Spectroscopie mécanique de la relaxation des contraintes d'interface dans les composites à matrice métallique

Metal matrix composites are known for their excellent specific mechanical properties. Nevertheless, because of the thermal expansion mismatch between the matrix and the reinforcements, thermal stresses arise at the interfaces of such materials. In order to relax these stresses, dislocations are emitted from the interface and propagate in the matrix, which can influence the mechanical behavior of the composite material. Mechanical spectroscopy, which characterizes the ability of a solid to dissipate energy under an external excitation, was used to study the relaxation mechanisms occurring at the interface of MMCs. Indeed, the mobile matrix dislocations near the interface are the main sources of damping, making this technique very sensitive to these mechanisms. Composites studied here were processed by gas-pressure infiltration of the reinforcement preform by the molten metal. The processed composites were based on aluminum, magnesium and Mg-2%Si alloy, which is known for its high damping level. They were reinforced by short misorientated alumina fibers or long and aligned carbon and silicon carbide fibers. In the case of long fibers, two types of orientation were obtained: parallel or perpendicular to the composite axis. In order to modify the interface morphology, a heat treatment was carried out on aluminium matrix composites reinforced by alumina fibers during the infiltration process. By increasing the contact time between the molten matrix and the fibers, alumina crystals were formed on the surface of the fibers, whose size increased with time. The specific elastic moduli of the processed composites were clearly superior to those of matrix alone and their value agreed well with the existing theoretical models. Composites were submitted to thermal cycles from 120 K to 500 K and the internal friction and dynamical modulus were measured as a function of temperature. It was shown that the behavior of these two parameters, the large maximum at low temperatures and the modulus anomaly in the case of magnesium composites was driven by the motion of the dislocations activated in the matrix in order to relax thermal stresses. The internal friction was also characterized by a transient contribution, depending on the heating or cooling rate dT/dt and the excitation frequency ω. By using a model developed by Mayencourt and al., it was possible to determine two parameters C1 and C2 which were sensitive respectively to the mobile dislocation density relaxing the thermal stresses and the interface strength. The difference in the behavior of these two parameters as a function of temperature tended to show the great potential of the magnesium matrix composites. Indeed, the interface strength was decreasing at low temperature, allowing a better toughness whereas it was increasing at high temperature, improving the creep resistance. Finally, in the case of the aluminum matrix composites reinforced by short fibers with alumina crystals at the interface, it was observed that the elastic modulus was decreasing as crystal size increased. However, when the crystals exceeded a certain size, they were acting as pinning points between matrix and fibers, resulting in the increase of the modulus almost to its initial value. By determining the parameter C1 from the transient damping, it was shown that this parameter followed the same trend as the elastic modulus, which made it a good probe for the interface quality.

High volume fraction particulate and interpenetrating phase composites (IPC)

Ghodratollah Roudini

The role of reinforcing phase contiguity in high volume fraction particulate composites is investigated using model composites of pure aluminium reinforced with α-Al2O3 particles. To produce the composites, alumina particle (5µm) preforms were either loosely packed or, alternatively, packed and CIPed; these were then sintered, varying the sintering time and temperature, and infiltrated with pure liquid aluminium using gas pressure infiltration. The microstructure of the resulting composites was characterized using image analysis in terms of reinforcement phase contiguity (β), defined as the ratio of particle surface that is in contact with other particles to that in contact with the matrix. The influence of this parameter on several characteristics of the composites and the preforms they were made from was then studied, using theoretical models in the literature to isolate the influence of this parameter from that of other variables, such as the volume fraction ceramic. To this end, the thermal conductivity of the sintered preforms, basic composite mechanical properties (hardness, tensile strength, and damage evolution during straining) and the thermal expansion of the composites were characterized and compared with theory; furthermore, quenching and neutron diffraction were used to probe in more depth the thermal expansion behaviour of the composites. The results show that the thermal conductivity of the preform increases, as expected, upon increasing the relative density (volume fraction) and the contiguity of alumina particle after sintering. Comparison of data with theory shows that, while experimental values for the CIPed samples agree with the prediction by Argento and Bouvard for the thermal conductivity of powder preforms as a function of densification, neither this model, nor that of Montes et al. , fits all experimental values. Rather, when pooled the data show that the thermal conductivity of powder preforms, normalized for relative density using the differential effective medium model, obeys relatively well a simple linear relation between contiguity and conductivity. The hardness of the composite increases with increasing relative density and increasing contiguity. Here again, after normalization for the dependence of hardness on ceramic volume fraction using current theory, a nearly linear relation is found between hardness and contiguity. Tensile testing results show that the strength of the composite increases with increasing fraction ceramic and increasing contiguity while the elongation decreases, composites with an interconnected ceramic phase rapidly becoming quite brittle, with elongations falling below half a percent. No clear relationship is found between contiguity and Young's modulus after normalization for the volume fraction ceramic. Measurements of internal damage evolution show that damage increases very rapidly with deformation in the present interconnected composites, in agreement with their brittle character. The thermal expansion results show that the CTE of the present composites often varies with temperature at a rate higher than that predicted to result from physical parameter variations by existing theoretical models. With regard to their thermal expansion, the composites can be separated into three classes that are characterized by the level of contiguity of the low expansion phase: low contiguity (i.e. β ≤ 0.045), medium contiguity (i.e. 0.05 ≤ β < 0.074) and high contiguity (i.e. β ≤ 0.074 ). The CTE values during heating for the low contiguity composites lie between Schapery's upper bound and the rule of mixtures, starting upon heat-up from the Schapery upper bound at low temperature and transiting above roughly 150°C to the rule of mixture prediction; upon cool-down the same behaviour is observed in reverse. The CTEs of the composites with medium contiguity at low temperatures are somewhat below the Schapery upper bound, increasing somewhat faster than predicted for this bound with increasing temperature to reach Shapery's upper bound at around 200°C. For the composites with high contiguity, the CTEs lie between elastic and plastic bounds predicted using the self-consistent model, the latter model being obtained by assigning a zero shear stiffness to the matrix. Physical reasoning and comparison of data with theory indicate that these transitions in expansivity of the composites are mostly a result of matrix yield following fully elastic deformation past a certain thermal excursion, this transition being prevented by increased ceramic phase contiguity. This interpretation is confirmed by neutron diffraction results. Increased reinforcement contiguity in the composites also affects the amplitude of strain hysteresis during thermal cycling, the magnitude of hysteresis decreasing in nearly linear fashion with increasing contiguity, reaching zero near β = 15%. Samples that were quenched into liquid nitrogen after a relaxation heat treatment and reheated to room temperature yielded data globally similar to those of as-processed samples. Nitrogen-quenched samples with higher contiguity (β ≥ 0.05) exhibit furthermore signs of ratcheting upon cycling, which was not observed in the composites with low contiguity.

EPFL2008

Fiber reinforced polypropylene nanocomposites

Chrystèle Houphouet-Boigny Favre

The aim of this thesis is to assess the feasibility of integrating nanoparticles into glass fiber (GF) reinforced isotactic polypropylene (iPP) composites via existing thermoplastic processing routes, and to investigate whether this results in significant improvements in the mechanical properties of the final composites. A longer term aim will be to extend the approach to the preparation of hybrid composites with added non-structural functionality. However, the nanoparticles that have provided the focus for the present project, montmorillonite layered silicates (MMT) and nanocarbons, were chosen for their potential as structural reinforcing elements. A melt-spinning grade and a film grade of iPP were used to prepare iPP-based nanocomposite precursors in the form of melt-spun fibers and extrusion-calendered films respectively. Long glass fiber (LGF) and glass mat thermoplastic (GMT) composites were then compression-molded from co-woven, co-wound and intercalated semi-finished products. The processing behavior and structural performance of the resulting composites are discussed in terms of the matrix morphology and its influence on the matrix rheological and mechanical properties, and interactions between the matrix and the reinforcing fibers. The nanocomposites were prepared by either (i) combined solvent and melt-mixing or (ii) direct melt-mixing. Combined solvent and melt-mixing was more suitable for dispersing carbon nanofibers (CNF), which tended to agglomerate. With iPP/MMT, both routes gave a mixed intercalated-exfoliated morphology with an MMT interlayer spacing up to 57 % greater than in the as-received MMT. However, direct melt-mixing was considered to be better suited to industrial requirements, and also more convenient for laboratory scale preparation. Melt-compounded iPP/MMT injection moldings showed a monotonic increase in stiffness with increasing MMT content, a 40 % increase in tensile modulus being measured at 13.5 wt% MMT, for example. The tensile strength, on the other hand, reached a maximum 10 % increase over that of the pure iPP at about 3 wt% MMT, but fell off at higher MMT contents. iPP/MMT and iPP/CNF fibers were melt-spun using a laboratory-scale industrial spinning line. Processability was consistent with the melt rheology, the maximum MMT content for which fiber spinning was possible being about 5 wt%. The MMT platelets were aligned with the fiber axis over the whole range of MMT loadings and fiber draw ratios. MMT particle aspect ratios of about 150 were observed by TEM in this case, i.e. greater than in the as-compounded iPP/MMT, for which the particle aspect ratios were about 50. An aspect ratio of 150 was found to be consistent with micromechanical modeling of the observed increases in fiber stiffness with MMT content, which reached 170 % for iPP/2 wt% MMT fibers melt-spun with a draw ratio of 1 and a drive-roll velocity of 360 m/min. The tensile strength again reached a maximum at about 3 wt% MMT. The thermal stability of the fibers, determined by thermal mechanical analysis, also increased on MMT addition, the onset of extensive fiber creep shifting from 90 °C for pure iPP fibers to about 110 °C for iPP/1.1 wt% MMT fibers. Moreover, significantly reduced shrinkage was observed in the presence of MMT, which is a potential advantage for textile based composite processing. In the case of iPP/CNF fibers, limited particle orientation and the presence of aggregates in all the formulations led to relatively poor tensile properties, about 50 % lower than those obtained with iPP/MMT fibers melt-spun with the same filler content (4 wt%) and processing conditions. iPP/MMT therefore provided the main focus for subsequent work. iPP/MMT films were produced by extrusion-calendering. Partial orientation of MMT platelets in the melt flow direction resulted in anisotropic stiffness and strength. However, both the tranverse and axial stiffnesses increased with MMT content, with improvements of up to 75 % at 5.9 wt% MMT with respect to those of the pure iPP films, consistent with Halpin-Tsai predictions for composites containing oriented platelets with the observed aspect ratio of 50. The fracture resistance of the films, determined using modified essential work of fracture (EWF) tests, was likewise strongly dependent on the testing direction. For axial crack propagation, the EWF decreased monotonically with MMT content, but for transverse crack propagation, it reached a maximum at about 3 wt% MMT. This was attributed to orientation dependent cavitation and crack deviation in the presence of the MMT particles. Rheological measurements indicated increases in the low shear rate melt viscosity by up to two orders of magnitude on MMT addition to the iPP, with a potentially significant influence on the impregnation behavior of composite preforms. For co-woven and co-wound LGF-matrix fiber preforms, impregnation was highly dependent on the fiber bed geometry. For 40 vol% glass fiber co-wound composites, the porosity increased from about 7 vol% for a pure iPP matrix compression molded at 0.6 MPa, to 14 vol% for a iPP/3.4 wt% MMT matrix compression molded at 1.8 MPa. However, the more intimate mixing between the fibers obtained in co-woven preforms led to more consolidated composites in each case (below 2 vol% porosity) with no filtering of the MMT particles. In modeling the impregnation kinetics of glass mat thermoplastic composites (GMT) based on iPP/MMT, the matrix was therefore considered to behave as a continuum and, for simplicity, to show Newtonian behavior. Consistent results were obtained, but in the presence of MMT, higher impregnation times were predicted than observed experimentally in model GMT preforms, owing to the nonlinear response of the nanocomposites. Moreover, under experimental conditions corresponding to the industrial process (0.2 MPa at 200 °C), iPP/5.9 wt% MMT-based hybrid composites were fully impregnated (porosity between 11 and 17 vol%) and the glass mat completely relaxed after about 30 s of compression molding, which is consistent with typical GMT industrial process cycle times (20 - 60 s). Fully consolidated 30 wt% GF - hybrid GMT specimens were prepared for mechanical testing by compression molding at 2 MPa and 200 °C for 10 min, resulting in a porosity of about 2 vol%. At room temperature, the flexural modulus and strength of iPP/MMT-based GMTs increased monotonically with MMT addition, the increases reaching about 45 % and 33 % respectively at 5.9 wt% MMT. The increase in the flexural modulus on MMT addition was greater than predicted on the basis of a conventional rule of mixtures taking into account glass fiber orientation and aspect ratio, and the measured Young's moduli of the matrix. This was tentatively attributed to improvements in the flexural properties of the matrix in the presence of the MMT higher than those observed in tension. Increases in the flexural modulus and strength were also observed at 50 °C and 90 °C, but were less marked than at room temperature. The impact strength of the hybrid composites decreased with increasing MMT content at room temperature owing both to the decrease in matrix fracture resistance inferred from the data for the precursor films, and to an improved fiber-matrix interface as reflected by SEM observations, and argued to be due to the presence of coupling agents. Given that the presence of MMT was shown not to have serious consequences for impregnation, taken as a whole these results are considered highly promising for the implementation of nanocomposite matrices in GMT, and to establish the general feasibility of producing hybrid fiber reinforced thermoplastic nanocomposites by conventional processing routes.

EPFL2007

Mechanical spectroscopy of interface stress relaxation in magnesium matrix composites

Abu Salek Md. Fahim Chowdhury

Magnesium matrix composites made of pure (99.98%) magnesium reinforced with long carbon (Mg/C) and stainless steel (Mg/steel) fibers were processed by low pressure infiltration method. Mg/C composites were then oriented from the crystallographic point of view by Bridgman technique and finally three composites were obtained with γ = 0°, 45° and 90° (γ is the angle between the matrix-fiber interface and the normal to the basal plane). The results show that the damping level in the composite for γ = 0° is almost 3 and 7 times higher than that of the composites with γ = 45° and γ = 90°, respectively. From the result analysis it was possible to conclude that the damping originates in the hysteretic motion of dislocations in the magnesium matrix. As such a mechanism is not thermally activated, high damping is observed over a broad frequency range. The complete evolution of the mechanical loss as a function of the vibration amplitude has been measured. The obtained result has been found to be in excellent agreement with the Granato-Lücke model for dislocation breakaway. The fit of the experimental points with the theoretical curve and the straight Granato-Lücke plot confirm that the microstructure evolution is controlled by the breakaway of dislocation segments from randomly segregated point defects (hysteretic damping). According to the Granato-Lücke model the critical stress for the breakaway could be estimated. As a consequence of this analysis, the transient damping due to interface thermal stress relaxation has been interpreted by a model based on a solid friction mechanism. It has been shown that the model of Mayencourt and Schaller justifies the whole mechanical loss behavior. The model predicts two fit parameters C1 and C2, which account for the respective evolution of the mobile dislocation density and interfacial strength. An anomalous behavior is observed for the parameter C2 as well upon heating as upon cooling, which is being reflected in the shear modulus evolution. This anomalous behavior is due to a "bonding-debonding" mechanism at the fiber-matrix interface due to the motion of dislocations, which depends on the orientation of the glide plane. Also, at high temperature, the interface is strong, which helps in creep resistance of the composite, and at low temperature, the interface is weak, which is positive for improving toughness by interface crack deflection.

EPFL2009