COMPOSITION GRADIENTS THROUGH RIBBON THICKNESS OF THE MELT SPUN AMORPHOUS Al70Fe13Si17 ALLOY

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1 COMPOSITION GRADIENTS THROUGH RIBBON THICKNESS OF THE MELT SPUN AMORPHOUS Al70Fe13Si17 ALLOY J. Legresy, P. Sainfort, M. Audier, J. Simon, P. Guyot To cite this version: J. Legresy, P. Sainfort, M. Audier, J. Simon, P. Guyot. COMPOSITION GRADIENTS THROUGH RIBBON THICKNESS OF THE MELT SPUN AMORPHOUS Al70Fe13Si17 ALLOY. Journal de Physique Colloques, 1985, 46 (C8), pp.c8-579-c < /jphyscol: >. <jpa > HAL Id: jpa Submitted on 1 Jan 1985 HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

2 JOURNAL DE PHYSIQUE Colloque C8, supplement au n 12, Tome 46, decembre 1985 page C8-579 COMPOSITION GRADIENTS THROUGH RIBBON THICKNESS OF THE MELT SPUN AMORPHOUS Al 70 Fe 13 Si 17 ALLOY J.M. Legresy, P. Sainfort, M. Audier, J.P. Simon and P. Guyot Laboratoire de Thermodynamique et Physico-Chimie Metallurgiques, ENSEEG, B.P. 75, Domaine Universitaire, Saint Martin d'heres, France Cegedur, Peahiney, Centre de Recherches, B.P. 27, Voreppe, France Résumé - La recherche d'inhomogénéités à travers l'épaisseur d'un ruban amorphe Al 7Q Fe 13 Si 17 élaboré par "melt spinning" a permis de mettre en évidence des gradients de composition chimique localisés au niveau de concavités "coté roue", vraisemblablement issues du piégeage de bulles de gaz pendant la fabrication du ruban. Ces gradients de composition ont été caractérisés par analyse "XEDS" en microscopie électronique analytique à balayage "STEM" sur des sections de ruban (ca.loonm) préparées par ultramicrotomie. Abstract - The investigation of inhomogeneities through the ribbon thickness of an A1 70 Fe i 3 Si 17 glass obtained by melt spinning has allowed to evidence the existence or composition gradients localized on the "wheel contact side" concavities, probably due to gas bubble trapping effects. The composition gradients were analyzed by XEDS in a scanning transmission electron microscope STEM on ultrathin ribbon sections prepared by ultramicrotomy. I- INTRODUCTION Experimental evidence of composition fluctuations through ribbon thickness of metallic glasses is rather rare /!/ although often assumed for interpreting crystallization behaviours 12/. In this study, ultrathin sections (ca. loonm) of an amorphous A1 7n Fe iap i 17 alloy ribbon have been analyzed by X-ray Energy Dispersive Spectroscopy CXEDs) Sh a Scanning Transmission Electron Microscope (STEM). II- MATERIALS and METHODS A1 7 0 Fe i3 Si i7 amorphous ribbons have been prepared by melt spinning on a cleanned copper wheel under He atmosphere ; they were supplied by the "Laboratoire de Metallurgie de l'ecole des Mines de Nancy" /3/. Their section sizes are regular : 0.6mm width and 20 ± 2)jm thick. Transverse ultrathin sectioning (fig.l) of the amorphous ribbon, embedded in a resin, was carried out by ultramicrotomy. For the XEDS analysis of the obtained thin foil, the electron probe diameter was 4nm at the entrance surface of the foil and because of the beam spreading through the specimen, the spatial resolution has been estimated to be 12nm /4/. The quantitative analysis of compositions was performed, for the beam positions indicated in fig.l, using the ratio method outlined by cliff and Lorimer /5/. Fig.l : Transverse ultrathin sectioning of the amorphous ribbon. Article published online by EDP Sciences and available at

3 JOURNAL DE PHYSIQUE 111- RESULTS and DISCUSSION Figure 2 shows Al, Fe and Si concentration profiles for the beam scanned accross the ribbon thickness. Both edges of this section have been previously identified as being representative of the wheel contact surface and external surface. The position of the analysis points along the thickness ribbon can be easily checked from the contamination spots due to each XEDS analysis. Moreover the sample thickness can be measured using the contamination spot method proposed by Rae et a1 /6/ (fig.3). In figure 2, strong Fe. Si and A1 concentration gradients are observed at proximity of the "wheel contact side" on ca. 1.3pm. In figure 4, which is an enlargement of Fig.2. it is clearly shown that one set of composition gradients extends between pure iron on the wheel side and the nominal composition A170Fe13SilJ, while the second one, starts at a composition A1 Fe Si instead of pure Iron. arious XEDS analyses have been performed along the wt18e1690n+%ct side parallely to the ribbon edge : the iron concentration results are reported in Fig.2 ; they indicate that the composition gradients do not exist everywhere. It seems from Fig.2 that the iron segregation could be associated with surface irregularities as, for example, gas bubble trapping shown on the SEM (scanning electron microscope) image of Fig.5. As plotted in the AlFeSi ternary diagram of Fig.6, the different chemical composition variations obtained for both runs of the XEDS analyses of Fig.4, seem to fit an unique smooth curve joining the pure iron vertice and the nominal composition A1 70 Fe E3Si17. In such a case, the strong variation of composition could be estimated o be somewhat concentric to the level of a concavity as proposed on the schema of Fig.5. We have checked by local diffraction that the ribbon is amorphous in the almost pure Fe segregation region, which is remarkable when considering that the amorphisable bulk composition is very narrow for that system. It would mean that the quenching rate is, even there, sufficiently high for enabling the formation of almost pure amorphous iron. It seems also in Fig.2 that each element concentration exhibits after the first strong gradient, weak oscillations through the whole ribbon thickness. These composition fluctuations are significative as can be affirmed from those of Si, for which the measurement relative error is smaller than the fluctuation amplitude. It has also to be noted that the concentration oscillations occur around the average composition values of the ternary alloy. It is tempting to consider these oscillations as resulting from a 'Ifrozen spherical composition waven generated at the gas bubble concavity centre. Further experiments are needed to clarify the exact origin of these composition fluctuations. The strong iron enrichment on the wheel side could be understood in terms of a rejection of aluminium and silicon during freezing of this "hypereutectic" alloy, at least in the gas trapped regions where the solidification rate is low enough (Newtonian cooling). It does not appear in the regions of ideal cooling where the heat transfer is almost perfect. Such interpretation would be in agreement with the Davis et a1 (1) results, who have observed by Auger electron spectroscopy, segregations attributed to air trapping on the "wheel surface" of FeSiB amorphous ribbons. The authors would like to thank K. Dehghan and, J.M. Dubois for supplying the amorphous rlbbons. (1) L.A. DAVIS, N. DECRISTOFARO, C.H. SMITH (1980) Metall. Glasses, Sci.Techno1. Budapest cited by J. BIGOT (1983) Les amorphes Metalliques, Aussois - Les Editions de Physique P.45. (2) U. KOSTER and U. HEROLD (1981) Topics in Applied Physics Vo1.46 Glassy Metals I-Ed. H.S. Guntherodt and H. Beck - Springer-Verlag P.252. (3) J.M. DUBOIS, K. DEHGHAN, Chr. JANOT and P. CHIEUX (1985) This conference (4) P. DOIG, D. LONSDALE and P.E.J. FLEWITT (1981) Quantitative Microanalysis with high spatial resolution, Manchester, The Metals Society London proceedings P.41. (5) G. CLIFF and G.W. LORIMER (1975) J.Microsc. 103, 203. (6) D.A. RAE, V.D. SCOTT and G. LOVE, Ibid (4) p.57.

4 1004 concentration at% 0 1 I distance pm 1 concentration at% Fig.2 : Al, Fe and Si concentration profiles analyzed on the imaged ultrathin section. Both set of curves correspond respectively to both contamination spot

5 C8-582 JOURNAL DE PHYSIQUE foi t thickness: tcw/sno Fig.3 : contamination spots profiles developped on both surfaces of the thin foil (a) for a tilt of 45' (b) for a tilt of Oa ( see ref.6 for details). so -- I * = - - Fig.4 : enlargement of fig of the wheel contact side Fe --.- edge. \ dlstance II~

6 Fig.5 : SEM imaging of both surface of an amorphous A1 70 Fe 13Si17 ribbon (a) external surface (b) wheel contact surface. (c) schematism of the proposed concentric variation of concentration at the level of a cavity. Fig.6 : composition values of the both runs of Fig.2 reported the AlFeSi diagram.