Intermetallics 40 (2013) 1e9

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Oxidation and crystallographic features of the new prototype structure Ti4NiSi4

N. Chaia a, M. Franois a, S. Mathieu a, *, E. Elkam b, F. Rouillard c, M. Vilasi a
a

Universit de Lorraine, Institut Jean Lamour e UMR7198, BP 70239, 54506 Vandoeuvre ls Nancy, France Synchrotron SOLEIL, LOrme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France c CEA, DEN, DPC, SCCME, Laboratoire dEtude de la Corrosion Non Aqueuse, F-91191 Gif-sur-Yvette, France
b

a r t i c l e i n f o
Article history: Received 15 February 2013 Received in revised form 19 March 2013 Accepted 20 March 2013 Available online 27 April 2013 Keywords: A. Silicides, various B. Crystal chemistry of intermetallics B. Oxidation B. Phase transformation C. Coatings G. Corrosion- and erosion-resistant applications

a b s t r a c t
The oxidation resistance and the crystal structure of the new Ti4NiSi4 compound were investigated. This compound was manufactured both as a single-phase and as the outer layer of a protective coating for vanadium alloys. The recorded oxidation rates were very low at 650  C and 750  C in air, which represents a more severe environment than those envisaged for the targeted application: fuel cladding for sodium-cooled fast reactors. The powder XRD measurements performed at the synchrotron SOLEIL allowed for the crystallographic structure determination of Ti4NiSi4 (S.G. Pnma; a 15.63931; b 5.08321; c 12.75151) with high condence factors (Rwp 0.07; RBragg 0.067). Its structure consists of atomic planes stacking along the b-axis with planes at coordinates y 0, , and 3/4 ; it can therefore be considered as a pseudolamellar structure. It has been suggested that this peculiar feature induces a low activation energy for the phase transformation of Ti4NiSi4 into Ti4Ni4Si7, which thus renders the transformation possible at moderate temperature. This structural rearrangement is accompanied by the liberation of Ti and Si, which leads to the formation of both TiO2 and SiO2 oxidation products, which are responsible for the high environmental resistance observed at 650  C in air. 2013 Elsevier Ltd. All rights reserved.

1. Introduction Research in coating solutions for structural materials used for fuel cladding in sodium-cooled fast reactors (SFR) in generation IV nuclear systems has led to the investigation of silicide compounds with high oxidation resistance at temperatures of 550e750  C. We have previously shown [1,2] that MSi2 compounds (with M V, Cr, Ti), deposited on the surface of vanadium alloys using the halideactivated pack-cementation (HAPC) technique have high oxidation performances, both in air and in impure helium, and have high compatibility with liquid sodium at 550  C. However, manufacturing these coatings with chloride species as the halide activator led to the formation of cavities at the substrate-coating interface. These cavities contained vanadium dichloride VCl2, which has high stability as evidenced by its Gibbs enthalpy of formation (Eq. (1)).

Vs Cl2 g VCl2 s

(1)

DGr 1200 C 262:8 kJ:mol1 3

Several strategies can be followed to limit the formation of this compound during deposition and to avoid the presence of defects in
* Corresponding author. Tel.: 33 3 83 68 46 70. E-mail address: stephane.mathieu@univ-lorraine.fr (S. Mathieu). 0966-9795/$ e see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.intermet.2013.03.014

the coating. One strategy consists of reducing the formation of VCl2 through modication of the gaseous phase composition. These modications, based on thermodynamic assessment of the packcementation process, were presented in [1] and [2]. A second method consists of the formation of a diffusion barrier to vanadium prior to the pack-cementation process. In this regard, Ni is an efcient diffusion barrier and is easy to manufacture on the vanadium surface using well-established electrolytic or electroless processes. Moreover, because Ni possesses a low activation energy, i.e., it generates no or few radioactive elements, we chose this metal to coat Ve4Cre4Ti alloys prior to the pack-cementation step. However, the choice of nickel has some consequences on the pack-cementation parameters. Because of the low temperature of the NiSieNiSi2 eutectic (960  C) [4], it is impossible to use a Si-rich master alloy (with high Si activity) to deposit a protective coating. Indeed, because pack-cementation is controlled by solid-state diffusion, this process has to be done at high temperatures typically above 1000  C, which would lead to the melting of the supercial part of the alloy and to a poor quality coating. Based on our experience with silicide coatings [5e8], ternary and quaternary silicide compounds containing only 45e46 at.% Si may have also high oxidation resistance. Their manufacture requires the use of a master alloy with a lower silicon activity than for

N. Chaia et al. / Intermetallics 40 (2013) 1e9

the manufacture of MSi2-type coatings to avoid supercial melting. For the present study, a TiSi TiSi2 mixture (aSi 0.12, value calculated at 1100  C using ThermoCalc software [9] and Seifert data [10]) was chosen as the master alloy to perform the coating. Therefore, the rst part of this paper deals with the metallographic characterisation and oxidation resistance both of the manufactured NieTieSi coating (considered here for the protection of vanadium substrates from oxidation in future generation IV reactors) and of the Ti4NiSi4 outer phase of this coating. The oxidation tests were mainly conducted in air at 650  C and 750  C, which corresponds to more harshly oxidative conditions than those expected in SFR applications (550  Ce650  C, w5e10 ppm O2). The second part of the present paper describes the new crystallographic structure of the outer phase Ti4NiSi4. To accomplish this, the Ti4NiSi4 compound was synthesised as a pure singlephase. The crystallographic data were obtained using the SOLEIL synchrotron facilities. 2. Experimental methods and materials 2.1. Manufacturing of NieTieSi coating Ve4Cre4Ti substrate was supplied by CEA Saclay. This alloy was provided by GfE Metalle und Materialien GmbH, Nuremberg, Germany; the manufacturing process is detailed elsewhere [11]. The samples were cut from a rolled plate and recrystallised at 1000  C; their dimensions were approximately 10 mm 10 mm 1 mm. Surface preparation consisted of polishing down to 1200 grid, and the corners were also rounded with SiC paper. Then, the samples were cleaned ultrasonically in ethanol and dried. The as prepared plates were coated with 30 mm of nickel using a Ni electroplating technique (Watts nickel plating bath, 50  C, current density 20 mA.cm2). Then, the Ni-coated Ve4Cre4Ti, the master alloy (TiSi TiSi2), the activator salt (CrCl3) and inert ller (SiO2) were placed in a closed silica tube under vacuum to carry out halide-activated pack-cementation (HAPC). The process was conducted isothermally at 1100  C for a period of 9 h. The master alloy used for HAPC (TiSi TiSi2) was synthesised by arc melting Ti and Si under argon using a non-consumable tungsten electrode on a water-cooled copper crucible. 2.2. Synthesis of the Ti4NiSi4 compound The Ti4NiSi4 compound was manufactured in two steps: the composition Ti4NiSi4 was prepared by inductive melting of pure metals and silicon (high purity Ti 99.7%, Ni 99.9% and Si 99.9999%) on a water-cooled copper crucible. Melting was performed three times to obtain homogeneous ingots. The ingots were handcrushed into a powder until a grain size less than 80 mm was obtained. A sample of the powder was retained for X-ray characterisation. The remainder was densied by uniaxial hot pressing under argon to produce single-phase samples of Ti4NiSi4. For uniaxial hot pressing, the powder was introduced onto a graphite die that had previously been coated with boron nitride (BN) spray. BN works as a diffusion barrier between graphite and metallic powders, and thus limits the formation of carbide. The die was heated to 1200  C for 4 h under a pressure of 27 MPa, after which the load was removed and heating was stopped. The cooling time to room temperature was approximately 4 h. Specimen dimensions were approximate ( 25 mm, h 12 mm). To characterise the microstructure and study oxidation, coupons 10 mm 10 mm 2 mm in dimension were cut from the hotpressed samples.

2.3. Crystal structure determination High-resolution X-ray powder diffraction (XRPD) data were collected at ambient temperature with synchrotron radiation at SOLEIL (Saint Aubin, France) on a CRISTAL beamline [12]. A monochromatic beam was extracted from the U20 undulator beam by means of a Si(111) double monochromator. Its wavelength A) was rened from a LaB6 (NIST Standard Reference (l 0.78912  Material 660, cubic Pm3m) powder diagram recorded just prior to the experiment. The high angular resolution was obtained using a two circle diffractometer (SMP, Lyon based company) equipped with a multi-analyser containing 21 perfect Si(111) crystals. The sample was enclosed in a capillary tube (r 0.3 mm) and mounted on a spinner rotating at 5e10 Hz to improve powder averaging. Patterns were recorded for one hour in the angular range 2 < 2q < 75 with an interval of 0.002 . Transmission of the lled capillary was measured using an X-ray camera, allowing a reliable mr value (where m is the absorption coefcient and r is the capillary radius) to be xed at 1.90 during Rietveld renement. 2.4. Metallographic characterisation Metallographic observations were performed using a JEOL JSM7600F equipped with an SDD-type EDX detector coupled with an Oxford INCA WAVE WDS spectrometer. Chemical point analysis was performed using a Cameca X100 microprobe. Metal disilicides (MSi2 with M V, Cr or Ti) and pure nickel were used as standards for the quantitative analysis. The oxidised samples were covered by a protective nickel electroplating layer, embedded with a cold epoxy resin, grinded from 240 to 2400 grid with SiC paper, and nished using a colloidal SiO2 suspension to characterise the cross sections after oxidation. 2.5. Oxidation tests For oxidation tests, the samples were grinded to 2400 grade using SiC paper and then cleaned in ethanol with ultrasonic waves. For the single-phase Ti4NiSi4, isothermal oxidation tests were conducted at 650  C and 750  C in air using both thermogravimetry and an open furnace (for long exposure times). During thermogravimetry, specimens were suspended in the hot zone of a thermobalance furnace using a platinum wire covered with thin

Fig. 1. Cross section of multilayer NieTieSi coating manufactured on Ve4Cre4Ti substrate (Step 1: RT Electrolytic Ni deposition, Step 2: Halide-activated packcementation with the master alloy TiSi TiSi2, 9 h, 1100  C).

N. Chaia et al. / Intermetallics 40 (2013) 1e9

Fig. 2. Microstructure of hot-pressed Ti4NiSi4 silicide compound.

alumina tubes. Air was introduced into the reaction chamber at a ow rate of 1.5 L h1. On the coated samples, cyclic oxidation tests were performed in a tubular furnace in air for a 1-h cycle at 650  C and at 1100  C. The specimens were then removed from the furnace, cooled for 10 min at room temperature and then weighed by hand using an analytical balance with a precision of 0.1 mg. 3. Experimental results 3.1. Characterisation of manufactured coatings and hot-pressed Ti4NiSi4 The result of cementation of the Ni-coated Ve4Cre4Ti alloy under the conditions dened is given in Fig. 1, where the cross section of the sample and the chemical compositions of each layer are presented. Co-deposition of Ti and Si by the HAPC process of Ni-coated vanadium alloy resulted in the growth of a multilayer silicide coating. The

interfacial vanadium substrate-coating did not present cavities like those observed when applying the chloride-activated pack-cementation technique directly to the vanadium alloy [1]. The outer four layers corresponded to ternary NieTieSi silicides, from the outer to inner layer: Ti4NiSi4, Ni4Ti4Si7, NiTiSi and Ni49Ti14Si37 [13]. The more internal phases contained a lower amount of Ti and corresponded to phases in the VeNieSi system [14]. Almost all of the nickel initially electroplated at the surface of Ve4Cre4Ti was incorporated into the multilayer coating after the pack-cementation step. The presence of a thin layer of s0 phase (VeNi) showed that a very small amount of nickel did not transform during the HAPC diffusion treatment. Fig. 2 displays the microstructure of hot-pressed Ti4NiSi4. The samples were well densied and free of porosity. Some cracks were observed, but they did not affect the integrity of the sample, as discussed in the section presenting the results of oxidation. The composition of the compound was determined using EPMA. Quantitative analysis indicated that the stoichiometry of Ti4NiSi4 was maintained. However, it appeared clearly that the very narrow composition range of this compound made obtaining a pure sample difcult. Many authors [13,15] have mentioned the Ti4NiSi4 compound, also called H phase or s8 phase, which is described in the NieTieSi phase diagram system as a point phase. Thus, the specimen also contained a small amount of two other phases with compositions of TiSi and Ti5Si3. 3.2. Oxidation behaviour of the NieTieSi coating in air Cyclic oxidation was performed both at 650  C, which corresponds to the highest temperature envisaged for SFR applications, and at 1100  C, which would be representative of an incidental increase in temperature. Cyclic oxidation conditions allowed for the evaluation of, in a single experiment, both the oxidation resistance of the coating and the effect of thermo-mechanical stresses applied to the coating-substrate system. Fig. 3a and b display the results obtained at 650  C and 1100  C, respectively. The test was stopped after 800 1-h cycles at 650  C because the weight of the sample had not changed (it is important to note the small change in weight in Fig. 3a). Indeed, the measured weight change remained in the range of the balance sensitivity. At 650  C, corrosion products were not detectable after 800 h of exposure using conventional XRD and SEM techniques. At 1100  C, the weight gain evolved slowly for the rst 50 h of exposure and then evolved exponentially up to 300 h. The test was stopped at 311 cycles because a trace of V2O5 liquid oxide (Tf 680  C) was visible on the surface of the sample. The presence of V2O5 was evidence that oxygen had reached the vanadium substrate and that the local integrity of the coating had been lost. Fig. 4 shows the cross section of the sample exposed for 311 cycles at 1100  C. Cracks were observed in the coating, but they generally stopped before reaching the substrate. A thick and dense scale of corrosion products at the top of the remaining coating was also observed. XRD (Fig. 5) revealed the formation of mainly rutile TiO2 and cristobalite SiO2; amorphous SiO2 should also be present in the corrosion products. A small amount of Ni-containing oxides (NiTiO3) was also observed. Under the oxide scale, the rich Nicontaining compound G00 (Ni49Ti14Si37) [13] was still present. 3.3. Oxidation behaviour of the Ti4NiSi4 compound in air Because Ti4NiSi4 was the outer phase of the coating, it represented the rst barrier to oxidation. Thus, the oxidation behaviour of this new compound was also studied. Isothermal oxidation tests were carried out using thermogravimetry at 650  C and 750  C (Fig. 6a). The evolution of weight gain as a function of time for 50 h was somewhat parabolic for both sets of data (Fig. 6a). However the

a) 0.075
weight change (mg.cm )
-2

0.050 0.025 0.000 -0.025

100 200 300 400 500 600 700 800 900 1000 Number of 1h cycles

b)
weight change (mg.cm )
-2

0.075 8

7
0.050 6

5
0.025 4

3
0.000 2

1
-0.025 0

0 50100 100 200 300 500 600 800 350 900 1000 150400200 250 700 300 Number of 1h cycles

Fig. 3. Mass change versus number of cycles (1-h cycle 100 at room temperature) for Ve4Cre4Ti coated with multilayer NieTieSi in air a) at 650  C and b) at 1100  C.

N. Chaia et al. / Intermetallics 40 (2013) 1e9

a)
Weight change (mg.cm )
-2

0.015
65OC 750C

0.010

0.005

0.000

10

15

20 25 30 Time (h)

35

40

45

50

b)
Weight change (mg.cm )
-2

0.4

750C
0.2 0.0

Fig. 4. Cross-sectional morphology of Ve4Cre4Ti coated with multilayered NieTieSi after 311 1-h cycles at 1100  C in air.

weight gains remained very low because of the very high oxidation resistance of Ti4NiSi4 in this temperature range. Thus, oxidation tests were performed for long times (Fig. 6b) at both temperatures to validate the high stability of the Ti4NiSi4. The results denitively demonstrated the high stability of this compound in air at 650  C and 750  C because the amount of oxidation products remained very low after 203 days of testing (the samples were not weighed after 80 days). The samples exposed at 650  C and 750  C gained 0.16 and 0.42 mg.cm2, respectively. Fig. 7 shows the cross section of the Ti4NiSi4 sample after 203 days of exposure at 650  C. A thin oxide layer (2e3 mm on average) was observed, consisting of small particles of TiO2 embedded in a silica layer. Below this oxide layer, a very thin layer of Ti4Ni4Si7 was identied using data not shown here and obtained at 850  C. At this temperature, the amount of Ti4Ni4Si7 that formed was higher; thus, quantication of the local composition using WDS was possible. 3.4. Structural determination of the Ti4NiSi4 compound Because the crystal structure of Ti4NiSi4 has not previously been investigated, Ti4NiSi4 powder was characterised using the SOLEIL synchrotron facilities. Fig. 8 shows the XRD patterns obtained.

650C
-0.2 -0.4 0 10 20 30 40 50 Time (days) 60 70 80

Fig. 6. Mass change versus time of a single-phase Ti4NiSi4 sample oxidised at 650  C and 750  C in air (samples were removed daily from the furnaces to be weighed).

Indexing of the 20 rst Bragg peaks and determination of the space group was performed using the XCell application implemented in the MStudio package software [16]. A solution was found in the orthorhombic space group Pnma with a 15.639  A, b 5.083  A, c 12.751  A. The space group Pnma was conrmed using the Fullprof program running in the prole matching mode (Le Bail decomposition) [17]. An initial model was found by direct-space methods using the FOX program [18] based on knowledge of i) the EPMA composition Ti4NiSi4, ii) the multiplicity of the space group and iii) density considerations. The following scatters have been considered in the unit cell, all initially placed in random position: eight scatters (Ti1Ti8) for titanium, seven scatters (Si1-Si7) for silicon and two

Fig. 5. X-ray diffraction pattern performed on the surface of Ve4Cre4Ti coated with multilayer NieTieSi after 311 1-h cycles at 1100  C in air.

Fig. 7. Cross-sectional morphology of a single-phase Ti4NiSi4 sample after 208 days of isothermal exposure at 650  C in air.

N. Chaia et al. / Intermetallics 40 (2013) 1e9

Fig. 8. Observed (red), Rietveld calculated (black) and difference (green) synchrotron A). The vertical bars indicate the Bragg positions. (For XRPD patterns (l 0.77752  interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

scatters (Ni1 and Ni2) for nickel. The global optimisation procedure used was a parallel tempering algorithm. A satisfactory solution (Rwp 15%) led to the retention of 15 independent crystallographic sites for the structure, 12 being in 4c and the other three in general positions. At this stage of resolution, allocation of the Ti and Ni elements (which differ by 6 electrons) on the various sites was not completely satisfactory and had to be made through Rietveld renement. The unit cell contains 72 atoms. 3.5. Rietveld renement The pattern (Fig. 8) was rst used in the prole matching mode of Fullprof in order to rene the cell and prole parameters. LaB6 (NIST, SRM 660a) was used as a standard reference material to dene the instrumental resolution function (IRF) le. This IRF le allowed for a description of the peak shape prole with the Thomson-Cox-Hasting pseudo-Voigt function for the sample

contribution. In addition, anisotropic peak broadening was necessary to model these high-resolution data, and a successful solution was found by rening 6 crystallite sizes and 6 strain effect parameters. The 6 size parameters corresponded to the spherical harmonic coefcients in the phenomenological model. They include, in the Scherrer formula, anisotropic size broadening as a linear combination of spherical harmonics. A Ti5Si3 impurity (SG P63/mcm), which is not visible in standard data from XRD, has been detected in the high-resolution data and was included in the renement. The impurity represents only 0.59 wt % of the sample, with the most intense impurity line appearing at 20.7 2q in the pattern. The 20 parameters rened over the course of the Le Bail decomposition were then xed to perform Rietveld renement of 48 intensity-dependent parameters. Coordinates and isotropic temperature factors were rened for several sites: Ti1-6, Si1-6 (4c) and Ti7, Si7 and Ni1 (8d). The normal values of the temperature factors indicated that the elements were correctly attributed to the sites. Moreover, the model led to the expected composition of Ti4NiSi4. The nal Rietveld renement of 69 parameters led to satisfactory condence factors: Rwp 0.07 and RBragg 0.067. The resulting crystallographic and renement parameters are given in Table 1, and the nal Rietveld plot is presented in Fig. 8. Atomic coordinates can be found in Table 2. The accuracy of these synchrotron powder diffraction results (see the standard deviations) was comparable to that of data obtained from a single crystal. 3.6. Structural description Projections of the new structural type Ti4NiSi4 along the a- and b-axis are given in Fig. 9a and b, respectively. The interatomic distances are reported in Table 3; the shortest distance 2.304(4)  A was found for the Ni1-Si1 bond. This value can be compared with the short distances of NieSi previously reported in known structures of the TieNieSi system (Pearsons crystal data): 2.342  A in A in Ni16.7Si7Ti6 Ni3SiTi2 (Mg2Cu3Si type, P63/mmc), 2.305  ((Ti0.42Al0.58)15Pt7Al8 type, Fm3m), 2.342  A in Ni3SiTi2 (Mg2Cu3Si A in TiNiSi (TiNiSi type, Pnma), and 2.230  A type, P63/mmc), 2.307  in Ni4Si7Ti4 (Zr4Co4Ge7 type, I4/mmm). The coordination polyhedra surrounding the 15 crystallographic sites are presented in Fig. 10. Their geometrical descriptions and compositions are given in Table 3: Ti2eTi4, Ti6 centred a 17-vertex pseudo-Frank Kasper polyhedron and Ti1, Ti5 and Ti7 centred a 17-, 16-, and 14-vertex Frank Kasper polyhedron, respectively; Si1-Si4 centred a monocapped square antiprism, Si5-Si6 centred a tricapped trigonal prism, and Si7 centred a bicapped

Table 1 Crystal data and structural renement parameters. Compound Fw (g.mol1) System Space group a ( A) b ( A) c ( A) V ( A3) Z Dx (g cm3) Wave length ( A) 2q range (deg) Nobs of points Nref Rp Rwp RBragg RF N prole parameters N intensity dependent parameters Ti4NiSi4 366.091 Orthorhombic Pnma 15.63931(4) 5.08321(1) 12.75151(3) 1013.718(5) 8 4.751 0.78912 2.0e75.0 14200 2345 0.0407 0.0704 0.067 0.079 20 48

Table 2 Fractional atomic coordinates and temperature factors for Ti4NiSi4. Sites Ni1 Ti1 Ti2 Ti3 Ti4 Ti5 Ti6 Ti7 Si1 Si2 Si3 Si4 Si5 Si6 Si7 Site 8d 4c 4c 4c 4c 4c 4c 8d 4c 4c 4c 4c 4c 4c 8d x 0.68454(8) 0.94569(16) 0.53699(16) 0.20964(16) 0.35171(17) 0.55384(17) 0.17851(17) 0.86604(10) 0.9317(3) 0.2685(2) 0.1216(3) 0.8027(3) 0.4849(3) 0.7828(3) 0.56411(16) y 0.9971(3) 0.25000 0.75000 0.75000 0.75000 0.75000 0.25000 0.4988(4) 0.75000 0.25000 0.25000 0.25000 0.75000 0.25000 0.4965(7) z 0.15816(10) 0.5293(2) 0.6504(2) 0.6793(2) 0.3177(2) 0.26304(20) 0.5427(2) 0.95817(13) 0.6117(3) 0.9830(3) 0.2099(3) 0.1150(3) 0.4455(3) 0.8092(3) 0.8397(2) B( A2) 1.13(2) 1.19(5) 1.28(5) 1.10(5) 1.46(6) 1.09(5) 1.19(5) 1.22(3) 1.48(9) 1.23(9) 1.32(9) 1.47(10) 1.29(8) 1.10(8) 1.26(5)

N. Chaia et al. / Intermetallics 40 (2013) 1e9

Fig. 9. Projections of the Ti4NiSi4 crystal structure along the a- and b-axis.

square antiprism. The only Ni site was located at the centre of an irregular icosahedron. 4. Discussion The results obtained showed that an electrolytic deposit of nickel prior to performing the HAPC process can be used to avoid both vanadium dichloride formation and the formation of cavities at the substrate-coating interface. However, the use of nickel renders the manufacturing of a protective silicon-rich coating impossible using a Si-rich master alloy (with a Si activity around 1), such as those previously used [1,2], because of the low temperature of the NiSieNiSi2 eutectic (954  C). Based on thermodynamic data of the NieSi system [4], the use of Si or TiSi2Si would be conducive to melting of the surface of the Ni-coated sample.

The choice of the master alloy TiSi TiSi2 was rstly governed by the fact that its silicon activity was strongly decreased (aSi 0.12, calculated value at 1100  C using ThermoCalc [9] and Seifert data [10]). As a consequence, NiSi and NiSi2 cannot form during the HAPC process. Secondly, the ternary compounds described in the NieTieSi thermodynamic database [13,15] exhibit high temperature capabilities that are essential in case of an unforeseen increase in operating conditions (e.g., temporary failure of the cooling system of the reactor). Thirdly, ternary NieTieSi compounds like Ni4Ti4Si7 and Ti4NiSi4 contain a sufcient amount of silicon (45e 46 at.%) to form silica-rich protective oxide scales [5,19]. The synthesised coating consisted of a succession of ten layers that were consistent both with the NieTieSi phase diagram [13] for the four outer layers (Ti4NiSi4, Ni4Ti4Si7, NiTiSi and Ni49Ti14Si37) and with the VeNieSi phase diagram [14] for the inner layers. Formation of the coating occurred by solid-state diffusion of elements

N. Chaia et al. / Intermetallics 40 (2013) 1e9 Table 3 Coordination, neighbourhood and interatomic distances ( A) in Ti4NiSi4. Atoms Ni1 CN 12 Atom Si1 Si2 Si4 Si3 Si6 Ni1 Ni1 Ti5 Ti6 Ti1 Ti4 Ti3 Ti1 CN 17 Si1 Si7 Si1 Si2 Si7 Ni1 Ti5 Ti1 Ti6 Ti3 Ti6 Ti2 CN 17 Si4 Si3 Si5 Si7 Si5 Ti4 Ti5 Ti7 Ti7 Ti3 Si1 Ti3 CN 17 Si2 Si7 Si4 Si3 Si6 Ni1 Ti6 Ti4 Ti7 Ti2 Ti1 d( A) 2.304(4) 2.315(3) 2.317(4) 2.335(4) 2.355(4) 2.512(2) 2.571(2) 2.747(3) 2.867(3) 2.903(3) 2.917(3) 2.947(3) 2.629(5) 2 2.744(4) 2 2.7589(18) 2.776(4) 2 2.791(4) 2 2.903(3) 2.981(4) 2 3.147(2) 2 3.328(2) 3.602(4) 3.645(4) 2.547(5) 2.594(5) 2.737(5) 2 2.769(4) 2 2.841(2) 2 2 2 2 3.107(2) 3.114(2) 3.148(3) 3.270(3) Ti7 CN 14 Ti6 CN 17 Ti5 CN 16 Atom Ti4 CN 17 Atom Si5 Si6 Si7 Si4 Si2 Ni1 Ti2 Ti7 Ti5 Ti3 Ti6 Si5 Si7 Si6 Ni1 Si3 Ti1 Ti7 Ti2 Si1 Ti4 Si6 Si1 Si7 Si2 Si4 Ni1 Ti3 Ti7 Ti1 Ti4 Ti1 Si3 Ti7 Ti7 Si4 Si5 Si2 Si6 Si5 Ti5 Ti4 Ti2 Ti6 Ti3 Ti2 Si1 CN 9/12 Ni1 Si3 Si7 Ti6 Ti1 Ti1 Ti5 Ti2 d( A) 2.645(5) 2.654(5) 2 2.708(4) 2 2.790(2) 2.824(4) 2 2.917(3) 2 3.107(2) 2 3.138(3) 3.237(4) 2 3.240(2) 3.538(4) 2.564(5) 2 2.586(4) 2.622(5) 2 2.747(3) 2 2.775(2) 2.981(4) 2 3.060(3) 2 3.114(2) 2 3.199(3) 3.237(4) 2.495(5) 2.617(5) 2 2.649(4) 2 2.780(2) 2.796(5) 2 2.867(3) 2 3.119(2) 2 3.194(3) 2 3.328(2) 3.538(4) 3.645(4) 2.502(4) 2.529(3) 2.554(3) 2.565(4) 2.568(4) 2.573(3) 2.627(4) 2.657(4) 3.060(3) 3.138(3) 3.148(3) 3.194(3) 3.269(3) 3.270(3) 2 2.304(4) 2.423(6) 2 2.516(5) 2.617(5) 2.629(5) 2 2.759(2) 2 3.199(3) 3.452(5) Si7 CN 10 Si6 CN 9/11 Si4 CN 9/11 Atom Si2 CN 9/11 Atom Ni1 Ti3 Ti7 Ti1 Ti6 Ti4 Si4 Ni1 Si1 Ti7 Ti2 Ti3 Ti5 Si6 Ni1 Ti2 Ti7 Ti3 Ti4 Ti6 Si2 Ti5 Ti7 Ti4 Ti7 Ti2 Ti2 Si5 Ni1 Ti6 Ti5 Ti7 Ti4 Ti3 Si3 Si7 Si1 Si7 Ti5 Ti3 Ti6 Ti4 Ti1 Ti2 Ti1 d( A) 2 2.315(3) 2.526(5) 2 2.573(3) 2.776(4) 2 2.780(2) 2.824(4) 2 3.043(3) 2 2.335(4) 2.423(6) 2 2.502(4) 2.594(5) 2.668(5) 2 2.775(2) 2 2.959(3) 2 2.317(4) 2.547(5) 2 2.565(4) 2.630(5) 2 2.790(2) 2.796(5) 2 3.043(3) 2.564(5) 2 2.568(4) 2.645(5) 2 2.657(4) 2.737(5) 2 2.841(2) 2 2.935(3) 2 2.355(4) 2.495(5) 2.622(5) 2 2.627(4) 2.654(5) 2 2.791(2) 2 2.959(3) 2.506(5) 2.516(5) 2.577(5) 2.586(4) 2.627(4) 2.649(4) 2.708(4) 2.744(4) 2.769(4) 2.791(4)

Si3 CN 9/11

Si5 CN 9/11

3.465(4) 3.452(5) 2.526(5) 2 2.627(4) 2.630(5) 2.668(5) 2 2.791(2) 2 2.947(3) 2 3.119(2) 2 3.240(2) 2 3.269(3) 3.465(4) 3.602(4)

both from the pack and from the substrate. Silicon and titanium diffused from the surface towards the Ni-coated substrate. These elements (Ti and Si) formed gaseous species with the chloride activator (SiClx and TiClx, respectively, with x 1e4) during the high temperature process that were easily brought to the substrate surface, where chemical reactions allowed for the co-deposition of Ti and Si [for more information, see also [1,20,21,22]]. Nickel and vanadium diffused from the Ni-coated substrate towards the outer layers to react mainly with silicon, which has a larger diffusion coefcient than Ti. This particular method of forming a coating, solid-state diffusion, resulted in excellent adherence between the coating and substrate.

With the experimental parameters employed (1100  C, 9 h), almost all of the nickel initially deposited electrolytically at the surface of Ve4Cre4Ti was included in the silicide compounds after the cementation step with the TiSi TiSi2 master alloy. The presence of a thin layer of the s0 phase (VeNi) showed that a very small amount of nickel did not transform during the HAPC diffusion treatment. This brittle phase can be easily eliminated by thermal treatment of the coated sample (after HAPC) or by slightly increasing the duration of HAPC. The coating contained the compound Ti4NiSi4 as the outer layer. This compound should control the oxidation behaviour under operating conditions. Several authors [23,24] mentioned the

N. Chaia et al. / Intermetallics 40 (2013) 1e9 Table 4 Stacking periods in various pseudolamellar parent phases in the TieNieSi system. Pseudo lamellar phases Stacking period Inter layer composition Average metallic radius in the interlayer Layer composition Ti4Ni4Si7 4.9343 Ni0.80Si0.20 1.2598 Ti0.40Si0.60 Ti4Ni1Si4 5.0832 Ti0.33Ni0.33Si0.33 1.3289 Ti0.50Si0.50 Ti5Si3 (hexagonal) 5.171 Ti1.00 1.462 Ti0.50Si0.50

Fig. 10. The 15 independent crystallographic sites for the structure of Ti4NiSi4 (12 are in 4c and the 3 others are in general positions).

existence of a compound named H having the composition Ti4NiSi4. Weitzer [24] indicated that this compound is stable up to 900  C. Hu et al. [15], as well as Tokunage [13], included this compound in a description of the isothermal section of the NieTieSi ternary phase diagram at 1100  C, also mentioning its narrow range of composition. In the present paper, the crystallographic structure of this compound was determined. From the XRD pattern obtained at the synchrotron SOLEIL, the crystal data (see Table 1) of this compound, which crystallises in the orthorhombic system (S.G. Pnma), was deduced. Possible isotypes with Ti4NiSi4 were searched in Pearsons crystal database using lattice parameter considerations. No results were found, thereby conrming that Ti4NiSi4 is a new structural type. The structure of Ti4NiSi4 consists of atomic planes that stack along the b-axis with planes at coordinates y 0, , and 3/4 (Fig. 8a). Therefore, it can be considered to be a pseudolamellar structure. The layers at y and 3/4 and the interlayer at y have compositions of Ti3Si3 and TiNiSi, respectively. The distance between the atomic planes of the related pseudolamellar structures is reported in Table 4 and can be discussed as a function of the

composition of these interlayers. In the three phases of the TieNie Si system, the stacking period increased with increasing titanium concentration in the interlayers: 4.93  A for 0% Ti in Ni4Ti4Si7 and A for Ti4NiSi4 was 5.171  A for 100% Ti in Ti5Si3; the period of 5.0832  intermediate with a Ti concentration of 33%. On the other hand, the stacking period appears to be less sensitive to the composition of the layers at y 0 and because for the three cases, the composition of these layers is close or even equal for Ti4NiSi4 and Ti5Si3 (Ti0.5Si0.5). These observations consolidate the points of view that these phases have a pseudolamellar character and that the structure of Ti4NiSi4 possesses a lot of similarity to that of Ni4Ti4Si7 and Ti5Si3. The very low oxidation rate of the Ti4NiSi4 compound in air could be nally attributed to these structural characteristics. Indeed, it was observed that the oxidation of Ti4NiSi4 at 650  C led to a very low oxidation rate. The oxidation products were identied with difculty using conventional characterisation devices (SEMFEG; XRD) after 203 days at this temperature, which would be the upper operating temperature in an SFR reactor. Such behaviour was not encountered with other silicides containing transition metals like TiSi2, VSi2, CrSi2, MoSi2 [2,26,27] in this temperature range although they all contained more silicon than Ti4NiSi4. These MSi2 intermetallic compounds developed thick (>500 nm) and observable oxide scales in this temperature range after a few hundred of hours of exposure. In our opinion, the very high chemical resistance of Ti4NiSi4 in air at 650  C and 750  C resulted in easy access of Si and Ti to the surface, where they formed a very thin SiO2 TiO2 protective lm. Such a lm can form at these moderate temperatures because the phase transformation of Ti4NiSi4 into Ni4Ti4Si7 requires a low activation energy, which is not the case with refractory silicides such as TiSi2, VSi2, CrSi2, MoSi2 because the phase transformation, e.g., of MoSi2 into Mo5Si3, requires a higher activation energy. Indeed, it was previously [27] observed that the phase transformation related to oxidation reaction, e.g., of MoSi2 into Mo5Si3, took place at a temperature above 800  C. Below this temperature, thermal agitation was not sufcient to activate silicon diffusion in MoSi2 [28] and to transform MoSi2 into Mo5Si3. Consequently, the simultaneous oxidation in air of Mo and Si led to the formation of a thick oxide scale that was not as protective at moderate temperatures as at the higher temperatures (>1000  C) at which the transformation can occur. In the present system, the phase transformation of Ti4NiSi4 in Ni4Ti4Si7 was observed after long exposure times (Eq. (2)). Thus, this reaction is possible at moderate temperature (650  C) because there is little energy expenditure to achieve structural rearrangement during phase transformation.

4Ti4 NiSi4 /Ti4 Ni4 Si7 12Ti 9Si

(2)

As presented above, both structures can be described by a pseudolamellar structure in which the coordinates of the stacked planes along the b-axis are y 0, , and 3/4 . During the phase transformation, the composition of the interlayers (y and 3/4 ) changed drastically from Ni0.33Ti0.33Si0.33 to Ni0.8Si0.2, thereby indicating that both Ti and Si had left the interlayer; however, the

N. Chaia et al. / Intermetallics 40 (2013) 1e9

composition of the layers at y 0 and did not change to a large extent (Ti0.5Si0.5 > Ti0.4Si0.6). As a consequence, the activation energy required for the phase transformation is low. Therefore, the diffusion of Ti and Si from the interlayer occurs readily and could explain the formation of a thin protective oxide lm even at moderate temperatures. When considering the oxidation resistance, the low oxidation rates obtained here are considered low enough to have applications in future generation IV nuclear reactors. We showed that, even in an oxidative environment (in air), the NieTieSi coating possessed very high oxidation resistance at 650  C. This temperature corresponds to those envisaged for fast reactors cooled with liquid sodium (SFR), with PO2 w106 atm. Another interesting feature of this system (vanadium substrate NiTiSi coating) is the high resistance in air at a temperature which could represent incidental conditions. Indeed, the system was able to withstand more than 300 cycles between 1100  C and room temperature in air, i.e., more than 300 h. Finally, considering its pseudolamellar characteristics, this original Ti4NiSi4 compound possesses the potential for being a host structure like clay, zeolite or Chevrel phases, for active species (e.g., H2, cations, CO, NOx). In the future, electrochemical measurements will be performed to investigate the reversibility of reactions engaging the atoms present in the interlamellar space. 5. Conclusions An electrolytic deposition of nickel onto a vanadium substrate, prior to performing a silicidation step using the HAPC process, can be used to avoid the formation of vanadium dichloride as well as the formation of cavities at the substrate-coating interface. - This process led to a multilayer coating with the Ti4NiSi4 compound as the outer layer. This compound possessed a very low oxidation rate in air at 650  C, which corresponds to a more severe environment than those envisaged for the target application (fuel cladding for gas and sodium fast reactors). - The crystal structure of the new Ti4NiSi4 compound was determined from the XRD pattern obtained at the synchrotron SOLEIL with Ti4NiSi4 powder. Its crystal data were deduced (S.G. Pnma; a 15.63931; b 5.08321; c 12.75151) with a very high condence ratio (Rwp 0.07; RBragg 0.067). The structure of Ti4NiSi4 consists of atomic planes stacking along the b-axis with planes at coordinates y 0, , and 3/4 . Ti4NiSi4 can therefore be considered to be a pseudolamellar structure.

- The structure of Ti4NiSi4 possesses strong similarities to that of Ni4Ti4Si7. It is suggested that this peculiar feature led to a lower activation energy for the phase transformation of Ti4NiSi4 into Ni4Ti4Si7 and that it is responsible for the high oxidation resistance observed at 650  C in air. With such characteristics, this system (vanadium substrate plus NieTieSi coating) could potentially be employed in future fuel cladding applications.

Acknowledgements The authors wish to thank GNR GEDEPEON, PF-MATERIAUX de NEEDS and CEA for their funding and O. Rouer and S. Mathieu of the Common Service of Microscopy and Microanalysis of the University of Lorraine.

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