Coupled model of initiation and propagation of corrosion in reinforced concrete

Corrosion of reinforcing steel in concrete due to chloride ingress is one of the main causes of the deterioration of reinforced concrete structures. Structures most affected by such a corrosion are marine zone buildings and structures exposed to de-icing salts like highways and bridges. Such process is accompanied by an increase in volume of the corrosión products on the rebarsconcrete interface. Depending on the level of oxidation, iron can expand as much as six times its original volume. This increase in volume exerts tensile stresses in the surrounding concrete which result in cracking and spalling of the concrete cover if the concrete tensile strength is exceeded. The mechanism by which steel embedded in concrete corrodes in presence of chloride is the local breakdown of the passive layer formed in the highly alkaline condition of the concrete. It is assumed that corrosion initiates when a critical chloride content reaches the rebar surface. The mathematical formulation idealized the corrosion sequence as a two-stage process: an initiation stage, during which chloride ions penetrate to the reinforcing steel surface and depassivate it, and a propagation stage, in which active corrosion takes place until cracking of the concrete cover has occurred. The aim of this research is to develop computer tools to evaluate the duration of the service life of reinforced concrete structures, considering both the initiation and propagation periods. Such tools must offer a friendly interface to facilitate its use by the researchers even though their background is not in numerical simulation. For the evaluation of the initiation period different tools have been developed: Program TavProbabilidade: provides means to carry out a probability analysis of a chloride ingress model. Such a tool is necessary due to the lack of data and general uncertainties associated with the phenomenon of the chloride diffusion. It differs from the deterministic approach because it computes not just a chloride profile at a certain age, but a range of chloride profiles for each probability or occurrence. Program TavProbabilidade_Fiabilidade: carries out reliability analyses of the initiation period. It takes into account the critical value of the chloride concentration on the steel that causes breakdown of the passive layer and the beginning of the propagation stage. It differs from the deterministic analysis in that it does not predict if the corrosion is going to begin or not, but to quantifies the probability of corrosion initiation. Program TavDif_1D: was created to do a one dimension deterministic analysis of the chloride diffusion process by the finite element method (FEM) which numerically solves Fick’second Law. Despite of the different FEM solver already developed in one dimension, the decision to create a new code (TavDif_1D) was taken because of the need to have a solver with friendly interface for pre- and post-process according to the need of IETCC. An innovative tool was also developed with a systematic method devised to compare the ability of the different 1D models to predict the actual evolution of chloride ingress based on experimental measurements, and also to quantify the degree of agreement of the models with each others. For the evaluation of the entire service life of the structure: a computer program has been developed using finite elements method to do the coupling of both service life periods: initiation and propagation. The program for 2D (TavDif_2D) allows the complementary use of two external programs in a unique friendly interface: • GMSH - an finite element mesh generator and post-processing viewer • OOFEM – a finite element solver. This program (TavDif_2D) is responsible to decide in each time step when and where to start applying the boundary conditions of fracture mechanics module in function of the amount of chloride concentration and corrosion parameters (Icorr, etc). This program is also responsible to verify the presence and the degree of fracture in each element to send the Information of diffusion coefficient variation with the crack width. • GMSH - an finite element mesh generator and post-processing viewer • OOFEM – a finite element solver. The advantages of the FEM with the interface provided by the tool are: • the flexibility to input the data such as material property and boundary conditions as time dependent function. • the flexibility to predict the chloride concentration profile for different geometries. • the possibility to couple chloride diffusion (initiation stage) with chemical and mechanical behavior (propagation stage). The OOFEM code had to be modified to accept temperature, humidity and the time dependent values for the material properties, which is necessary to adequately describe the environmental variations. A 3-D simulation has been performed to simulate the behavior of the beam on both, action of the external load and the internal load caused by the corrosion products, using elements of imbedded fracture in order to plot the curve of the deflection of the central region of the beam versus the external load to compare with the experimental data.

Evaluation of the BEASY program using linear and piecewise linear approaches for the boundary conditions

The boundary element method (BEM) was used to study galvanic corrosion using linear and logarithmic boundary conditions. The linear boundary condition was implemented by using the linear approach and the piecewise linear approach. The logarithmic boundary condition was implemented by the piecewise linear approach. The calculated potential and current density distribution were compared with the prior analytical results. For the linear boundary condition, the BEASY program using the linear approach and the piecewise linear approach gave accurate predictions of the potential and the galvanic current density distributions for varied electrolyte conditions, various film thicknesses, various electrolyte conductivities and various area ratio of anode/cathode. The 50-point piecewise linear method could be used with both linear and logarithmic polarization curves.

Stress corrosion cracking and hydrogen diffusion in magnesium

Evaluation of recent data for hydrogen (H) diffusion in magnesium (Mg) yielded a new equation for the diffusion coefficient of H in Mg. This indicates that there can be significant H transport ahead of a stress corrosion crack in Mg at ambient temperature and that H may be involved in the mechanism of stress corrosion cracking in Mg.

An evaluation of steels subjected to rock bolt SCC conditions

In order to understand the metallurgical influences on Rock Bolt SCC, an evaluation has been carried out on carbon, carbon + manganese, alloy and microalloyed steels subjected to the conditions previously identified as producing laboratory SCC similar to that observed for rock bolts in service. The approach has been to use the LIST test (Linearly increasing stress test) for samples exposed to a dilute pH 2.1-sulphate solution, as per our prior studies. SCC was evaluated from the decrease in tensile strength, ductility and fractography as revealed by SEM observation. A range of SCC susceptibilities was observed. Ten of these steels showed SCC, however there was no SCC for one carbon, two carbon + manganese and two alloy steels.

Corrosion protection of PVD and paint coatings for selective solar absorber surfaces

The selective solar absorber surface is a fundamental part of a solar thermal collector, as it is responsible for the solar radiation absorption and for reduction of radiation heat losses. The surface’s optical properties, the solar absorption (á) and the emittance (å), have great impact on the solar thermal collector efficiency. In this work, two coatings types were studied: coatings obtained by physical vapor deposition (PVDs) and coatings obtained by projection with different paints (PCs) on aluminum substrates. The most common industrial high performing solar selective absorbers are nowadays produced by vacuum deposition methods, showing some disadvantages, such as lower durability, lower resistance to corrosion, adhesion and scratch, higher cost and complex production techniques. Currently, spectrally selective paints are a potential alternative for absorbing surfaces in low temperature applications, with attractive features such as ease of processing, durability and commercial availability with low cost. Solar absorber surfaces were submitted to accelerated ageing tests, specified in ISO 22975-3. This standard is applicable to the evaluation of the long term behavior and service life of selective solar absorbers for solar collectors working under typical domestic hot water system conditions. The studied coatings have, in the case of PVDs solar absorptions between 0.93 and 0.96 and emittance between 0.07 and 0.10, and in the case of PCs, solar absorptions between 0.91 and 0.93 and emittance between 0.40 and 0.60. In addition to evaluating long term behavior based on artificial ageing tests, it is also important to know the degradation mechanism of different coatings that are currently in the market. Electrochemical impedance spectroscopy (EIS) allows for the assessment of mechanistic information concerning the degradation processes, providing quantitative data as output, which can easily relate to the kinetic parameters of the system. EIS measures were carried out on Gamry FAS2 Femostat coupled with a PCL4 Controller. Two electrolytes were used, 0.5 M NaCl and 0.5 M Na2SO4, and the surfaces were tested at different immersion times up to 4 weeks. The following types of specimens have been tested: Aluminium with/without surface treatment, 3 selective paint coatings (one with a poly(urethane) binder and two with silicone binders) and 2 PVD coatings. Based on the behaviour of the specimens throughout the 4 weeks of immersion, it is possible to conclude that the coating showing the best protective properties corresponds to the selective paint coating with a polyurethane resin followed by the other paint coatings, whereas both the PVD coatings do not confer any protection to the substrate, having a deleterious effect as compared to the untreated aluminium reference.

Raman spectroscopy of the copper chloride minerals nantokite, eriochalcite and claringbullite - implications for copper corrosion

The application of Raman spectroscopy to the study of the copper chloride minerals nantokite, eriochalcite and claringbullite has enabled the vibrational modes for the CuCl, CuOH and CuOH2 to be determined. Nantokite is characterised by bands at 205 and 155 cm-1 attributed to the transverse and longitudinal optic vibrations. Nantokite also has an intense band at 463 cm-1, eriochalcite at 405 and 390 cm-1 and claringbullite at 511 cm-1. These bands are attributed to CuO stretching modes. Water librational bands at around 672 cm-1 for eriochalcite have been identified and hydroxyl deformation modes of claringbullite at 970, 906 and 815 cm-1 are observed. Spectra of the three minerals are so characteristically different that the minerals are readily identified by Raman spectroscopy. The minerals are often determined in copper corrosion products by X-ray diffraction. Raman spectroscopy offers a rapid, in-situ technique for the identification of these corrosion products.