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Bei der Erhaltung von Stahlbetonbauwerken ist der Chloridgehalt im Beton ein wichtiger Parameter zur Festlegung geeigneter Instandsetzungsmaßnahmen. Die bisher etablierten Verfahren basieren auf der nasschemischen Analyse einer Probe, Bohrmehl oder aufgemahlener Segmente eines Bohrkerns. Das Verfahren liefert einen Chloridgehalt je Tiefensegment, was mit einer starken Homogenisierung der Probe einhergeht, wodurch detaillierte Informationen zu Chloridunterschieden im Millimeterbereich verloren gehen. Eine alternative Methode ist die laserinduzierte Plasmaspektroskopie (LIBS), die nicht nur die quantitative ortsaufgelöste Bestimmung des Chloridgehalts im Bezug zur Zementmasse ermöglicht, sondern auch simultan detaillierte Informationen über die Verteilung vieler anderer chemischer Elemente liefert. Die räumliche Auflösung liegt in der Regel im Bereich von einigen Millimetern, kann aber bei Bedarf auf 0,1 mm oder weniger erhöht werden. Das neue Merkblatt B14 „Quantifizierung von Chlorid in Beton mit der laserinduzierten Plasmaspektroskopie (LIBS)“ der Deutschen Gesellschaft für Zerstörungsfreie Prüfungen (DGZfP) regelt und vereinheitlicht erstmals die zuverlässige und reproduzierbare Ermittlung des Chloridgehalts mit LIBS. In diesem Beitrag wird das Merkblatt vorgestellt und anhand praktischer Anwendungsbeispiele das Potenzial von LIBS für Fragestellungen in der Betonerhaltung verdeutlicht.
Die chemische Analyse von Beton gehört bei der Ermittlung des Ist-Zustandes von Stahl- und Spannbetonbauwerken zu den grundlegenden Untersuchungen bei der Zustandserfassung. Der tiefenabhängige Chloridgehalt sowie der Karbonatisierungsfortschritt müssen bei der Bewertung des Ist-Zustandes, beim Instandsetzungsbedarf und ggf. bei der Planung eines erforderlichen Instandsetzungskonzeptes mit einbezogen werden. Seit Mitte der 1990er Jahre wird an der Bundesanstalt für Materialforschung und -prüfung die laserinduzierte Plasmaspektroskopie (engl. Laser-induced Breakdown Spectroscopy) – kurz LIBS – stetig für die chemische Analyse von Beton weiterentwickelt. In diesem Beitrag wird der aktuelle Stand der Forschung/ Technik und der Normungsarbeit präsentiert, sowie zukünftig mögliche Anwendungen vorgestellt. Mit den aktuellen LIBS-Systemen (mobiles LIBS-System sowie kommerziell erhältliche Laborsysteme) ist es möglich den Chloridgehalt ortsaufgelöst in wenigen Minuten zu quantifizieren, sogenannte Elementlandkarten zu erstellen und somit die Elementverteilung innerhalb des Betons zu visualisieren. Durch das Scannen eines Bohrkernquerschnittes und der simultanen Erfassung von mehreren Elementen mit einer Messung, ist es zudem möglich, die Gesteinskörnung in den Messdaten zu identifizieren und den Chloridgehalt auf die Zementsteinmatrix zu beziehen. Fehlerquellen aus der Umrechnung der betonbezogenen Chloridgehalte können dadurch minimiert werden. Neben den Grundlagen von LIBS werden vor allem aktuelle Praxisbeispiele vorgestellt, die die aktuellen Möglichkeiten des Verfahrens veranschaulichen.
The effect of particle grain sizes in different cement-based mixtures on the laser-induced plasma evolution is studied using two experimental methods: (i) temporal and spatial evolution of the laser-induced shock wave is investigated using shadowgraphy and two-dimensional plasma imaging, and (ii) temporal and spatial distribution of elements in the plasma is investigated using two-dimensional spectral imaging. This study is motivated by the interest in applying laser-induced breakdown spectroscopy (LIBS) for chemical analysis of concrete, and subsequently obtain information related to damage assessment of structures like bridges and parking decks. The distribution of grain sizes is of major interest in civil engineering as for making concrete different aggregate grain sizes defined by a sieving curve (64mm to 0.125 mm) are needed. Aggregates up to a size of 180 μm can be excluded from the data set, therefore only the amount of small aggregates with a grain size below 180 μm must be considered with LIBS. All components of the concrete with a grain size smaller than 0.125mm are related to the flour grain content. Tested samples consisted of dry and hardened cement paste (water-cement ratio w/z=0.5), which served as a reference. Aggregate mixtures were made by adding flour grains (size 40 μm) and silica fume (size 0.1 μm) in different ratios to cement: 10%, 30%, 50% and 60%, all combined to the remaining percentage of dry or hydrated cement. The visualization results show that a dependance in the evolution of the plasma as a function of sample grain size can be detected only in the initial stages of the plasma formation, that is, at the initial 3 μs of the plasma life. Spectral information reveals the elemental distribution of the silicon and calcium in plasma, in both neutral and ionized form. Here also, a significant effect is observed in the first 1 μs of the plasma lifetime.
Due to the penetration of harmful chlorides into concrete, e.g. from de-icing salt, damage processes such as chloride-related pitting corrosion can occur if critical values are exceeded. In this study, multiphase materials such as chloride-contaminated concrete are examined in detail. A direct comparison is made by analyzing the spectroscopic information of simultaneously measured atomic and molecular emissions with laser-induced breakdown spectroscopy (LIBS). In addition, the influence on the calibration is examined on the basis of the combined spectral information of both reaction paths of the penetrated chlorides. The calibration models of univariate and multivariate methods were validated using reference samples with wet chemical analysis. The results are applied to a concrete sample of a parking deck, which was also analyzed by potentiometric wet chemistry. In order to account for the heterogeneity of concrete, spatially (200 μm) and spectroscopically (0.1 nm) resolved LIBS measurements were performed using a fully automated laboratory system. Simultaneous measurements with three spectrometers allow the analysis of the emission processes of several elements such as Cl, Ca, O, Si and Mg as well as the newly formed molecules CaO and CaCl. The evaluation of the molecular emission in combination with atomic lines extends the analytical performance, since different concrete phases such as aggregates and cement matrix can be better represented. The measurements were carried out in ambient air and with helium purge gas. The limit of detection (LOD) achieved for a combined evaluation of atomic and molecular emission was determined to be 0.028 wt%.
The analysis of the chemical composition of cement-based materials like concrete is a crucial task in civil engineering. Concrete is a multi-phase material made of cement, water, aggregates, additives and admixtures. During the damage assessment of concrete structures, the external ingress of harmful species like chlorine, alkalis or sulfates needs to be determined. In order to provide a fast and precise analysis of concrete the application of LIBS offers unique possibilities as the technique can detect all elements at air atmosphere.
To determine the condition of concrete, the information about the chemical composition, the ingress of harmful species as well as the evaluation of characteristic values like the used cement type or the type of aggregates are needed. This work presents the two-dimensional evaluation of concrete samples using LIBS and multivariate data analysis of atomic and molecular emission. For the evaluation of the main components different classification methods will be applied to identify the heterogeneity of the samples. With respect to their specific phase, different species will be quantified using multivariate regression (PLS) and important figures of merit will be presented. All results will be verified using Standard procedure of wet chemistry (XRF, potentiometric titration and ICP-OES).
In civil engineering concrete is the most used building material for making infrastructures like bridges and parking decks worldwide. It is as a porous and multiphase material made of aggregates with a defined grain size distribution, cement and water as well as different additives and admixtures depending on the application. Different grain sizes are important to ensure the needed density and compressive strength.
The resulting porous cement matrix contains a mixture of flour grains (aggregates with a grain size below 125 lm) and cement particles (particle size≈50lm). Harmful species like chlorides may penetrate together with water through the capillary pore space and may trigger different damage processes. The damage assessment of concrete structures in Germany is estimated due to the quantification of harmful elements regarding to the cement content only. In the evaluation of concrete using LIBS a two-dimensional scanning is necessary to consider the heterogeneity caused by the aggregates. Therefore, a LIBS system operating with a low energy NdCr:YAG laser, a pulse energy of 3 mJ, a wavelength of 1064 nm, a pulse width of 1.5 ns and a Repetition rate of 100 Hz has been used. Different Czerny-Turner spectrometers with CCD detectors in the UV and NIR range have been used for the detection. Large aggregates (macro-heterogeneity) can be excluded from the evaluation, whereas small aggregates in the range of the laser spot size (flour grains) cannot be spatially resolved. In this work the micro heterogeneity caused by flour grains and their impact on the quantification with LIBS will be discussed. To analyze the effect of changing grain sizes and ratios, the ablation behavior has been determined and compared. Samples with defined grain sizes were made and analyzed using LIBS.
The grain size distributions were analyzed with laser diffraction (LDA).
The determination of chloride is still one of the main tasks for the evaluation of reinforced concrete structures.
The corrosion of the reinforcement induced by the penetrating chlorides is the dominant damage process affecting the lifetime of concrete structures. In the recent years different research groups demonstrated that LIBS can be a fast and reliable method to quantify chlorine in cement-bound materials. Because chlorine in concrete can only occur as solved ions in the pore solution or bound in salts or hydrated cement phases, the detected emission of chlorine can be correlated with the chloride concentration determined e.g. with potentiometric titration. This work inter alia describes the production of reference samples and possible side effects during the production process. Due to transport processes in the porous matrix of the cement a misinterpretation of the concentrations is possible. It is shown how to overcome these effects and higher precisions of the single measurements can be realised. Using the calibration method, blank sample method and noise method, three different ways of calculating the limit of detection (LOD) and limit of quantification (LOQ) are compared. Due to the preparation of the reference samples a precision of the whole calibration model of sx0 = 0.023 wt% is determined.
The validation of the model is based on different test sets, which are varying in their composition
(different Cl-salts, water-to-cement ratios and additives). The determined mean error of the validation is
0.595 ± 0.063 wt%, which is comparable to standardised methods like potentiometric titration, direct potentiometry
or photometry (0.40 ± 0.06 wt%) [1].
In civil engineering, the laser-induced breakdown spectroscopy has been applied as a fast and reliable method for a quantitative evaluation of concrete cores. Due to a two-dimensional scanning, the heterogeneity of concrete can be evaluated and elements like Cl, Na, and S are related to the cement matrix only. This study deals with the temporal evaluation and imaging of laser-induced plasmas on cement-based materials, in order to investigate the impact of aggregates with diffrent grain size on the spectral response in LIBS.
A big part of the infrastructure is made of concrete, which is a multiphase system made of cement, aggregates, water and pores. Concrete is often used in combination with steel as reinforced concrete. Environmental influences, especially the ingress of harmful ions in combination with the ingress of water, trigger different damage processes which reduce the designed lifetime of a structure. The ingress of chlorides from de-icing salt or sea water leads to corrosion of the reinforcement. In addition, the carbonation of the concrete may trigger the corrosion of the reinforcement. The ingress of alkalis from deicing salts may cause the expansion of the amorphous silica aggregates (alkali-silica reaction) through
formation of a swelling gel of calcium silicate hydrate if water is present. The ingress of sulphates may cause spalling of the concrete surface due to ettringite formation.
For the standard procedure in civil engineering cores are taken, cut in slices, grinded and the obtained homogenized powder is solved in acid and investigated by standard procedures.
BAM has developed the LIBS technique for the 2D evaluation of the chemical composition of concrete. The technique is established for automated laboratory use with high numbers of samples to investigate transport processes of harmful species (Cl-, CO2 , SO4 2-and alkalis) in concrete. Information about ingress depth and the quantitative values are important to estimate the remaining lifetime of the infrastructure. LIBS is a surface technique. To get information about the ingress depth, a drill core has to be taken and cut in the middle. The measurements are carried out at the cross section. The main advantages of LIBS are the direct measurement on the surface of the concrete, fast analysis (sample rate 100 Hz) with a spatial resolution of up to 100 µm, the consideration of the heterogeneity of the concrete and the possibility of automated measurements which save a lot of manpower and time. As an example the investigation of ingress profiles for standard diffusion and migration tests in civil engineering takes hours in comparison to just a few minutes using LIBS. At the same time a 2D-evaluation provides information about hot spots of elemental concentration which may not be found by standard methods.
The state of the art of LIBS technique for applications in civil engineering will be presented, including typical results of 2D investigation of concrete in laboratory. The performance is also demonstrated by examples for onsite applications using a mobile LIBS system. The road map to standardization is presented as well.
Die Laserinduzierte Plasmaspektroskopie (engl.: Laser-induced Breakdown Spectroscopy, kurz: LIBS) ist eine Kombination aus Laserablation mittels eines energiereichen Laser-Pulses, der Erzeugung eines Plasmas auf der zu untersuchenden Oberfläche und dem quantitativen Nachweis der Elementzusammensetzung durch spektroskopische Untersuchung der vom Plasma emittierten Strahlung. Ein LIBS-Gerät liefert dem sachkundigen Planer Daten für die Bewertung des Ist-Zustandes von Bauwerken unserer Infrastruktur durch die zweidimensionale Erfassung von Elementverteilungen. Typische Anwendungen sind die Erfassung von Chlor, Schwefel, Kohlenstoff, Natrium, Kalium und Lithium in Beton oder als – Qualitätssicherung – der Nachweis der mit einem Marker versehenen Tiefenhydrophobierung.
In Zusammenarbeit zwischen Industriepartnern und der BAM wurden ein Labor und ein mobiles LIBS-System für die Vor-Ort-Messungen entwickelt. Die Analyse erfolgt vollautomatisch. Die Ortsauflösung beträgt bis zu 0,1 mm x 0,1 mm. Es können Messflächen von 140 mm x 170 mm gescannt werden. Die Erstellung von 2D-Elementverteilungen im Beispiel unten benötigt weniger als 10 Minuten.