The Hall-Héroult process uses prebaked carbon anodes as electrodes. The anode’s quality plays a crucial role in the efficiency of the aluminium production process. During the baking process, the anode undergoes complex physicochemical transformations. Thus, the production of high-quality anodes depends, among others, on the efficient control of their baking process. This paper aims to investigate the evolution of some physical properties of the anode paste mixture during the baking process. These properties include the mass loss fraction, real and apparent densities, the ratio of apparent volume, the permeability, and porosities. For this purpose, experiments consisting of thermogravimetric analysis, dilatometry, air permeability, and helium-pycnometric measurements were carried out. The anode permeability at high temperatures was linked to the air permeability through a permeability correlator due to experimental limitations. Moreover, the real density at high temperatures was estimated by combining real densities of the coal tar pitch and coke aggregates. Different porosities, such as the open porosity and the closed porosity related to the pitch binder, were estimated by taking the permeability at high temperatures into account. In this context, the effect of the permeability correlator, which was introduced to link the permeability at high temperatures to the air permeability, was investigated through a sensitivity analysis. These results allow an estimation of the shrinking index, a new variable introduced to reflect the baking level of the anode mixture, which is linked to the volatile that is released in both open and closed pores. Afterwards, the pore pressure inside closed pores in the coal tar pitch was estimated. The obtained results highlight some new insights related to the baking process of the anode mixture. Moreover, they pave the way for better modeling of the thermo-chemo-mechanical behavior of anodes at high temperatures.

The electrical resistivity of carbon anodes is an important parameter in the overall efficiency of the aluminum smelting process. The aim of this work is to explore the Van der Pauw (VdP) method as an alternative technique to the standard method, which is commonly used in the aluminum industry, in order to characterize the electrical resistivity of carbon anodes and to assess the accuracy of the method. For this purpose, a cylindrical core is extracted from the top of the anodes. The electrical resistivity of the core samples is measured according to the ISO 11713 standard method. This method consists of applying a 1 A current along the revolution axis of the sample, and then measuring the voltage drop on its side, along the same direction. Theoretically, this technique appears to be satisfying, but cracks in the sample that are generated either during the anode production or while coring the sample may induce high variations in the measured signal. The VdP method, as presented in 1958 by L.J. Van der Pauw, enables the electrical resistivity of any plain sample with an arbitrary shape and low thickness to be measured, even in the presence of cracks. In this work, measurements were performed using both the standard method and the Van der Pauw method, on both flawless and cracked samples. Results provided by the VdP method appeared to be more reliable and repeatable. Furthermore, numerical simulations using the finite element method (FEM) were performed in order to assess the effect of the presence of cracks and their thicknesses on the accuracy of the VdP method.

In the Hall–Héroult process, prebaked carbon anodes are utilized to produce primary aluminium. The quality of the anode plays a crucial role in the efficiency of electrowinning primary aluminium. In the production of anodes, the anode baking is considered as the stage most frequently causing anode problems. During the baking process, the anode undergoes complex physicochemical transformations. Moreover, the anode at a lower position, imposed by loading pressures from upper anodes, will creep during this process. Thus, the production of high-quality anodes demands efficient control of their baking process. This paper aims to investigate the thermo-chemo-mechanical properties of the anode paste mixture at high temperatures. These properties include kinetic parameters of pitch pyrolysis such as the activation energy and the pre-exponential factor, the thermal expansion coefficient (TEC) and relevant mechanical parameters related to the elastic, the viscoelastic and the viscoplastic behaviours of the anode. For this purpose, experiments consisting of the thermogravimetric analysis, the dilatometry and the creep test were carried out. Based on the obtained results, the forementioned parameters were identified. Relevant mechanical parameters were expressed as a function of a new variable, called the shrinking index, which is related to the volatile released in open and closed pores of the anode. This variable would be used to highlight the chemo-mechanical coupling effect of the anode mixture. New insights into the phenomena such as the expansion due to the increase of the pore pressure and the chemical shrinkage of the anode during the baking process were also gained in this work. These investigations pave the way for modeling the thermo-chemo-poromechanical behaviour of the anode during the baking process.

Aluminum is reduced from alumina by the Hall–Héroult electrolysis process in which the anode is utilized as the positive electrode. The quality of the prebaked anode plays a crucial rule in the efficiency of the aluminum electrolysis process. To produce high-quality anodes in the aluminum industry, the anode baking process calls for a deep understanding of mechanisms that govern the evolution of the anode mixture properties under the high-temperature condition. Therefore, the aim of this paper is to establish a thermo-chemo-poromechanical model for the baking anode by using the theory of reactive porous media based on the theory of mixtures within the thermodynamic framework. For this purpose, an internal state variable called “shrinking index” is defined to characterize the chemical progress of the pitch pyrolysis in the anode skeleton, and the Clausius–Duhem inequality is developed according to the Lagrangian formalism. By introducing a reduced Green–Lagrange strain tensor, a Lagrangian free energy is formulated to found a set of state equations. Then, the thermodynamic dissipation for this pyrolyzing solid–gas mixture is derived, and a constitutive model linking the chemical pyrolysis with the mechanical behavior is achieved. A dissipation potential is consistently defined to ensure the non-negativeness of the thermodynamic dissipation and to obtain the constitutive laws for viscous behaviors. Field equations governing the volatile diffusion and the heat transfer through the draining mixture body are derived from the entropy balance.