Interface Engineering of CarbonFiber Reinforced MgAl Alloys**

By Armin Feldhoff, Eckhard Pippel, and Jrg Woltersdorf*

Metal matrix composites of the system C-fiber/Mg-matrix enable the outstanding combination of the high strength and elastic modulus of carbon fibers and the low density of both the carbon fiber and the magnesium matrix in structural metallic materials. However, the efficiency of the fiber reinforcement depends mainly on the characteristics of the fiber/matrix interlayers. Optimized materials can be achieved only by an appropriate interface design. The interfacial bonding can be adjusted by modifications of both the matrix composition and the fiber surface. Two strategies are reviewed in this paper: Firstly, to control the fiber/matrix reactivity by appropriate chemical and structural properties of the partners. Secondly, to coat the carbon fibers with a suitable material prior to the composite fabrication.

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1. Introduction
Metal matrix composites (MMCs) of the system carbon-fiber/magnesium-matrix allow the outstanding combination of i) the high strength (34 GPa) and Young's modulus (some 100 GPa) of the carbon fibers, ii) the low density of both partners (<2 g/cm3), and iii) the metallic ductility of the matrix.[1,2] Hence, the optimization of the fiber/matrix interlayers and the prevention of fiber degradation would yield in materials having densities of only a fraction of that of steels but much higher strengths. As is well-known, the efficiency of the reinforcement depends mainly on the properties of the interlayers between fiber and matrix.[36] Among the various processing routes for MMCs that have been developed, those employing melt infiltration techniques[712] are favorable as they provide a near net-shape fabrication of components, even in complex geometries: In a die, evacuated preforms made of carbon fiber yarn are infiltrated with magnesium at temperatures above its melting temperature of 650 C, applying an external pressure. In the chemical literature, the pure system C/Mg is considered as chemically non-reactive, because the two binary magnesium carbides MgC2 and Mg2C3 are supposed to be endothermic compounds as they are known to start to decompose at about 500 C and 650 C, respectively.[1318] Therefore, the formation of MgC2 or Mg2C3 at MMC processing temperatures (700 800 C) should be very unlikely, and a good compatibility of the MMC components is expected.

Unfortunately, the non-reactive character of the system C/Mg leads to very weak bonding between fiber and matrix, requiring the enhancement of the interfacial bonding. In principle, this can be achieved by modifying the chemistry of the matrix or of the fiber surface.[19] Both approaches are reviewed in this paper: Section 2 describes the control of the fiber/matrix reactivity by alloying different amounts of a carbide-forming element (aluminum) with the matrix including the usage of carbon fibers of different surface microstructures. Section 3 discusses the interface optimization by coating carbon fibers with a suitable material (TiN) prior to composite fabrication. However, for the optimization of these materials and, even more, the comprehensive exploitation of the outstanding properties of the fibers it is decisive to investigate the evolution of interface structures as well as their influence on the mechanical properties. Advanced transmission electron mi-

[*] PD Dr. J. Woltersdorf, Dr. A. Feldhoff, Dr. E. Pippel Max-Planck-Institut fr Mikrostrukturphysik Weinberg 2, D-06120 Halle (Germany) Email: wolt@mpi-halle.de

[**] The authors would like to thank Prof. Dr. R. F. Singer (University of ErlangenNrnberg) and his co-workers for providing the MMC samples and for many stimulating discussions on C/MgAl composites.

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Feldhoff, Pippel, Woltersdorf/Interface Engineering of Carbon-Fiber Reinforced MgAl Alloys croscope techniques offer powerful tools to gain structural and chemical information of the fiber/matrix interfaces down to the atomic scale: High voltage electron microscopy (HVEM), high-resolution electron microscopy (HREM), energy-filtered transmission electron microscopy (EFTEM), and scanning transmission electron microscopy (STEM) in combination with energy dispersive X-ray spectroscopy (EDXS) and electron energy loss spectroscopy (EELS) with particular emphasis on energy loss near edge structures (ELNES). The latter method allows one to characterize the chemical bonding state in the interlayers on the nanometer scale by analyzing the fine structures of the relevant ionization edges, which can be attributed to transitions of coreshell electrons into unoccupied states above the Fermi level.[2024] As characteristic ELNES details the edge onset as well as the shape, the position and the intensity of individual peaks in the fine-structure can be employed. Furthermore, using an

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energy-selective device, transmitting only electrons with a predetermined energy, EFTEM becomes possible, allowing the imaging of elemental distribution in the fiber/matrix interregion with a spatial resolution of about one nanometer.[2527]

2. Alloying the Matrix with a Carbide Former

Aluminum, which is the technologically most important alloying element for magnesium,[2831] can be used to increase the fiber/matrix interactions via the formation of carbides. Some of the MgAl alloys most frequently used are AM20, AM50, and AZ91 with Al contents of approximately 2, 5, and 9 wt.-%, respectively.[2831] In contact with carbon fibers, aluminum may form the stable binary carbide Al4C3,[3234] or it may cause the formation of stable ternary carbides of approximate composition Al4Mg2C3[35] or Al2MgC2.[3639]

A. Feldhoff studied physics at the Westphalian-Wilhelms-University, Mnster until 1994. Since then he worked as a research scientist at the Max-Planck-Institute for Microstructure Physics in Halle. In 1997 he graduated at the Martin-Luther-University Halle-Wittenberg with a Ph D thesis on interface optimization of carbon-reinforced magnesium alloys.

E. Pippel is working as a research scientist in the group Interfaces/ New Materials at the Max-PlanckInstitute for Microstructure Physics, Halle. He graduated 1982 with a thesis on pseudomorphous growth in epitaxial bicrystal systems and won the Bhler award in 1993. He authored 130 scientific publications and is also co-author of several technical books.

J. Woltersdorf is head of the research group Interfaces/ New Materials at the Max-Planck-Institute for Microstructure Physics, Halle, and lecturer at the Martin-Luther-University Halle-Wittenberg. He received his habilitation in 1988 and was in 1992 appointed as professor of surface technology at the Technical University Dresden. He also won the Bhler award in 1993 and authored 200 scientific publications as well as several technical books and monographs.

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Feldhoff, Pippel, Woltersdorf/Interface Engineering of Carbon-Fiber Reinforced MgAl Alloys face, with the graphitical basal planes in preferentially parallel orientation to the fiber surface. In comparison the surface of the less graphitized hightensile-strength fibers is rougher, with many basal planes ending freely on it.[5,4548] As the free-ending graphite layers show a higher chemical reactivity than the graphitic basal planes,[48,49] the high-tensile-strength fibers are generally more reactive than the high-modulus ones. In general, by combining carbon fibers of different surface microstructures with MgAl matrices of different Al contents, the fiber/matrix reactivity of C/MgAl composites can be varied over a wide range. With the interface reactivity increasing three characteristic failure mechanisms occur, which correlate with the strength of the composites.[5,6,5057] They are illustrated in Figure 1, showing results of in-situ bending tests[5,5358] on three composites of increasing fiber/matrix reactivity: At the beginning of the bending test with a C/MgAl composite of low interface reactivity (Fig. 1a), the load increases linearly with increasing deflection. With accumulation of damage events, the slope decreases. After the load maximum at Fmax = 240 N (rB 544 MPa) the curve declines continuously. The fracture surface in Figure 1a is characterized by pull-out and fracture of single fibers due to a very weak fiber/matrix bonding. This is affected by the absence of any carbides at the fiber/ matrix interface as is proven by transmission electron microscopy (TEM) investigations.[4,5,54] In the bending test with a C/MgAl composite of medium interface reactivity (Fig. 1b), the load increases linearly with increasing deflection until the load maximum is reached at Fmax = 410 N (rB 929 MPa). The subsequent decrease in load shows characteristic steps, which can be attributed to the failure of individual fiber bundles. Bundles of 30 to 80 fibers, which are joined by matrix metal emerge from the fracture surface. Such a bundle fracture behavior implies a bending strength of the composite that is approximately 1.7 times higher than that Fig. 1. Load-deflection diagrams and SEM images of the fracture surfaces: a) High-modulus fiber/ of the first material. AM20-matrix composite with the load maximum at 240 N (rB 544 MPa) showing single-fiber A composite of high interface reactivity (Fig. 1c) fracture, b) high-tensile-strength fiber/AM20-matrix composite with the load maximum at 410 N (rB 929 MPa) showing bundle fracture, c) high-tensile strength fiber/AZ91-matrix composite with shows a much lower strength. In the corresponding the load maximum at 70 N (rB 158 MPa) showing brittle fracture. bending test the load increases linearly up to its maximum, which is reached already at Fmax = 70 N (rB 158 MPa). The flat fracture surface hints at a brittle fracA further parameter influencing the fiber/matrix reactivity ture as known from monolithic ceramics. is the surface microstructure of the carbon fiber itself. As a Figure 1 illustrates that the interface reactivity should consequence of their production process, which is a conneither be too low nor too high to enable the maximum use of trolled pyrolysis of a polyacrylonitrile (PAN) polymer precurthe fiber strength. With increasing fiber/matrix reactivity the sor fiber,[4043] commercially available carbon fibers are classicomposite strength correlates with three characteristic failure fied in two types that differ mainly in the degree of patterns: single-fiber fracture, bundle fracture, and brittle graphitization of the turbostratic carbon[44]: The more graphifracture. tized high-modulus fibers possess a relatively smooth sur-

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Feldhoff, Pippel, Woltersdorf/Interface Engineering of Carbon-Fiber Reinforced MgAl Alloys Depending on their fiber/matrix reactivity, C/MgAl composites show extents of plate-shaped precipitates at the fiber/matrix interfaces.[46,54,56] With the fiber/matrix reactivity being rather high, many mm-sized precipitates are formed (Fig. 2). Amount and size of the precipitates characterize the respective interface reactivity and control the mechanical properties.[5,6,5057] Therefore, the optimization of the C/Mg Al composite materials requires the almost comprehensive characterization of the nature of the precipitates. EDXS and EELS investigations revealed that the precipitates are composed of the three elements Mg, Al, and C.[35,54,57] The fine-structures of the ionization edges in the EEL spectra contain further information that goes beyond the composition as the ELNES peculiarities are determined mainly by the bonding states, thus reflecting the chemical neighborhood (cf. Sec. 1). In the following, the ELNES features of the interface precipitates are discussed referring to Figure 3, where the fine-structures of the MgL23, AlL23, and CK ionization edges are compared to those of standard substances. The MgL23 ELNES curves of Figure 3a show a significant difference in the chemical neighborhood of the magnesium atoms of a precipitate compared to that of metallic (top) or oxidic magnesium (bottom). In addition, for the precipitate phase the ELNES shows a peak structure at about 73 eV (onset), which can be attributed to the L23 ionization edge of aluminum. In Figure 3b, this peak structure is compared to the L23 edge of different Al compounds. The AlL23 ELNES (Fig. 3b) of the Al4C3 standard and of the precipitate phase clearly differ from those of metallic and oxidic aluminum. Between each other they show similar profiles. In both cases, the edge-onset energy is at about 73 eV, followed by a small peak at about 77.5 eV after a steep rise of the signal. At the CK ionization edge (Fig. 3c), the spectra of the Al4C3 standard and of the precipitate phase show a steep rise in the signal, with its maximum peak at about 291 eV. For the precipitate phase, however, the slope decreases slightly on the left of this peak, viz. at about 287 eV. Furthermore, at about 30 eV above the onset energy, another broader peak occurs, which differs by about 3 eV in the energy position of its maximum (at about 305 eV for Al4C3, and at about 302 eV for the precipitate). Because of the strong similarities in the AlL23 and CK ELNES (Figs. 3b and 3c), these ELNES peculiarities suggest the precipitate phase to be considered as an aluminummagnesium-carbide, the crystal chemistry of which is closely related to that of the binary carbide Al4C3. Indeed, detailed crystallographic and morphological investigations[38,54,56] including the comparison with X-ray powder diffractometry studies[36] identify the observed precipitate phase as the ternary carbide Al2MgC2, which has an (0002) lattice fringe distance of 0.62 nm. The proposed crystal structure describes the ternary carbide Al2MgC2 as an interstitial carbide, analogous to the well-known binary carbide

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Fig. 2. HVEM bright-field image of a high-tensile strength fiber in a composite with an AZ91 matrix (middle), revealing plate-shaped precipitates in the fiber/matrix interregion.

Fig. 3. ELNES profiles of carbidic precipitates in a C/MgAl composite and of standard substances at different ionization edges: a) MgL23, b) AlL23, c) CK.

Al4C3.[38,5456] According to Figure 4, showing a projection on the (1120) plane, the carbide Al2MgC2 consists of a metal atom arrangement, with the Al atoms in a cubic close-packed (c) and the Mg atoms in an hexagonal close-packed (h) stacking. The carbon atoms fill two kinds of interstices of the metal atom host lattice: octahedral interstices between two adjacent aluminum layers, and trigonal-bipyramidal ones within the magnesium layers. The ternary carbides having formed in the C/MgAl composites have the morphology of hexagonal-shaped plates, i.e., their lateral extension is in perpendicular orientation to their c-axis. Figure 5 demonstrates that the interfaces between the side faces of the Al2MgC2 plates and the metal matrix exhibit many growth ledges, whereas the interfaces between the

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Fig. 4. Projection of the atomic arrangement of Al2MgC2 on the (1120) plane.

Fig. 6. HREM image showing an Al2MgC2 plate grown directly on the surface of a high-tensile-strength fiber in a composite with an AZ91 matrix (fiber below).

Fig. 5. Ternary carbide in the matrix of a C/MgAl composite.

(0001) habit planes and the matrix are flat on the atomic scale. These two distinct interface structures between the Al2MgC2 plates and the Mg matrix indicate the action of two different growth mechanisms,[5457,59] which were observed also for Al4C3 in Al matrixes:[60,61] l The atomically-rough interface moves in a continuous diffusion-controlled growth mode, which is determined by the diffusion rates of the reaction partners Al and C. l In directions normal to the atomically-flat interface (i.e., along the c-axis of the carbide), the crystal grows by an interface-controlled ledge mechanism, which requires a multiple two-dimensional nucleation or a spiral growth mechanism. With the driving force being low, the diffusion-controlled growth process is several times faster than the interface-controlled one,[62,63] yielding the observed plate-shaped morphology of the ternary carbides. Of course the carbides nucleate and grow preferentially in the liquid matrix state, when all the species have the highest mobility.[39,54,64] The velocity of the growth of the Al2MgC2 plates in C/MgAl composites can be estimated by comparing it with the analogous growth of Al4C3 in C/Al composites: For melt/fiber contact times of 0.3 s, the C/Al composites showed

an amorphous band of approximately 5 nm in thickness to have formed around the fibers, which obviously was aluminum with dissolved carbon.[65,66] This amorphous band contained nuclei of Al4C3. After raising the melt/fiber contact time to 1.3 s, mm-sized Al4C3 plates have formed. In C/Mg Al composites, the Al content is minor, and Al has to diffuse to the fiber/matrix interface prior to its incorporation into carbides. Consequently, the growth of Al2MgC2 in C/MgAl systems is expected to be slower than that of Al4C3 in C/Al systems. Nevertheless, if the Al content of the Mg matrix is high enough, mm-sized Al2MgC2 plates should form within a few seconds. In C/MgAl composites with a high fiber/matrix reactivity, the carbidic plates are grown directly on the fiber surfaces (Fig. 6). Hence, if such a composite is loaded in the direction of the fiber axes, the fibers may be notched by the carbides, revealing the observed brittle fracture behavior (cf. Fig. 1c).[5,5358] The studies reviewed have shown that it is possible to control the interface reactions in C/MgAl composite materials by varying the aluminum content of the matrix and by using carbon fibers of different surface microstructures. For a medium interface reactivity, an MMC of optimum properties can be produced, which, in the three-point bending test, is characterized by a bundle fracture behavior. Contrary to the widespread assumption of the major role of the binary carbide Al4C3 in the fiber/matrix chemistry of C/MgAl composites, the properties of the composites proved to be affected by the formation of plate-shaped ternary carbides (Al2MgC2). Furthermore, note that in some manufacturing processes large amounts of oxygen are incorporated into the MMC, inducing the formation of thick, passivating MgO interlayers (100 nm, or thicker) between fiber and matrix.[6771] In those C/MgAl composites, the remaining aluminum occurs as MgAl intermetallic in the matrix, but not as carbide at the fi-

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Feldhoff, Pippel, Woltersdorf/Interface Engineering of Carbon-Fiber Reinforced MgAl Alloys ber/matrix interface, leaving a weak fiber/matrix bonding.[6774] This kind of passivation of the reaction front by oxide interlayers is well-known for C/Al systems, where wetting usually occurs if the oxide interlayer loses its compactness (at temperatures above 900 C, or due to some alloying with elements of higher affinity to oxygen than to aluminum).[19,75] The next section discusses another possibility of achieving an appropriate interface bonding, which, at the same time, prevents the formation of carbides in C/MgAl composites. Regarding the above, for the use in C/MgAl composites, TiN is an attractive coating material among the others[8490] that have been deposited on carbon fibers by CVD routes. Titanium nitride has the cubic rock-salt structure, which is the simplest structure of interstitial compounds, and it can be brought onto the carbon fibers via CVD from TiCl4N2H2 precursor gas mixtures,[9193] even in thin films (i.e., some 10 nm in thickness):[59,9194] Using a TiN coating of some 10 nm in thickness between a high-tensile-strength fiber and a cp-Mg matrix (commercially pure Mg), a relatively high tensile strength perpendicular to the fiber axis (approx. 25 MPa) was measured, indicating a good adhesion of the matrix to the coated carbon fibers.[92,93] In addition, the tensile strength parallel to the fiber axes (approx. 1200 MPa) as well as the bending strength (approx. 1900 MPa) of this composite are extremely high.[92,93] In this material, the interfacial structure is mainly characterized by an almost stringent separation of matrix and fiber by the coating as it is shown in Figure 7, in the bright-field image (a) and corresponding EFTEM images taken at the ionization edges TiL23 (456 eV) (b), CK (284 eV) (c), and MgK (1305 eV) (d), with the fiber on the left and the matrix on the right. The elemental distribution of titanium (Fig. 7b) reveals the continuous covering of the fiber with the coating, here 10 to 20 nm in thickness. The distribution of carbon (Fig. 7c) represents mainly the fiber, and that of magnesium (Fig. 7d) the matrix. In Figure 7d, some bright contrast features on the left of the coating indicate that Mg penetrates it (the coating) slightly towards the fiber. The HREM image of Figure 8 shows the turbostratic carbon of the fiber (left) and the (1010) lattice fringes of the Mg matrix (right) ending at the coating (middle part). Clearly revealed is the polycrystalline nature

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3. Modification of the Fiber Surface by Coating

Quite a different way to generate an appropriate interlayer is the direct fiber coating prior to the matrix infiltration. The coating should meet the following conditions: i) to provide an adequate fiber/matrix adhesion and ii) to act as a diffusion barrier. The latter results because a potential application of C/Mg composites, with a strength of 1 to 2 GPa, is the partial reinforcement of highly loaded parts in mechanical components (hybrids).[7679] In those parts of the components where lower stresses are applied, the strength of Mg alloys with 5 to 9 wt.-% Al (approx. 250 MPa at room temperature) is sufficient, which is also considerably higher than that of pure Mg (150 to 180 MPa). However, as described in Section 2, in contact with carbon fibers (high-strength part of the hybrid), MgAl alloys with a high Al content will cause an extensive formation of Al2MgC2 leading to an embrittlement of the composite. Coating the fiber surface to slow down the detrimental mass transfer across the interface is a promising way to suppress the carbide formation and to provide a mechanical protection of the fibers. As coating materials interstitial compounds seem to be suitable for this purpose as they consist of close-packed metal atom sublattices, with their interstices (octahedral and/or tetrahedral) being filled with smaller non-metallic atoms (hydrogen, carbon, nitrogen, boron, etc.) thus having a low permeability.[80] In general, interstitial compounds are hard and brittle, and therefore the coating should not exceed a critical thickness of about 1 % of the fiber diameter (df = 7 mm) to avoid notch effects, which might arise from microcracks in the coating and which would lower the fiber strength.[81,82] As it is necessary to achieve appropriate films each filament of the multifilamentous carbon fiber yarn, chemical vapor deposition (CVD) seems to be the appropriate technique. As the coating has to be compatible to both fiber and matrix, the number of possible interstitial compounds to be used for the system C-fiber/coating/Mg-matrix is restricted. In addition, a melt infiltration of the fiber prepreg is favorable (cf. Sec. 1), and hence a good wetting of the metal on the coating is necessary.[19] In general, the wettability of metal-like compounds by metals is better than that of covalent ones as a high percentage of delocalized electrons in the solid phase favors the electron exchange, which is necessary for the formation of stable chemical bonds with the liquid-phase metal.[83]

Fig. 7. TiN-coated high-tensile-strength fiber in a cp-Mg matrix: a) bright-field image, bd) EFTEM at ionization edges.

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Feldhoff, Pippel, Woltersdorf/Interface Engineering of Carbon-Fiber Reinforced MgAl Alloys band, respectively.[21] At the coating/matrix interface, oxygen is present, which is indicated by an OK ionization edge (cf. Fig. 9a). Reaching the first matrix areas, again carbon occurs. A detailed analysis of the EEL spectra of Figure 9 showed that within the coating the CK and NK edges have similar ELNES profiles,[94] resembling those of stoichiometric TiC and TiN,[9597] which have a similar crystal chemistry.[95] Both compounds exhibit the rock-salt structure, where the Ti atoms form an face-centered cubic (fcc) lattice, with the octahedral interstices being filled completely with C and N atoms, respectively. The occupation of some octahedral interstices with carbon and others with nitrogen, leads to the formation of titanium carbonitrides TiCxNy (x + y 1) substitutional solid solutions with a wide range of the C and N solubility.[98] Changes in the stoichiometry affect the CK and NK ELNES of these carbonitrides only slightly.[99] Including quantification of the EEL spectra of Figure 9, the coating was proven to consist of a substoichiometric titanium carbonitride (TiCxNy), with a high carbon content at the fiber/coating interface, and gradually becoming richer in nitrogen to the middle of the film.[94] The compositional changes within the coating indicate that the reactor gas mixture (TiCl4, N2, and H2)[9193] reacts with carbon from the fiber at the beginning of CVD. Thus, the term of reactive chemical vapor deposition (RCVD)[85] seems to be suitable here. Locally, carbon is transported from the fiber to the matrix (cf. Figs. 7c and 9). It is assumed that, first of all, liquid Mg penetrates through fissures in the film towards the fiber (cf. Fig. 7d):[94] In successive steps, carbon from the fiber dissolves and diffuses in the liquid Mg through the coating and precipitates as graphitic ribbons at the coating/matrix interface. Of course, in presence of Al in the matrix carbides would form at these locations. Inherently, in the composites, both graphitic ribbons[4,5,54,94] and Al2MgC2[39,94] form via isothermal dissolutiondiffusionprecipitation mechanisms, which are driven by a gradient of the chemical potential of carbon.[100,101] Conclusively, when the Mg matrix is alloyed with 5 wt.-% Al (AM50), locally isolated carbidic plates are observed, with dimensions above 1 mm, which may pierce the TiCxNy film and reach underneath the fiber surface.[94] This effect is not very pronounced, and the microstructure of the C/TiN/ AM50 composite, which is shown in Figure 10, resembles that of the corresponding C/TiN/cp-Mg composite (cf. Fig. 7a), with its fiber/matrix interfaces being mainly free of carbides. This is due to the fact that the TiCxNy coating serves well as an inhibitor of deleterious carbide formation, even if Mg alloys with large amounts of Al as matrices are used. However, combining the same MgAl matrix with the uncoated fiber results in the substantial formation of many carbidic Al2MgC2 plates of different size at the fiber/matrix interface (Fig. 11). Here, many carbides extend up to 1.5 mm into the matrix[94] and embrittle the composite (cf. Sec. 2). Of course, in the C/TiN/AM50 composite at those locations where the carbidic plates have formed notching may oc-

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Fig. 8. TiN-coated high-tensile-strength fiber in a cp-Mg matrix: HREM image showing the (1010) lattice fringes of the Mg matrix ending at the coating (fiber left, matrix right).

Fig. 9. TiN-coated high-tensile-strength fiber in a cp-Mg matrix: a) three-dimensional plot of EEL spectra taken at 30 equidistant points across the fiber/matrix interregion, arranged from fiber (back) to matrix (front), b) STEM bright-field image showing the analysis distance as a white line.

of the coating, with grain sizes comparable to the film thickness. Figure 9a show a three-dimensional plot of EEL spectra recorded across the fiber/matrix interregion at 30 equidistant points at spacings of about 1.3 nm along the white marker in the STEM bright-field image (Fig. 9b). In the energy interval chosen between 250 and 750 eV, there appear the CK, NK, TiL23, and OK ionization edges with their associated finestructures. In the region of the fiber (spectra in the background, Fig. 9a), only the CK ionization edge at 284 eV arises from the exponentially decreasing background. At the fiber/coating interface, a TiL23 ionization edge appears, and the CK ELNES changes. Within a gradient of approximately 5 nm, an NK ionization edge arises and the CK edge disappears. The TiL23 ELNES remains very clear above the background due to the presence of sharp white lines. The latter occur at the L23 ionization edges of the transition metals and at the M45 ionization edges of the rare-earth elements, because the Fermi energy is located in the narrow 3d or 4f valence

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Feldhoff, Pippel, Woltersdorf/Interface Engineering of Carbon-Fiber Reinforced MgAl Alloys 2 wt.-%) and carbon fibers of the high-tensile-strength type via moderate formation of the ternary carbide Al2MgC2 in the fiber/matrix interlayer, thus adjusting the interfacial bonding. Secondly, for hybrid components higher Al contents of the matrix are needed. Here, the formation of Al2MgC2 becomes stronger and embrittles the composite material. An appropriate TiCxNy coating on the carbon fiber prior to the composite manufacturing prevents this deleterious carbide formation and enables the use of MgAl matrices with high Al contents. A further improvement of C/MgAl composites with large amounts of Al in the matrix alloy requires a tailoring of the TiCxNy interlayer with respect to compactness and grain size distribution, which is one challenging topic for additional attempts of interface engineering in metal matrix composites.

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Fig. 10. Bright-field image of a TiN-coated high-tensile-strength fiber in an AM50 matrix showing the fiber/matrix interfacial region to be mainly free of carbide precipitates.

Fig. 11. Bright-field image of an uncoated high-tensile-strength fiber in an AM50 matrix showing many platelets of Al2MgC2 in the fiber/matrix interregion.

cur, which can initiate fiber cracking. But, as there are only a few of these large carbidic plates formed in the C/TiN/AM50 composite, the effect is very limited here. Accordingly, the strength of this composite turned out to be only slightly lower than that of the corresponding C/TiN/cp-Mg composite.[92,93] Thus, the manufacturing of hybrid components based on MgAl matrices is enabled by the diffusion retarding effect of the chemical vapor deposited TiCxNy coating. Besides suppressing deleterious carbide formation the TiCxNy interlayer offers a further benefit: For uncoated hightensile-strength carbon fibers, the penetration of significant amounts of magnesium into the body of the fibers has been reported, which seems to cause a degradation of the fiber strength.[11,54,94,102105] A TiCxNy interlayer has been proven to reduce the magnesium penetration remarkably.[94] Thus, fiber degradation as well as carbide formation can be avoided simultaneously by a proper interlayer.

4. Conclusions
Depending on the intended purpose of the special C/Mg Al composites two strategies of interface optimization are applicable: Firstly, the fiber/matrix reactivity of C/MgAl composites can be controlled by varying i) the Al content of the Mg matrix and ii) the carbon fiber type. Appropriate interface properties can be achieved with small amounts of Al (approx.

[1] A. Kelly, G. J. Davies, Metall. Rev. 1965, 10, 1. [2] J. G. Morley, Int. Met. Rev. 1976, 21, 153. [3] M. K. Shorshorov, L. E. Gukasjan, L. M. Ustinov, J. Compd. Mater. 1983, 17, 527. [4] O. ttinger, C. Grau, R. Winter, R. F. Singer, A. Feldhoff, E. Pippel, J. Woltersdorf, in Proc. Tenth Int. Conf. Comp. Mater. (ICCM-10), Vol. VI (Eds: A. Poursartip, K. Street), Woodhead, Cambridge 1995, pp. 447454. [5] A. Feldhoff, E. Pippel, J. Woltersdorf, J. Microsc. 1997, 185, 122. [6] A. Hhnel, E. Pippel, A. Feldhoff, R. Schneider, J. Woltersdorf, Mater. Sci. Eng. A 1997, 237, 173. [7] R. Asthana, P. K. Rohatgi, S. N. Tewari, Proc. Adv. Mater. 1992, 2, 1. [8] O. ttinger, R. F. Singer, Z. Metallkd. 1993, 84, 827. [9] H. P. Degischer, in Metallische Verbundwerkstoffe (Ed: K. U. Kainer), DGM Informationsgesellschaft, Oberursel 1994, pp. 139168, [10] K. U. Kainer, in Metallische Verbundwerkstoffe (Ed: K. U. Kainer), DGM Informationsgesellschaft, Oberursel 1994, pp. 219244. [11] O. ttinger, Herstellung, Mikrostruktur und Eigenschaften von kohlenstofflangfaserverstrkten Magnesiumlegierungen, Fortschrittberichte Nr. 450, VDI-Verlag, Dsseldorf 1996. [12] H. Hu, J. Mater. Sci. 1998, 33, 1579. [13] F. Irmann, Helv. Chim. Acta 1948, 31, 1584. [14] A. Schneider, J. F. Cordes, Z. Anorg. Allg. Chem. 1955, 279, 94. [15] B. Hjek, P. Karen, V. Brozek, Collect. Czech. Chem. Commun. 1983, 48, 1963. [16] B. Hjek, P. Karen, V. Brozek, Collect. Czech. Chem. Commun. 1983, 48, 1969. [17] H. Fjellvag, P. Karen, Inorg. Chem. 1992, 31, 3260. [18] P. Karen, A. Kjekshus, Q. Huang, V. L. Karen, J. Alloys Compd. 1999, 282, 72. [19] F. Delannay, L. Froyen, A. Deruyterre, J. Mater. Sci. 1987, 22, 1.

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