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Joach~m Grobner. Dmytro Kevorkov, Rainer Schmid-Fetzer Technical University of Clausthal. Institute of Metallurgy, Robert-Koch-Str. 42 D-38678 Clausthal-Zellerfeld. Germany


which direction to go. In this report we want to s h o ~that thermodynamic calculations can provide much more than that.

In tradit~onalalloy development. expenmental investigations mith many different alloy compositions are performed. The selection criter~a for multicomponent diffuse alloying in a elements traditional and the~r cornpos~tions become approach.

Computational thermochemistry is a modem tool that supplies quantitative data to guide the development of alloys. It enables the calculation of rnulticomponent phase diagrams and the tracking of individual alloys during heat treatment or solidification by calculation of phase distributions and phase compositions. These are the basic data to understand and control the behavior of any novel or modified Mg-alloy. Large-scale experiments for new multicomponent alloys can then be focused on most

Computational thermochemistry can provide a clear g ~ ~ i d e l ~ for ne such selections and helps to avoid large scale experiments with ~ t on less promising alloys. Thus. ~t is a powerful tool to c ~ down cost and time during development of Mg-alloys. As an example. me report on recent developments of nem, creep resistant alloys that show about 100 times less creep than the best con~mercial alloys. Also outlined are the methods we use in our long-term project of construction of the necessary therrnodynam~cdatabase for several prom~singalloying elements like Al. Li. SI. Mn. Ca. Sc. Y. Zr and Rare Earths. using the Calphad method cornb~ned ~ ~ key t experiments. h

alloys identified in that approach. Long-term experiments with less promising alloys can be avoided. Thus, it is a pom'erful tool to cut domn on cost and time during development of magnesium alloys.

Database Develournent
In the core of this method a h ~ g h quality thermodynamic database

There is an urgent need for the development of new or improved magnesium alloys if \4e want to fully exploit the potent~alof this t'asc~nating lightue~ght mater~al that also offers excellent cxstah~llty, ma china hi lit^ and b~o-compat~bility. Experiments on a technological scale f o r preparation and testing o f new a l l q s are \er> eupensl\e and time









thermodynamic database for multicomponent alloys requlres a combination of experiments and computational thermochenlistrq with data Prom alloy application. Since numerous binary and ternary subs)stenis have to be treated and validated \v~th key experiments before multicomponent alloys can be calculated reliably. t h ~ sdevelopment becomes a long-term project. In our group at the TLI Clausthal a thermodynamic database for seberal alloying elements like Al. Li. Si. Mn, Ca. Sc. Y. Zr and Rare Earth elements (Fig. I ). has been under construction for more than fi\e bears and is still ongoing. M a g n w u m Technologj 2001 Edited by J Hr?n TMS (The Mnerais. Metals & Materials Society). 2001

In vie^ of the huge number

oi' posvhle allo) components. compositions and

parameters. one \\auld like to hale at least an "educated guess" in

The in b~naryphase d~agram had to be re-investigated (91. 3). Therefore. Ho\+ever. Mg-AI-Ca-Si) [2. 61 The thermodynamc and technical application of the temarj Al-Mg-Sc 15 alreddb discused In l~terature[7. Mg-AI-Ca-RE) and density reduct~on (M~-LI-AI-SI. phase d~agram data and t h e r m o d ~ n a m ~ proprrt1e5 c Therefore. The principle of this method I S shoan in Fig. dur~ng ageing and improve the mechanical properties on14 slightly because of their incoherent interface. seheral exper~mentalmethods are b a n g applied in our group to produce a sufficient exper~mentaldatabase (Fig. Example\ for d~rect applicat~ons are given in the followng chapters. MgSc l5Mn l or . hinary MgSc precipitates form Lery slo~.l! neta astable equil~hr~a for process simulat~onor direct applmt~ons. The parameters are optimi~ed by avmlable expenmental data integrating both thernwdynamic and data. 3: Experimental methods. Thermodynamic Modelling Our a o r k focuses on ternary and quaternary systems for ) ~mprovementof creep reslstance [ I ] . 81 Here the quaternary systems Mg-Mn-Sc-Gd and Mg-Mn-Sc-Y are shown as example for the selection of new creep resistant alloys uslng computational thermochem~stry. Neu.I Creep resistance ' \ Density reduction I In Mg-system5 the exper~mentall ~ t e r ~ t u r data e \+ere \ery q w s e In both. Opt~cal Mlcroscopy Fig. thermal s t a b ~ l ~ tzpra? forrmng (Mg-Mn-Sc-RE. Scandium \\as In a multicomponrnt.STA) X-ray Dlffractornetry ( X R D . Fig 2 Schemat~c approach of database development and the Imks to First generation of creep resistant ternary hIg-Mn-Sc alloys appl~catlons In~est~gations started w t h binary Mg-Sc alloys. it is s h o ~ n Fig. Mn uas added as second alloy~ngelement. 3. 2 5 .1 5 0 0 " ) Electron Mlcroscopy (SEMIEDXIWDX) Metallography. 2 Fig. I: Currently selected alloying elements in the Mg-database. The calculat~onsare ~ m p r o ~ e cont~nuously d by new espcnrnental data coming from apphcations nnd are checked hy key evperlments to improve their r e l ~ a b ~ l ~ An t y . 4. Tn_ls data set is used to calculate stable and phase equil~bnurn chosen for precipitation hardenmg because of its large solub~lity In (Mg) and the retrograde solubility at louer temperatures. Experimental Methods Sample Preparation Levltatlon Meltlng Arc Meltlng Electron Beam Meltlng Reaction Slnterlng Sample Analysis ThermalAnalys~s(DTA. The precipitatmn of Mn& \+as predicted by thermodynamic calculat~ons Mn& precip~tatmnsform coherently and uere found very useful for ~rnproi ing creep reslstance and hardness.example for process simulat~on1s the coupl~ng u~th 3D-sol1d1ficat1on n~odel~ncp. niult~phase system each phase is described in a suitable model for the G h b s energy. 5 . 3 . To create the thermodynamc phase descriptions the Calphad method is used.

Therefore phase d~ayraiii and other cillculatlons \\?I-eperformed to ~ d e n t ~ proini~ing f) canddatts I Phaw diagram feature I Kele\ance for alloy Ulo\ selection in the 51~-\In-Sc-(.MgSc6Mnl alloys shou about 100 tlmes better creep resistance than the best commercial IY E43 alloy at 350°C and 30 hIPa [ I ] At this point the questlon arose. Y and Zr were considered for t h ~ \ purpose to achieve a sufficient quantity of suitable preclpltatcs to Improve rncchan~cnlpropertics u u n g n mlnlmum (>I' eupensi\e alloy element add~tion.lg-hlnS c alloys.% SC 50Gd 1 OVn 94 0 Mg 0 0 Sc 93 0 Mg 1 osc UI Add~t~ona alloyng l elements Gd. 5 hlg-MII-(Sc.6 FIE 1 Thc b ~ n a ) Mg-SL \)\tern atter [9] Wt. O 6 S c sc 50Gd 1 OMn 0.nougti c Alp) 51nglcplia\e field Enable\ Iiomogeni/ation ailnealing . The most Important polnts are g l w n In Table I In spite of the good properties of t h ~ sfirst generation of h.' Whal is needed is a list of beneficial phahe diagram feature\." What phase diagram features are related lo what alloy processing steps . d r r ~ ~ e d from the relevant alloy processing steps.'? S c o r more) ~ n ~ t ~ a tae dsearch for a second generation by i n v e s t ~ g a t ~ n g quaternary systems. These elerncnt comb~nations F I ~ 5: . pronilslng a l l q cand~dates from all these calculated diagrams.4 0. Z r ) f o ~ m a i a n e t y o l quatcrnar) systems and thin tho\c there is a huge amount o f p o s s i h i l ~ t ~ toe ~ select allog Table 1: Beneficial phase equilibrium features and their relevance for (5Ig)-alloy processing compo\itions. 0 l 0 I I I I I I 20 40 60 80 100 Mg at.\stem Larpe t.Mn.Gd. the high cost of S c add~tlon ( 6 wt. Y. "ho14 to ldent~t:. Phase d ~ a g r a msection n ~ r h constant I n t i .2 0.d.

6 : Phase amounts of MgMnIGdiSc0. 200 Mg24Y5 Mn. which can he seen In the enlarged Insert in Fig. first results for this alloy shows a creep resistance similar to the prevlous ternary high-scandium Mg-Mn-Sc alloys.8 alloy Alloy selection in the hIg-Mn-Sc-Y system liquid In the Mg-Mn-Sc-Y system heveral ~ e r t i c a l\ectlon\ In the I-anyer 01'0-1. 6. Diftercnces cornpal-cd to the Gd \)stern can he o h w r \ c d concernln? the htablc s o l ~ dphases and the forniat~on 06 08 10 Phase amount [moll Fig 8 .Sc preclpltate f'orms only at temperatures he lo^ 500'C. Sc.Q Mn.08 0 1 M n .'/. start forming at 325'C. 5 Sc. about 100 times better than best commercial WE33 alloy at 350cC and 30 MPa as detailed later. 7. MgSc 0 06 0. The des~red LIn.G S c ) .For an alloy ~vith I wt.% Gd and 0 8 ut. 5 \\t. 0-10 wt. Similar features are ohserved for an alloy with even less s c a n d ~ u m ( 0 3 wt. ' i Y \\ere stud~ed 0 7 i h o u s a T-x sectlon of a calculated cjuaternar> phase F I ~ e q i ~ ~ l ~ h~11th r i a constant I u t C. sol~d~fication and heat treatment are piken Fig. In h c t . In the whole ranye ot primary c r ) \ t a l l ~ / a t ~ o ioi i by arrow In Fig. like in the con-espond~ng d~agranif'or (id. 7 4 hln. 0 02 04 A large one-pha\e ticld o f ( M g ) and se\e~-a1 d~ffcrcntr o l ~ d pham \table at Iouer ternpcratures can be seen.8 allo! . 0 1 0 02 I I I 04 06 08 1 0 Phase amount [moll Fig. 5 Fig. Phase anioilnts of LIgLln I1'5Sc0. prlrnary ( M g ) is formed and consumes the melt totally up to the sohdus polnt at 6 1 9 T At 590°C the first prcclpltate Mn2Sc starts forrmnp. 7: Phase d~ayrani L I '~i Y from 0. Large amounts of the second preclpltate Gdhlg. 1' from 0. Sc and 0-10 u t . 5 nt. section ulth constant I ~ t . This alloy fulfills all features illustrated In Table 1 and was classified as ver) promising for further alloy development.5 LI~.':. wh~cti decrease ~ ~ decreas~ng t h Sc c o n m t .'? Sc (indicated temperatures. 5 ) e q u ~ l i b r ~ uphase m amoilnts during In (My) the secondary phase is M n l l Y .'. At the I~qu~dus temperature 650°C.I \ i t . ' .1 w t .

.The estahllshcd Mn2Sc and the ncu hlg24'r'5. Zrj \\11l he publishecl \eon [ 101 . Thls alloy d~squalilied LIncc Mn2Sc forms a j the prlrnar) phase from the I ~ q u ~ clearly d. The Mn12\r'phase would onl! be stable In the \()I111\tat? In a high temperature range from 605 to 322°C and n i ~ ! not form at all d u r ~ n gfast cool~ng.lllo)< iuth 1 ~ 4 t . s l000'C are reached for less than 0. Y. Moreover. the entire quaternary Mg-Mn-Y-Zr alloy \) ztem 1s disqualified.eien In \cry large amount.MnzZr in cornparlaon to the other phases. and e\en Lln. prirnar! Y and 0-1 u t . could form by agtlng in a favorable temperature range.tant I \ \ t c. In 01-der k-r checA if the amount o f MnJc Increasing could he raised h j ' . 5 i\t r'i 'r' and 0. q ' Mn.I \4t 3 Zr. ' i Zr.1 wt. wen In thc Inset of F I ~9. Xln.5Sc0. But this \\auld also drastically reduce the amount of beneficial Mn-conta~n~ng F I 9 ~ J'or the alloy MpMnl.5 i4t. and actually the reason for the steep liqu~dusline. he the only \\. 111t goal ofdrclaticall)~rrduclng the Sc-contc~il c m he ac~cc~rnpl~hcd illo. L 1 1 ~1s ) formed and consumes the ~ ~ i etotally lt up to the sol~dus po~ntat 613-C. Since yttrlurn does not play a significant role In that part.1 I I I 0 0 02 04 06 08 10 Phase amount [moll F I ~10: .a)' to dimrn~shthe L+Mn2Zr prlmar} ficld ~~l. .an alloy \ \ ~ t h I I \\ t ' i ivln.Such a ! anneal~ng nilcrwtructure cannot be "repalred" h preclpltates. 10.5 u t u e can examine IS drastic reduct~onof the manganese content. is a prlmary (hlg) sol~diiicat~on expected The reason for thls destructi\e phase dlagram f e a t ~ ~ rIe S the extremely high thermodynamic stabihty of .S also a promis~ng alloy. \\stern More cletails of alloy selection In the q~iate~nary s) \ k m s 112-kln.not d~sccrnible In Fig. LlyhlnI Y5ScO. 4.Sc.SY.8 Mt ' i Sc u~bstlt~ltlon can he srudled In Flg. Xr [he 11qu1du\ temperature 644°C. 2 - L t (Mg) + Mn'Zr cn 0 1 0020040060080. As a result. Phase d l a ~ r a m sectlon wtli con. Gd.I the manganese content to 1. 10 for scandli~nifrt'c . (Mg) fornis only secondar!.% Zr.:\r' limns as a terliary phase d u r ~ n gsolld~fication. T h ~ s makes + Mn2Zr.q ~nd~caie b) d arrou In Fi?. 10 Only for extremely small Zr-add~tions. 7 ) phaw amounts durlng soiid~licat~on gl\cn In F I ~ 8. I d~agrarn sectlon sho\<sa ver) steeply rlslng I ~ q u ~ d u lint. \election in the \lg-hln-'l -%I. stretches over the entire composition range In Fig. 5 \ \ t 1' lrom 0.Pol. a huge primary crystali~zat~on tield.ould .8. T h ~ sphase ai.

The current end point of commercial alloys is given by the WE series containing Y and Rare Earths. The history of commercially developed creep resistant alloys is briefly summarized in Fig. "Magnesium Technology". 14.l Fig. the influence decreases In the order Nd (Pr) > C e > L a MPa 1S I . 12: Creep properties of commercial magnesium alloys.Comparison to commercial creep resistant Mg alloys In order to assess the results on the creep resistance of the selected new alloys we have to choose a commercial alloy as a benchmark. Yield strength and creep rates of these alloys were measured in the as cast Alloy Composition (mass%) Zn Ag Y RE Year condition and also after heat treatment [I I]. are not included in the listing of Fig. It is clearly seen from Fig. The alloy WE43 with T6 heat treatment was chosen as the benchmark alloy. 12. SEM and TEM investigations and energy dispersive X-ray microanalysis. known to be more creep resistant as standard AZ or AM alloys. Alloy preparation and creep resistance measurements The most promising alloy compositions identified by the thermochemical calculations were prepared by squeeze casting by our project partners within the Thrust Research Project SFB 390. -30 . 13: Creep curves of first generation (high scandium) alloys compared to the WE43 benchmark [I 11. 185 time [s] 181 Lord 100 h. . I I since they rank below the ZE alloys. 200'C Fig.13 that the secondary creep rate of our first generation (highscandium) alloys is better by a factor of 100 compared to the WE43 benchmark alloy.R E . T=350°C.most of these alloys conlain as gram refmer about 0 7% Zr . 11. Fig. A micrograph showing finely dispersed Mn& WE54 18 WE43 16 OE22 18 ZE41 T5 A281 T4 Alloy precipitates in a MgSc6Mnl alloy after T5 treatment is given in Fig. The existence of the MnzSc precipitates was confirmed by X-ray diffraction.Sc precipitates. 2 6 elongation is highest for the WE series as seen in Fig. at the TU Clausthal. the maximum stress that can be tolerated at 200°C for 100 h and 0 . The first generation of alloys showed a strong annealing response due to the formation of the Mn. 1 1: Commercial creep resistant Mg-alloys Alloys like AE42 or AS21. In fact.

However. The best alloy MgGdSMnlSc0.Conclusions Focused magnesium alloy development is now possible using the powerful tool of thermodynamic calculations. U. Again. Material Scie. Dead Sea. R.% Sc. 1997. von Buch. Draugelates.3 w t . November 10-12. . Steinbom. -30 MPa References 1. alloys with 6 or 15 wt. "Simulation of Laser beam welding of Magnesium alloys". F. F I ~ 15: Creep curves of second generation low-scandium alloys 2. S. considering the huge number of less promising alloy The creep curves for these low-scandium quaternary alloys are shown in Fig. Alloy compositions with promising possibilities of alloy microstructure design can be selected by means of thermodynamically calculated phase diagrams. This IS substantial progress compared to the first generation of Science&Technology. Pisch. R. an almost 100 times lower creep rate is achieved at 35OoC and 30 MPa compared to the best commercial alloy WE43. 8 of expensive Sc. First Israeli international Conference on Magnesium compared to the WE43 benchmark. Pisch. 1 0contains ~~ only 0. & Ene. Bouaifi. the experimental study of mechanical properties of identified promising alloys has Fig. The next step. Schmid-Fetzer. A 263 ' O time [ l o 4s] l5 (1999). phase amount charts and solidification curves. thus reducing the experimental effort to a reasonable volume. B. Schmid-Fetzer.. element combinations and compositions with unwanted properties can be recognized before starting large-style experiments. A. the focused alloy development following this approach avoids a waste of time and effort. Acknowledgement This work is supported in the thrust Research Project SFB 390: Magnesium Technologya by the German Research Council (DFG).3 with the smallest elongation after 1 5 . 14: Micrograph of MgSc6Mnl T5 alloy. T=35OoC. 15. Israel. Further work on the selected alloys is in progress. "Properties of Mg-Mn-Sc-Alloys". The second generation (low-scandium) alloys were selected from the most promising candidates identified by the thermodynamic calculations given in the previous sections. B. Mordike. combinations that could have been selected from multicomponent systems. shown excellent results both in the first generation (ternary) and second generation (quaternary) of new creep resistant alloys. A.L. 1-7. Obviously. Most importantly. these experiments cannot be replaced by thermodynamic calculations.

G . P. N Parodi. Riani. Pisch. A. 7 . 4. Material Scie Er En<. measurements and a5sescrnent of the AI-Sc system". A289 (3000). 171-177. Saccone. Ll. "Expenmental In\ectigations and Thennodynamic Calculation In the AI-Mg-Sc Slstern". Ferro. G. 123-139 9 ."Applrcat~onof Computat~onalThcrmocheni~st~-y to Al. A P M R. Mordrhe. Pisch. Intermetall1c5 7 ( 1999). Z. Saccone. Buch.L. . Ferro. R . P. R . J . P. "My-rlch phase e q u ~ l ~ band r ~ athermodynamrc :is\cssmcnt ofthc Llg-Sc \>\teni".hlordtke. . 89 ( 1 0 ) 11998).A.A Prwh. R~ani. Schmid-Fctzcr. \ .'crkstoff-lnfc~r~nattonsgesellschaf rnbl I.Inteniat~onal Magnesium Conference . 6.-W Bach. P ~ s c h R . F. Z. J .Wolfsburg.186. P~sch. A. R. Cacclamanl. 1998. A. . Fen-o. P Rrmi. Ci Cacc~amanr. Saccone. In M a ~ n e s ~ u Alloys ni and the11 Applrcations. Cirohner. ~ S c h n ~ i d .F c t ~ e"Thermodynamic r. 89 ( 7 ) (1998). A. 101-108. G. ( B . G. Juchniann. A. R.: "Computer a d e d deslgn of novel Mg-allo\s". Metallkd.). Schmid-1:et~er. Saccone.72-880. Ferro. Pi5ch. F. K. 18 I . L . A . Z. R . R ~ a n iA . Bormne. 700-703. R . Schmid-Fetrer. Frankfurt ). H. "Mg-rlch phase e q u ~ l ~ b rand ia thermod~nam~c assessment of the Mg-Sc system". 5 . Grohner. R. 171-177. April 28-30. Haferkanip. Schmld-Fet7er. Schrnld-Fetm. R Sclim~d-Fetter. "Experimental Stud) and Thermodynanilc Assessnient of Phase Equilihria in the Mn-Sc System". Z Metallkd.3. Cacc~aman~. R. Cacciamanl. Metallkd. S A . Kralner ieds. Metallkd 89 ( 7 )( 1998). B L.and Mg-alloy p~mcessing \\rth Sc additions". P. 90 ( 8 )(1999).