Chemical Penetration in Sand Molds in Steel Castings AFS Research DM, Stefanescu AM. Lane TS. Piwonka University of Alabama Tusealoosa, Alabama ABSTRACT ‘The investigation of the causes penetration inferrous castings hhas been extended to steel castings, which, uulie iron castings, can exhibit chemical as well as mechanical penetration. Measurements of the atmosphere present at the mold-metal interface shove that this armosphere varies according towhether {green sand, resin-bonded sand or sodium silicate-bonded sand is used, and that the atmosphere produced hy these binders affects the occurrence of penetration ‘Twosimple models are proposed to predict whether chemical penetration will occur; one ses equilibrium thermodynamic calculations, andthe otheraddeacalculation of earbon diffusion Inthe casting 10 the mald-metal interface, Bester agreement with ‘experiment is obtained with the carbon diffusion model. INTRODUCTION Anextensiveinvestigation ofthe causes of metal penetration defects ~ found that penetration in est ironis always theresult of mechanical forces resulting from the metalostatic head of the iron or the expansion of graphite durin solidification. The pressure generated by the metallostaic head and graphite expansion forces the metal int the sand, whee i surrounds the molding aggregate, Ths force ‘is normally opposed by the surface tension acting between the mold aggregate and the liquid metal, Chemical reactions between te iron and the sand mold do not occur, because the high carbon content of theiron supplics sufficient carbon athe surface ofthe casting toreaet with oxygen in the mold, to produce a reducing atmosphere atthe ‘mold-metal interface and prevent oxidation of the liquid. Steels, however, contain substantially less carbon than cast iron, ‘and numerous investigators have reported the occurrence of penetration defects that clearly involve a reaction between the metal ‘and the sand mold Penetration in steel, therefore, can arise from either mechanical or chemical cduses. This investigation was undertaken to determine the conditions under which penetration defects can occur in steel castings, PENETRATION CAUSES ‘Mechanical Penetration ‘As desesibed in Reference I, mechanical pecetationinsteel castings can be analyzed by a pressure balance at the mold-metal interface. Penetration will occur when the static (Py) and dynamic (Pays) pressure exerted by the metal exceeds the pressure gonerated by ges expanding at the interface (P,), the frictional sistance ofthe sandto the flow of the metal (P) and the resistance to flow from capillary forwes(P). Prat Payy> Ppt Pet Py @ ‘Suibsttuing analytical expressions for eech term, and realizing ‘that when both sides ofthe equation are equal penetrationisjustabout te occur, allows us to solve fora extical contact angle between the ‘mold aggregate and the molten metal. Tis critica} contzet ange is, the contact angle at which penetration is likely to occur: a ‘hav where d__ is the equivalent capillary diameter of the spaces be- tween dhe sand gr isthe iquid-vapor surface energy of the alloy isthe metallostatc head Js the density ofthe Tiguid alloy isthe acceleration due to gravity enue is the velocity with which the metal bits the mold A penetration index (Pi) has been developed. I! compares this citcal contact angle (@,) with the actual contact angle (9,), which is measured between the molten alloy and the mold aggregate: P,= 04/0 8 ‘When the penetration index is greater than 1, penetration is unlikely t occur; whenitis less than 1, penetration slike to occu. ‘Theactual contact angle isa funetionof te alloy composition andthe pouring tempersture, This relationship has been fully explored for castiron.*A similar equation is under development n ou laboratory for steel castings. Chemical Penetration (Chemical penetration occurs when there isa reaction between the ‘metal und the molding agpregate, or between the metal and the ‘atmosphere atthe mold-metal interface, which produces phase that ‘can react with andlor dissolvé the molding aggregate Tastee), zany investigators have founda fayalite phase (FeySiO,) on the surface of castings where penetration has taken place. This phase forms when iron oxide (FeO) is formed on the molten iron 2s ‘result ofa reaction wit the oxygen in the mold atmosphere, and ‘thon thisiron oxide reacts with and dissolves silica sand, Fayalitehes ‘melting point below that of steel, soit s possible that ts formation ‘might cause penetration to continue ater the eating has cooled below its solidification temperature, AFS Transactions 74145 325EXPERIMENTAL WORK ‘Atmosphere at Mold-Metal interface ‘When motte see is poured into sand mold, the beat fom the steel firs expands the air in tho spaces between the sand grains. Theo, if the mold isa green sand mold, the heat converts the moistae inthe sand at the interface into steam. This steam then flushes the air from. theaterface and from the mold area, whichis ata temperatureabove ‘the boiling point of water. Ths dry sand zone expands asthe casting solidifies and heat is transferred into the sand. The water vapor can react with either carbonaceous materials or binders in the mold, the carbon éissolvedin thesteel, or withthe iron orotber alloy elemeats inthe sce. The reaction with carbon will occur preferentially tothat ‘vith ion, In olaer words, oxy gen in the interfacial atmosphere will, react with the carbon preset, either in the mold atmosphere ot C0 + Reaction 4—At the mold-metal interface, the won can be oxi ized by COr Fe+ CO; FeO +CO Inresin-bonded molds, there is no moisture except that which is present as humidity in the ambient ar, Instead, the oxygen in the ai inthe mold burns the carbonaceous materia in the resin according to Reaction I.Insodiumsilicate-bonded mold, thereisna carbonaceous ‘material present in the mold, only air and moisture (he sodium. silicae-bonded molds used in these experiments contained about 2.5% moisture). Here, there i a reaction between the oxygea inthe air and the earbon dissolved in the stxk: Reaction S— C+(1/2)0,3C0, ‘These reactions indicate that if we start witheitherair or moistare inaclay bonded, wesin-bonded or sodium silieate-bonded mold, after ‘pouring, teatmosphereatthe moli-metal interface should primarily, ‘consist of hycrogen,casbon monoxide and carbon dioxide gases. “The gases present can react with te stool secording to Reaction 4,t0 produce iron oxide, FeO. lronoxideisstrongly wetting on silica (it has wetting angle of 21°, which is very wetting, wheceas pare iron has a nonsitting angle of 154.5°)29 soit wots the sand and is drawn up around it. FeO also ea react with and dissolve the sila sand aecorting to: Reaction 6— FeO 4 Si» FeaSiQy is this last reaction that produces the familiar evidence of penetration: a layer of fayalite (Fe,SiO4., 226 ‘These equations can be summed up as follows: When molten ‘metals pouredint thermo, the moisture present lashes nto seam, ‘which reacts with carbon addition in the mold and/or the dissolved carbon inthe alloy to form carbon monoxide, If theres insufficient carbon presen to react with all of the oxygen in the mold, carbon, 2FO#COH(LIDE Assuring that ion and iton oxide are pure phases, thei activity is unity, The equilibrium constant, ke fr this reaction is Ky o ‘here p isthe respective partial pressures ofthe subscript gases in the atmosphere is the carbon dissolved in seein w% AG is the free energy in Winol TR isthe ideal gas constant in 4mol"K) ‘Tis the absolute temperature, “This equation may now be evaluated at various temperatures, solved for the eriticl carbon content, Cy, and Bit tan exponential fimetion of temperature t give? Peo, Cy = P20. -exp60.002-7)] o Peo ‘The values used forthe partial pressures of CO and COs were ‘hose obtained from the experimental gas measurements. Equation 5 can be used to predict whether the nominal composition ofthese) ‘bing pouredis above the critical carbon contentto prevent cetnical peneitation. However, because the carbon that i initially present a 229the interface reacts with the oxygen, a more accurate model includes determining whether the diffusion rate of carbon tothe surface 10 replace the reacted carbon is suficient to prevent peneteation, Calculation of Carbon Diffusion to the Interface A decarbarized zane is often noted on the surface of steel castings 1 the carbon is deplete at the surface during o after solidification, ‘oxidation of the inn will occur, which leads to chernical penetration bythe formation of fayalite. The problemsto calculate the diffusion of carbon through the solidifying layer of steel, to predit the ‘occurrence of his decarburized zone. Thiseane estimated by using 8 simple one-dimensional finite difference model in rectangular ‘coordinates. ‘The governing equations ae those for energy and solute diffo- ar _ #7, Aly af, Pg Ty Mes, a aC, ae o ac_ vc ae pFe a) a a Au where Tis the temperature 1 isthetime 1% is the distance from the interface 0 isthe thermal diffusivity AH is the heat of fusion Cy, is the specific heat {isthe faction solid Cis the carbon concentration isthe diffusivity ofarbon in ste! “The faction sold is assumed inthis approximation to bea linear function of temperature: ® where Tis the liquidus temperature and'Ts isthe solids tempera ture. ‘Theone-dimensional grdundthe boundary conditions ate shown in Fig. 10. "Te initia condition i that the carbon content is constant ‘across computational domain andequalto the average carbon content ofthe stecl Therumerial schemeusedisa one-dimensional explicit model ats forward in tine and central in space, The models fist ‘order accurate in time and second-order accurate in space. ‘The results ofthe model have been applied foreach ofthe casting conditions discussed in the previous section, Steel carbon contents used inthe model calculations are those shown i Table 1. A frst ‘example s given in Fig, 11, which isthe case for casing #15, which 0 et aio i be | . Spc coe wand Fig, 10. Computational grid ana boundary conditions used inthe finite ctferonce carbon fusion model. 330 ‘vas poured into a sodium slicate-bonded motd, Shown area caleu- lived cooling curve at the core-metal interface, the core-reta inter {cial carbon content (the heavy black line), andthe eritieal carbon content atthe interface, which is aeded to avoid chemical penetra tion, derived using Equation 5. “The eritical carbon levels init ly greater than the carbon level at the interface, up to approximately 380 seconds afer pouting, During this period, iron oxide forms, which leads to chemical ‘penetration. Although, late, during solidification, theeritcal carbon level falls below the interfacial earbon level, penetration has aleady ‘occurred, Thus, the model predicts that penetration will occur in casting #15, as confirmed by experiment. ‘Similar curves are shown in Fig. 12 fo the resin-bonded mold (casting #1) anda green sand mold containing seacoal (casting #14), For the resin-bonded mold, the critical carbon does not exceed the interfacial carbon curve at any time during solidification, so no penetrations predicted. The green sanderiticalcarboncurveexceeds thecrticalcarboncurveforashorttime, which couldallow penetration to cour Prediction of Chemical Penetration ‘The carbon diffusion model and the CO3/CO equilibrium valve of (0.28 were both used to predict whether penetration would be found fn the castings poured where the atmosphere atthe mold-metal Inesface was measured, as described in the section on atmosphere of the mold-metal interface. A summary of the results is shown in Table 2, ‘While the agreement is not perfect, clearly the diffusion model is agreatimprovementover the use ofthe 0.2 CO2/CO satio found from quilibrium considerations. Although the diffusion model does not includeallofthefactrsthatcontrbitetothe formation of ironoxide atthe interface (the most important omission is the lack of a model oot Ss pone “ ewe {8g foo 10 3 i ost a A | so eH asta sant slog Fg. 11. Ditusion model calovations for sodium sileato-bonded mod (415). ‘Temperature, C Fig. 12. Ditusion mode calculations forthe rasin-bonded mold and the green sand mold containing seacoat AFS Transactionscag 1 | pests ovies | Yes No 1s | Sawn Sows| vos Ye ye. Sexeoaition onsen alien forthe flux of oxygen through the mold to the interface) it captures ‘one of the major factors, as shown by the good agreement with ‘experiment CONCLUSIONS ‘The results ofthis investigation clearly show thar th typo of binder toed affects the atmosphere at the mold-metal intecace during solidification. Oxidizing atmospheres produce castings with penetration defects unless a mold coating isused. Pormation of iron ‘oxide, the first step in the penetration reaction, depends both on the presence of oxyigea ia the mold atmosphere and the absence of ‘earbon at the surface ofthe casting. When these conditions are met, ‘chemical penetration can be expected to occur in silica sand molds, ‘The use of afinite difference model to calculate carbon diffusion to thointerface appears tobe apromising methodto vse to predictthe ‘occurrence of chemical penetration in steel castings. Improvemenis inthis modelmay be expected when tisextended othree dimensions ‘and coupled with corresponding model for oxygen diffusion tothe imerface inthe mo. AES Transactions ACKNOWLEDGMENTS “This research bas been funded by a consortium of foundries and ‘foundry suppliersandby the Metal Casting Competitiveness Program of the U.S. Department of Energy (DoE Cooperative Agreement DE-ECO7-941D13324), However, any opinions, findings, conclu sions or recommendiions expresied herein are those ofthe authors ‘and do not necessarily reflect the views of DoB. "The authors acknowledge the assistance of K. Hayes in preparing the castings, ‘and the active support of te industrial sponsors, without which the ‘rogram could not have succeeded. REFERENCES 1, DM, Stetanesn, SR, Giese, TS. Hiwonka and A.M. Lane, “Cast eon Penetration in Sand Molds Part Physics ofPeneszationand Penetration Made." APS Transactions, vl 04 (1995), 1233. 2. SK Giose, DM, Stefanos, J. Bulow sndS. Penk, “Cas Loa Penetation in Sand Molds Par I: Experimental Evaluation of Soe of ‘he Main Parameters Responsible for Penetration,” ARS Tronsoctons vo} 108 (1996), p 1249. 4, R.Palabhi, A.M Lage snd'TS Pion, “Catton FenetatoninSand Molde, Part Il Measarement of Mokt-Metal Interfacial Gas CComposition:” APS Transactions, vl 1041986), p 1259. 4, P.Delaanoy,D.M, Stefaneseu and T'S Pwonka, Meal Penetration ix Sand Molds A Critical Literature Review, APS Research Rep. #2. ‘Ape 1980 5. 1M. Svoboda aod GLH. Geiger, “Mechanisms of Metal Pentation in Foonry Mold," AFS Trameactions, vol 77 (1969), p28 6. M. Chakraorg, 8 K. Dhindaw and R. Kher, "Moulé-Meta Reactions in Casing High Manganese tee in Sodium Sifcae-toned Sand Moulds” The Brisk Found yman, Jane 1986, p 229. 1. LL Gaindhar and A.B, Drape, “The Role of Mold Atmospheces inthe Penetation of Stel in Sand Modis” AFS Transnoon, va 8 (1973), p33. 8, LS.Darkenand RW. Gun, “The Sysemlion-Oxyzen Ll Boia sd Toermodysamnios of LiguidOxides and OtherPhase,"J.Am. Chem. ‘Soe. vol 68 (1846), p75, 9. DR Gaskill, nvxueron to Metallurgical Thermodynamies, second dion, Hemisphere Publishers, New York, 1981, p 585.