation, they are not very effective Prinary Poe Salute en XK — Buoyant Laud aoael Seconsoy Pipe _ ‘ Fig Pm of Poste ‘Buoyant ged Seprepiten ‘Channa anne ae Segrates| Sogregaos ~ Dencete Fragments cone ot Segregaten Partly Sottied Casing Fig, BY se ton in ile stel ingot. Source: Ref 8.1 as published in Ref 8.2 sane yeasrewstances for macrosegregation, Because macrosegregation Ochs, ott one ie ranging from 1 to 100 cm (04 to 40 in), the diffusion fenBU™ too long and the times required are prohibitive. Segregation § pies prime reasons that wrought prodiicis are often preferred over Ot ‘The severe plastic deformation that occurs during hot working internal porosity and help break up and eliminate segregated area B.5 Grain Refinement and Secondary Dendrite Arm Spacing Rapid solidification rates are usually desirable because they tend to pro= duce finer grain sizes and finer dendrites. Grain size control for castings is important because fine grain sizes result in higher strengths and greater ductility, Because the size of porosity in a casting often corresponds some~ what with grain size, finer porosity also goes with finer grain sizes. In addition, shrinkage and hot cracking are more prevalent in castings with a coarse grain size. Grain size is a function of pouring temperature, solidi- fication rate, and the presence or absence of a grain-refining agent, Low pouring temperatures, faster solidification rates, and grain refiners, such as titanium and boron in aluminum, all produce finer grain sizes The solidification rate also affects the size of the dendrites that form during freezing. The dendrite size is normally measured as the distance | between the secondary dendrite arms, referred to as the secondary dendrite arm spacing (SDAS). As shown in Fig. B.10, faster solidification rates pro- duce smaller SDAS. The SDAS is related to the solidification time. f, by: SDAS = kr" (Eq B2) where k and n are constants that depend on the composition of the metal ‘Small secondary dendrite arm spacings are associated with higher strengths and improved ductility (Fig. B.11). Homogenization heat treatments are also dependent on the time, ¢, required to diffuse a solute over a given average distance, x. Ifthe coefficient of diffusion in the solid is D, then the relationship between time and distance is approximately: x=\Dr (Eq B.3) Thus, finer SDAS results in shorter homogenization times, or better homogenization in similar times B.6 Porosity and Shrinkage Porosity is the presence of pores in the casting, These pores may be con- nected to the surface, or they may be wholly internal, While mild por ‘2 er6.8.0111n08 440Appendix B: Fundamentals of Solidification / 441 {fA Sey rae fas lis | Se ot oe a Het BZ 5 Za eh aR NER nea Se NS Sotcfeaon Tene (3) Fig. B.10_llect of solicaon time on secondary dendrite arm spacing. Source: Ref 8.5 as published in Re Be ngaten (1) Tense Sergi (MPa) ° 900s acid 0018 ‘Secondary Denne Arm Spacing (em) i Ec of scconiay ets spcng on roves of si Fig. B11 ir casing alloy, Source: Ref BS os publehed Rel 8.2 | eres 0 save saasiaew4442 / Phase Diagrams—Understanding the Basics as tensile strength. itcan does not normally degrade static properte Peerage ‘However, a severely impact dynamic properties sich 25 ate eT nough reduction in lati properties can occur if he porosity is eer or, to significantly reduce the cross-sectional area or if BAS TT that produce stress concentrations. If the surfaces of smal! FTES ingots are not oxidized, they will generally be welded shut CONE working uch as rolng or forging, Small porosity in ished’ ets either be accepted or healed by processes such as hot isostatic Pres here the metal is subjected to significant heat and pressure, Porosity tt is open to the surface in finished castings is sometimes ground out and weld repaired, Both gas evolution and metal shrinkage during casting roduce porosity Gas porosity is caused by the absorption of gases in the liguid met. prior to casting. The most troublesome gas is hydrogen, which ustally Comes from either moisture inthe air or from burning fossil fuels for heat- ing and melting, Moisture and liquid metal can react to form molecular hydrogen according to: ies, (EqB4) XM + yH,0 > M,O, + 9H, ints balane where M is the metal, and « and y are stoichiometric coeffic ing the equation, At the high temperatures in the liquid melt, molecular hydrogen decomposes into atomic hydrogen that dissolves in the metal The solubility of hydrogen in liquid metals increases sharply with tem- perature, as shown in Fig. B.12 for nickel and iron. If the hydrogen is hot removed prior to solidification, the large decrease in solubility during freczing results in the formation of porosity. One problem with gas poros- ity is the formation of blisters during subsequent processing such as heat treating or annealing. The equilibrium gas concentration in a liquid metal can be determined by Sievert’ law: G=k lp, (Eq BS) where Gis the equilibrium gas solubility, is the equilibrium constant, and Pp; is the partial pressure of gas at the metal surface. Hydrogen is often removed by vacuum degassing prior to casting. For example, premium-quality steels are commonly vacuum degassed. In addi- tion, some metals, such as titanium, are so reactive that all melting and casting operations must be done under vacuum. In open-air casting opera- tions, hydrogen is removed from the melt by using degassing fluxes. The removal of hydrogen is a mechanical, not chemical, process in which the hydrogen attaches itself to the fluxing gas. The presence of nonmetallic inclusions has an effect on gas porosity formation. It has been shown that nucleation of pores is difficult in the sare rosie‘Appendix: Fundamental of Solidification / 443 Temperate 0) 400 _e00 e 800 1000 1200 1409 1600 1000 ” 2 » Solsaty (er2100 om) fe 7501110 14701690 2190 2580 2919) 3270 Temperate (F) 8 B12 HT mbished kel 82 : absence of some sort of substrate, such as a nonmetallic inclusion, a grain refiner, ora secon-phase particle. Investigations have shown that castings free of inclusions have less porosity than castings that contain inclusions. "As ametal casting cools and solidifies, the volume decreases, contribut- .: liquid shrinkage, solidification shrinkage, fand solid shrinkage. The shrinkage occurring in the liquid metal itself ddoes not cause casting problems. The extra liquid metal required to com pensate fr this small reduction in volume is provided by a slight extension to the pouring time or by a slight fallin feeder level Solidification shrinkage occurs at the freezing point when the metal transitions from a liquid to a more highly ordered crystalline solid. The volume change on melting for a number of metal i Table B.L Solidification shrinkage is usually compensated for by de ‘pith reservoirs for liquid metal, called risers, which allow liquid metal to ow in and fill the areas being vacated by the solidifying metal, Shrink age porosity often forms in areas that the liquid metal from the risers ca mot reach. For example, itis difficult to effectively feed metal into the ‘aerdendritic areas where shrinkage is occurring, Because this type of ing to three types of shrinka coz ons 9 iis are weaker444. / Phase: Diagrams—Understanding the Basics. ; FEO | sin est | Lowel Alc qganstes Pb-Sn ) enn sco 9 611.083 446 Table B.1 Volume changes on m es ses On CLUS Er a Mel ‘Ca races Yolame cue on meting 60 a he ae fee si cy fee a Ze he. “a Me ee a ” fe 3 fe te a Sn tet 28 x bes a9 Sb Rhombatedea -095 Distond cube “2 Porosity occurs late in solidification, especially in alloys with wide freez- ing ranges and a large mushy zone, itis particularly difficult to eliminate, ‘A comparison of shrinkage porosity and gas porosity is shown in Fig. B.13, Shrinkage porosity tends to follow the directions of the dendritic arms and forms along the grain boundaries, while gas porosity occurs throughout the matrix, Solid shrinkage occurs after the casting has solidified and is cooling down to room temperature. As cooling progresses, and the casting attempts to contract, itis constrained to some extent by the mold. This constraint always leads to the casting being somewhat larger than would be expected from free contraction alone. This can lead to difficulties in accurately designing the size of the pattern, because the contraction allowance is not a8y to quantify. Mold constraint during cooling can also lead to problems such as hot tearing or cracking of the casting. Shrinkage Poroety (Gas orca Fig. B.13 Porosy in casi meals, Soutce: Ref 8.735 publshed in Ret B2