Materials Science and Engineering A 495 (2008) 181186

Wetting induced by near-surface Ti-enrichment in the CaF2/InTi and CaF2/CuTi systems

N. Froumin a , S. Barzilai a,b , M. Aizenshtein b , M. Lomberg a , N. Frage a,
a

Department of Materials Engineering, Ben-Gurion University, P.O. Box 653, Beer-Sheva 84105, Israel b NRC-Negev, P.O. Box 9001, Beer-Sheva 84190, Israel Received 22 March 2007; received in revised form 15 October 2007; accepted 19 October 2007

Abstract This paper is concerned with the wetting of CaF2 by liquid Cu and In and with the effect of Ti additions to the melt. According to thermodynamic analysis and to the experimental observations, the signicantly decreased contact angle following the addition of Ti to the molten metals is not due to the formation of interfacial uoride phases, in contrast to previously reported results. Ab initio density functional calculations indicate that preferential Ti adsorption takes place at the near CaF2 surface. It is suggested that the presence of a Ti-enriched liquid, adjacent to the substrate, gives rise, by means of heterogeneous nucleation, to the formation of a thin intermetallic compound layer that stands behind the experimentally observed enhanced wetting. The suggested wetting mechanism is supported by the notable correlation that has been observed between the temperature dependence of the contact angle and the temperature domains, associated with the presence of intermetallic compounds in both MeTi (Me = Cu, In) binary systems. 2008 Elsevier B.V. All rights reserved.
Keywords: CaF2 ; Metals; Wetting; Interface interaction; Thermodynamic analysis

1. Introduction Calcium uoride (CaF2 ) is a thermodynamically stable compound and is often used for reactive melt containers, in which chemical interactions between the melt and the container have to be avoided. Naidich and Krasovsky [13] have reported results obtained by sessile drop wetting experiments, regarding the wettability of alkaline earth uorides by various liquid metals (Cu, Au, Ag, Ga, Sn, and Al) and by their alloys with active elements (Ti, Zr, Hf, V, Cr, and Nb). The pure metals do not wet the CaF2 substrate over a wide temperature range, up to 1423 K. The contact angle of Ti-containing melts strongly depends on the nature of the molten solvent metal and temperature. Ti additions to liquid In provide a remarkable decrease of the contact angle ( = 20 ) in the 11731423 K temperature range [4] even at low titanium content (<0.5 at.%). The effect of titanium on the wetting of liquid Sn and Ga in the same temperature range is less signicant with a nal contact angle of about 90 and 70 , respectively. An unusual wetting behavior, namely an increas-

Corresponding author. Tel.: +972 86461468; fax: +972 86479441. E-mail address: nfrage@bgu.ac.il (N. Frage).

ing contact angle with increasing temperature was observed in a Sn2 at.%Ti alloy above 1273 K. The additions of Ti to liquid Cu (up to 10 at.%) did not affect wetting in the 13731423 K temperature range. Initially, it was suggested [3] that improved wetting is due to the formation of liquid titanium uorides at the interface, while the dewetting phenomenon was attributed to their evaporation at elevated temperatures. The lack of wetting in the CaF2 /CuTi system was not explained. The interaction between pure metals (Me = Al, Ga, In, Ge, and Cu) and CaF2 has been reported previously [5]. It was demonstrated that, in theory, the interaction in these systems leads to the formation of gaseous Me-uorides and Ca transfer from the substrate into the melt. However, in practice, even an extremely small amount of Ca in the melt prevents the interaction and these systems may be considered as non-reactive. The initial contact angle between CaF2 substrate and pure metals is higher than 100 and its evolution depends on the evaporation rates of the substrate and the melts [6]. Wetting in the CaF2 /Me systems and, in particular, the effect of active elements in the melt, is not yet fully understood, and requires further investigation. In the present study, the effect of Ti additions to non-reactive metals (In and Cu) on the wetting behavior and the interface interactions were investigated in the 11231423 K temperature

0921-5093/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2007.10.103

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range. The experimental observations were related to the thermodynamic properties of the liquid metals and the substrate and to the results of an ab initio analysis of Ti, Cu and In adsorption on the CaF2 substrate using the density functional theory (DFT). 2. Thermodynamic considerations Titanium displays high afnity to uorine, forms various stable uorides [7] and may be used as an active additive. The most stable titanium uoride in the 9001473 K temperature range is TiF3 , which melts at 1473 K [8]. The reaction between titanium, dissolved in the liquid Me, and the CaF2 substrate at temperatures below 1473 K may lead to the formation of titanium uoride in solid or gaseous states, according to the following reactions: [Ti] + 1.5CaF2(s) TiF3(g) + 1.5[Ca] TiF3(s) = TiF3(g) (1) (2)

where the brackets denote that Ti and Ca are dissolved in liquid Me; (s) and (g) correspond to solid and gaseous states of CaF2 and TiF3 , respectively. The partial pressure of titanium uoride may be calculated using the equilibrium constant (K) of reaction (1), derived from the standard formation Gibbs energy [8], and the activities of Ti and Ca in the melt K = exp G RT =
1.5 P aCa TiF3 aTi

shown in Fig. 1 together with the partial pressure of TiF3 , which corresponds to the evaporation of the solid uoride (curve 3) [8]. The partial pressure of TiF3 , formed as a result of reaction (1), decreases according to the calculated results with increasing Ca activity (curves 1 and 2), and is very low. The formation of solid TiF3 at the interface may take place if the Ca activity is less than 4 1013 and 1 1012 for the In and Cu based alloys, respectively. The activity coefcient for the dilute InCa solu0 (In) = 3 105 was estimated using the excess Gibbs tion Ca energy derived from [11]. The value of the activity coefcient 0 (Cu) = 0.2 was derived from for the dilute CuCa solution Ca thermodynamic properties reported in [12]. Thus, the formation of the solid titanium uoride phase may be suppressed by even an extremely limited Ca transfer from the substrate to the melts (the Ca atomic fractions in the melts are 108 and 1011 for the In and Cu based alloys, respectively). According to this analysis, the CaF2 /(InTi) and CaF2 /(CuTi) systems may be considered as non-reactive and high contact angles are expected. The wetting behavior reported by Naidich et al. [4] in the CaF2 /(InTi) contradicts this expectation. Furthermore, low contact angles for the system have been also observed in this study for both systems (see below). We put forward an alternative explanation for the wetting behavior in these systems, based on new experimental results and using an ab initio analysis of the metal/ceramic interaction at an atomic level.

3. Ab initio DFT analysis (3) An alternative reason for the improved wetting may be related to preferential Ti adsorption at the CaF2 surface. Ab initio calculations were performed using the full potential method, based on the augmented plane waves + local orbitals (APW + lo) density functional theory formalism [13,14], as was implemented in WIEN-2k code [15,16]. The adsorption energies of Ti, In and Cu atoms at the CaF2 (1 1 1) surface were calculated using a supercell model (periodic boundary conditions) contains 3 layers of CaF2 and one Me atom on top of each uorine atom of

The formation of solid uoride at the interface may take place if the partial pressure for reaction (1) is higher than its value for reaction (2). The calculation was conducted for Cu10.0 at.%Ti and In1.5 at.%Ti alloys containing various Ca activities. The activity of titanium was calculated using its activity coefcient for 0 ): 0.87 [9] and 0.36 [10] for the InTi and dilute solutions (Ti CuTi alloys, respectively. The results of the calculations are

Fig. 1. The partial pressure of TiF3 as a function of temperature for the In1.5 at.%Ti and Cu10.0 at.%Ti alloys at various Ca activities (aCa ): (1) 108 ; (2) 1010 . Curve (3) corresponds to the equilibrium partial pressure of solid TiF3 .

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varied within the 02 and 040 at.% concentration ranges, for the In and Cu alloys, respectively. These concentrations correspond to single-phase regions in the binary phase diagrams. The contact angles were measured using a Nikon 990 Coolpix digital camera and derived from the magnied images using the Image Pro 4 software. The structure and the composition of metal/ceramic interfaces were studied using a scanning electron microscope (JEOL GSM 5600) equipped with energy-dispersive and wavelength-dispersive X-ray spectrometers. 5. Experimental results The wetting behavior in the CaF2 /In and CaF2 /Cu systems was reported and discussed in our previous publication [5]. These two systems are non-reactive and display high contact angles of about 110 and 130 for Cu and In, respectively. The rst set of the experiments with InTi (02 at.%) alloys was conducted at 1123 K. Because of the relatively high In vapor pressure, careful considerations had to be given to possible In loss due to evaporation in the course of the high temperature wetting experiments. The evaporation of In alters the composition of the melt and could affect the contact angle. Simultaneous measurements of the contact angle , height (h) of the drop and its base diameter (d) were conducted in order to take into account such effects [17]. The drop base diameter remains constant, while its height and contact angle continue to decrease after 27 min contact (Fig. 3a). The decrease of the contact angle reects two processes, namely the In weight loss and the drops spreading. The measured weight loss after 37 min of contact was about 0.5%. If one attributes the entire weight change of the dropsubstrate system to the evaporation of In, the Ti content does not yet exceed solubility limit and, consequently, should not lead to the appearance of a Ti-enriched second phase within the volume of the melt. Thus, the signicant change of the contact angle has to be attributed to specic reactions that take place at the interface. Because the evaporation is a continuing process and it affects the contact angle, difculty arises in dening the nal contact angle. The angle corresponding to the break in the drop base diameter curve (denoted by vertical line in Fig. 3a) appears to be a suitable quantitative estimate of this angle, since we interpret it as the angle at which the spreading of the drop due to interface reaction was completed. The Ti composition dependence of the nal contact angle is shown in Fig. 3b and is in agreement with the results reported by Naidich et al. [1,4]. The experiments with CuTi (040 at.%) alloys were performed at 1423 K, the initial contact angle is relatively high (about 115 ), independent on the Ti content and remains constant during 40 min. At this temperature no evaporation of Cu takes place. Scanning electron microscopical characterization of the CaF2 /Cu40 at.%Ti interface (Fig. 4) shows no evidence for the presence of any uorine-containing phase and supports the results of the thermodynamic analysis. Second phase, intermetallic particles are present within the solidied drop and at the interface. These particles must have been formed during the cooling of the melt, since the contact temperature was

Fig. 2. Adsorption energies for CaF2 (1 1 1)/Me systems according to density functional calculations.

the surface (see insert in Fig. 2). The adsorption energy of the Me atom to the F terminated surface was calculated according to Eq. (6)
slab Me Eadsorp = Etot (Etot + Etot ) sys sys

(6)

slab where Etot is the total energy of the CaF2 Me system, Etot Me is the total energy of the CaF2 slab and Etot refers to the total energy of the Me atoms. The adsorption energy for In, Cu and Ti, as a function of the distance between the substrate and the metal atom, is presented in Fig. 2. According to the calculated results, the adsorption energy of Ti is about 69 times higher than the adsorption energy values for In and Cu. Thus, density functional analysis predicts Ti-enrichment of a near substrate region in the liquid. If the Ti concentration in this region reaches the solubility limit in equilibrium with the intermetallic phase, the formation of a very thin continuous intermetallic interfacial layer is generated as the outcome of a heterogeneous nucleation process.

4. Experimental procedure The details of dense CaF2 substrates preparation were reported in Ref. [5]. The substrate of 10 mm diameter and 3 mm width was polished down to 1 m diamond paste level and the surface roughness (Ra) was 0.1 m. Prior the wetting experiments, the samples were cleaned ultrasonically in acetone and ethanol. Wetting experiments were performed by the sessile drop method in the 11231423 K temperature range for 2060 min in a dynamic vacuum [(14) 103 Pa]. MeTi alloys were prepared in situ by co-melting of an appropriate amount of metals. The droplets weight was about 0.3 g and the purity of the used metals was higher than 99.9%. The titanium content

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phase, while the composition of the particles in the volume corresponds to intermetallic phases with lower titanium contents. 6. Discussion The variations of the contact angle are connected to changes occurring at the substratemelt interface. In the Ti-free melts, the contact angles are high and the changes that occur in the Ti-alloyed melts clearly reect the effect of the Ti additive. In general, such changes are attributed to the formation of an interfacial layer generated by the reaction between the active additive in the melt and some component of the substrate [17]. This approach was applied by Naidich and Krasovsky [13] in order to explain the effect of Ti on the wetting behavior in the CaF2 /MeTi systems. Naidich suggested that the contact angle evolution is controlled by the formation of liquid titanium uorides at the interface at a relatively low temperature and their evaporation at elevated temperatures. However, as shown by the thermodynamic analysis and conrmed by the interface characterization (Figs. 4 and 5), the interaction between the CaF2 substrate and the liquid MeTi alloys does not lead to the formation of any condense uoride phase. At the present stage of our understanding, we suggest that the improved wetting is connected to the Ti-enrichment of the interface region. This enrichment is associated with the preferential Ti adsorption, as predicted by the DFT analysis, which may lead to the formation of an extremely thin, possibly irresolvable, intermetallic layer. The thicker compound layer over a part of the interface (Fig. 5a) is built from connected relatively coarse TiIn intermetallic compound particles that had been nucleated heterogeneously on the thin layer and subsequently grew during cooling and solidication. In order to conrm the proposed mechanism, additional experiments with Cu25 at.%Ti at 11231423 K and In1.5 at.%Ti alloys at 1273 K were conducted. These conditions were chosen in accordance with the binary CuTi and InTi phase diagrams (Fig. 6). In the CuTi system the intermetallic phases coexist with liquid alloys only at temperatures lower than 1278 K. In the InTi system the intermetallic phases are stable at 1273 K. The spreading kinetics for the In1.5 at.%Ti alloy at 1273 K are shown in Fig. 7. The vertical line corresponds to the time

Fig. 3. The contact angles variations in the CaF2 /(MeTi) systems: (a) the contact angle ( ), drop base diameter (d) and height (h) variations for CaF2 /(In1.5 at.%Ti) system at 1123 K; (b) contact angles variations as a function of Ti content for the CuTi alloys at 1423 K and for the InTi alloys at 1123 K. The initial Ti concentrations were considered.

above the melting points of compounds in the CuTi binary system. The substratemelt interface in the CaF2 /In0.5 at.%Ti system (Fig. 5) is not uniform. Over part of the interface, the presence of Ti-rich layer with varying thickness is clearly visible (Fig. 5a). A wavelength-dispersive spectrometry (WDS) scan analysis over this part is shown in Fig. 5b and conrms the absence of any uorine-containing compound. An interface region, in which only separated particles are detected, is presented in Fig. 5c. The composition of the particles attached to the substrate corresponds to the Ti3 In intermetallic

Fig. 4. Interface in the CaF2 /Cu25 at.%Ti after wetting experiment: (a) scanning electron micrograph (back scattered electrons) and (b) WDS line (white line) scan across the interface. The drop partially detached from the substrate in the course of cooling.

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Fig. 5. Interface in the CaF2 /In0.5 at.%Ti after wetting experiments at 1123 K: (a) secondary electrons image of the region, where non-continuous Ti-rich layer attached to the substrate; (b) WDS line scan (white line) across this interface; (c) intermetallic particles within the drop and attached to the substrate. The black particles are diamond grains, which are pinned to the In drop during the sample preparation.

(17 min), at which the liquid drop reached its maximal extension and after which only further In evaporation affects the continuously decreasing contact angle. At this stage, according to the measured weight loss, the molten phase composition is still in the single-phase region. Although, the rate of spreading varies substantially (see Figs. 3a and 7) as a function of the temperature, the nal contact angle is temperature independent (30 ). The lack of temperature dependence of these contact angles supports the suggestion that wetting is induced not by preferential Ti adsorption at the interface only, but by the formation of a very thin continuous intermetallic interfacial layer.

In contrast to the monotonous variation of the contact angle for the InTi melt, the temperature dependence of the contact angle for the CuTi melts displays a different behavior, as shown in Fig. 8. At 1283 K, a 97 contact angle is observed, no intermetallic compound is stable and therefore, the substrate is necessarily in contact with a thin Ti-enriched region. With decreasing temperature, the contact angle decreases to as low as 52 at 1183 K. This temperature corresponds to the conditions at which the intermetallic compound is stable and it may appear at the Ti-enriched interface as a very thin layer. At 1423 K no intermetallic compound subsists, wetting vanishes, yet the contact angle is higher than that observed at 1283 K. The increased

Fig. 6. The binary InTi [18] and CuTi [19] phase diagrams.

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theless, the wetting of CaF2 by liquid Cu or In is signicantly improved by Ti additions to the melt. DFT calculations indicate preferential Ti adsorption at the CaF2 surface and Ti-enrichment of a near substrate region of the melt. The low contact angle for the InTi melt over the 11231273 K temperature range and the decreased contact angle for the CuTi melt, observed below 1283 K, are attributed to the formation of a very thin continuous non-detectable Ti-containing intermetallic layer at the interface. We can thus summarize that improved wetting may be achieved only in the temperature ranges, over which intermetallic phases are stable and coexist with the liquid alloys. Acknowledgements
Fig. 7. The contact angle, drop base diameter and height variations for CaF2 /(In1.5 at.%Ti) system at 1273 K.

This work was supported by the Grant No. 138-05 from the Israeli Council of High Education and the Israeli Atomic Energy Commission. The authors are grateful to Prof. D. Fuks for the help in DFT calculations and to Prof. M.P. Dariel for helpful discussion on wetting mechanisms in the Halide/Me systems. References
[1] Y.V. Naidich, V.P. Krasovsky, J. Mater. Sci. Lett. 17 (1998) 683685. [2] Y.V. Naidich, Powder Metall. Met. Ceram. 39 (2000) 355362. [3] V.P. Krasovsky, Y.V. Naidich, Powder Metall. Met. Ceram. 41 (2002) 7275. [4] Yu.V. Naidich, V.P. Krasovskii, Yu.N. Chuvashov, Adgeziya Rasplavov i Paika Materialov 24 (1990) 3336. [5] S. Barzilai, M. Aizenshtein, M. Lomberg, N. Froumin, N. Frage, J. Alloys Compd. 452 (2008) 154160. [6] S. Barzilai, M. Aizenshtein, M. Lomberg, N. Froumin, N. Frage, Solid State Sci. 9 (2007) 338343. [7] Handbook of Chemistry and Physics, 56th ed., 19751676. [8] Thermodynamic Data-Base SSUB3, produced by Scientic Group Thermo-data Europe, Thermo-Calc Group. [9] Y.V. Nikolaenko, G.N. Batalin, E.A. Beloborodova, Y.V. Vorobey, V.S. Zyravlev, Zhurnal Fizicheskoi Khimii 59 (3) (1985) 728730. [10] P. Wei, L. Jie, Mater. Sci. Eng. A269 (1999) 104110. [11] H. Okamoto, V.P. Itkin, C.B. Alcock, J. Phase Equilib. 12-3 (1991) 379383. [12] D. Risold, B. Hallstedt, L.J. Gauckler, H.L. Lukas, S.G. Fries, CALPHAD 20-2 (1996) 151160. [13] W. Kohn, P. Vashishta, in: S. Lundqvist, N.H. March (Eds.), Theory of the Inhomogeneous Electron Gas, Plenum, New York, 1983, pp. 79147. [14] W. Kohn, A.D. Becke, R.G. Parr, J. Phys. Chem. 100 (1996) 1297412980. [15] K. Schwarz, P. Blaha, G.K.H. Madsen, Comp. Phys. Commun. 147 (2002) 1776. [16] S. Cottenier, Density Functional Theory and the Family of (L) APW-Methods: A Step-By-Step Introduction, Institute Voor Kern-en Stralingsfysica, K.U. Leuven, Belgium, 2002, ISBN 90-807215-1-4. [17] N. Eustathopoulos, M.G. Nicholas, B. Drevet, Wettability at High Temperatures, in: Pergamon Materials Series, 1999. [18] L.D. Gulay, J.C. Schuster, J. Alloys Compd. 360 (2003) 137142. [19] T.B. Massalski, Binary Alloy Phase Diagrams, second ed., ASM International, Materials Park, OH, USA, 1990.

Fig. 8. Spreading kinetics in the CaF2 /Cu25 at.%Ti system during continuous heating and cooling.

contact angle at 1423 K, as compared to that at 1283 K, may be attributed to the titanium adsorption level at the interface, which decreases with increasing temperature. With decreasing temperature to 1183 K (after heating to 1423 K), the contact angle again decreases and reaches the value of about 77 , which is higher than that (50 ) observed after the rst cooling stage. This difference may be attributed to wetting hysteresis [17]. The signicant correlation between contact angle and particular features of the CuTi binary system strongly support the assumption regarding the presence of a thin continuous intermetallic compound layer at the interface (non-detectable by the available characterization techniques) and which stands behind the wetting behavior. 7. Conclusions According to the results of the thermodynamic analysis, the CaF2 /CuTi and CaF2 /InTi systems are non-reactive. Never-