Surface and Interface, Chemical Reactivity of Materials group

Oxidation rates and mechanisms for metallic materials at high temperatures

The development of new metallic materials (nickel-, cobalt- or niobium-based alloys, TiAl, skutterudites) or alloys produced by new methods such as additive manufacturing requires the identification of levers allowing to optimise their resistance to the environment and estimate their durability in conditions as close as possible to those encountered in service. The research involves the synthesis of model systems that are simplified in comparison with industrial alloys. This makes it possible to highlight the relationships that exist between the composition and microstructure of the materials and their reactivity.

Projects:

• BPI FAIR (Additive Fabrication to Intensify Reactors, Air Liquide Responsible) 2016-2020
• ANR NANOSKUT 2013-2016 ; PSEUDO 2014-2017
• Collaborations with Saint Gobain SEVA 2015-2018, Fives Cryogénie 2016-2019

Thesis:

CIFRE M. Ritouet 2015-2018; Doctoral contracts M. Bolmont 2016-2019, T. Perez 2016-2019, N. Ramenatte 2017-2020.

Articles:

• A comparison of the high-temperature oxidation behaviour of conventional wrought and laser beam melted Inconel 625, N. Ramenatte et al., Corrosion Science 2020, 164
   
• Oxidation and creep properties at 1200 °C of cast quaternary Ni-Cr-C-Ti alloys, P. Berthod et al., Materials Science and Engineering : A 2017, 699, 145
   
• Effect of oxygen partial pressure on the semiconducting properties of thermally grown chromia on pure chromium, Y. Parsa et al., Corrosion science 2018, 52, 141.
   
• Oxidation behavior of microstructured and nanostructured Co0.94Ni0.06Sb3 thermoelectric materials, R. Drevet et al., Oxidation of Metals 2020, 93, 559
   

Study of the degradation mechanisms of metals and ceramics in the presence of a liquid phase by oxidation, corrosion, dissolution

The behaviour of materials in the presence of liquid phases is evaluated from room temperature to very high temperatures. Electrochemical techniques are implemented to identify the nature of the electroactive systems and the rate laws in extreme conditions. The treated subjects concern the degradation of waste incineration unit exchangers, the hot corrosion of aeronautical alloys by salt mixtures, the corrosion of chromino-forming alloys by silicate media (glass industry, waste vitrification) or the corrosion of thermal and environmental barriers by CMAS.

Projects:

• ANR SCAPAC 2012-2016; ANR CINATRA 2013-2016
• Collaboration SAFRAN TECH 2018-2021
• Collaboration ONERA 2012-2019

Thesis:

• Doctoral contract E. Schaal 2013-2016
• Ministry E. Schmucker 2013-2016, V. Szczepan 2017-2020
• CIFRE SAFRAN R. Malacarne 2018-2021

Articles:

• Corrosion and depassivation of a chromia-forming Ni-based alloy in the 0.75Na2O-B2O3-2.75SiO2 melt, V. Szczepan, Corrosion Science 2020, 168.
   
• Influence of rare-earth oxides on kinetics and reaction mechanisms in CMAS silicate melts, F. Perrudin et al., Journal of the European Ceramic Society 2019, 39, 4223.

Development of protection solutions through the study of new materials and multifunctional coatings

The functionalization of the surfaces of metal alloys is often necessary to adapt the properties of structural materials to the physico-chemical characteristics of the environment or to the conditions of use. In this context, the research covers both aspects related to the inhibition of corrosion phenomena and the development of functional coatings. The group concentrates on chemical (in aqueous and gaseous phases) and electrochemical methods. Especially methods of high-potential (micro-arc oxidation) are used to propose new and multiple use properties (anti-oxidants and anti-fuels; anti-oxidants and wear-resistance; anti-oxidants and lubricants; self-healing coatings; etc.):

-    Study of the growth and sealing of anodized coatings
-    Functionalization by wet process of internal surfaces of complex 3D printed components
-    Vapor deposition of coatings

Project:

BPI FAIR (2016-2020), Collaborations Graphocolor, De Buyer, AML

Thesis:

• CIFRE Graphocolor V. Cartigny 2017-2020, Ministry A. Gasco-Owens (2019 -)
• A. Ben Romdhane (2018-)
• Doctoral contract N. Ramenatte 2017-2020, CIFRE AML R. Soukrat (2020-) 

Articles:

• Electrochemical behaviour of titanium in KOH at high potential, D. Veys-Renaux et al., Electrochimica Acta 2016, 202, 253
   
• Rapid sealing of an alumina nanoporous network grown by anodizing and dye-filled, V. Cartigny et al., Surface and Coatings Technology 2019, 364, 369
   
• On the interdiffusion in multilayered silicide coatings for the vanadium-based alloy V-4Cr-4Ti, N. Chaia et al., Journal of Nuclear Materials 2017, 484, 148
   

Kinetic and thermodynamic modelling

The study of degradation processes and the implementation of thermochemical treatments require thermodynamic data. When these are available, they make it possible to identify the present species and the nature of the expected phases. When they are not available, they must be determined experimentally and the corresponding equilibrium diagrams modelled. Modelling is also carried out to predict the lifetime of materials. The durability of a protective oxide layer, e.g. in a liquid silicate medium at high temperature, depends on the competition between growth and dissolution. Analytical models must then be established to predict the behaviour of these oxides as a function of the system parameters (T, P(O2), basic nature, viscosity).

Projects:

Orano (2013-2016), CAPES COFECUB

Thesis:

Joint supervision A.A.A.Pinto Da Silva; Ministry E. Schmucker 2013-2016, V. Szczepan

Articles:

• The Ta-B system: Key experiments and thermodynamic modeling, A.A.A.Pinto Da Silva et al., Calphad 2018, 63, 107.
   
• Thermodynamic modeling of the V-Si-B system, A.A.A.Pinto Da Silva et al., Calphad 2017, 59, 199.
   
• Correlation between chromium physicochemical properties in silicate melts and the corrosion behavior of chromia-forming alloy, E. Schmucker et al., Journal of Nuclear Materials 2018, 510, 100.

The group has its own fleet of equipment and the associated specific know-how enabling to perform degradation studies and to evaluate the potential of different coating solutions:

Methods for the development of structural materials and coatings

• Arc melting
• Induction melting
• Sintering of powders
• Chemical conversion
• Anodizing and oxidation by electrolytic plasma
• Pack-cementation (chemical vapor deposition)
• "Slurry" method (Liquid metal-substrate reaction)

Thermal analysis methods

• Differential thermal analysis
• Thermogravimetric analysis
• Dilatometry
• Calorimetry
• Predictive calculations (ThermoCalc, FactSage)

Specific electrochemical characterisations

• Stationary methods for the determination of kinetics and corrosion processes
• Electrochemical impedance spectroscopy
• Electrochemistry in molten salts and molten silicate media (up to 1300°C)
• Pulsed electrochemistry up to 700 V

Environmental demands

• Treatment furnaces in controlled atmosphere up to 1700°C
• Thermogravimetry in corrosive atmosphere (SO2, HCl)
• Thermal cycling devices
• Climatic chambers: salt fog tests, VDA, etc.

Technological transfer

• Patent: Method for depositing an anti-corrosion coating, N. Ramenatte et al. (Université de Lorraine, CNRS, Air Liquide) (2015) WO2015044559 A1
   
• Patent: Method for manufacturing a part coated with a protective coating, S. Knittel et al. (Université de Lorraine, SNECMA, SAFRAN) (2018) WO2016087766 – 2016
   
• Patent: Turbine engine part covered with a protective ceramic coating, Method for manufacturing and for using such a part, L. Portebois, S. Mathieu, P. Berthod, M. Vilasi, M. Podgorski (Université de Lorraine, SAFRAN) (2019) EP 3359707 B1
   
• Patent: Process for depositing a corrosion-protection coating on at least one portion of the surfaces of a metallic substrate having at least one cavity , N. Ramenatte et al. (Université de Lorraine, CNRS, AIR LIQUIDE), Accepted n° US10053780

Professors, assistant professors

• Patrice BERTHOD
• Nicolas DAVID
• Jean-Marc FIORANI
• Stéphane MATHIEU
• Carine PETITJEAN
• Christophe RAPIN
• Emmanuel ROCCA
• Delphine VEYS-RENAUX
• Michel VILASI

Technical and support staff

• Lionel ARANDA
• David BONINA
• Louise COLIN
• Pierre-Jean PANTEIX

PhD students

• Thomas BRUNET
• Djeneba DIOMANDE
• Grégoire DUFOUR
• Bruno JACQUARD
• Roua KADDAH
• Elise PERUSE
• Yasser RASSIF
• Louis SAINT-JEAN