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Acta mater. Vol. 47, No. 2, pp. 619629, 1999 # 1999 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved Printed in Great Britain S1359-6454(98)00368-1 1359-6454/99 $19.00 + 0.00

IN SITU TIME-RESOLVED DIFFRACTION COUPLED WITH A THERMAL I.R. CAMERA TO STUDY MECHANICALLY ACTIVATED SHS REACTION: CASE OF FeAl BINARY SYSTEM
F. CHARLOT1,2, F. BERNARD1, E. GAFFET2{, D. KLEIN3 and J. C. NIEPCE1
1 2

activite des Solides, UMR 5613 CNRS, BP 400, F-21011 Dijon, France, Lab. de Recherches sur la Re UPR CNRS A0423 ``Far from Equilibrium Phase Transitions'' Group, F-90010 Belfort Cedex, France liard, BP 427, F-25211 Montbe liard, France le Universitaire BelfortMontbe and 3LMIT Po (Received 11 November 1997; accepted 4 October 1998)

AbstractMechanically activated self-propagating high-temperature synthesis (MASHS) provides an attractive practical alternative to the conventional methods of producing intermetallic compounds, such as iron aluminides. This process involves mainly the combination of two steps; the rst step, a mechanical activation, where pure elemental (Fe + Al) powders were co-milled inside a planetary mill, for a short time at given frequency and energy shocks and, the second step, a self-propagating high-temperature synthesis (SHS) reaction, which uses the exothermicity of the Fe + Al reaction. Once ignited with an external source, these reactions become self-sustained and propagate to completion within seconds. The combustion front directly leads to the formation of a nanometric FeAl intermetallic with a relative density of 70 80%. To understand this self-sustained reaction, an in situ study in real time was investigated on samples which dier by the shock power during milling and the compaction pressure (porosity). When the combustion front goes through the sample, the time-resolved X-ray diraction experiment (TRXRD) using synchrotron radiation coupled with an infrared thermography allows the in situ study of the phase formation and the temperature evolution during the MASHS process. # 1999 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved.

1. INTRODUCTION

The iron aluminides Fe3Al and FeAl show promise for a broad range of applications. They form protective oxide scales in hostile environments [1]. They exhibit lower densities and good high-temperature properties compared to many structural alloys currently used [2, 3]. However, cold working these materials causes them to exhibit brittle fracture and low ductility at room temperature. Their use as engineering materials has been thus far restricted due to this limitation. Conventional methods of processing iron aluminides, including casting, hot rolling, and powder metallurgy, have been investigated [4, 5]. An alternative processing method, variously known as combustion synthesis, reactive sintering, or selfpropagating high-temperature synthesis (SHS) [6], has also been used to synthesize several aluminides. The advantages of SHS processing include inexpensive and easily compacted powder starting materials, low processing temperature, and exibility in composition and microstructure control. The formation of the FeAl compound in the Fe Al system by mechanically activated self-propagating high-temperature synthesis (MASHS) was inves{To whom all correspondence should be addressed. 619

tigated. In fact, MASHS processing associates, on the one hand, a mechanical activation of a powder mixture which is carried out inside a planetary ball mill [7] and, on the other hand, a self-propagating high-temperature synthesis (SHS) reaction. It has been noted that the mechanical activation has been successfully applied to the synthesis of MoSi2, FeSi2, and WSi2 induced by low-temperature annealing [810] and this activation has been also reported to be eective in the case of the solid and/ or liquid phase sintering [11]. Thus, MASHS keeps the benet of the SHS process to prepare dense materials and allows with this new preliminary step, the mechanical activation, to improve the mechanical properties making possible the elaboration of nanometric bulk materials [12] by decreasing the SHS ignition temperature. MASHS is a relatively novel mode of preparing high-temperature materials via solid-state reactions. These reactions are often accompanied by the release of a large amount of heat. Once ignited with an external heat source, the SHS reactions become self-sustained and propagate through the sample within seconds. These processes are characterized by a fast moving combustion front (1100 mm/s) and a self-generated heat which allows a rapid increase of the temperature from 1000 to

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4000 K [13]. Although the basic concepts of this method of materials synthesis are relatively easy to apply in principle, there remain a number of basic questions concerning the physical and chemical nature, as well as the dynamics of the phase transformations within the moving combustion front. Until recently, it has been dicult to investigate these reactions by conventional techniques due to the high temperature and to the fast rates of combustion velocity. Indeed, these techniques do not allow the study of the mechanisms which control these reactions (i.e. the role of liquid formation, the eect of the intermediate phases and of the other parameters which induced a modication of the end products' microstructure). At the moment, in situ investigation of structural changes and chemical dynamics in the combustion area in real time with synchrotron radiation is possible. Table 1 sums up the dierent technical improvements which are supplied by the time-resolved X-ray diraction (TRXRD) technique. The investigated parameters of such a new powder processing method, combining a short duration ball-milling step hereafter called ``mechanical activation'' (leading to nanoscale three-dimensional polyinterfaces of the elemental components [11]) with a SHS reaction, are as follows: (i) the shock energy, the shock frequency concerning the mechanical activation part, and, (ii) the ignition temperature, the combustion temperature and the velocity of the combustion front concerning the SHS reaction. Their inuence on the solid (liquid) state phase formation kinetic paths were characterized. TRXRD studies were carried out in order to understand the part played by this mechanical activation on the diusion paths. The TRXRD system uses a synchrotron X-ray beam (LURE D43, Orsay), a fast detection system [17] and an X-ray high-temperature chamber [18, 19] to monitor the phase transformation during the reaction.

Moreover, the SHS reaction was monitored by an infrared camera allowing direct observation of the heat release leading to a temperature increase of about 15002000 K/s. The in situ high-temperature investigations of the SHS reaction of the Fe/Al system allows quantitative results to be obtained during the full reaction, which occurs in a few seconds. Then, the various parameters corresponding to the distinct stage of the MASHS process are reported.
2. EXPERIMENTAL CONDITIONS

2.1. Mechanical activation (MA) Two preparation modes of the rst step leading to the formation of the Fe/Al mixture were performed to study the ball-milling inuence on the SHS process: (i) Mechanically inactivated Fe + Al (hereafter called B0). This mixture was blended in a turbula mixer for 4 h. (ii) Mechanically activated Fe + Al (hereafter called B1 and B2). Mixtures B1 and B2 were comilled using the following ball-milling conditions: a mixture of pure elemental Al (40 mm) and Fe (10 mm) powders, corresponding to Fe50Al50 stoichiometry, was sealed in a 45 ml stainless steel vial with ve stainless steel balls (15 mm in diameter and 14 g in weight) under enclosed air. The ball to powder ratio in weight was 7/1. The mechanical activation treatment was carried out using a specially designed planetary ball mill (hereafter called G5). This machine was rst used to determine the parameter phase diagram which was found to be controlled by the injected mechanical power in the case of Ni10Zr7, Ni11Zr9, Ni3Al compounds [23, 24]. The frequency and the energy of the shocks occurring during this process may be selected independently. The physical

Table 1. Technical improvements of in situ time-resolved X-ray diraction experiments System NiAl TiC, NiTi, AlNi TaC, Ta2C AlNiTi FeAl FeAl, FeSi2 FeAl, MoSi2 Year 1981 1990 1993 1993 1996 1997 1997 1997 Reference Boldyrev et al. [14] Wong et al. [15] Larson et al. [16] Berar et al. [17] Javel et al. [18, 19] Gaet et al. [20] Bernard et al. [21] Charlot et al. [22] Experiment detector 88 (2y) 0.51 s each scan detector 68 (2y) 200 ms per scan, 200 discreet measurements detector 2 88 (2y) 100 ms per scan 500 discreet measurements + i.r. thermography rapid detector 178 (2y) 30 ms per scan 2048 discreet measurements detector 178 (2y) coupled with i.r. thermography 180 ms per scan 2048 discreet measurements detector 178 (2y) coupled with i.r. thermography 180 ms per scan 2048 discreet measurements detector 308 (2y) coupled with i.r. thermography 50 ms per scan 2048 discreet measurements

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parameters of the G5 machine were as follows: the vials are xed onto a rotating disk (rotation speed O) and rotate in the opposite direction to the disk with a speed of o. The O and o were checked and controlled by an ultrasonic tachometer. The selected O/o values are expressed in r.p.m. The duration of the milling process is denoted Dt. So, milling conditions are characterized by three important parameters O,o ,Dt. Two milling conditions were selected, one of them G5(150/200/4 h) so-called B1 corresponding to the friction mode and the other G5(150/50/ 4 h) so-called B2 to a direct shock mode. The duration of the milling process was determined from a kinetic study performed on milled powders taken at dierent times (i.e. 1, 2, 3, 4, 6, 12 h). Finally, from XRD analysis, the milling duration was xed at 4 h in order to avoid the formation of some intermetallic fractions during the MASHS processing steps but to enable the formation of the chemical gradient at a nanoscale (layered structure of Fe and Al).

2.2. Post-mortem SHS experiments SHS processes are those which involve exothermic reactions and which are able to selfpropagate, or even self-accelerate. As the reaction Fe Al AFeAl is exothermic (DH 51 kJamol [25]; 32 kJ/mol [26]), the combustion of Fe and Al starts at the hottest point of the system and, if the thermal conditions are favorable, propagates through all the sample. A homogeneous sample is generally the result of a homogeneous reaction in each combustion zone and a stable value of combustion velocity. The sim-

plest way of ignition is local heating of a powder compact when the enthalpy of reaction is suciently exothermic to produce a self-sustained reaction. After extraction from the milling vials, the mechanically activated particles were introduced into a cylindrical tempered steel die (f 13 mm) and were cold compacted using a uniaxial pressure system. In this case, samples were made at several distinct pressures from 200 MPa to 2 GPa. A geometric measurement of the green density was carried out in order to study the inuence of the initial green density on the MASHS reactions. In this part, cylindrical samples were put on a pre-heated sample holder at a xed temperature T controlled by a thermistor probe in the range of 3504508C, the reaction is ignited after a short delay, simultaneously an infrared camera studies the thermal evolution on the sample surface. This temperature T will be assimilated to the ignition temperature. To exhibit the contribution of the ball-milling and compaction pressure conditions on the MASHS process in the Fe/Al system the ignition temperature and the nature of the end products were chosen. The latter is carried out by Xray diraction analysis using a D5000 Siemens high resolution powder diractometer.

2.3. In situ time-resolved experiments A specic device described in Fig. 1 was especially used to study simultaneously the structural evolution using a time-resolved X-ray diraction (TRXRD) system and the surface temperature eld using an infrared camera.

Fig. 1. Diagram of the in situ time-resolved instrument.

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2.3.1. Time-resolved X-ray diraction (TRXRD). The high-temperature chamber which was previously developed by Gachon and coworkers [18, 19] is built in stainless steel with a vacuum technology. It supports the alumina sample holder which is centered at the goniometer axis and supports an electrical heater. The compacted samples were ignited at one end by this heating tungsten resistor located on the sample holder. During this experiment, a rectangular geometry of the sample (20 10 mm) having a plane surface was imposed to lead the XRD investigations. In this case, only two compaction pressures were chosen, 200 and 600 MPa, respectively. This reaction chamber can be used with various atmospheres, in our case, all the Fe + Al reactions were performed in a helium atmosphere to avoid material oxidation and to minimize air attenuation of the incident and diracted X-ray beams. The chamber includes a 1808 mylar window to allow access of incident and diracted X-ray beams and of i.r. beams. This apparatus was designed to accept a synchrotron beam at an angle of about 308 on a combustion sample. During our experiments, a position sensitive detecting system designed by Berar et al. [17] for rapid acquisition was used. Its beryllium window has an aperture of 120 6 mm2. It is located at a distance of 400 mm from the diracting center and in these conditions, it has an equivalent angular aperture of 178 in 2y. The structural evolution of the X-ray diraction experiment was performed at LUREDCI (Orsay, France) on the beamline D43 (Head: J. Doucet) using a focused beam monochromator (l = 0.099 nm). The detector was centered at 248 to collect simultaneously the Al(111) and Fe(110) + Al(200) diraction peaks at the starting point of the reaction, as well as the major diraction peaks of FeAl(110) products. Two distinct congurations to record XRD patterns can be chosen: (i) one favoring a short acquisition time to follow kinetics reactions, which is characterized by the collection of 2048 XRD patterns having a spatial extension on 256 channels and an acquisition time of 30 ms and (ii) one favoring a long acquisition time to dene the initial and nal states which is characterized by the collection of one XRD pattern with an acquisition time of 30 s. In addition, from this apparatus, it is possible to record simultaneously all thermal and structural events during 1 min. Standard aluminum powder, using Al(111) and Al(200) peaks, was used to calibrate each diractogram in the angular range dened above. Nevertheless, taking into account the high random component of the XRD background, it was necessary to sum at least ve elemental scans to eectively reveal the diraction peak.

Fig. 2. (a) Spatial coupling. The white rectangle represents the irradiated area in an infrared image. One pixel represents about 1 mm2 (case of B1 200 MPa sample). x and y labels represent the number of lines which dene a pixel on this picture. (b) Temporal coupling. Determination of the beginning of X-ray acquisition on the i.r. image. The incandescent lamp is switched on image 47 (t = 0 2 200 ms).

2.3.2. Time-resolved infrared thermography. The sample temperature was simultaneously recorded with the TRXRD measurements using an imaging infrared camera (AGEMA THERMOVISION 470). This apparatus is equipped with a lens (208) having a eld of view of 13 13 cm2 and each pixel of one infrared picture corresponds to 1 1 mm2. Thermal infrared images were continuously recorded with a video system using the Broadcast Standard for U-matic magnetoscope. Emissivity measurements which were performed by Klein with this camera, show a change of the sample emissivity between initial and nal states. Nevertheless, in order to obtain a real temperature from i.r. signals, only one value of the emissivity must be used with this camera. So an average value which is determined from previous measurements was used and was equal to 0.8. The mylar

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window of the chamber was transparent in the range of wavelength where the i.r. captor was sensible (25 mm). 2.3.3. Spatio-temporal synchronization. Nevertheless, it is essential to perform a spatio-temporal synchronization of X-ray diraction and infrared data. 2.3.3.1. View Of The Irradiated Area On The Sample: SPATIAL COUPLING With a uorescent paper representing the sample size, the X-ray spot was revealed and recorded by a visible camera. After the analysis of this image, the coordinates of the irradiated area were dened knowing the pixel size of the numerical infrared image. This area must be now rened on the infrared image [Fig. 2(a)]. 2.3.3.2. Determination Of The Acquisition Starting Time (T0): TEMPORAL COUPLING Temporal coupling is essential to correlate the Xray diraction acquisition (recorded in steps of 30 ms) to i.r. images (recorded in steps of 200 ms). Nevertheless, it is essential to set the beginning of X-ray acquisition on the corresponding i.r. image number. This was performed with an incandescent lamp located in the camera eld, which was switched on when the diraction data collection was activated [Fig. 2(b)]. These various operations were performed to clearly dene the temperature

map within the irradiated area in real time as the reaction front propagates through the sample.

3. EXPERIMENTAL RESULTS

3.1. Post-mortem MASHS results Using the SHS procedure described in Section 2.2, for each ball-milling condition [B1 (150/200/ 4 h), B2 (150/50/4 h) and B0] and each compaction pressure, Table 2 was established. In Table 2, the XRD analyses were performed to determine which kinds of intermetallic phases were formed after the MASHS process. In the case where only the FeAl compound was observed (except some iron oxides), the size of the crystallites (size of a region over which the diraction is coherent) was determined from HalderWagner plots [12] using the XRD line prole analysis [27]. Table 2 shows that the friction mode (B1) is more eective to activate the MASHS process in comparison with the direct shock mode (B2). Indeed, such a mode (B1) was shown to lower the ignition temperature. This result can be explained by an increase of the polyinterface number and surface fracture: i.e. the number of contact surfaces is increased. In addition, it seems that the ignition temperature depends on the porosity. Indeed, for example in the case of the B1 condition at 3508C, only the sample having 20% of porosity has

Table 2. Post-mortem MASHS results obtained for each ball-milling condition (B0: turbula mixer 4 h; B1: O = 150 r.p.m., o = 200 r.p.m., Dt = 4 h; B2: O = 150 r.p.m., o = 50 r.p.m., Dt = 4 h) vs the compaction pressure (200, 600 and 2000 MPa) and the sample holder temperature (350, 400 and 4508C). For each case: the nature of the end products and the size of the FeAl crystallites (denoted S) determined by XRD investigations are listed. In addition, the value of the porosity before the reaction and the relative density after the reaction are indicated too B0 (without mechanical activation) Each pressure B1 (150/200/4 h) Compaction pressure Green porosity 3508C 3508C 4008C No reaction 4008C 4508C Maximum of relative density after reaction 70% 80% 50% 4508C

200 MPa 600 MPa 2000 MPa B2 (150/50/4 h) Compaction pressure

20% 10% <5%

FeAl, a-Fe2O3, S = 34 nm Fe, Al Fe, Al, (Fe2Al5), g-Fe2O3 3508C

FeAl, a-Fe2O3, S = 31 nm FeAl, a-Fe2O3, S = 34 nm FeAl, FeAl2, g-Fe2O3

FeAl, a-Fe2O3, g-Fe2O3, S = 32 nm FeAl, a-Fe2O3, S = 29 nm 4508C

Green porosity

4008C

Maximum of relative density after reaction 71% 80% 47%

200 MPa 600 MPa 2000 MPa

20% 10% <5%

Fe, Al, (Fe2Al5), g-Fe2O3, a-Fe2O3 Fe, Al, g-Fe2O3, a-Fe2O3 Fe, Al, (g-Fe2O3)

FeAl, a-Fe2O3, S = 29 nm FeAl, Fe2Al5, FeAl2, Fe, a-Fe2O3, g-Fe2O3 Fe, Al, (Fe2Al5), g-Fe2O3

FeAl, a-Fe2O3, S = 29 nm FeAl, Fe2Al5, Fe, a-Fe2O3, g-Fe2O3 FeAl, FeAl2, a-Fe2O3

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Fig. 3. Structural evolution and temperature prole of a mechanically activated (B1, 200 MPa) sample: (a) Fe[110] + Al[200]; (b) Al[111]; (c) FeAl[110].

reacted. This observation will be discussed later (Section 4.2). Finally, it has been shown that the MASHS process is eective in producing a nanocrystalline Fe Al intermetallic compound starting from an initial equimolar FeAl (2934 nm) with an average relative density of 80%. In the time-resolved X-ray diraction studies, only samples prepared using the friction mode (B1) and pressed with a charge of 200 and 600 MPa will be compared with the mechanically unactivated samples (B0, 200 MPa). 3.2. In situ time-resolved results Typical examples of such an analysis coupling the structural and the temperature evolution are listed in Fig. 3. In this gure, we can notice that the rst XRD patterns recorded just before the ignition of the reaction show that the intensity of the Al(111) peak increases as a function of time. This observation can be due to a reorganization of the aluminum phase in the temperature range close to 4508C. Then, as the combustion wave propagates inside the irradiated area, the FeAl intermetallic phase grows up. In the case of a B1 sample, at 23.7 s when the combustion wave goes through the diracted area (whose temperature is about 7508508C), the intensity of the Fe(110) + Al(200) peaks decreases and

the major FeAl peak (110) appears. At the end of this SHS reaction, only the FeAl phase was detected by the XRD experiment. The ignition and the propagation of the combustion front induced by the SHS reaction were recorded using an infrared camera. From these infrared data, dierent thermal parameters can be deduced as shown in Fig. 4 in which the origin of the time is the beginning of the X-ray collection. The dierent parts of this gure are as follows: (i) Fig. 4(a) represents the location of the irradiated area on the sample which allows a thermal analysis to be performed along a vertical line. (ii) Fig. 4(b) shows the shape and the velocity of the combustion front (12 mm/s) on this line vs time. (iii) Fig. 4(c) represents the temperature evolution at one point of this line, the intersection of two slopes leads to the determination of the ignition temperature (Tign=4008C), the combustion temperature (Tcomb=9308C) is the highest temperature reached in the combustion front. (iv) Fig. 4(d) is the derivative plot of the temperature prole, an increasing temperature rate is dened. In order to exhibit MASHS characteristics in comparison with classical SHS characteristics, parameters such as the SHS ignition temperature, the velocity of the combustion front and the increasing temperature rate were chosen.

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Fig. 4. Thermal analysis on a (B1, 200 MPa) sample: (a) location of the area irradiated; (b) visualization of the combustion front on the whole sample; (c) evolution of the temperature during the time on the irradiated area (t = 0 corresponds to the beginning of the X-ray data collection); (d) increasing temperature rate vs time on the irradiated area.

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Table 3. (a) Comparison of the thermal parameters deduced from i.r. data for a mechanically activated sample (B1: 150/200/4 h) and for a mechanically unactivated sample (B0: turbula) in the case of 200 MPa compaction pressure. (b) Comparison of the thermal parameters deduced from i.r. data for two mechanically activated samples (B1: 150/200/4 h) pressed at 200 and 600 MPa, respectively (a) Sample compacted at 200 MPa B1 B0 (b) Sample B1 Ignition temperature (8C) 400 480 Ignition temperature (8C) 400 470 Combustion temperature (8C) 930 900 Combustion temperature (8C) 930 900 Combustion velocity (mm/s) 12 2.5 Combustion velocity (mm/s) 12 7.5 Increasing temperature rate (8C/s) 1600 480 Increasing temperature rate (8C/s) 1600 800

200 MPa 600 MPa

4. DISCUSSION

The reproducibility of these experiments has been shown by using the X-ray synchrotron beam over a period of four days. The short duration of one experiment (close to 1 h) enables measurements on 20 samples per day. Consequently, during four days, 80 samples can be studied. 4.1. Eect of the mechanical activation It is clearly shown in Table 3(a), for a compaction at 200 MPa, the mechanical activation, introduced during the MASHS milling step noted B1 (friction mode), signicantly decreases the ignition temperature (more than 1008C) and, signicantly increases the front velocity (2.512 mm/s) in comparison with the classical SHS process represented by sample B0 (without mechanical activation). Moreover, the analysis of the heat release by the SHS reaction, shows that this heat induces a temperature increase of 16008C/s for sample B1 and only 4808C/s for sample B0. These observations can be due to the release of the mechanical energy stored during the co-milling inside of grain powders and/or the decrease of the diusion paths because of the existence of the chemical gradient at a nanoscale. 4.2. Eect of the compaction pressure In Table 3(b), in the case of the mechanical activation sample (B1), it is shown that a low pressure compaction sample exhibits an ignition temperature lower than that corresponding to a high compacted pressure green sample. A low pressure (200 MPa) decreases the SHS ignition temperature (about 508C), increases the front velocity (7.512 mm/s) in comparison with a sample higher pressure (600 MPa), for the same co-milling mode. Moreover, the analysis of the heat release by the SHS reaction, shows that this heat induces a temperature increase of 16008C/s for the sample compacted with 200 MPa and only 8008C/s for the sample compacted with 600 MPa. This fact can be associated with a porosity dierence which was

found to be equal to 37 and 15% for 200 and 600 MPa pressures, respectively. The dierence of porosity between these samples and those used for the post-mortem SHS experiments, for the same compaction pressure, is due to the dierence of the sample geometry (rectangular instead of cylindrical). These observations are in agreement with the conclusion of Munir [28] about the part played by the porosity on the thermal parameters of self-sustained reactions. This observed dierence may be assumed to be due to a modication of the thermal conductivity in the whole sample: a higher porosity, a lower thermal conductivity. Thus, a larger thermal gradient has to be taken into account in the case of the low pressure compacted sample. Moreover, the eect of the porosity on the velocity (v) is similar to observations on aluminide intermetallics. Previously, it was shown [29, 30] that the curve representing the velocity evolution vs the porosity presents a maximum which is located at 40% of porosity for Al50Ni50 and Ni50Ti50 compounds and 35% of porosity for the Al50Co50 phase. 4.3. Future improvements on in situ time-resolved experiments Many improvements are necessary, such as a new rapid detector with a larger angular aperture in order to conrm or to invalidate the presence or absence of transitory phases during this process. Recently, two main developments were performed on the TRXRD device at LURE: (i) the use of a new rapid detector with an angular aperture of 308 2y which can couple with the old rapid detector with an angular aperture of 178 2y, thus allowing an X-ray diraction analysis on an angular domain of 478 2y. (ii) The use of a parallel slit system which reduces the irradiated area in the propagation direction of the combustion front. These improvements have enabled the selection of a more useful wavelength (0.183 nm instead of 0.099 nm) allowing the expansion of the diraction patterns, to easily identify phases which can be observed during the propagation of the front. In this new conguration,

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Fig. 5. Observation of a transitory phase during the FeAl elaboration by MASHS.

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we have observed transitory phases during the FeAl elaboration by the MASHS process as shown in Fig. 5. This latter observation shows the interest in using TRXRD experiments coupled with an i.r. camera in order to obtain the diusion paths which are used to form these materials. The next steps of this work will be to determine the nature of this transitory phase and better understand the contribution of the mechanical activation and the compaction pressure on the reactivity of this system by thermal model development.

formations and direct observations of the heat release during this process. It has been found that the mechanical activation of the initial powders has been eective in accelerating the ignition of the SHS intermetallic phase in the FeAl system. MASHS appears a promising technique in comparison with the classical SHS reaction.
Acknowledgements M. Bessiere (LURECNRS), M. Gailhanou (LURECNRS), M. Gramond, J. F. Berar (ESRF CNRS), J. Doucet (LURECNRS), J. C. Gachon (CNRSUniv. Nancy), Ch. Gras, J. F. Javel and B. Zeghmati are gratefully acknowledged for their valuable help during the experiments. V. Mathae is especially acknowledged for his assistance and his availability for the thermal analysis. One of the authors (F.C.) gratefully acknowledges the nancial support of the Regional Council of Bourgogne (France) and the General Council of Territoire de Belfort (France). REFERENCES 1. Takasugi, T., Masahashi, N. and Izumi, N. A., Acta metall., 1987, 35, 381. 2. Wang, K., Nishikata, A., Shinoda, D. and Suzuki, T., Z. Metallk., 1990, 81, 581. 3. Watchel, E. and Bayer, E., Z. Metallk., 1984, 75, 61. 4. Sikka, V. K., Proc. of the Fifth Annual Conference on Fossil Energy Materials, Oak Ridge, Tennessee, 1991, p. 97. 5. Knibloe, J. R., Wright, R. N. and Sikka, V. K., in Advances in Powder Metallurgy, compiled by E. R. Andreotti and P. J. McGeehan. Metal Powder Industries Federation, Princeton, New Jersey, 1990, p. 219. 6. Merzhanov, A. G. and Borovinskaya, I. P., Dolk. Akad. Nauk. SSSR, 1972, 204, 366. 7. Gaet, E. and Yous, L., Mater. Sci. Forum, 1992, 383, 88. 8. Malhouroux-Gaet, N. and Gaet, E., J. Alloys Comp., 1993, 198, 143. 9. Gaet, E. and Malhouroux-Gaet, N., J. Alloys Comp., 1994, 205, 27. 10. Gaet, E., Malhouroux-Gaet, N., Abdellaoui, M. and Malchere, A., Revue Metall./CIT-Sci. Genie Materiaux, 1994, May, 757. 11. Chausse, C., Nardou, F. and Gaet, E., Mater. Sci. Forum, 1995, 179181, 391. 12. Charlot, F., Gaet, E., Bernard, F., Zeghmati, B. and Niepce, J. C., Mater. Sci. Engng A, in press. 13. Munir, Z. A., Ceram. Bull., 1988, 67(2), 342. 14. Boldyrev, V. V., Aleksandrov, V. V., Korchagin, M. A., Tolochko, B. P., Gusenko, S. N., Sokolov, A. S., Sheromov, M. A. and Lyakhov, N. Z., Comb. Explo. Shock Waves, 1981, 259(5), 722. 15. Wong, J., Larson, E. M., Holt, J. B., Waide, P. A., Rupp, B. and Frahm, R., Science, 1990, 249, 1406. 16. Larson, E. M., Wong, J., Holt, J. B., Waide, P. A., Nutt, G., Rupp, B. and Terminello, L. J., J. Mater. Res., 1993, 8(7), 1533. 17. Berar, J. F., Lemmonier, M., Bartol, F., Grammond, M. and Chevreul, J., Nucl. Inst. Meth. Phys. Res., 1993, B82, 146. 18. Javel, J. F., Dirand, M., Nazzik, F. Z. and Gachon, J. C., J. Physique IV, 1996, 6(C2), 229. 19. Javel, J. F., Dirand, M., Kuntz, J. J., Nazzik, F. Z. and Gachon, J. C., J. Alloys Comp., 1997, 247, 72. 20. Gaet, E., Charlot, F., Klein, D., Bernard, F. and Niepce, J. C., Mater. Sci. Forum, 1998, 269272, 379.

5. CONCLUSION

This paper clearly shows the inuence of the mechanical activation and the compaction pressure on the SHS process. Starting from a mixture of elemental powders, the rst MASHS milling step is basically a solid state mixing process due to chaotic processes (fracture and welding) which leads to the formation of micrometer-sized powders which contain nanoscale three-dimensional polyinterfaces between the elemental Fe and Al components. In the mechanical activation studies, the solid state reaction which forms the target phases occurs only during the subsequent SHS step. The inuence of milling conditions on grain sizes and residual stresses were reported to modify the phase transformation kinetics by the nal SHS process. The mechanical activation allows an ignition temperature decrease and an increase of the combustion front velocity over the classical SHS process. Using this particular planetary mill, it is possible to select a friction mode or a direct shock mode to activate powders during this initial step of the MASHS process. Our experiments demonstrate that the friction mode is more ecient in decreasing the ignition temperature than the direct shock mode. We conclude that mechanical activation depends on the mode of transfer of mechanical energy to ground powders. It thus constitutes a very exible way of inuencing phase transformations. Experimental results call for more rened models to understand such a process in more detail. The compaction pressure (or more precisely the porosity value) enables to decrease the ignition temperature and increase the front combustion velocity. This MASHS process produces nanometric bulk materials, but the weakness of the relative density (from 70 to 80%) requires some future development to obtain fully dense bulk materials. This paper clearly demonstrates the usefulness of using a monochromatic high energy synchrotron Xray beam (LUREOrsay, France) coupled with a thermal i.r. camera to study in situ the mechanically activated self-propagating high-temperature synthesis (MASHS) reactions. Indeed, the timeresolved XRD coupled to an infrared camera provides information on the structural phase trans-

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21. Bernard, F., Charlot, F., Gaet, E. and Niepce, J. C., Int. J. SHS, 1998, 7(2), 233. 22. Charlot, F., Gras, C., Gramond, M., Gaet, E., Bernard, F. and Niepce, J. C., J. Physique IV, 1998, 8, 5. 23. Gaet, E. and Yous, L., Mater. Sci. Forum, 1992, 8890, 51. 24. Gaet, E., Mater. Sci. Engng A, 1991, 135, 291. 25. Rabin, B. H. and Wright, R. N., Metall. Trans. A, 1991, 22A, 277. 26. Yi, H. C. and Moore, J. J., J. Mater. Sci., 1992, 27, 6797.

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