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Eingeladener Vortrag
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Laser induced breakdown spectroscopy (LIBS) - visualization of ion transport processes in concrete
(2014)
Laser induced breakdown spectroscopy (LIBS) is a combination of laser ablation and optical emission spectroscopy. Due to the possibility of direct measurements on the sample surface and a minimum of sample preparation investigations of building materials can be conducted quite fast. In combination with a scanning technique (translation stage or scanning mirrors head) the element distributions are evaluated with mm resolution. Thus the heterogeneity of the material may be considered. This is a significant advantage compared to standard procedures. LIBS measurements are also time and cost saving in comparison to standard methods. The automated measurement procedures minimize the liability for errors. All elements are detectable. Results can be quantified after calibration. At BAM LIBS has been successfully applied for the investigation of distribution and transport of different ions in building materials. Quantitative measurements are performed for chlorine, sodium, potassium, sulfur, lithium and hydrogen. In addition the identification of substances and the evaluation of quantitative ratios by means of an integrated marker are possible. An overview about the principle and the possibilities of LIBS investigations of building materials is presented and typical applications are shown. The LIBS technique is close to practical application on-site.
Laser Induced Breakdown Spectroscopy (LIBS) is a combination of laser ablation, plasma formation and optical emission spectroscopy. The possibility of direct measurements on the sample surface, the minimum of necessary sample preparation and the automated setup allows for fast investigations of building materials. In combination with a scanning technique (translation stage or scanning mirrors head) the element distribution can be evaluated in consideration of the material's heterogeneity. LIBS measurements are also time-and cost-saving. The ingress profile of chlorine on a 50mm diameter concrete core up to a depth of 50mm can be measured and evaluated in less than 10 minutes. The results are normally referred to the evaporated mass, which is approximately the cement mass of the specific concrete. As a completion to micro XRF measurements also light elements like sodium or hydrogen can be detected. The spatial resolution of the measurement may reach 50 ìm at a maximum measurement frequency of up to 100 Hz. On the basis of calibration curves, results can be quantified.
The laser induced breakdown spectroscopy (LIBS) gives an alternative to the standard techniques for the direct investigation of a building material. It utilize a high energy pulsed laser beam for ablation and vaporization of a small amount of material, a plasma is formed and the plasma radiation is investigated using optical emission spectroscopy. Due to the principal all elements are detectable during one measurement. In combination with a translation stage or scanner system the heterogeneity of concrete is considered in the results. Thus an element concentration may be correlated to the cement content. After calibration with a set of reference samples quantitative results are obtained. The system is automated and allows rapid measurements and minimizes the possibility of errors. At BAM a laboratory LIBS system has been successful applied for the investigation of transport processes of different ions in building materials. The spatial resolution of the measurement may rich 100 μm and the frequency of the measurements is 100 Hz. The concentration of chlorine, sulfur, carbon, sodium, potassium, lithium and hydrogen where quantitatively determined. A mobile system for on-site analysis on bridges or parking decks is available. It is a tool for the estimation of the condition of concrete structures and for quality assurance during concrete repair work on-site. In these work an overview of the possibilities of LIBS for automated investigation of building materials are given.
Cracks are always present in reinforced concrete structures. In the presented research, influence of mechanical cracks on chloride ingress is studied. A compact reinforced concrete specimen was designed, mimicking the cracking behaviour of beam elements. Cracks of different widths were induced by means of mechanical loading. These cracked specimens were then subjected to weekly cycles of wetting and drying with NaCl solution. After the exposure, the specimens were cut, and chloride distributions were determined using Laser Induced Breakdown Spectroscopy (LIBS), an innovative technique which enables simultaneous determination of different elements with high spatial resolution and minimal specimen preparation. By combining element distributions of different elements, it is possible to discriminate between coarse aggregate particles, and the mortar matrix. It was found that the wider the crack is, the higher the ingress of chloride ions. This was, however, different for two tested concrete mixes. Due to highly inhomogeneous chloride distribution around the cracks, use of fine-scale experimental techniques for chloride mapping is advised, based on the presented study.
Cracks are always present in reinforced concrete structures. In the presented research, influence of mechanical cracks on chloride ingress is studied. A compact reinforced concrete specimen was designed, mimicking the cracking behaviour of beam elements. Cracks of different widths were induced by means of mechanical loading. These cracked specimens were then subjected to weekly cycles of wetting and drying with NaCl solution. After the exposure, the specimens were cut, and chloride distributions were determined using Laser Induced Breakdown Spectroscopy (LIBS), an innovative technique which enables simultaneous determination of different elements with high spatial resolution and minimal specimen preparation. By combining element distributions of different elements, it is possible to discriminate between coarse aggregate particles, and the mortar matrix. It was found that the wider the crack is, the higher the ingress of chloride ions. This was, however, different for two tested concrete mixes. Due to highly inhomogeneous chloride distribution around the cracks, use of fine-scale experimental techniques for chloride mapping is advised, based on the presented study.
Die Laser induzierte Breakdown Spektroskopie (LIBS) bietet für die Analyse heterogener, mineralischer Baustoffe, wie z. B. Beton, deutliche Vorteile gegenüber konventionellen Methoden. Sie ermöglicht neben der Quantifizierung von Elementgehalten und -verteilungen im Baustoff auch die Differenzierung von Elementkonzentrationen innerhalb einzelner Phasen im Baustoff. So können beispielsweise die für die Alkali-Kieselsäure-Reaktion (AKR) interessanten Natriumkonzentrationen bestimmt und hinsichtlich ihrer Verteilung aufgelöst werden. Es lassen sich Natriumgehalte, welche sich in der Gesteinskörung befinden, separat von denen der Betonmatrix bestimmen. Der vorliegende Artikel befasst sich mit den Vor- und Nachteilen von LIBS als alternative Methode für die chemische Analyse von Baustoffen. Anhand von Beispielen aus der Praxis wird der derzeitige Stand der Technik dargestellt und ein Vergleich mit etablierten Messmethoden vorgenommen. Compared to conventional methods the Laser Induced Breakdown Spectroscopy (LIBS) provides significant advantages for analysis of heterogeneous, mineral building materials as e.g. concrete. Besides providing the possibility to quantify element concentrations and distributions in building materials, this technique enables also to differentiate concentrations within different phases of the material. It is possible to determine sodium concentrations and distribution directly, which e.g. is important when regarding Alkali-Silica-Reaction (ASR). Sodium contents provided by the aggregates can be distinguished from those provided by the concrete matrix. The present article is concerned with the advantages and disadvantages of LIBS as alternative method for chemical analysis of building materials. On the basis of samples from practice the current state of the art is shown and different measurement techniques will be compared.
LIBS is on the step from a laboratory application to on-site analysis. A validated mobile LIBS-system for on-site application on building materials is under development at BAM in cooperation with industrial partners (system developers and companies), who will use this technique for investigation on building structures like bridges and parking decks. The system is designed to measure the content of harmful species like chlorine, sulfur or alkalis, to give the engineer a tool for the estimation of the condition of concrete structures and for quality assurance during concrete repair work on-site. In these work results of on-site measurements on a chloride contaminated bridge are shown. Further work will focus on providing guidelines to establish LIBS as a standard procedure for chemical investigations of building materials.
Parkhaus "Am Gericht" in Frankfurt am Main - Eine Sanierung mit kathodischem Korrosionsschutz
(2007)
Parkhäuser haben nach mehreren Jahrzehnten der Nutzung häufig Sanierungsbedarf in Bezug auf die tragende Stahlbetonkonstruktion, die durch eingedrungene Chloride aus eingeschlepptem Tausalz und die hierdurch hervorgerufene Korrosion der Bewehrung in der Tragfähigkeit erheblich beeinträchtigt sein kann. Das Verfahren des kathodischen Korrosionsschutzes kann hier als elektrochemisches Instandsetzungsverfahren eine wirtschaftliche und zuverlässige Alternative zu herkömmlichen Sanierungsverfahren bieten. Voraussetzungen sind intensive Voruntersuchungen, die Kenntnis der sinnvollen Anwendungsgrenzen des Systems, eine qualitativ hochwertige bauliche Umsetzung des Systems und die Nutzung der Möglichkeiten der Überwachung des Instandsetzungserfolges durch Monitoring, was am Beispiel des Parkhauses Am Gericht in Frankfurt am Main erläutert wird.
Parking garage Am Gericht in Frankfurt am Main - a refurbishment with cathodic corrosion protection.
After several decades in use a refurbishment is often necessary for the bearing structure of reinforced concrete parking garages due to chlorides, which have been brought into concrete by road salt, and the resulting corrosion of the reinforcement, which may lead to a serious decrease of the bearing capacity. With the system of the cathodic protection of the reinforcement exists a cost-effective and reliable technique as an alternative to common solutions. An intensive investigation of the structure, the knowledge of the reasonable limits of the system, excellent design and execution of the construction work and the monitoring of the working system are nevertheless required, which is illustrated by the example of the parking garage Am Gericht in Frankfurt am Main.
Pitting corrosion of carbon steel and iron in chloride containing alkaline environment is already well investigated, although a couple of questions are not clarified satisfactorily. The critical chloride content for steel in concrete and the critical chloride to hydroxide ion ratio for steel in alkaline solutions is still a major concern, considering chloride induced corrosion problems of steel in concrete. Another not satisfactorily clarified point is the repassivation of carbon steel in consequence of cathodic polarization. In the recent literature some indications are shown that repassivation occurs after a certain time of polarization. GLASS [4-9] and PEDEFERRI [1-3] draw the conclusion that the ennoblement of open circuit potentials (OCP) indicates re-passivation effects due to cathodic polarization. SAGÜÉS [10] carried out potentiodynamic repassivation tests and draws the conclusion that the repassivation potential Er is nearly independent of the solution composition, but influenced by severity of corrosion attack and is in the potential range from - 0.8 V to - 0.4 V vs. Saturated Calomel Electrode (SCE). The transferability of SAGÜÉS results to questions concerning cathodic protection (cp) is questionable, as potentiodynamic polarization tests (PPT) give no information on changes induced by long time polarization.
Therefore, the investigations discussed in this paper aim to clarify, to what extend the re-passivation of carbon steel due to cathodic polarization occurs, and if the ennoblement of OCP is a sufficient indication for repassivation. In a first step the corrosion state of five nominal equal test specimens was determined by electrochemical techniques, i.e. electrochemical noise measurements (ENM) and electrochemical impedance spectroscopy (EIS). After determining the initial corrosion state by evaluating the charge transfer resistance and the polarization resistance respectively as well as evaluating potential and current noise signals, the specimens were polarized cathodically. Impedance data were recorded previous to, during and after polarization. The impedance data were evaluated by equivalent circuit fitting with special attention to charge transfer resistances and diffusion properties. The results show that reduction of oxides and oxygen diffusion during cathodic polarization has strong impact on the systems behavior.