Interstitial defect | EPFL Graph Search

In materials science, an interstitial defect is a type of point crystallographic defect where an atom of the same or of a different type, occupies an interstitial site in the crystal structure. When the atom is of the same type as those already present they are known as a self-interstitial defect. Alternatively, small atoms in some crystals may occupy interstitial sites, such as hydrogen in palladium. Interstitials can be produced by bombarding a crystal with elementary particles having energy above the displacement threshold for that crystal, but they may also exist in small concentrations in thermodynamic equilibrium. The presence of interstitial defects can modify the physical and chemical properties of a material. History The idea of interstitial compounds was started in the late 1930s and they are often called Hagg phases after Hägg. Transition metals generally crystallise in either the hexagonal close packed or face centered cubic structures, both of which can be cons

Effect of ZnO on the reactivity of cementitious systems

Andrea Eloisa Teixeira Pita

One of the biggest driving forces in cement research today is the mitigation of the CO2 emissions caused by its production. A potential solution to reduce the environmental impact is to replace cement with supplementary cementitious materials (SCMs). This replacement results in low strength at early ages because they are slow to react. The incorporation of minor elements has shown the potential to improve cement reactivity. A few percent of ZnO in C3S causes a signifi- cant increase in reactivity. This effect was related to the incorporation of zinc into the C-S-H struc- ture, which increases its needle length. This research investigates the effect of ZnO in more realis- tic systems such as alite, C3A-polyclinker, and C4AF-polyclinker. The positive effects observed in C3S are translated in the alite system, but differences were found in the polyclinkers, which have a prolonged induction period. This resulted due concentration of zinc in the interstitial phases and a small amount of zinc in alite phase. An amorphous phase was identified in the C3A polyclinker; it is believed to react rapidly with water, releasing Zn ions into the solution, which delays the reaction of alite. The addition of more gypsum controls the reaction of this phase, and thus the induction period is shortened.This work explores the possibilities of retaining Zn in alite to enhance the reactivity of more realis- tic cementitious systems. The cooling rate was critical, as a slow cooling rate promoted more Zn in the alite, less amorphous, and hence, an enhancement in the hydration of C3A-polyclinker doped with ZnO. The recalcination of this system did not affect the hydration of alite but increased the amount of crystalline C3A, which reacted faster. Thus, the amorphous phase was related to an aluminate phase. Moreover, a C4AF-polyclinker and a system with a lower amount of interstitial phase were investigated. The results showed a higher Zn concentration in alite but also extended induction periods. This was associated with the free ZnO and the amorphous content. Even when the hydration was delayed, the height of the alite peak increased with Zn doping, probably due to the incorporation of Zn into the C-S-H observed in pure C3S.In addition, the interaction between sulfates and zinc in the alite system doped with ZnO was in- vestigated. Severe retardation was observed, and the reason is proposed to be the formation of amorphous Zn compound. The presence of aluminum, ettringite formation, or an amorphous layer were discarded as the cause of the retardation.

EPFL2022

Utilisation de la spectroscopie mécanique dans l'optimisation des traitements thermiques d'aciers au carbone

Ronan Martin

This work is motivated by the industrial need to improve the thermal treatments of carbon steels used for the production of files. It aims at clearly defining the role that carbon plays in hardness and wear resistance of files. Three steel grades with different carbon content have been studied. The samples underwent various austenizing treatments, including treatments under carburizing atmosphere, followed by a quenching process leading to an essentially martensitic microstructure. This microstructure has been studied by mechanical spectroscopy. Several complementary techniques have been used : microscopy, thermopower, calorimetry, measurement of the microhardness and of the file performance. The damping spectra show three relaxation peaks, attributed to the interaction of interstitial atoms with dislocations in martensite. Two of these peaks, M2 and M4, are related with the presence of interstitial carbon. Peak M2 is related with the migration of geometrical kinks along screw dislocations, and peak M4 with the kink-pair formation and migration on screw dislocations. Both peaks are controlled by carbon dragging. This interpretation is supported by the measured activation enthalpies. The amplitude of peak M4 depends on the interstitial-carbon content, which apparently contradicts its physical interpretation. This dependence is attributed to the increase of the quench-induced dislocation density with interstitial-carbon content. The peak amplitude is in fact proportional to the dislocation density. The mechanical spectroscopy measurements are also sensitive to tempering effects. In particular, the precipitation of transition carbides at 380 K is associated with a decrease of the damping background, attributed to the depletion of martensite from interstitial carbon. The decomposition of retained austenite, occurring at 520 K or 670 K depending on the grade, is associated with a modulus anomaly, attributed to a sudden decrease of the dislocation density in martensite. A damping maximum coinciding with this transformation can also be observed at low frequency. This study lead to the use of new thermal treatments under carburizing atmosphere. The used gas mix gives rise to an efficient carbon enrichment of the samples. However, the increase of interstitial-carbon content may also lead to a higher content of retained austenite, thus reducing hardness. Calorimetry measurements allow the quantification of such content, which varies according to the steel grade and the thermal treatment. Martensite hardness and wear resistance of the files clearly increase with the interstitial-carbon concentration, that can be quantified by thermopower measurements, after correction of the effect of retained austenite. Long carburizing treatments can cause the formation of carbides on the sample surface. The presence of carbides in a high-carbon martensite does not seem to improve the mechanical performances, and can even be detrimental. The present study leads to the assessment of an optimal treatment duration of 30 min, which produces a hard martensite with maximum interstitial-carbon content and limits the amount of retained austenite and carbides. This carburizing time seems to produce the saturation of both the content of interstitial carbon at the steel surface and of the amplitude of damping peak M4. The amplitude of this peak seems to be an effective criterion for the evaluation of the ideal carburizing time. Indeed, the peak amplitude increases with the content of interstitial carbon and decreases with the content of retained austenite and carbides. The estimated optimal carburizing time is compatible with production demands. A cryogenic treatment proves to lower efficiently the amount of retained austenite.

EPFL2009

Magnetization Reversal Dynamics in Ferromagnetic Semiconductors

Liza Herrera Diez

This thesis is dedicated to the study of the magnetization reversal dynamics in compressively strained (Ga,Mn)As and differently functionalized (Ga,Mn)As materials. In the first part the domain wall dynamics of pure (Ga,Mn)As/GaAs materials is in the focus. The changes in the magnetic anisotropy energy landscape occurring as a function of temperature are monitored in detail by different experimental techniques. These measurements provide the necessary information for the identification of the temperature ranges corresponding to different magnetic anisotropy regimes. Knowing the biaxial anisotropy and uniaxial anisotropy dominated regimes the dependence of the domain wall dynamics on the magnetic anisotropy landscape is studied. Critical changes in domain wall alignment observed by Kerr microscopy are found upon changing from biaxial to uniaxial anisotropy. These changes could be partially attributed to the tendency of the system to minimize magnetic free poles at the domain boundaries. To complement the space resolved studies of the magnetization reversal, magnetic time relaxation effects are addressed. In particular the magnetic aftereffect in (Ga,Mn)As/GaAs is studied in detail. The irreversible aftereffect is evidenced as a critical reduction of the domain wall velocity with time under a constant applied magnetic field below coercivity. This time relaxation is tracked as a function of both time and magnetic field. The measurements show that the overall relaxation is composed of two relaxation processes acting in parallel at short and long time scales. By fitting these experimental results the values of the relaxation times of both relaxation processes were obtained. By this modeling also the values of the activation volumes for two independent (Ga,Mn)As materials are estimated. In the second part of this thesis the possibilities of tuning the electrical and magnetic properties of (Ga,Mn)As by volume and surface treatments are explored. As for the volume modification, oxygen species were incorporated into the (Ga,Mn)As films by means of exposure to an oxygen plasma. The incorporation of oxygen was evidenced by depth profile X-ray photoelectron spectroscopy. This treatment is found to weaken the ferromagnetism, visible as a reduction in the Curie temperature, and to hinder the electrical transport evidenced as an increase in the electrical resistance. In agreement with theories accounting for the hole mediated ferromagnetism in (Ga,Mn)As this behaviour was related to a hole compensation mechanism arising from the presence of oxygen impurities sitting in interstitial positions of the (Ga,Mn)As Zinc blende structure. In the last part, the modulation of the electrical and magnetic properties via surface functionalization is presented. The effects produced by the adsorption of molecular species on (Ga,Mn)As are similar to those found after oxygenation, namely a strong weakening of the magnetic properties and an increase in the values of the electrical resistance. However, in this case the distinctive feature is provided by the possibility of regulating the hole quenching effect by exploiting the additional degree of freedom provided by the chemical properties of the adsorbates. The adsorbate chosen for these experiments are dye molecules that absorb light in the visible range, in this way allowing for a light modulated interaction with the substrate. Using this concept is was possible to observe a modulation of the ferromagnetic transition temperature, the coercive field and the electrical resistance upon illumination. These observations provide a proof of principle for the realization of photo-sensitized (Ga,Mn)As devices where the magnetic properties can be regulated by light.

EPFL2011