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    40 views7 pages

    Tool Wear by Solution

    Uploaded by

    cemalbalci
    wear

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    of 7
    scere bey pled to the Mert Pre Toa nto, musasanst | ermal ae Prjomars 1. Mime (CaN Speci "Dabinbet bled Mae Proje See the ASME 3M. Kramer N.P. Suh Tool Wear by Solution: A Quantitative Understanding ‘The mechanism controling the crater wear of single phase carbide cutting tool materials ‘thcnaueate at Techy ‘Senay umsacso3 8 inthe high speed cutting of steel hasbeen identified. A simple model has been developed {o describe the wear proveas. Cutting texts employing inserts coated with Group 1VB and VB carbides show excellent apreement with the relative wear rates predicted from the ‘hermodynamic properties ofthe tocl-wark system. Thus, for the fis ime, quantitative ‘aleulation of the relative ear rates of various potentil tool materials from thermedy. ‘namie datas possible. The technique is believed to have brad application to ather tol. ‘work combinations. Implications for future research ore discussed Introduction ‘The following analysis rests those wea process where solution ‘ofthe too materi the teil being ct primarily responsible forthe wear ofthe tol material Ie wil be seen herein that solution weae predominates fr the eatbde clas of mates nthe frontin| of present carbide application. Iti suggested thatthe oxides ‘lens, are not eo Limited, ‘Trent [1,2] described wea by solution of the tol material in the material being et qualitatively bat had dil expaining observed ‘wear rates on the hase of the difason of tol constituents into he ‘hip and settled on a mechanism in which velting occurs then terface between the tool andthe chi, Infact, the soliton wear rate is independent ofthe ditfusion characteristics ofthe tol material in "he material bring cut Strong evidence is presented herein sngestng = previously identified mechanisn femoral tol water based ‘onthe maintenance of mass continuity within the chip ster ad Jicent to the tal. “Autoradicgraphic tues by Conk and Nayak] show leary that tungsten carbide bse tool materials wear by the solution of tungsten ‘arbido in tel. Su [has emphasized the importance of chemical stability in detersining the solubility ofthe tool material in the me tera being cul and hs suggested the fee energy of formation as ‘vide to the chemial stability. The precent work refine this test ‘nent allow fr chemical reaetons between the tal and the materia Ieing ent ‘The resulting analysis ise powerful predictor of thesolution west rate of potential stel-catting materials explains the superiority of faim carbide to tania earide nthe machining of ste nd the superiority of tungstn carbide to ttanium carbide nthe machining ‘of nickel: based alloys, Te theory leo explains the relatively bigh ‘wear ate of cubic boron siteide in the machining of tel or the first time, quantitative prediction ofthe relative wear ate of potential tol materials rom their chemical properties posible Experimental results verity the soliton wear theory for the carbide ‘lat of tool materials ‘Theoretical Anal With reference to Fig. 1, the Mux of tol material may be expressed ntebuted by the Producto nlaerng Divito for plato in the octet Or ExeepaaNe Fon INbUsTRN Mars eve st ASM darters Oe 8 Journal of Engineering for Industry the wear rte of the ool material cm/s) he ratio of the molar volumes ofthe tol material and the workpiece materia respectively he diffusivity of the slowest ifwsng too constituent atom inthe material being eut (més) the concentration of the too material in Ue material bing ewe ‘the equilibria concentration (slubility) ofthe ool ‘material inthe material being eat he bulk: velety ofthe ehip material atthe tol-chip Interface perpendiculer tothe interface (m/sec) ‘he ist vem ithe dffsion fax. The driving fore fo difution isthe concentration gradient, e/y- The concentration gradient Strongly inflanced by the welt profil within the chi. In pace, itisknown that the chip material in contact with the too slowed cule CHIP-TOOL ‘CONTACT LENGTH TOOL Fig. Schematic ueation a the Chip Flow Geometry NOVEMBER 1980, VOL. 102 / 303 ig. Adherent Workplace Material n the To! Cater cannih lg.2 Hest Generation wai the Chip (bay wn) 8 dove at pases actos th toa face, forming the oll secondary ae rena” Ara consequence of his fct, continuity corsidertions sees tht there be eopenanting lw of chip material avy fore Fea sow fe responsible forthe second termin equation (0) Tee et due tothe bul flow ofthe chip material. 1 wil be seen that thst predominates in most cases of practical interest ‘The Mechanics of Chip Flow “Available information suggest several features ofthe mechascs cof chap om, Nea the oo tp the ciples across he fol face an Hee reicty Ascott acre Ue interac, Heats generate ve fac. Aa canbe sen in Fi 2, after Boothroyd [Sl the aus aoe nine of manic heat generation shift from the chiptook care elntn the chip asthe chip averse the tool fee the ransition aaaeng a the areow in the figure. This would be expected if Teenie from aiding to sticking occured at this point. Tr tenable to expt thatthe maximurn deceleration ofthe chip masta occur inthe region where the transition from sling ‘Beckng occur This wil sult inthe seats bulk velocity perpen Sieln the interface and, consequenty, n the rents solution “te tows con seton fhe crater oa hafoium carbide cote ined efter penetration of the hafnium carbide surface lye Tea ee tee ial of Ux workpiece begins to adhere tothe tool ner the maxima wear point “then sm doubt that such ean be learned from a detailed study cot chip low patteras a high magnifeston, Suh and Austen (6) rear nucstody forthe sliding wear of metal that helps ie state the neat surface deformation patterns in this case. A de ANY clectron microseopic study of chip ow might ye iia in teresting results. eee rtcent tine, itis impossible to predic the transition pot a Stalag vostiching from theoretical considerations The ested trabler, prediction ofthe chip-tol ntact length rom basi materiat properties, bas not been solved Peers our nay to determine, eholut wear rates cannot vc eietated from purely theoretial considerations, However, ity Ie Saiar for eifferent ool materia under sila cating conditions, virtue wear ries ofthe materi can be determined athe aioe aoe rdcts of the solubility and e geometric factor foreach mae SaaeT Mhotefore the solublitic are derived thermodynaialy, he ralative wear rates tay be evaluated wsing thermochemical ata TRlatve wear rates provide all ofthe information that i required to choose among the various potential too! material foro given ‘pplication. 304 / VOL. 102, NOVEMBER 1980 tn this study, solubilities have been estinated from reported tharitynamie propeties and phase diagrams. Approximate au tae tol material in body-centered bic iron a GK erimated fom avaiable data, ee listed in Table A2 The ae tered to Reference [7] for details concerning the tech ‘igues uted in estimating these sobiiies A et ted th the short ties characteristic ofthe euting prea ntl efit time forthe sash body entre ere ace centered eubictrsnafrmation i rn to occur. Wile Sagi strained material in the euttng zone defies proper ste La on i elicved that tix best approximated as meta able body: sentere cubi iro, st dhows compari of predictions ofthe relative wen etn wth tent els (om inserts contd withthe oie capatentd prowess developed at MIT [5], The wer ate cea raid arbiter st oqualtouity a each temperate aera taive waar ates the ater carbides are auld foc ra avatur o this bass may be seen thatthe predicted relate (eee oe bt wth the eat reclts inthe range o 1 00°K 9 100°. Discussion ae rrpancy nthe wear rate of TICs explained by the pick ratte 1 Comparison of Thera Predictions wih Test Rete 1 Pas pao tn a Saar go) 62) ae ore) Gre) wa) * Gon) aa es) GRAB Sate Serine etter ae ble sree re ‘Transactions of the ASM a iy & rom reported ‘oritate sl cubic ian at Fable A2. The sing the tech 26 the cutting | vody-centered occur While sted ae mete tive wea tes ‘ad with these Thewearrate Ihtemperatare ‘lated a cach Ute relative oF 1, S00°K to oy the pickup 1 1 4 the ASME ‘of oxygen from the steel workpiece. As punted out by Carson (9), the ‘umber of oxygen atoms per unit velame in normal stcel exceeds the ‘number of oxygen atoms per unit volume at normal stinpherie oxygen partial pressure, Thus, ample oxygen is available fr reetin ‘with the ool material. Shor after engagement of the tol tip, the ‘ool material at the chip-col interface establiheschemial quite rium withthe workpiece material. The effective composition ofthe tool material in cutting is determined by this equilibrium. While al ‘ofthe carbides studied can substitute oxygen for carbon ta various extents, only titanium and niobium form stable monoxiden Suh, Carson and Leung {10] have noted litle diferenc inthe weer rates of sputtered coatings of TH and TiO asin the machining of tel ‘The predicted wea rate of ICO is included in Teble ‘The data clearly shows thatthe wear of aluminurn oxide isnot contzolled by the solubility of aluminutn oxide in ton. Thi ine ‘ouraging for tool development since the mechanical properties of ‘materials are subject ofa greater maniplation than the chemiea! properties ‘The fart that the solution hardening of aluminum oxide increases the oo ie [11 12] suggests that plastic deformation operate inthe ‘wear process. Kane and Hasselman [11] show strong evidence of plastic deformation in aluminum oxide tooe in steel-cuting and suggest that dislocation pile-up nucaats crack, Carson [1] shows Dhotographs of microcracking at submicron interval in aluminum ode coated insets ater uee in cutting, Subramanian U4] has ela) noted microcracks, ‘Tho work Suh and Filion [15] on metl-bonded oxide tools ea ew approach to improving the mechanical properties of oxide ‘Accurate determinations of the diffsivitis of the element in- terest in diron would settle the kev of the eae of diffusion in tot ‘wear. In the absence of such data, no final determination can be tad, ‘Lack of experimental dita sho makes it impossible to preclude the ost that wea is limited bythe Knee ofthe separation of ool ‘toms from the ool lattice, a perarster elated tothe self-diffusivity af the ool material. This is the question of whether tol wer is an quills proces, Explanation ofthe inversion ofthe relative wea rats titanium carbide and tungsten carbide when cutting tee and nickel-based alloys extremely ifcult if wes i controlled by the kineties of ‘partion. The phenomenon i explained by the greater solubility of itanium carbide in nickel This eelt expected from thermo. ‘dynamic considerations and inde othe lower relative partial molar fee energy of solution of titanium in niekel ‘Thermodynamic analysis hae bread application to cutting tol development fa outside wear rae prediction, as hasbeen demon: strated by the truly revoltionay tool microstructures developed hy Ray [16] through spinodal decompition reactions. The major ad ‘vances of the coming years in tol development wil undoubtedly be through thermodynamic insight and an understanding ofthe exe thanical wear processes, Conclusions For the first ime, its posibl to predict the relative solution wear ‘tes of potential tol materials rom thermodynamic properties. Tt ‘Suggested that solution wear donates the wear of the cides and that there is ite potential for farther improvement inthe wer fe stance of the carbides. Conversely, substantial improvement in the ‘wear resistance of the oxides is expected with improvement inthe ‘mechanical properties ofthe oxides References 1 Then "Some Paco Aeing Wea on Cmte Cade Too” ‘roening ofthe Inttation of Machel Enger (A), Ye 196998, 2 Tren "War Prec on Cmte Cie ok ain Catng ‘Sth Prodigy ofthe Raya Sot of Landon, Seis A Vol 21 1883, 1 Cook, and Ney, P "Daven of Improved Catng Tel Mati" 0." Alr Force Techie! Rept AFML-TIOS 185 6 TB Ny “Suita rennet and Costing Fes or Coast Journal of Engineering for Industry Geshe Ton” Prceoting ofthe Nor Americ Metalwork Conference, in Boothroyd, G, “Temperstars in Orthogonal Met Ctting” Pro swig hn hehe ar a ay 6 "Aginton, Gy 8: Thess, Deparinent of Mechanical Ragan tao 1 ‘Rear, An Anaya! Approach Tool Wear Prediction, PRD. ‘The Depertineat uf Meche! Engnnrng MT. fon 9. 1 Cake Nv and Karr H“Tunpten Cutie Tick rated with Grp 18 and VE Mota” US Patent Nur 400,801, 208 0 Canon, Wate cmmantion 10, Suh Carson, Wand Leung C>“OssearbdesasCsing oo Mu teria” ASME, deurol of Boncrg fi ada, Wel 3990 9 8 1 “Maswtan D and Kae, G, NSE Hard Matas Reach ol 2, MIT cuatro NTIS Number PHLBDION TT 28. 12 “Fama Prin Adonces in Herd Material Pehneeey, Proeeiog ot shoe nto Contrenc om ard Mati ecg, Cae 19 "carn, Wee a NSP Hard Metros Research, Volume 2 MET Contre NTS Numba PE 22808, 7%, p28 TH" Subramanian PK pete conimunenton, 15, Suk Ny abd Flin P, “Opinion of Caltng Tot Propertie throug the Despont Alamo Cares Wear topper 180 i Ry. NSF Hard Matra esearch, Votan & MP Caner, [NTIS Numfar Ph anton, 0. 17 Bava and Raine, "The Sali Sb of Same 8 Gates in Cobalt Nike! ad ic at 350°C" Pe Prose E Banmoray (ol, Metallwers Panes Gon MINH, Rest/ Tyr 5889, 18 Dow, Wand Prac, 8, cba Phe a Tange Ce 19 Cig, W, Berni, 2, Gin Ctl gram, M. "Terman inti Sara aon li Carion oro Poa Chee 20 Asis Ry "Phe Tarmac Stability of Moocaries Tran sion Mra fas Sabroape WV" Sout Poder Meter ond Netal ‘eromies, Vat), ns. 2 21" Giman. Harden Cubes nd Osher Refectory Hard Metals” urna of Apped Plone, Vol thy No 1, 8 "2 Lye Hand Srciare apd Bonding nanan Cabin tome gu len Sirctre of Metal Amen Set for Na Ness Pak, ‘ho te pom 30 Keir and Nec Inet the Cries of roe 1B and VB Tent Metal wih Vargo sn in Chemeal Proper nd Arby erect Conran 6 Soman eh Conan Bs ot Mulyen cl, Selected Value the Thermodyae ropes, f Binary Alo, perc Sst or Nay Metals Pr Oh ok, 25" Schick I, Thermodynamteof Coats Refrastry Compound, As ec Pren Nock 68 ‘2 Sl Du and Propet H. JANAF Themochercal Tables Second ation, US Sopra f Doesnt Naber C817 21 Tat, Jy Cleary and Rar Vy Thrmethemy for ‘Stornghing Adon Wee Reading Masarhanie 6 2 "Stoona The efetary Carey, Ace ies New Yor, 187 29” Hillard, 4 ton Cale Phan Dagam: Lobe Seton ofthe uted Mego ct. had 8 Kloary” Poneto of the Meal Scenes Ya ip a ‘naan Condensed Stats Raxco High Preares"in En: ratics in Metluial Prono Vlune I. W. Ms el, Condon ‘Sh Breach New Varc ,p “1 Kabuscova,O, nd Dench, W. “The Hent of Fara in the ‘Syste ini Akane Fein” Ata tore, Ve 32 Waatan D. ota, Slced Veins the Chama! Thermodyranie Properties, NBS Tesh Noes 2703 (0, 99-409) and 0 GT US! Goverment Pring Ofte, Washing, DS, pcb, Kelme Oa Bom, Br Mtge Themaceniy '3t"Htnsn My Contin he ine Alle McGraw Hl New York, ER Cotati of he Binary Asis Supplement, Mir ew York 18 Shik Comtituion of the Binary Als, Second Supplement, Mora Hl New York, 135 Sater P Plenum Pres Handbook of High Tomperaure Metro Matevatndee, Panu re, New Yk et 2 Appendix A Eatimation ofthe Solubilitie of Potential Tool Materials at 1,600°K. Data concerning the solubility of refractory material in ‘the iron-group metas is sant. The dta of Edwards and Raine [1], NOVEMBER 1980, VOL. 102 / 305 hin Tobie AL_the Sohios of he Caries athe Hon Croup Meal at ieee Solubitity tn wt, £ (rote x) bie Taba hick ron we mins) 238) (R.2) ne Ta 848) <5 te8) a ie) 7066) 32.7) me si) 307) 1 ne ahs 80) 5 (18) which athe only systematic study of the sold soubiities ofthe xt Bide in the Iron-group metal, reproduced in able A Dawih etl, [18] cite conclusions made by Pau and Rix inthe German iveratue tothe effec that, when tungsten carbide goes into solution in coat, tungsten atoms substitute for cobalt while carbon ‘toms il interstitial ites. The wil undoubtedly be the ase for tool ‘onatitutents dissolving in rn, If disocation ie rqulred, at equilibrium: aay = Gs + aco ay sohere: ‘Aly = the fee enengy of formation ofthe tol materia ATM the relative patil molar free energy’ of solution of component fan the relative partial molar fre energy of solution of component ‘The relative partial molar fre energy of solution of component ‘can be expres in terms of the relative partial molar excess ‘energy of elution, the exces foe ener): AGM = Ati+4 RTIne any where ¢ 40 he concentration of component and the relative patil molar exces fre energy of solution ‘of component i Ifa rluton obeys Henry's Law, the excs re energy wil ein constant with solute concentration st a iven temperature culated constant values ofthe exces free energy fr the tool constituent of interest are ited in Table B2. The assumptions ard techniques employed in calculating these values are discussed in deta In Appendices B through ‘Tocalelat the solubility of TIC in edron, tequilla: AGre= AnM+ Ae From Table BE: ATip! = 6900 + RTIncr camo and ATicM = 47,600 + RTince cal/mole ce. Therefore, with reference to Table A2: 99,520 = 700 + 28TInCe For TC, ers "Therefore: Cne= 1.86% 10-9 at 1,600°K By simile ealelation: ype = 191 x 10-4 1,800°K ‘Therolative wer rtes of TC ad H/C at 1.600°K can be calculates, from equation (1) ifthe molar volumes of the two components are Known, From reference (J, the malar volumes of TIC and H/C are 12:20 and 15:06 emole respectively. Therefore: Wear Rate of IC _ (1.86 10-8) (2.20) eat Rate of HC (197 X10) (15.00) 306 / VOL. 102, NOVEMBER 1980 "This value sented in Table 1 Eatimated solubilities of potential tool materials at 1 800°K are listed in Table AZ "Tool constituents may accumulate carbon o other interstitial a rmospheres once they are diseoved in the chip, lowering thelr re nergy. However, beeae ofthe complex and larga metalicnatre ‘tthe bonding nthe efractoy carbides, te expected tat an solated peir dissociated frm the parent lattice, wll not exhibit strong bonding Mas spactroraphic sts [10] indieate that TIC dias ates completely on evaporation, the ony gaseous species detected Ting 11, C, Cs and Cy The oer carbides of interest in this study probably exhibit simiae behavior (2). "As explained ly Giltnan [2] afer Lye (22, In THC the d orbitals ‘of si Glanium atoms overlap at each octahedral ole in the face. ‘centered euble taniam ara. The carbon atoms relocated in tees ‘ctahedral holes, Due to the ovelap, electrons in the eatbon ome fare ale to rodce thelr hinetic energies by moving in the d band of the titanium subatie, This interaction serves to stabilize both ‘ublattion Gilman eliminates the possibilty of any substantial ionic ‘character in the bonding of THC onthe Bais ofthe observation that {he priary lide system of TC i111 (110. Ti lide ster would justapse lon of ik polarity during slip an would be inhibited by {ny substantial one character in the bonding: Kolyar and Naxr ‘hulk (20] sugges hat there ete fnie character in the boeing of THC, VC, NUC and TaC onthe basso thee study of the reaction of these eatbides with acids They suggest on the same basi hat the bonding in 270 and H/C although nt predominant tne, displays mote ionic character than that in the her earbides. Trone-sinth ofthe difference between the heat af vaporization ot the metalic constituent ofthe carbide nit elrmental form and the rll het of vaporzstion af the metal the carbide iter aan Upper Limit forthe covalent bond etrength of soled pai, git Sim bond energies esl [7]. Inthe absence of strong itereton, iti onder unlikely that interttl atoms will ocupy the alread Stsined interstices djacen to oversize sbatitational lute tons Table A2_ Eline and Reported Sohibiis of Polen Tox Malas Dein tear mage’ epee, dear, yt? wt ie Ea Sa 16, v0.00 6) a a8 na moon) 585x107 ma mn vs) at 1p nord ata ws We si (3) haa es saat) sat we eee pout! an Ne pey -aM)8e ne cemced ae a sei) ot Me cstewe ee) at ara He Ginny -aest0 ee) 18 ean? we seats) 20) can? tgp) 2600 (28s « eo asx? * sawun sane? ne (iat anor atte? Gane? oh ste) 88 ssi sets) anon ‘Transactions of the ASME ies of potential + interaiielat- fering their foe ‘metalic atre that an acted exhibit strong that TiC dso ecis detected sin this study > the orbitals dle in the face located in these seatbon atoms inthe d band of sable both lbstantial nie beervation that {esystem would be inhibited by yar and Nazar the bonding of the reaction of oasis that the ‘nde dsp saporiasion of ‘form andthe veistakenasan sed pain quite py the already solute toms eae) atthe | Tle Bt Estimated Soy Lint of he Elements nee in Boy ‘entre Cie won st 400"X(33) ® 2 ear a neat fre " Oa fat tal te eat 1 26 fags te eat 8 TODS AGN hat Oe AFT tie Aeroestae (14% teeentee ana heise Its expected that no substantial interaction wil take place wnt precipitation of «refractory phate can cecur For tool constituents Forming lke precipitates, since the equilibrium concentration ofthe tool materia inthe material being cut ix never exceeded, na preci tation wll ocur, Po ool constituents forming presiptaes th ace Icssoluble than the tool material, substantial supersaturation may be required to muceate precipitate inthe submiliscond tie frame of the metal cutting proces. Diffsion Kinetics are relatively slow at ormal cutting temperatures Thought has also been given tothe effect of pressure, Most re. feacory materials contract om formation from Usir element. ‘Therefore, the stability ofthe refractory material ends to increase sith pressure, Powe cutting este this study, average pressures ‘over the toa face ang from 6,000 to 10,000 atrospheres. The eect ‘teatting pressure on phase stability is evaluated in reference (7 ‘Typically, the pressure term amount oles than one percent of the free energy of formation a atmospheric pressure. Pstimatin ers ‘rowhero are ch that no serious oor wil be introduced by ne Het wich snl terms The lft of preatue i therefore neglected herein, However, if ation of SC influnces the wer of SiC genoa in prioding. the effect of pressure may be significant in this case io Appendix B Estimation of the Relative Partial Molar Free Eneruies of Solution of Tot Constituents in the Chip. ‘Th relative partial ‘na fe ners of elton of the tol eonstibes in the ip must Iekaown before the solubility ofthe tol materia ean beestinated ‘The purpose ofthis Appendix and Appendices CD and Bs toe rate the fre energies solution fom the ited data hat is avail the ‘All tol constituents ar assumed to dnsolve inthe chip in cco. dance with Henry's Law. Therefore, the relative partial molar fee ‘nergy of solution of component may be expresed AG! = Reina, = RNC wn whet of, and; are the activity, aetvty coefficient and the con ‘ntration of component, respectivaly andy; is «constant inthe solution range. Alternatels AGM = RTiny, + RTIne) = AGi""+ RMN, (B) ‘where A0/* isa constant within the solution range ata given ten erstare ‘Ac the solubility imi, the solution will be in equilibrium with a second phase, Therefore the free energy of oltion of component ‘tthe solubility Limit must equal the fee energy of formetio ofthe Second phase per raat of, Many free energies feluton ate Journal of Engineering for Industry ols 82 sia Een Foe om of abn el Conon Tot am const vent (catories/a 1 6,900 1H (M) 26,600 n ‘ caw) ‘stimated herein using this technique The solubility Limit ar st ‘mated from phase digrams and are summarized in Table Bl Tall ears of atelcuting too contents are sesomed to be Aissolving in body-centered cubic iton."The fee energy change for transformation tothe facecentered cubie modifiation at 1,600°K ‘sry smal, ~6 calories permoleat atmospheric pressure [27]-The ‘magnitude ofthe fe energy change wil be sight large tthe igh pressure encountered in metal eating doe tothe volume contraction {hat ocersontansformation [29,0 In addition, the severe defor ration nthe cutting zone mey provide signifiant opportunities for Inecharical activation of the transformation. However, given the served sloggshness of the — a tennaformation intel and rea. ining that the total time of heating of the chip ison the oder of milseconds the asumptinn of ametatablea-phase inthe y tai Feld seems the mor reasonable one. "The relative partial molar exces fre energies of formation of in teres are ummarined in Table B2. Phe techniques used to eatinate the values are detailed in Appendices CD and E, Appendix C Extimationof the Free Energies of Solution ofthe Group IVB. sand VE Metals. Kubsachewsli and Dench [1] have invertigated the system Fe-T by heating colé-pressed pomder compacts until reaction occured. They were unable to produce Fez by thismeans Instead, mixtures of FeTl and Fe were obtained. Specimens chong ray powder difeaction peaks for FeyT¥ have boen produced in the ‘carte investigation by cooing Fe-7i malts in vacua. Kubaschewski ‘sorests that, when more than one intermetallic compound form betnen elements nelling point may be indative of the telative ‘heats of formation, those compounds with similar meting points having similar eats of formation per gram-atom, FeT decomposes peritectic to FeyTt and gud at 1.590°K. FeyTi melts omgraently| 41 1.700°K. These temperatures are quite similar, Therefor, iis feapected that Peg and Fe have similar heats of formation on @ ‘ram atom basi "The beat of formation of FeTi in ~4880 150 elories per gram stom [SI]. Taking the heat of formation of FesT tobe equal on 2 tram-atom basis, the heat of formation of the compound Fes is 714.550 450 calories pet mele. ‘The etry of formation of FeyTi a unknown. The fact that Fe,75 canbe produced on cooling fom the melt but not on heting suggests NOVEMBER 1980, VOL. 102 / 907 ‘Tobie C1 Moting Poi ad Voune Change on Fomaton of Grew VB {na i terete Compound wth woe [3a] femay Sy “Sei? eta ese reo sng a.m) lt attr faye tay te cae Conaty a postive entzopy of formation and inereased stability at high em perature. [AAT (296°K) ~ AG (208°K)] of FeaNb reported as 700 alors per mole [2 indicating AS (288°) of 235 elas per male *K for PesN, Rather than introducing sgificant term on the bass of one de termination of unknow securay, the heat of formation of the i termetali compounds have Been taken as a measure ofthe fee ‘ergo of formation, eS = 0 Ttshould be kept in mind tha the ‘ioe energies wl probably be overestimated inthis way and that the terror may be significant, In the care of FegNB, if AS (1600°K) = AS {GaseK}, PAS (1600°K) is alto ~8,780eaores pr mol. When more reliable data concerning the entropies of formation and the ‘aatons ofthe heats af formation with temperature forthe com pound of interest become availabe, determination car be made As pointed out (5), Uh methods estimating heats formation are not very relable abd their uncertainty i such that as ray ‘methods as possible shouldbe used to etimatea single value. ‘he sractures and melting points ofthe Group 1VB and VB in termetali compounds ofthe type FegX ate summarized in Table Ci All five compounds are ofthe Laves type and have very closely related structures, All ive compounds melt congruenty and have Inelting point maxina corresponding to the composition FesX. Within a given grup, maybe remsonable to estimate relative heats ‘ot formation by means of abate wlting point ratio. Pre energies tt formston for FexZr and Fesif ae estimated from that of Fey Ti tn this way. The fee energy of formation of FesTa is estimated from the known value for FeaNb, Results are summarized in Table C2, ‘Determinstions from malting point ratios show regular variation instability with nernee in atomic mraber within group In Keeping ‘with obeeved homologous relationships in other systems [3 However, it should he noted that the quantitative determination of heats of formation fom melting point ratio is somewhat sovel ‘Therefore, independent checks are requted. ‘Heats of formation can alo be caeulte from the volume change on formation of a compan [3] Elective volume changes on for: ‘tion ae summarized in Table CL Reference [7] gives details ofthe {echniques wed incleulation, These calcultons inca a geometric Factor that compensates for lack of eloepacking in non-

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