Tribological and tribocorrosion behavior of nickel sliding against oxide ceramics

Nickel is widely used as a coating material in electroplating because of its good corrosion and wear resistance even at high temperature. Tribocorrosion has been identified as one of the main degradation mechanisms of nickel. This study evaluated the tribocorrosion behavior of pure nickel in citrate buffer solution (pH 4.5) under controlled mechanical, chemical and electrochemical conditions as well as wear of pure nickel in dry condition sliding against alumina or zirconia balls, respectively. The results showed that the wear of nickel was higher in passive domain due to wear accelerated corrosion compared to that in the cathodic domain. Surprisingly, both alumina and zirconia were worn by nickel in tribocorrosion condition under passive potentials as well as in dry condition. However, in the cathodic domain, negligible wear was observed on the alumina and zirconia balls. The formation of mixed nickel and aluminum/zirconium oxides was proposed as the wear mechanism of alumina and zirconia.

A comparative surface analysis of explanted hip joint prostheses made of different biomedical alloys

Angela Bermudez Castañeda, Adriana Esguerra Arce, Johanna Esguerra Arce, Stefano Mischler

The introduction of modular design in total hip arthroplasty has enabled the use of different materials in one single configuration and the adjustment of the prosthesis to the patient's body, and facilitated medical revisions. However, modularity leads to the presence of new interfaces created between pieces in contact, raising the issue of degradation. Tribocorrosion phenomena have been identified as the main degradation mechanism due to the mechanical, chemical, and electrochemical conditions acting on the materials. In addition, conditions inside the human body are unclear, regarding electrochemical settings and the interaction between the electrochemical and mechanical action. This work is focused on the degradation of monopolar hip joint implants made from biomedical alloys such as stainless steel, Ti, and CoCr alloys. Three cases are presented and analyzed in terms of the degradation level along the trunnion length. Surface analysis done on a titanium trunnion showed a significant ploughing on the distal part, compared to what was found for stainless steel and cobalt-chromium alloys, which can produce a stuck in this area. Meanwhile, in the proximal part, wear debris is found, which suggests more movement in the internal part. Although few debris particles were identified in CoCr trunnion, a large amount of material inside the contact was observed. This could be related to the ploughing generated in the distal thread pattern, which allowed the material to come inside and outside the contact.

IMPRENTA UNIV ANTIOQUIA2021

High Temperature Behavior of Nano-Structured Ceramic Composites Studied by Mechanical Spectroscopy

Mehdi Mazaheri

Silicon nitride based ceramics (SiAlONs); tetragonal polycrystalline zirconia (3Y‐TZP); alumina and their composites reinforced with different amount of multi‐ walled carbon‐nanotubes (CNTs) have been processed by Spark Plasma Sintering (SPS). High temperature mechanical spectroscopy measurements were performed in each material between room temperature and 1600 K. In each of these materials, anelastic and viscoplastic relaxation phenomena were investigated and responsible mechanisms were explained. In particular, grain boundary (GB) sliding, which is responsible for high temperature plasticity in fine grained ceramics, gives rise to a peak or an exponential increase in the high temperature mechanical loss. Peak and exponential background depend on two forces, which control the GB sliding: a friction force due to the GB viscosity and a restoring force due to the elasticity of the surrounding grains. In the present thesis, ceramics and composites have been processed, which allow one to study the role played by these forces on the thermo‐ mechanical behavior of these refractory materials. SiAlON ceramics were chosen for studying the viscous force due to the inter‐granular glassy phase. In zirconia and alumina, it is shown how the CNT reinforcements may improve the restoring force and consequently the creep resistance. Different grades of SiAlON ceramics, processed with different sintering aids (Ca2+, Y3+, Yb3+), with oxygen rich (CaO, Y2O3 and Yb2O3) and nitrogen rich (CaH2, YN and YbN) compounds, have been studied. Mechanical spectroscopy has been used to analyze the behavior of the residual glassy phase, present after sintering, either as grain‐boundary glassy (GB) films or glass pockets located in GB triple junctions. The mechanical loss spectra show a relaxation peak, which is due to a relaxation phenomenon (the so called “α‐relaxation”) associated with the glass transition in the amorphous phase. The peak position depends on the glass viscosity and the peak height is mainly affected by the glassy phase amount and the SiAlON bimodal microstructure, namely equiaxed versus elongated grains. Moreover the peak height depends on the restoring force provided by the neighboring grains, which limit the GB sliding process. As a matter of fact, a good correlation between the mechanical loss peak and plastic deformation in a compression test has been observed. It is concluded that the elongated grains in the bimodal microstructure provide a higher restoring force, which limits the GB sliding of smaller equiaxed grains. In the case of equiaxed fine grained oxide ceramics, such as zirconia and alumina, the restoring force has been increased by CNT additions, which can reinforce the GBs. 3Y‐TZPcomposites with a homogenous distributions of CNTs, ranging within 0.5 – 5 wt%, were processed by SPS. A significant improvement in room temperature fracture toughness and shear modulus as well as creep performance at high temperature were obtained, and interpreted as due to the GB reinforcing role of the CNTs. To support this interpretation, high‐resolution electron microscopy and Raman spectroscopy have been carried out. Moreover, a remarkable enhancement of the electrical conductivity up to ten orders of magnitude due to CNT additions has been obtained with respect to the pure ceramics. The isothermal spectrum of the 3Y‐TZP composites (measured at 1600 K) is composed of a mechanical loss peak at a frequency of about 0.1 Hz, which is superimposed on an exponential increase at lower frequency. This is interpreted as primarily due to GB sliding. The absence of a well‐marked peak in monolithic 3Y‐ TZP is justified by considering that the restoring force decreases at low frequencies or high temperatures. Therefore, GB sliding is no more restricted and the mechanical loss increases exponentially, which is correlated to macroscopic creep. With CNT additions the mechanical loss decreases and the relaxation peak is better resolved with respect to the background. This is interpreted by the pinning effect of CNTs on GBs, providing addition source of restoring force, which can hinder GB sliding at high temperature, resulting in a creep resistance improvement. Similarly to 3Y‐TZP based composites, alumina specimens (3 different types of alumina powders) reinforced with different amount of CNTs were sintered by SPS. It is shown how the initial particle size of the powders may affect the dispersion of CNTs. Measurement of different properties, such as hardness, fracture toughness and mechanical loss at high temperature, have evidenced the crucial role of the CNT dispersion in the obtained mechanical properties.

EPFL2013

Modélisation de la tribocorrosion d'aciers inoxydables dans l'eau à haute pression et haute température

Jonathan Perret

Several metallic components of pressurized water reactors (PWR) used in nuclear power plants are exposed to the combined degradation by friction and corrosion (tribocorrosion). In PWR, corrosion arises from the water pressurized at 150 bars and maintained at 300°C and results in the build up of a micrometer thick surface oxide film. Tribocorrosion is of complex nature as it involves multi-scale interactions between mechanical, chemical and material factors. Nevertheless, PWR component manufacturers are interested in understanding the deterioration mechanisms in order to select appropriate materials as well as predicting the component lifetime. This thesis is a contribution towards the elucidation of the tribocorrosion mechanisms of a specific PWR component (austenitic stainless steel control rods). The research is focused on two inter-related aspects related to the subsurface deformation induced by friction and to the high temperature and high-pressure oxidation kinetics of austenitic stainless steel under tribocorrosion conditions. The subsurface deformation is investigated by using a model tribocorrosion system consisting in an alumina ball sliding against a 304L austenitic stainless steel in sulphuric acid at ambient temperature under electrochemical control. This model system allows studying subsurface deformation in absence of a thick high temperature oxide films that can complicate the interpretation of the results. Subsurface deformation was characterized using SEM, EBDS and FIB cross-sections. Good correlation was found with the deformation found in pressurized water. Subsurface deformation was found to result in the formation of a recrystallised layer of nano-grains close to the surface and an underlying layer exhibiting a deformation gradient. The thickness of the recrystallized zone is highly affected by the presence or the absence of a few nm thick oxide in the contact. However, no obvious correlation between the thickness of the recrystallized zone, or any other measured deformation appearance, and wear could be found. The effect of oxidation was studied using a simulator (Aurore), reproducing the chemical and mechanical PWR conditions of control rods. It includes an electrochemical set-up allowing measuring in-situ and in real time the oxidation kinetic. The oxidation kinetic was found to follow a parabolic law (diffusion controlled oxide growth). Rubbing resulted in repeated scratching of the surface leading to a thinning of the oxide film and thus to an enhanced anodic oxidation. A quantitative model of the electrochemical response of stainless steel in PWR conditions was developed. Based on these results and on the third body theory of wear, a mechanistic model was proposed for describing the material behaviour in contacts operating in pressurized water. This model explains a certain number of practical observations obtained in nuclear plants or in simulators concerning chemical and materials effects on component degradation.