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International audience; This study compares the (nitrogen oxides) NOx photocatalytic degradation performance of the commercial bare semiconductors, titanium dioxide (TiO2 P25) and zinc oxide (ZnO), with that of the homemade gold (Au)-decorated semiconductors, Au/TiO2 and Au/ZnO (1 wt% Au). A plasmonic absorption band was observed at 550 nm for Au/TiO2 and around 700 nm for Au/ZnO. Aqueous dispersions based on these oxides were sprayed on mortar surfaces. The results revealed that Au/ZnO had a high NO degradation capability, comparable to that of TiO2 P25, and the best selectivity towards the formation of nitrates instead of NO2. The Au decoration clearly improved the photocatalytic response of ZnO, notably by avoiding the production of NO2. This positive effect was attributed to the better charge carrier separation and higher OH• production induced by the presence of Au. To the best of our knowledge, this was the first study on Au/ZnO used for NO photocatalytic degradation.

International audience

“Almost real-life” experiments of abatement of a pollutant, actually nitrogen monoxide, were carried out in a 10-m3 chamber, the walls of which were covered with plasterboard samples, themselves coated with a photocatalytic dispersion. The experimental protocol consisted in first injecting NO polluted air into the chamber to a certain level, then maintaining a steady level of pollution by tuning the flow rate to balance the leaks and, finally, illuminating the chamber. In a first stage of analysis, a three-flow (injection, leakage and renewal flows) model was used in order to characterize the leakage flow rate. This model was based on the difference of NO concentration between the interior and the exterior rather than on a pressure difference. A two-parameter empirical law was specially formulated for this purpose. In a second stage, the photocatalytic phenomenon was described by a four-flow model completing the previous one, the fourth flow being associated with the photocatalytic oxidation of NO. This flow was described by a rate law derived from the Langmuir-Hinshelwood (L-H) law, which was generalized to the experimental chamber. The parameters K (adsorption constant) and k (abatement kinetics constant) of the rate law were identified using a standardized lab-scale reactor. The equations, integrated by finite differences, fitted the experimental results correctly. The “diffusive zone thickness” was introduced as the thickness of the air layer potentially concerned by the photocatalysis and was quantified. This first attempt to model photocatalysis on a large scale was promising. However, further research work is needed to enable the model to take more parameters into account.

International audience; itanium metal is widely used in the aeronautical sector for its specific properties and corrosion resistance. The design of titanium workpieces is based on chemical milling: a fast, precise, low cost technique popular in the aerospace industry. Material is removed from selected areas of a part by immersing it in a strong chemical reagent. This process produces shallow cavities on plates and sheets or removes shallow layers of materials from large aircraft components to optimize the strength/weight ratio. However, it leads to large volumes of wasted acid baths, which are harmful to the environment and have to be sent to an approved waste facility. The objective of this paper is to highlight a cleaner production process based on the circular economy concept, i.e. reduce, reuse and recycle to limit environmental pollution and operating costs. Waste from chemical milling baths used in the design of titanium parts was recovered with the aim of synthesizing titanium dioxide and using it for air depollution applications. The waste consisted of hexafluorotitanate compounds. Various processing techniques to synthesize titanium dioxide from hexafluorotitanate compounds were tested and resulted in powders having different physicochemical characteristics. The synthesis parameters studied were the nature of the decomplexing agent, the dehydration temperature and the heating period. Photocatalytic coatings were then formulated on the basis of the synthesized powders. They were applied to a mortar surface to evaluate their efficiency to degrade nitric oxide under two UV lighting intensities, 5 and 20 W/m2. Depending on the synthesis process conditions, the concentration and crystal form of titanium dioxide particles varied, leading to more or less efficient photocatalytic coatings. The proportions of anatase and rutile phases in the synthesized powders were between 3 and 13%, and 5 and 30%, respectively. Concerning the particle size distribution, the variations observed were dependent on the D-values. D10% was quite similar for all powders. However, D50% and D90% differed by a factor of two for some powders, notably because of the presence of impurities or remaining decomplexing agent particles. NO degradation varied depending on the photocatalytic dispersions and could reach 7% under an irradiation of 20 W/m2. This article highlights the possible valorization of a massive industrial waste for specific applications provided that the conditions of processing techniques are optimized.

Air pollution is a serious public health concern in France and many other countries. Nitrogen oxides (NOx) include nitrogen monoxide (NO) and nitrogen dioxide (NO2). They are mainly outdoor pollutants produced during combustion of fossil fuel. These gases can easily infiltrate buildings and thus increase indoor pollution. The recommended guideline values for NO2 are 200 μg/m3 (short-term exposure) and 40 μg/m3 (long-term exposure). Although no guideline values exist for NO, this gas can be oxidised by atmospheric ozone and thus produce NO2. This paper studies the depollution efficiency of photocatalysis towards indoor NO. Experiments were conducted at real scale, in a 10-m3 experimental chamber developed at the LMDC and used as a reactor. The interior walls of the chamber were equipped with painted plasterboards treated with photocatalytic coating (3 g/m2 of TiO2). Gas was continuously injected into the chamber according to a specific procedure: (1) pollutant injection at high flow rate to reach 200 ppb of NO, (2) pollutant injection at low flow rate in order to keep the NO concentration constant at 200 ± 10 ppb and (3) photocatalysis activation by switching on the light. Typical indoor lighting systems (fluorescent tubes, LED and halogen bulbs) were tested and UV fluorescent tubes were also used to optimise the photocatalytic efficiency. Results showed that NO indoor concentration was reduced by photocatalysis in real-world conditions. Significant NO degradation was obtained under visible light. In addition, using the experimental procedure presented in this paper, a new method for evaluating air depollution efficiency by photocatalysis at real scale is proposed.

This paper deals with the degradation of NO by photocatalytic oxidation using TiO2-based coatings. Tests are conducted at a laboratory scale through an experimental setup inspired from ISO 22197-1 standard. Various parameters are explored to evaluate their influence on photocatalysis efficiency: TiO2 dry matter content applied to the surface, nature of the substrate, and illumination conditions (UV and visible light). This article points out the different behaviors between three kinds of substrates which are common building materials: normalized mortar, denser mortar, and commercial wood. The illumination conditions are of great importance in the photocatalytic process with experiments under UV light showing the best results. However, a significant decrease in NO concentration under visible light is also observed provided that the TiO2 dry matter content on the surface is high enough. The nature of the substrate plays an important role in the photocatalytic activity with rougher substrates being more efficient to degrade NO. However, limiting the roughness of the substrate seems to be of utmost interest to obtain the highest exposed surface area and thus the optimal photocatalytic efficiency. A higher roughness promotes the surface contact between TiO2 and NO but does not necessarily increase the photochemical oxidation.

International audience; The objective of this study is to develop bio-sourced waste chemicals for use as asphalt release agents. Glycerol was extracted from bio-sourced waste and transformed by transesterification into the surfactants undecenoates of glycerol (MUG) and undecenoates of diglycerol (MUDG). They were composed of glycerol, monoglycerol, diglycerol, triglycerol, tetraglycerol and water. The formulations were mixed separately with water at quantities of 5-50%, along with acetone and commercial bio-sourced ARAs in order to observe the effects. The formulations were subjected to performance testing with the asphalt slide test, finding significant reduction in adhesion for a number of different formulations. The interaction of the formulations with bitumen was tested by the bitumen degradation test, which was combined with FTIR-ATR analysis, finding that the formulations do not dissolve the bitumen, but rather were adsorbed by the bitumen. The effects on asphalt mix of the best performing formulation, MUG at 20% in water, was tested by indirect tensile strength, determining that the formulation was acceptable for use in the field.

International audience; Indoor air is contaminated by numerous pollutants, which impact human health, comfort and productivity. These pollutants have various indoor sources such as building materials, furniture, combustion appliances or tobacco smoke. However, the pollution also comes from outside. In urban area, nitrogen oxides (NOx) emitted into the atmosphere can reach alarming levels. These traffic-related pollutants, which seriously impact the global environment and human health, can infiltrate inside buildings. Therefore, limiting the amount of breathable NOx in outdoor and indoor environments is an important priority for the modern society. The photocatalytic process has attracted particular attention in the last two decades and has proved to be efficient to reduce the concentration of NOx. However, further work has to be conducted to assess its efficiency in real indoor environments. The purpose of this paper was to report on the indoor air quality in an open space office in Manchester, UK. Focus was made on nitric oxide (NO) and nitrogen dioxide (NO2). The indoor concentrations of both gases were monitored from 14 January 2019 to 7 April 2019. During this period, a photocatalytic coating was applied to a part of the indoor wall. The influence of this coating on the level of NOx was assessed by comparing the indoor concentrations before and after the application. An attention was paid to the correlation between outdoor and indoor pollution and to the effect of other parameters such as temperature, humidity, pressure and O3 concentration. The results showed that the photocatalytic process led to a decrease in the NOx concentration. The likelihood to find concentrations above 35 ppb for NO and 7.5 ppb for NO2 was clearly reduced after the coating application.

Corrosion of steel in reinforced concrete structures is a recurrent problem affecting civil engineering structures and costing the world billions of dollars per year. This physical phenomenon mainly results from chloride ingress or concrete carbonation. Corrosion can be diagnosed through a nondestructive method such as half-cell potential measurements. The present paper studies this method on a reinforced concrete wall containing eighteen unconnected steel bars and subjected to chloride-induced macrocell corrosion. Three corrosion systems with different configurations of connections between the steel bars are generated, involving three different anode-to-cathode surface ratios. Then, half-cell potential variations are observed versus macrocell corrosion current. The results lead to a critical discussion regarding the physical relevance of the usual potential threshold method to detect corroding rebars in reinforced concrete structures. In addition, the experiments demonstrate that electrical continuity between reinforcing steel bars is not necessary to get meaningful information about the macrocell corrosion system. At last, the paper show that the electric field (potential gradient) relative to a macrocell corrosion system may be measured by connecting the measurement system (reference electrode + voltmeter) to any electrochemical system in electrolytic contact with the concrete.

WOS:000400765900008; International audience; This paper investigates a new test method to assess the photocatalytic activity of plasterboards coated with a TiO2 dispersion under real-world conditions. The degradation of nitrogen oxides NO (x) (NO and NO2) is studied and the photocatalytic efficiency under UV illumination is evaluated in a 10-m(3) room after a constant gas injection. Two ultrafine TiO2 dispersions are used: 0.85% TiO2 and 5% TiO2, and three types of gas are tested: an NO/NO2 mixture (8/8 mol-ppm), NO (45 mol-ppm) and NO2 (45 mol-ppm). The test method presented here is midway between laboratory and real-scale procedures and allows better control of the experimental parameters than a real field experiment. Testing a mixture of NO and NO2 is a way to get closer to real-world conditions as air is polluted by various gases. This study focuses on the degradation of NO and NO2 under UV illumination when two types of TiO2 dispersions are used and highlights the difference in behaviour between these two molecules in terms of photocatalytic degradation. The results show that photocatalytic activity does not appear to be efficient to degrade NO2 molecules. Another mechanism seems to be responsible for the reduction of the concentration of NO2, namely adsorption. Encouraging results are obtained with NO molecules, which can be degraded by photocatalysis. The degradation observed is even greater with the more concentrated TiO2 dispersion.

WOS:000373963700024; International audience; The objective of this study is to develop testing methods of asphalt release agent (ARA) performance and the degree to which they may damage the asphalt. The testing of ARA performance demonstrated their ability to reduce the adhesion between the asphalt and the surface of steel (asphalt tools, truck bedsaEuro broken vertical bar) by the asphalt slide test, which provided two indicators for quantifying performance. The testing of the their damage to asphalt consisted of the measurement of the degree to which the compacted asphalt is damaged by the ARA including CBR resistance, indirect-tensile strength and bitumen degradation testing, the latter also serving as a test to find the most effective bitumen remover (BR). For asphalt degradation, the indirect tensile strength test provided more consistent results than CBR resistance.

International audience; This article deals with the degradation of NO present in the air by means of a photocatalytic oxidation process based on TiO2 nanoparticles incorporated in a polymer-matrix-based coating. The experimental set-up consisted of a flow type reactor adapted from the ISO 22197-1 standard. NO2 in the gas phase, and nitrate ions adsorbed on the photocatalytic surface were detected as finals products. Various parameters influencing the NO degradation efficiency were studied: the coating composition, the substrate nature, the initial concentration of NO, the polluted air flow rate and the humidity. Compared to glass, the use of mortar as the substrate enhanced the photocatalytic performance of coatings by reducing the generation of gaseous NO2 as a by-product.

This study aimed to evaluate the effectiveness of a mechanism responsible for the mitigation of expansion when reactive aggregate powders (RAP) were used in concrete containing the same reactive aggregate. In the first part, it was shown that RAP were efficient in reducing the expansion of concrete by 35 to 95%. The most efficient powders were those coming from aggregates having high active silica contents (glass, opal). Powders of siliceous limestone were less effective. In a second part, experimental evidence of the pozzolanic activity of RAP was obtained. It was shown that RAP were similar to pozzolan, since they consumed lime and produce calcium–silicate–hydrate (C–S–H) having a lower calcium/silica (C/S) ratio than normal C–S–H. The third part showed experimentally that these low C/S C–S–H could increase the redistribution of alkalis of the pore solution, thus reducing the alkalinity of the pore solution to a level that was sufficiently low to limit the attack of coarser reactive aggregates. In the final part, numerical simulations using a modified version of the hydration model CEMHYD3D were carried out to support this assumption.

Aesthetics of external concrete walls can be altered in various constructions by fast developing algae and it is useful to propose technical solutions to prevent this problem. Laboratory tests are thus necessary, on the one hand to accelerate the growth of algae on concrete and, on the other, to quantify such growths. The first part of this article was dedicated to the description of two growth tests. This second part presents the advantages and drawbacks of three complementary techniques used to analyze the colonized areas. Two methods are non-destructive and estimate either the area covered, using image analysis, or the density of algae, which directly influences the stain intensity, by spectrophotometry. The third method is destructive and is based on the measurement of chlorophyll a. It is used to obtain information on the state of vitality of the algae on the colonized surface.

A possible practice to prevent disorders due to alkali-silica reaction (ASR) in concretes containing reactive aggregates is the use of chemical admixtures (lithium salts) or, more commonly, mineral admixtures such as fly ash, silica fume, ground granulated slag or metakaolin. An analysis of the literature concerning ASR revealed some papers devoted to the mitigating activity of reactive aggregate powders (RAP) when associated with their parent aggregates. These RAP result from the grinding of the reactive aggregate. To verify the efficiency of this method of mitigation, tests were performed on concrete prisms cured at 60°C and 100% R.H., using four reactive aggregates, associated or not with their RAP. The results showed that the use of RAP reduced or suppressed ASR-expansion, suppressed surface cracking and counteracted the loss of compressive strength due to ASR. If these findings are confirmed by trials on other types of aggregates, the addition of RAP would be a simple way of avoiding ASR disorders.

This work is the fourth part of an overall project the aim of which was the development of general mix design rules for concrete containing different kinds of mineral admixtures. The two first parts presented the separation and quantification, by means of an empirical model based on semi-adiabatic calorimetry measurements, of the different physical effects responsible for changes in cement hydration (short terms) when chemically inert quartz powders were used in mortars. Part three dealt with an intensive experimental program, presenting and commenting more than 2000 compressive strength measurements. This program concerned 1 day to 6 months old mortars containing up to 75% of inert and pozzolanic admixtures. All these compressive strength results are analyzed in this fourth part and the influence of three effects, namely dilution, heterogeneous nucleation and the pozzolanic effect, are discriminated and quantitatively evaluated. An efficiency concept is proposed in order to take into account the effect of mineral admixture in mortars from both the physical and chemical points of view. It uses an efficiency function ξ(p) that has notable properties: it is independent of time, independent of fineness and independent of the type of mineral admixture.

This work is the third part of an overall project the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures (also named mineral additions or mineral constituents). It deals with the compressive strength of mortars made with up to 75% of crushed quartz, limestone filler or fly ash of different fineness. The paper presents all the experimental results as a sort of database and emphasizes the effects on strength of the nature, amount and fineness of mineral admixtures. For short hydration times (1 to 2 days), the nature of mineral admixture is not a significant parameter, as mortars containing the same amount of different kinds of admixtures having equivalent fineness present similar strengths. For long hydration times (up to 6 months), the excess strength due to fly ash pozzolanic activity is quantified by the difference between the strengths of mortars containing the same proportions of inert and pozzolanic admixtures with the same fineness. In the case of inert mineral admixtures, the increase in strength with the fineness of mineral admixtures cannot be explained by the filler effect, but can be attributed to the physical effect of heterogeneous nucleation. In the next part of this work, these results will be used for the elaboration of an empirical model leading to the quantification of both physical and chemical effects. This model presents strong similarities with the previous model based on calorimetric results.

This work is the second part of an overall project, the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The first part presented the separation of the different physical effects responsible for changes in cement hydration when chemically inert quartz powders are used in mortars. This second part describes the development of an empirical model, based on semiadiabatic calorimetry measurements, which leads to the quantification of the enhancement of cement hydration due to the heterogeneous nucleation effect at short hydration times. Experimental results show that not all the admixture particles participate in the heterogeneous nucleation process. Consequently, the concept of efficient surface Seff is introduced in the model. Seff is the total admixture surface S (m2 of mineral admixture/kg of cement) weighted by a function ξ(p). The efficiency function ξ(p) depends only on the replacement rate p and is independent of time, fineness and type of mineral admixture used. It decreases from 1 to 0: Low replacement rates give an efficiency value near 1, which means that all admixture particles enhance the hydration process. An efficiency value near 0 is obtained for high replacement rates, which indicates that, from the hydration point of view, an excess of inert powder does not lead to an increase in the amount of hydrates compared with the reference mortar without mineral admixture. The empirical model, which is mainly related to the specific surface area of the admixtures, quantifies the variation of the degree of hydration induced by the use of inert mineral admixtures. One application of the model, coupled with Powers' law, is the prediction of the short-term compressive strength of mortars.

This work is the first part of an overall project the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The separation of the different physical effects responsible for the modification of cement hydration, when chemically inert quartz powders are used in mortars, is presented. The phenomenological approach, based on semi-adiabatic calorimetry, is only associated with first-order phenomena, and the study excludes the complex physicochemical details involved in the chemistry of cement. The results, obtained for a wide range of fineness (between 180 and 2000 m2/kg) and replacement rates (up to 75%), show that short-term degrees of hydration in mortars containing a chemically inert mineral admixture (quartz) are always higher than for a reference mortar. This study confirms that cement hydration is enhanced by inert mineral admixtures. The two main physical effects responsible for the modification of the hydration of cement are identified as the dilution effect and heterogeneous nucleation. The dilution effect of the cement is highlighted with a coarse mineral admixture. The heterogeneous nucleation effect, although it increases with fineness of mineral admixtures, presents an optimum depending on the replacement rate. In the following part of this work, these results will be used for the development of an empirical model allowing us to quantify both physical effects.

WOS:000333782100017; International audience; Building materials are regularly affected by the growth of microalgae. The consequences are mainly aesthetic but the colonization can cause biodeterioration of the material in the most extreme cases. This study investigates two building material treatments that can potentially inhibit or slow down such growth: photocatalytic coatings and water repellent treatments. The efficiency of these treatments in terms of biological growth inhibition was tested on the algae species Graesiella emersonii. Algal growth on building materials was investigated using two accelerated tests simulating different types of humidification (water capillary ascent and water run-off) under different lighting conditions. Mortars treated with photocatalytic coating or with water repellent were studied. The algal growth on the mortar surface was evaluated using image analysis (area covered and intensity of fouling). No slow down of the biological growth kinetics could be attributed to photocatalytic substrates. However, for mortars impregnated with a water-repellent preparation, algal growth slowed significantly under water run-off and even stopped under water capillary ascent. (C) 2014 Elsevier Ltd. All rights reserved.

WOS:000328713000018; International audience; Photocatalytic coatings intended for building materials were formulated using TiO2 nanoparticles incorporated in a polymer-matrix-based coating. Their air purification performance levels were assessed on a VOC (volatile organic compound) mixture representative of atmospheric pollution (benzene, toluene, ethylbenzene and xylenes, or BTEX). Experiments were performed using a flow type reactor adapted from the ISO 22197-3 standard under UV-A illumination (6 W m(-2)) at different ranges of inlet concentration (260-2600 ppbV of BTEX), relative humidity (RH: 0-90%) and flow rate (0.1-1.5 L min(-1)). Analysis was conducted by using an automated thermal desorption technique coupled to a GC-FID instrument. At low initial concentrations of pollutants, increasing humidity had a negative impact on the degradation of BTEX. In this case, the reaction was limited by the competition between pollutant and water at the absorptive sites. At higher initial concentrations of pollutant, the conversion of the pollutants increased with the increase in air humidity to an optimum value beyond which the conversion of pollutants decreased. The reaction may have been limited by a lack of hydroxyl radical at the low humidity level while, at higher humidity, competition at the absorptive sites limited pollutant removal. (C) 2013 Elsevier Ltd. All rights reserved.

The decision of public authorities to recycle industrial wastes leads to the quasi-systematic use of mineral admixtures in concrete. Predicting the strength of these concretes induces the engineer to characterise the mineral, admixtures: ordinarily, a single coefficient is used, calculated with an empirical law like Bolomey's or Abrams' formulas. Many results, reported in bibliography and completed by the authors, show that the determination of this single coefficient is not sufficient to characterise the activity of the admixture. Many factors like the nature of cement, the substitution rate, the fineness of the admixture and the age of concrete induce a great variability of the efficiency coefficient of the admixtures. Up to now, there is no general law explaining this variability. The authors warn against the excessive use of a single equivalence coefficient and recommend to take into, account not only the physicochemical parameters but also the nature of the works themselves.

In the first part, the definition and the methods for estimating the coefficient of activity of a mineral filler are presented. The calculation relies on predictive laws of strength, here Bolomey's and Feret's laws. In the second part, experimental results concerning the strength of mortars allow us to calculate the coefficient of activity of a fly ash. It is shown that it is not realistic to characterise the activity of the fly ash by a unique coefficient because the strength of mortars is not accordant with a linear law of the substitution ratio. Therefore, it is necessary to evaluate the coefficient of activity as a function of the substitution ratio.

The ion diffusion process in mortar is different from the one which occurs in cement paste. This difference is due to the presence of transition zones, which take place around the grains in mortar and which are very porous regions. Based on mercury intrusion porosimetry experimental data and on the analysis of percolation through a 3D mortar model, a computation of the transition zone porosity and of the bulk paste porosity has been carried out. The porosity of the transition zone has been analyzed as a function of the mortar composition and of the degree of hydration.

This paper is the second part of a study of cement paste structure by image analysis. Solid concentration and granulometric measurement have been carried out on the original binary image, then on the same image whose morphology had been modified. These results revealed anhydrous cement grains dispersed in the fresh paste. The effect of concentration and the state of the solid phase can influence this dispersion and we suggest that our method can be used to investigate both these phenomena.

International audience; This study concerns the assessment of non-coated concrete surfaces in civil engineering structures and buildings. Imaging is used as an objective tool for evaluation of the surfaces. Because images of surfaces taken under different conditions of illumination are difficult to compare, this paper presents a method suggested by the building firm GTM Construction and the laboratory LMDC for obtaining images of luminance L∗ simulated for one standard illuminant (D65). Concrete surfaces can be qualified with respect to uniformity of tint and distribution of surface bubbles. The process described is based on image analysis. Not only can the results be compared with current standards, but the method also gives access to additional, accurate information such as the distribution of defects and the size of surface bubbles. This method is already applied on building sites for experts’ assessments and in the laboratory for the study of the parameters influencing surface quality.

The relationship between microscopical damaging of concrete and its mechanical parameters such as Young's modulus and degree of reversibility is a basic issue. In the same time, transport properties and of course the durability of civil engineering and hydraulic structures are linked to the state of microcracking.The replica technique has been developed in our laboratory in order to study microcracks with a scanning electron microscope. This non-destructive method allows observation of the imprint of the concrete surface and to follow the evolution of the alterations with time. An objective quantitative analysis requires numerous replicas and many microscopic fields within each replica.After a brief state of the art of the automatic method of extraction of lines by image processing, we propose a specific algorithm of image analysis which allows the cleaning of the pictures and the extraction of the microcrack skeleton. Today, this procedure has been validated on cement paste samples. It has to be improved to be applied on concrete.The measured parameters are the microcrack specific lengths and their orientation. The objective values measured by means of this procedure compare favorably to results obtained by hand drawing.

Fly ash from power stations is used as concrete additive to improve strength and durability. Surprisingly, studies of ashes of identical mineralogical composition from two different places have reported different results in terms of the rheological properties of the fresh material. The viscosity of the pastes made from these different fly ashes seems to be linked to the proportion of spherical and smooth-shaped grains found in them. A quantitative image analysis was carried out to characterize the shape of the grains of these two ashes from different geographical origins. The main result proves that the higher the glassy particle content of the fly ash, the more the hydraulic matrix is fluid.

Preliminary to the modeling of the fracture of concrete, it is necessary to make observations at low scale for a better understanding of the phenomena. In this paper, the author shows how to follow the development of the microcracks in a sample during a compressive loading experimentation by the mean of non-destructive takings of replicas observed under S.E.M. The quantification by the stereological method of total projection. Enables to establish a relation between the observed damages and the global behaviour of concrete.

Preliminary to the study of the microcracks evolution in loaded concrete samples, it is necessary to know the initial state of this material. In this paper, first the possibilities of an indirect visualisation by single replica are presented. Then, this technique is used to study the initial state of concrete, stored in a wet conservation chamber which exhibits an absence of microcracks.

The stereological method of total projection was practically not applied yet because of the difficulty to use it manually. Yet, determinist, it is more precise than the oriented secants technique which is statistic. The author shows how it may be applied to the study of microcracking in concrete, providing its computerization.

The PhD thesis "Exploratory studies dedicated to computer-assisted corrosion diagnosis of civil engineering structures" deals with the phenomenology and modeling of corrosion of structural steel. The safety, societal and environmental impact of aging infrastructures makes this theme a major economic issue for the development of any country. The proposed developments focus mainly on the corrosion of reinforcements in reinforced concrete. The corrosion of buried metallic structures is also addressed concerning the problems related to galvanic couplings induced by the heterogeneity of soils and stray currents. The usual methods of investigation (measurements of steel potential, concrete resistivity or polarization resistance), combined with empirical hypotheses established by experience, lead to interpretations that are often uncertain or have only a qualitative value. The ambition of this thesis, motivated by the issues at stake, is to show how a better understanding of the physics of corrosion, combined with the power of finite element calculation, allows the construction of elaborate and robust models, useful for a quantified and reliable diagnosis and/or prognosis. The thesis is abundantly illustrated by real or numerical case studies and supported by original laboratory tests. In order to improve the understanding of the phenomena prevailing in the corrosion process, the key concepts of thermodynamics and electrochemical kinetics are recalled and contextualized. The assembly of different physical, chemical and electrochemical laws allows the elaboration of an advanced modeling approach, integrating in particular the diffusion of oxygen to the reinforcement in an unsaturated context, but also the production and precipitation of corrosion products and their influence on the dynamic equilibrium of a corrosion system. This modeling approach, necessarily three-dimensional or at least two-dimensional, gives rise to a transcription in a finite element calculation code. It is first applied to the numerical study of a first typical case of corrosion: a reinforced concrete pile partially submerged in the sea. The influence of the role of oxygen (availability and diffusion) on the dissolution kinetics of the steel and on the nature of the corrosion products formed is studied in particular. In order to illustrate the effective contribution of 3D modeling in the process of corrosion diagnosis, a real case study is proposed concerning a buried steel structure, in this case sheet piles used to support the abutments of a freeway overpass, located near a pipe buried under cathodic protection. Measurements carried out in-situ but also in the laboratory from judiciously chosen samples are used to feed the calculation model. The numerical model thus constructed, qualified as a digital twin, makes it possible to highlight the existence of stray currents circulating in the structure, but also the risk of galvanic corrosion induced by the heterogeneity of the soil. The electrochemical digital twin is then a powerful tool for estimating the kinetics and the corrosion facies of the structure and making a prognosis in terms of service life. Within a concrete structure, the presence of chlorides is associated with various effects, notably associated with the local electric field. If this phenomenon is ignored, the interpretation of field data, for example potential maps, can lead to a biased diagnosis. This thesis addresses the question of corrosion initiation.[...]; La thèse "Études exploratoires dédiées au diagnostic de corrosion assisté par ordinateur des structures de génie civil" traite de la phénoménologie et de la modélisation de la corrosion de l'acier de construction. Le poids sécuritaire, sociétal, environnemental du vieillissement des infrastructures fait de ce thème un enjeu économique majeur de développement de tout pays. Les développements proposés portent principalement sur la corrosion des armatures dans le béton armé. La corrosion des structures métalliques enterrées est également adressée concernant les problématiques relatives aux couplages galvaniques induits par l'hétérogénéité des sols et aux courants vagabonds. Les méthodes d'investigation usuelles (mesures de potentiel des aciers, de résistivité du béton ou de résistance de polarisation), jointes à des hypothèses empiriques consacrées par l'usage, conduisent à des interprétations souvent incertaines ou n'ayant qu'une valeur qualitative. L'ambition de cette thèse, motivée par les enjeux évoqués, est de montrer comment une meilleure compréhension de la physique de la corrosion, conjuguée à la puissance du calcul aux éléments finis, permet de construire des modèles élaborés et robustes, utiles pour poser un diagnostic et/ou un pronostic quantifié et fiable. La thèse est abondamment illustrée par des études de cas réels ou numériques et étayée par des essais originaux conduits en laboratoire. Afin d'améliorer la compréhension des phénomènes prévalant dans le processus de corrosion, les concepts-clés de thermodynamique et de cinétique électrochimique sont rappelés et contextualisés. L'assemblage de différentes lois physiques, chimiques et électrochimiques permet d'élaborer une approche de modélisation avancée, intégrant notamment la diffusion du dioxygène jusqu'aux armatures en contexte insaturé, mais aussi la production et la précipitation des produits de la corrosion et leur influence sur l'équilibre dynamique d'un système de corrosion. Cette approche de modélisation, nécessairement tridimensionnelle ou a minima bidimensionnelle, donne lieu à une transcription dans un code de calcul par éléments finis. Elle est appliquée dans un premier temps à l'étude numérique d'un premier cas typique de corrosion : pile en béton armé partiellement immergée en mer. L'influence du rôle du dioxygène (disponibilité et diffusion) sur la cinétique de dissolution de l'acier et sur la nature des produits de corrosion formés est notamment étudiée. Afin d'illustrer l'apport effectif de la modélisation 3D dans le processus de diagnostic de la corrosion, une étude de cas réelle est proposée concernant un ouvrage métallique enterré, en l'occurrence des palplanches servant au soutènement des culées d'un passage supérieur d'autoroute, situées à proximité d'une conduite enterrée sous protection cathodique. Des mesures effectuées in-situ mais aussi en laboratoire à partir d'échantillons judicieusement choisis, permettent d'alimenter le modèle de calcul. Le modèle numérique ainsi construit, qualifié de jumeau numérique, permet de mettre en évidence l'existence de courants vagabonds circulant dans la structure, mais également le risque de corrosion galvanique induit par l'hétérogénéité du sol. Le jumeau numérique électrochimique constitue alors un outil puissant pour estimer la cinétique et le faciès de corrosion de l'ouvrage et poser un pronostic en termes de durée de vie. [...]

The growing health and environmental concerns brought on by the use of petroleum based products in the asphalt construction industry have necessitated the development of alternatives. Infrastructure, especially that involving transportation has many uses for petroleum products including, as fuel, as well as in asphalt pavement construction - where petroleum products have traditionally constituted the binder for the mix as well as the rejuvenating agents (for asphalt recycling) - along with various agents used in the construction process including bitumen removers and asphalt release agents. Thus, there is a need to replace petroleum base agents with bio-sourced and biodegradable substitutes. The present work is part of a project to develop bio-sourced (recycled from agricultural waste) products for the construction industry. This work is dedicated to developing products relating to the asphalt industry. Two types of product applications were envisioned: i) an asphalt release agent (ARA) and ii) an asphalt rejuvenating agent. Additionally, a bitumen remover (BR) developed as part of the work on the ARA. ARAs prevent asphalt from adhering to tools and equipment used in asphalt production, without producing overly negative side effects with regards to the pavement. Three principal tests methods were developed and optimized for the performance and damage to asphalt of the ARAs. The asphalt slide test was developed to quantify the performance of the ARA by sliding hot asphalt mix down a plate with the ARA applied. The testing of the damage to asphalt from ARAs consisted of testing an asphalt cylinder - in contact with an ARA for seven days - in indirect-tensile strength (ITS). The bitumen degradation test consisted of submerging a bitumen sample in an agent over a certain time and weighing the bitumen that did not dissolve in the agent. This was followed by the observation of the bitumen-ARA chemical interaction by FTIR spectrometry. This test served as an assessment of ARA damage to bitumen as well as of the performance of BRs. The testing of the commercial ARAs from both the French and USA markets found that they had two primary modes of functioning: i) by softening the bitumen and ii) by forming an interface between the asphalt and the metal surface. While some agents had elements of both, it was found that interface agents are preferable, due to the ability to use a single ARA application for multiple occasions. With this completed, a water-based bio-sourced substrate ARA - based on glycerol derived from agricultural waste - was developed. The commercially available BRs were tested as well, finding that i) the most effective BRs had the highest ester concentration and ii) that highly concentrated short chained ester (C7-10) were very effective bitumen dissolvers. The goal of rejuvenating agents is to regenerate the old bitumen from recycled asphalt pavement (RAP) by restoring the original properties and ensuring the stability of these properties over time. This part consisted of the development of methods for bitumen and aging, as well as characterization of the chemical rejuvenation of bitumen by FTIR spectrometry (including imaging) and thermogravimetric analysis. A bio-sourced rejuvenating agent was evaluated as well. For the imaging, a mastic polishing method was developed in order to attain as samples as flat as possible for the analysis. The bitumen rejuvenation was observed using FTIR spectroscopy analysis. Several peaks (notably IC=O and IS=O) were observed for bitumen oven aged up to 42 days (long term). It was found that an oven aging period of 14 days was roughly equivalent to bitumen aged by a RTFOT+PAV cycle it terms of rheology and penetration. The mastic (aged for 14 days) was then combined with a bio-sourced agent (at 7.5%w of mastic). It was found by FTIR imaging that the oxidation indicator IS=O, was reduced by the incorporation of the rejuvenating agent.; La croissance de caution vis-à-vis l'utilisation des produits pétroliers dans la construction a nécessité le besoin de développement des alternatives. Le BTP, en particulaire pour le secteur routière, a un certain nombre des piste ou les produits pétrolières ont utilisés, par exemple le liant pour les enrobés comme les agents régénérant (pour recyclage des enrobés), mais aussi le produits qui sont utilisés sur le chantier comme les anti-adhérents (ARA) et les débituminants (BR). Alors, il y a une besoin de remplacer les produits d'origines pétrolières par les alternatives bio-sourcés. Ce présent ouvre est une partie d'un projet qui va développer une nouvelle filière dédiée à la production de nouvelles formulations pour le BTP à partir de la transformation des huiles végétales et des graisses animales. Ce thèse concerne les produits développés seront destinés au l'asphalte, et alors, deux types d'applications sont particulièrement visés : (i) des agents anti-adhérents et (ii) des agents régénérants. Un débituminant sera développé aussi. Les produits anti-adhérents ont pour fonction d'empêcher le bitume d'adhérer aux engins de travaux sans effet secondaire, théoriquement, sur la matrice liante.. L'objet du travail est de caractériser l'efficacité et l'innocuité des agents anti-adhérents développés dans le cadre du projet et de développer les méthodes expérimentales visant à les évaluer. Trois essais principaux ont été développés pour caractériser la performance et innocuité des anti-adhérents vis-à-vis des essais qui ont optimisé leur implémentation et paramètres. La performance des anti-adhérents a été caractérisé par l'essai de glissance des enrobés. L'innocuité des anti-adhérents ont été caractérisés par des essais de fendage sur les enrobés et par l'essai de la dégradation de bitume. L'essai de la dégradation de bitume a servi aussi comme une mesure de la performance de débituminant. Les essais sur les anti-adhérents commerciaux d'Etats-Unis et la France a trouvé que ils ont deux modes de fonctionnement : i) lixiviation du bitume et ii) en formation d'une interface entre le les enrobés et la surface métallique. Même comme les deux modes ont été trouvé dans des certains anti-adhérents, le mode interface ont été trouvé préférable, grâce à l'option de garder les mêmes applications du produit pour plusieurs cycles de usage. Ensuite, un produit - basé sur glycérol sourcé de l'agro-industrie - a été développé. Les débituminants commerciaux ont été essayé, aves les conclusions : i) les débituminants plus effectifs ont eu les plus grande % des esters et ii) que les esters chaines courtes (C7-10) d'hautes concentrations ont été trouvé les plus efficace. L'agent régénérant est destiné à régénérer le bitume vieilli issu des agrégats d'enrobés (RAP) en lui redonnant ses propriétés originelles et en assurant leur maintien dans le temps. Le travail sur les agents régénérants se compose de la caractérisation physico-chimique du vieillissement du bitume et du bitume vieilli avec l'agent. Plus précisément, le travail se serve des techniques de spectrométrie IRTF (avec imagerie) et thermogravimétrie. Dans ce contexte, une produit bio-sourcé a été évalué comme une régénérant. Pour la spectroscopie FTIR, une moyenne de polir le mastique a été développé pour rassuré la platitude des échantillons. La régénération du bitume a été observé avec la spectrométrie ITRF, donc quelques peaks (notamment les indices IC=O and IS=O) pendant 0-42 jours de vieillissement dans l'étuve (loin-durée). Il a été trouvé qu'une période de vieillissement de 14 jours à l'étuve était à peu près équivalente au bitume vieilli par un cycle de RTFOT + PAV en termes de rhéologie et de la pénétration. Le mastic (vieilli 14 jours) a ensuite été mélangé avec un agent de bio-source (à 7,5% en poids de mastic). Il a été constaté par imagerie FTIR que l'indicateur de l'oxydation IS=O a été réduit par l'incorporation de l'agent régénérant dans le bitume.