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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).
Accuracy of calibration-free (CF) methods in laser-induced breakdown spectroscopy (LIBS) depends on experimental conditions and instrumental parameters that must match a CF LIBS model. Here, the numerical study is performed to investigate effects of various factors, such as the optical density, plasma uniformity, line overlap, noise, spectral resolution, electron density and path length on the results of CF-LIBS analyses. The effects are examined one-by-one using synthetic spectra of steel slag samples that fully comply with the mathematical model of the method. Also, the algorithm includes several new features in comparison with previously proposed CF algorithms. In particular, it removes limits on the optical thickness of spectral lines that are used for the construction of the Saha-Boltzmann plot; it retrieves the absorption path length (Plasma diameter) directly from spectral lines; it uses the more realistic Voigt line profile function instead of the Lorentzian function; and it employs the pre-calculated and tabulated thin-to-thick line ratios instead of approximating functions for selfabsorption correction.
Analyse des Tausalzeintrages in Fahrbahndeckenbetone im Kontext der Alkali-Kieselsäure-Reaktion
(2018)
In den letzten Jahren sind im deutschen Bundesautobahnnetz (BAB-Netz) vermehrt AKR-Schäden an Betonfahrbahndecken aufgetreten, die zum Teil zu einer Halbierung ihrer geplanten Nutzungsdauer von 30 Jahren führte. Ursächlich hierfür ist die Verwendung alkaliempfindlicher Gesteinskörnung, die bei gleichzeitiger Anwesenheit von Wasser infolge der Exposition der Fahrbahndecke und dem alkalischen Milieu durch den Einsatz alkalireicher Portlandzemente bei der Betonherstellung zu einer Alkali-Kieselsäure-Reaktion (AKR) führt. Zusätzlich wird der AKR-Schädigungsprozess in Betonfahrbahndecken durch den externen Tausalzeintrag (primär NaCl) im Winter begünstigt. Vor diesem Hintergrund kommt der Ermittlung des Tausalzeintrags in den Fahrbahndeckenbeton eine große Bedeutung zu. Die Analyse des Tausalzeintrags erfolgte bisher ausschließlich nasschemisch an gemahlenen Bohrkernsegmenten. Nachteilig ist hierbei die fehlende differenzierte Betrachtung des Natriumgehaltes im Zementstein und in der Gesteinskörnung. Der alternative Einsatz von LIBS (Laser-induced breakdown spectroscopy) eröffnet in diesem Kontext neue Möglichkeiten. So wird in diesem Beitrag an Hand von Bohrkernen aus einem AKR-geschädigten BAB-Abschnitt exemplarisch die Vorgehensweise bei der LIBS-Analyse zur Ermittlung der Na- und interagierenden Cl-Verteilung an vertikalen Schnittflächen des Bohrkerns aufgezeigt. Da der Tausalzeintrag primär über den Zementstein erfolgt, wurde der verfälschende Na-Grundgehalt der Gesteinskörnung mittels Zementsteinkriteriums (Nutzung unterschiedlichen Ca-Gehalts in Zementstein und Gesteinskörnung) eliminiert. Vergleichend durchgeführte Cl-Mappings mit Mikroröntgenfluoreszenzanalyse (MRFA) belegen die Güte der durchgeführten LIBS-Messungen.
Aber auch bei der Verifizierung der Übertragbarkeit der Ergebnisse der zum Ausschluss reaktiver Gesteinskörnung bei Neubau und Erneuerung im BAB-Netz eingesetzten Performanceprüfungen mit externem Alkalieintrag auf Praxisverhältnisse hat sich das LIBSVerfahren bewährt. So wurde festgestellt, dass die mit NaCl-Lösung beaufschlagten Laborprüfkörper aus einem repräsentativen Fahrbahndeckenbeton bei der Klimawechsellagerung (KWL) über ihre gesamte Höhe von 10 cm einen Eintrag von Na und Cl erfahren. Weiterhin konnte im Gegensatz zu bisherigen Annahmen erstmals mit LIBS und Nasschemie gezeigt werden, dass die Frost-Tauwechsel-Phase bei der KWL zu keinem erhöhten Tausalzeintrag führt.
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].
This paper will address the relevance of chloride measurements in practice for durability condition assessment and a description of the working principle of LIBS will be given. Examples of chloride profiles obtained by the common wet chemical analysis will be shown and compared with results from LIBS measurements as to demonstrate the accuracy of the LIBS-technique. The latter will be supported by clear graphs. In addition examples on the extra information resulting from measurements performed with LIBS for improvement of condition assessment and prediction will be shown.
The relevance of chloride measurements in practice for durability condition assessment and a description of the working principle of LIBS will be given. A comparison of chloride profiles obtained by the common wet chemical analysis and results from LIBS measurements are shown to demonstrate the accuracy of the LIBS-technique. In addition, an example on the extra information resulting from measurements performed with LIBS for improvement of condition assessment and prediction will be shown.
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. Also the carbonation of the concrete may trigger the corrosion of the reinforcement. The ingress of alkalis from de-icing 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 sulfates may cause spalling of the concrete surface due to ettringite formation.
BAM has developed the LIBS technique for automated laboratory use with high numbers of samples to investigate transport processes of harmful species (Cl-, CO2, SO42- and alkalis) in concrete. Information about ingress depth and the quantitative values are important to estimate the remaining lifetime of the infrastructure. To get information about the ingress depth, a 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. The possibility of automated measurements saves a lot of manpower and time. At the same time a 2D-evaluation provides information about hot spots of elemental concentration which may not be found by standard methods.
Typical results of 2D investigation of concrete in laboratory will be presented. 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 „Laser Induced Breakdown Spectroscopy“ (LIBS) bietet die Möglichkeit, direkt auf der optisch zugänglichen Oberfläche von Baustoffen 2-dimensional die Elementverteilung zu erfassen. Durch das zugrundeliegende Prinzip sind alle Elemente des Periodensystems detektierbar, auch leichte Elemente wie Wasserstoff oder Lithium.
Einerseits können alle für die Zusammensetzung des Zementes und der Gesteinskörnung relevanten Elemente erfasst werden, andererseits auch die für Schädigungsprozesse in Beton wichtigen Elemente Chlor, Schwefel, Natrium, Kalium, Kohlenstoff und Stickstoff. Der Nachweis kann simultan erfolgen.
Der Vorteil des Verfahrens liegt in der einfachen Probenvorbereitung, der direkten Messung auf der Oberfläche des Festkörpers und der Schnelligkeit der Messung. Die Heterogenität von Beton wird im Ergebnis berücksichtigt. Die Konzentrationen von schädigenden Ionen lassen sich bezogen auf den Bindemittelgehalt angeben. LIBS liefert standardmäßig qualitative Werte. Durch Kalibrierung anhand von Referenzproben ist eine Quantifizierung der Ergebnisse möglich.
Das Potenzial des Verfahrens wird am Beispiel der Bestimmung der Chlorid-Verteilung in der Bindemittelmatrix vorgestellt. Andere Anwendungen sind die Bestimmung der Karbonatisierungstiefe, die Bestimmung des Eintrages von Alkalien oder die Bestimmung der Verteilung von Schwefel.
Das Verfahren kann im Labor zur Untersuchung einer großen Anzahl von Proben oder vor-Ort zur schnellen Entscheidungsfindung eingesetzt werden. Kommerzielle Geräte sind seit kurzem verfügbar.
Die örtliche Auflösung der Messung beträgt bis zu 0,1 mm × 0,1 mm. Ein Messpunkt hat einen Durchmesser von ca. 100 μm. Die Messfrequenz liegt bei 100 Hz. Als Ergebnis entstehen für jedes Element eine 2D-Darstellungen der Konzentration über der Messfläche.
Der Scan eines Bohrkerns von 50 mm x 70 mm dauert bei einer Auflösung von 0,5 mm lateral und 1 mm vertikal ca. 7 min. Es können auch raue oder gebrochene Oberflächen durch Nachführung der z-Achse untersucht werden. Die Nachweisgrenze für die Bestimmung des Chlorgehaltes bezogen auf den Bindemittelgehalt liegt bei 0,03 M-%.
Der Unterausschuss LIBS im Bauwesen im FA ZfP im Bauwesen der DGZfP arbeitet an der Erstellung von Merkblättern und Regelwerken zur Anwendung des Verfahrens.
For the determination of the remaining life-time and the degree of damage of reinforced concrete structures such as marine construction, bridges or parking decks, a highly precise measurement of harmful species is also required for trace elements. One of the most interesting elements is chlorine, because above a certain threshold corrosion is triggered. To increase the intensity of the chlorine line, helium is usually used, which is costly. To overcome this problem, low electrical discharge reheating is used which operates in air atmosphere. A comparison between results obtained by measuring with helium and reheating by electrical discharge is presented. The performance is compared by the resulting calibration curves and the calculated limit of detection obtained by 15 reference samples based on cement with NaCl. Concentrations of reference samples range from 0.05 to 2.5 wt% chlorine.
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.
The Laser-induced Breakdown Spectroscopy (LIBS) is an useful analytical technique for the chlorine detection in building materials, specifically in the reinforcement concrete. If chlorine exceeds a specific concentration threshold, the result can be pitting corrosion of the reinforcement, which affects the stability and lifetime of building structures like marine constructions, bridges or parking decks. The critical chlorine content based to cement is 0.4 wt.-% based to the cement for reinforced concrete. The ingress of chlorides from sea water or de-icing salt leads to corrosion of the reinforcement.
The chlorine spectral line Cl I at 837.59 nm shows a good performance in helium atmosphere. For measurements without helium we used a electric discharge setup to reheat the Laser-induced plasma with a voltage below 100 V. In this case the reheating shows an increasing chlorine emission in air atmosphere.
This work shows chlorine calibration curves with LIBS in a helium flow and LIBS with electric discharge reheating in air atmosphere. The determination of the limit of detection (LOD) for both setups and the measurement results of a drill core sample with a quantitative chlorine ingress profile will be presented.
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.
In den letzten Jahren sind im deutschen Bundesautobahnnetz vermehrt AKR-Schäden an Betonfahrbahndecken aufgetreten. Ursächlich hierfür ist die Verwendung alkaliempfindlicher Gesteinskörnung. Dies führt bei gleichzeitiger Anwesenheit von Wasser infolge der Exposition der Fahrbahndecke und des alkalischen Milieus durch den Einsatz alkalireicher Portlandzemente bei der Betonherstellung zu einer Alkali-Kieselsäure-Reaktion (AKR). Zusätzlich wird der AKR-Schädigungsprozess in Betonfahrbahndecken durch den externen Tausalzeintrag (primär NaCl) im Winter begünstigt. Vor diesem Hintergrund kommt der Ermittlung des Tausalzeintrags in den Fahrbahndeckenbeton eine große Bedeutung zu.
Die Analyse des Tausalzeintrags erfolgte bisher ausschließlich nasschemisch an gemahlenen Bohrkernsegmenten. Nachteilig sind hierbei der relativ hohe prüftechnische Aufwand und die eingeschränkte Ortsauflösung. Der alternative Einsatz von LIBS (Laser-induced breakdown spectroscopy) eröffnet in diesem Kontext neue Möglichkeiten. So wird in diesem Beitrag anhand von Bohrkernen aus einem repräsentativen AKR-geschädigten BAB-Abschnitt exemplarisch die Vorgehensweise bei der LIBS-Analyse zur Ermittlung der Na- und Cl-Verteilung an vertikalen Schnittflächen von Bohrkernen aufgezeigt. Da der Tausalzeintrag primär über den Zementstein erfolgt, wurde der verfälschende Na-Grundgehalt der Gesteinskörnung mittels eines Ausschlusskriteriums (Ca-Gehalt) eliminiert. Vergleichend durchgeführte Cl-Mappings mit Mikroröntgenfluoreszenzanalyse sowie nasschemische Analysen belegen die Güte der durchgeführten LIBS-Messungen. Allerdings bedarf es bei der quantitativen Ermittlung des Natriumgehaltes in der Betonfahrbahndecke noch weitergehender Untersuchungen.
Two calibration-free LIBS techniques are used for the quantitative analysis of synthetic cement samples: the CF-LIBS based on the Boltzmann plot method and the Monte Carlo (MC) LIBS based on the iterative spectrum fitting. In CF-LIBS, the inverse problem is solved, i.e. the elemental concentrations are determined by the reconstruction of plasma parameters from spectra. The MC-LIBS technique solves the direct problem by finding the highest correlation between the model-generated and experimental spectrum. The accuracy of both calibration-free LIBS methods suffers from factors such as inaccurately determined instrumental function, the deviation of experimental plasma from the mathematical model used, not taking into account the collection geometry and from the uncertainty of spectroscopic data. Therefore, the both calibration-free LIBS approaches are applied to synthetic spectra which perfectly suit the mathematical model of the method. This test yields the accuracy of both the approaches for the ideal case. In addition, the accuracy of both methods is investigated for non-isothermal plasma, because real laser-induced plasma often has high gradients in temperature. Both methods assume an isothermal plasma.
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.
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.
Auf dem Weg zum gläsernen Beton neues Analyseverfahren mit laserinduzierter Plasmaspektroskopie
(2018)
Die laserinduzierte Plasmaspektroskopie (LIPS) oder englisch: Laser Induced Breakdown Spectroscopy (LIBS) ist eine Kombination aus Laserablation mittels energiereichem Laser-Puls, der Erzeugung eines Plasmas auf der zu untersuchenden Oberfläche und dem quantitativen Nachweis der Elementzusammensetzung durch die spektroskopische Untersuchung der vom Plasma emittierten Strahlung. Das Verfahren wird z. B. in der Prozessanalytik, der Sortierung von Rest- und Rohstoffen oder zur Qualitätssicherung in der pharmazeutischen Industrie angewendet.
Das LIPS arbeitet scannend und liefert die zweidimensionale Verteilung der Konzentrationen ausgewählter Elemente – und das auch auf rauen Oberflächen. Alle Elemente können auch gleichzeitig erfasst werden. Damit lassen sich beispielsweise Unterschiede im Eindringverhalten von Chlor und Natrium dokumentieren. Nach einer Kalibrierung stehen quantitative Werte zur Verfügung.
Zurzeit sind Geräte für automatisierte Messungen im Labor und vor Ort verfügbar. Die scannende Messung, mit einer Ortsauflösung von bis zu 80 µm, erfasst die Heterogenität des Betons. Damit kann die ermittelte Konzentration direkt auf den Bindemittelgehalt bezogen werden. Die Messfrequenz beträgt aktuell 100 Hz. Beispielsweise dauert die Erfassung des Chlorgehaltes in einem Bohrkern mit 50 mm Durchmesser und einer Länge von 80 mm, bei drei Mittelungen pro Messpunkt und einer Auflösung von 0,5 mm, nur 8 Minuten. Das Ergebnis steht direkt nach der Messung als „Elementlandkarte“ zur Verfügung. Durch die hohe Ortsauflösung des Verfahrens können z. B. fundiertere Eingangsparameter für Modellrechnungen erzeugt oder der Transport durch Risse visualisiert werden.
Ein LIPS-Gerät liefert Daten für die Bewertung des Istzustandes von Infrastrukturbauwerken. Typische Anwendungen sind die Erfassung von Chlor, Schwefel, Kohlenstoff, Natrium, Kalium und Lithium im Beton oder der Nachweis, der mit einem Marker versehenen Tiefenhydrophobierung, welcher zur Qualitätssicherung herangezogen wird.
Die Messungen sind schnell und automatisiert, so dass eine große Anzahl von Betonkernen in kurzer Zeit ausgewertet werden kann. Die Nachweisgrenze für die Bestimmung der Chlorid-Konzentration liegt mit 0,04 % deutlich unterhalb der allgemein akzeptierten Grenze für die Initiierung der Bewehrungskorrosion von 0,5 % (bezogen auf den Bindemittelgehalt). Dies bestätigten auch Vor-Ort-Messungen, wo Staub und Erschütterungen wenig Einfluss auf die Ergebnisse hatten und das Messsystem sich als stabil und robust erwiesen hat.
Eine technische Spezifikation und Regeln für die Anwendung des Verfahrens erarbeitet der neu gegründete Unterausschuss LIBS im Fachausschuss Zerstörungsfreie Prüfung im Bauwesen der Deutsche Gesellschaft für Zerstörungsfreie Prüfung e.V..
The majority of the built 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. Also the carbonation of the concrete may trigger the corrosion of the reinforcement. The ingress of alkalis from de-icing 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 sulfates 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 [1-11]. The technique is established for automated laboratory use with high numbers of samples to investigate transport processes of harmful species (Cl-, CO2, SO42- 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 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.
Ingress of chlorides due to a crack in a repair mortar. Left: Photo of the cross section of a concrete core and the surface investigated by LIBS (area 70 mm x 70 mm). Right: Color coded chlorine intensity on the cross section of a concrete core, dark red represents high chlorine content.
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.
Detection of ion ingress by LIBS for Evaluation of the remaining lifetime of a concrete structure
(2018)
The majority of the built 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. Also the carbonation of the concrete may trigger the corrosion of the reinforcement. The ingress of alkalis from de-icing 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 sulfates 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 [1-11]. The technique is established for automated laboratory use with high numbers of samples to investigate transport processes of harmful species (Cl-, CO2, SO42- 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 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.
Ingress of chlorides due to a crack in a repair mortar. Left: Photo of the cross section of a concrete core and the surface investigated by LIBS (area 70 mm x 70 mm). Right: Color coded chlorine intensity on the cross section of a concrete core, dark red represents high chlorine content.
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.
Quantitative on-site analysis of harmful elements in building structures with a mobile LIBS-System
(2018)
Environmental influences and damage processes drastically reduce the durability of concrete and reinforced concrete structures. Much of this damage can be traced back to the penetration of harmful elements into the concrete. These elements cause damage processes such as the chlorine-induced corrosion, the alkali-silica reaction or the carbonization. For the maintenance the knowledge of the element concentration and the penetration depth of these harmful elements is essential. Based on this data, a maintenance concept can be developed and an estimation of the remaining service life-time can be carried out.
Typically, chemical analyzes are used to determine harmful elements in concrete, which are costly and time consuming. As an alternative method LIBS is used. On-site measurements were carried out with a mobile LIBS-System to determine harmful elements in a parking garage. A scanner is used to obtain a two-dimensional element mapping. For the quantitative analysis, a calibration of the system is carried out with 15 reference samples based on cement with NaCl with a concentration range of chlorine of 0.05 to 2.5 wt.%. To determine the penetration profile of the harmful element chlorine, concrete cores were drilled, split and analyzed directly on-site.
The durability and the lifetime of reinforced concrete structures can be drastically reduced by the influence of damage processes. One of the most common causes is chloride-induced corrosion, which is triggered by increased chloride content near the reinforcement. In a study, the chloride content should be determined directly at corrosion areas. The LIBS system used consists of a micro-chip laser (3 mJ, 100 Hz, 1.5ins) and two compact spectrometers covering the wavelength range of 177-355 nm (UV) and 750-940 nm (NIR). The analysis of the chloride content was carried out via the atomic chlorine spectral line 837.59 nm, using helium for signal amplification. Calibrations were carried out for quantitative chlorine measurements with 15 reference samples in the working range of 0.05 to 6.00 wt% chlorine. The calibration of the LIBS system was done according to DIN 32 645 and was tested for linearity. The determination of the quantitative chlorine contents was carried out on samples which were broken and thus have a high surface roughness. This requires real time correction of the focus point to compensate for the roughness of the samples. The poster shows spatially resolved element distributions and determined quantitative chloride concentrations near the corrosion Areas.
In civil engineering, the investigation of existing infrastructure is of major importance for maintaining and ensuring stability of the structures. To ensure durability, uniform regulations and standards apply e.g. the European standard EN 206-1. In some countries, the EN-standard is supplemented by additional standards, as in Germany with DIN 1045-2. Here, specific application rules are described, e.g. for the cement type, to ensure the resistant to different exposures. Therefore, the knowledge of the materials originally used is important in assessing the condition of existing concrete structure. Unfortunately, these are often unknown and must be determined retrospectively. Therefore, we present the application of the laser-induced breakdown spectroscopy to distinguish between different types of cement. Spectral information’s are used to build a classification model. First, the accuracy of the classification is analyzed on ten pure laboratory cement samples. To investigate possible sources of error, the model was then applied to cement samples with different moisture content. The study shows that LIBS is a promising tool for distinguishing between cement types. For further industrial application, however, factors influencing the LIBS signal must be included to ensure a robust model.
Es geht auch einfacher
(2019)
Mit laserbasiertem Verfahren Zustand von Betonbauwerken erfassen: Die Laserinduzierte Breakdown Spektroskopie (LIBS) stellt eine Alternative zur nasschemischen Analyse dar, um den Zustand von Betonbauwerken zu erfassen. Bei diesem Verfahren laufen der Analysevorgang und die Auswertung automatisiert ab. Ein Prototyp für die mobile Anwendung auf der Baustelle steht zur Verfügung. So kann auf Knopfdruck ein schriftlicher Bericht erstellt werden, der einen genauen Wert für die Eindringtiefe eines relevanten Elements wie Chlorid ausgibt.
The application of a LIBS system is presented. A diode-pumped low energy laser (3 mJ, 1.5 ns, 100 Hz) and a compact NIR spectrometer are used. A scanner allows the two-dimensional element mapping. For the quantitative analysis calibration of the system is carried out with reference samples in a concentration range of chlorine of 0.05 wt.% to 2.5 wt.%. To determine the 2D distribution of harmful elements (Cl, C), concrete cores were drilled, split and analyzed directly. By comparing the chloride ingress and the carbonation, the interaction of both processes can be visualized in one measurement that takes less than 10 minutes with a drill core of 50 mm x 100 mm. Results obtained were compared and verified with standard measurements.
Es wird ein alternatives Verfahren zur schnellen zweidimensionalen Analyse der chemischen Zusammensetzung von Baustoffen vorgestellt. Dieses beruht auf der Kombination des Abtrags einer geringen Materialmenge durch einen gepulsten Laser, der Plasmaerzeugung und der Analyse der Lichtemission des Plasmas mittels optischer Spektroskopie. Es können prinzipiell alle Elemente gleichzeitig nachgewiesen werden. Damit ist es möglich einerseits Informationen über den Baustoff an sich als auch über den Eintrag potentiell schädigender Elemente (z. B. Cl, C, Na, K, S) zu gewinnen. Das Verfahren kann automatisiert im Labor oder als mobile Version direkt vor Ort eingesetzt werden. Es liefert zweidimensionale Bilder der Elementverteilung in Echtzeit. Es kann ohne große Probenvorbereitung z. B. direkt an der Querschnittsfläche eines Bohrkernes gemessen werden. Die Messung dauert nur wenige Minuten. Das Prinzip der Messung, die Vor- und die Nachteile, sowie die verfügbare Gerätetechnik für den Einsatz im Labor oder direkt am Bauwerk werden vorgestellt. Abschließend werden praktische Beispiele für die Anwendung des LIBS-Verfahrens zur Erfassung des Chlorid-Eintrages, der Karbonatisierung und der Verteilung von Schwefel präsentiert.
Es wird ein alternatives Verfahren zur schnellen zweidimensionalen Analyse der chemischen Zusammensetzung von Baustoffen vorgestellt. Dieses beruht auf der Kombination des Abtrags einer geringen Materialmenge durch einen gepulsten Laser, der Plasmaerzeugung und der Analyse der Lichtemission des Plasmas mittels optischer Spektroskopie. Es können prinzipiell alle Elemente gleichzeitig nachgewiesen werden. Damit ist es möglich einerseits Informationen über den Baustoff an sich als auch über den Eintrag potentiell schädigender Elemente (z. B. Cl, C, Na, K, S) zu gewinnen. Das Verfahren kann automatisiert im Labor oder als mobile Version direkt vor Ort eingesetzt werden. Es liefert zweidimensionale Bilder der Elementverteilung in Echtzeit. Es kann ohne große Probenvorbereitung z. B. direkt an der Querschnittsfläche eines Bohrkernes gemessen werden. Die Messung dauert nur wenige Minuten. Das Prinzip der Messung, die Vor- und die Nachteile, sowie die verfügbare Gerätetechnik für den Einsatz im Labor oder direkt am Bauwerk werden vorgestellt. Abschließend werden praktische Beispiele für die Anwendung des LIBS-Verfahrens zur Erfassung des Chlorid-Eintrages, der Karbonatisierung und der Verteilung von Schwefel präsentiert.
The presented work discusses the accuracy of Laser Induced Breakdown Spectroscopy (LIBS) in determining the total chloride content in cement pastes. LIBS as an emission spectroscopy method is used to detect simultaneously several elements present in cement-based materials. By scanning surfaces the variability in the spatial distribution of elements can be visualised. However, for a quantification of the results, studies are necessary to characterise possible influences due to the wide variation of the chemical compositions in which cement can occur. It is shown how the calibration can be done, how the calibration samples were produced, and which statistical parameters are necessary to describe the precision of the regression. The performance of LIBS is estimated by detecting chloride in validation samples. Therefore, 55 samples and 7 ets with changing mix ompositions were produced. The presented study deals with possible influences of different mix compositions, ncluding different cations of chloride, varying w/c-ratios and the artial replacement of Portland cement with last furnace slag (50% BFS) and limestone (30% LS). Comparing the LIBS results with otentiometric titration, n accuracy of±0.05 wt%/total has been determined.
The composition of concrete determines its resistance to various degradation mechanisms such as ingress of ions, carbonation or reinforcement corrosion. Knowledge of the composition of the hardened concrete is therefore helpful to assess the remaining service life of an existing structure or evaluate the damage observed during inspections. For example, for most existing concrete structures the type of cement originally used is not known and must therefore be determined afterwards. This paper presents a preliminary study on the application of laser-induced breakdown spectroscopy (LIBS) to identify the type of cement. For this purpose, ten different types of cement were investigated. For every type, three cement paste prisms were produced: (i) prisms dried, ground and pressed into tablets, (ii) prisms dried and (iii) prisms untreated. LIBS measurements were performed with a diode-pumped low energy laser (1064 nm, 3 mJ, 1.5 ns, 100 Hz) in combination with two compact spectrometers which cover the UV and NIR spectral range. A reduced subset of spectral features was used to build a classification model based on linear discriminant analysis. The results show that the classification of homogenized pressed cement powder samples provides a high accuracy, however, factors such as a different sample matrix and moisture content can affect the accuracy of the classification. The study demonstrates that LIBS is a promising tool to identify the type of cement.
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.
New possibilities for concrete analysis 4.0 with the Laser-Induced Breakdown Spectroscopy (LIBS)
(2020)
In civil engineering the damage assessment of concrete infrastructures is an important task to monitor and ensure the estimated life-time. The aging of concrete is caused by different damage processes like the chloride induced pitting corrosion of the reinforcement. The penetration depth and the concentration of harmful species are crucial factors in the damage assessment. As a highly cost and time-consuming standard procedure, the analysis of concrete drill cores or drilling by wet-chemistry is widely used. This method provides element concentration to the total mass as aggregates and binder are homogenized. In order to provide a method that is capable to detect the element concentration regarding the cement content only, the laser-induced breakdown spectroscopy (LIBS) will be presented. The LIBS method uses a focused pulsed laser on the sample surface to ablate material. The high-power density and the laser-material interaction causes a laser-induced plasma that emits elemental and molecular line emission due to energy transition of the excited species in the plasma during the cooling phase.
As each element provides element-specific line emission, it is in principle possible to detect any element on the periodic table (spectroscopic fingerprint) with one laser shot. In combination with a translation stage the sample under investigation can be spatially resolved using a scan raster with a resolution up to 100 µm (element mapping). Due to the high spatial resolution, the element distribution and the heterogeneity of the concrete can be evaluated. By using chemometrics the non-relevant aggregates can be excluded from the data set and the element concentration can be quantified and referred to a specific solid phase like the binding matrix (cement) only. In order to analyze transport processes like diffusion and migration the twodimensional element distributions can provide deep insight into the transport through the pore space and local enrichments of elements. As LIBS is a multi-elemental method it is also possible to compare the ingress and transport process of different elements like Cl, Na, K, S, C, and Li simultaneously and evaluate cross-correlations between the different ions. Furthermore, the element mapping allows to visualize the transport along cracks. This work will show the state of the art in terms of hardware and software for an automated LIBS system as well as different application for a concrete analysis 4.0. Focus will be the application of LIBS for a fast concrete analysis.
Schnelle ortsaufgelöste Chloridbestimmung mit der laserinduzierten Plasmaspektroskopie (LIBS)
(2020)
Im Zuge der Ist-Zustandserfassung von Stahl- und Spannbetonbauwerken spielt die chemische Analyse von Beton eine zentrale Rolle. Durch den externen Eintrag von schädigenden Substanzen wie Chlorid oder Alkalien aus Tausalzen oder Meerwasser, kann u.U. der Beton und/oder die Stahlbewehrung angegriffen werden. Bei Überschreitung kritischer korrosionsauslösender Chloridgehalte, z.B. bei Stahlbeton 0,4 M.-% (bzw. 0,5 M.-%) und Spannbeton 0,2 M.-% bezogen auf den Zement, erhöht sich das Risiko für eine Chlorid-induzierte Korrosion. Für die Beurteilung eines Instandsetzungsbedarfs und, sofern notwendig, der Erarbeitung eines Instandsetzungskonzeptes muss nach der Rili-SIB1 ein sachkundiger Planer herangezogen werden. Standardmäßig werden für die chemische Analyse Bohrkerne bzw. Bohrmehlproben aus dem zu untersuchenden Bauwerk entnommen und nach aufwendiger Probenvorbereitung nasschemisch analysiert (nach DAfStb Heft 401 oder DIN 14629). Dabei wird der Gesamtchloridgehalt bezogen auf die Einwaage angegeben. Eine Umrechnung auf den Zementgehalt erfolgt i.d.R. durch Schätzwerte. Der Einsatz der laserinduzierten Plasmaspektroskopie (LIBS) wird seit Mitte der 90er Jahren an der Bundesanstalt für Materialforschung und -prüfung erforscht, um den Chloridgehalt durch eine ortsaufgelöste Elementanalyse an einer Betonprobe möglichst genau zu ermitteln. Die zweidimensionale LIBS-Messung mit einer lateralen Auflösung von 100 µm x 100 µm erlaubt die Berücksichtigung der Heterogenität von Beton. Dabei lassen sich die Bindemittelmatrix und die Gesteinskörnung separat betrachten, wodurch sich die Aussagekraft der Ergebnisse und somit die Sicherheit der chemischen Zustandserfassung erhöht. Durch die stetige Weiterentwicklung von Komponenten wie Laser, Spektrometer und analytischer Auswerteroutinen sind mittlerweile automatisierte Systeme für die schnelle LIBS-Analyse auf dem Markt verfügbar. In diesem Vortrag wird der aktuelle Stand der Technik anhand von Praxisbeispielen präsentiert und entscheidende Vorteile gegenüber dem Standardverfahren herausgestellt. Aufgrund der Möglichkeit für eine simultane Multielementanalyse mit LIBS werden weitere Anwendungen, wie z.B. die Ermittlung der Karbonatisierungstiefe, Untersuchungen von Transportprozessen, Chlorideintrag entlang von Rissen oder Untersuchungen von Elementverteilungen im Kontext einer AKR vorgestellt.
Im Zuge der Ist-Zustandserfassung von Stahl- und Spannbetonbauwerken spielt die chemische Analyse von Beton eine zentrale Rolle. Durch den externen Eintrag von schädigenden Substanzen wie Chlorid oder Alkalien aus Tausalzen oder Meerwasser, kann u.U. der Beton und/oder die Stahlbewehrung angegriffen werden. Bei Überschreitung kritischer korrosionsauslösender Chloridgehalte, z.B. bei Stahlbeton 0,4 M.-% (bzw. 0,5 M.-%) und Spannbeton 0,2 M.-% bezogen auf den Zement, erhöht sich das Risiko für eine Chlorid-induzierte Korrosion. Für die Beurteilung eines Instandsetzungsbedarfs und, sofern notwendig, der Erarbeitung eines Instandsetzungskonzeptes muss nach der Rili-SIB1 ein sachkundiger Planer herangezogen werden. Standardmäßig werden für die chemische Analyse Bohrkerne bzw. Bohrmehlproben aus dem zu untersuchenden Bauwerk entnommen und nach aufwendiger Probenvorbereitung nasschemisch analysiert (nach DAfStb Heft 401 oder DIN 14629). Dabei wird der Gesamtchloridgehalt bezogen auf die Einwaage angegeben. Eine Umrechnung auf den Zementgehalt erfolgt i.d.R. durch Schätzwerte. Der Einsatz der laserinduzierten Plasmaspektroskopie (LIBS) wird seit Mitte der 90er Jahren an der Bundesanstalt für Materialforschung und -prüfung erforscht, um den Chloridgehalt durch eine ortsaufgelöste Elementanalyse an einer Betonprobe möglichst genau zu ermitteln. Die zweidimensionale LIBS-Messung mit einer lateralen Auflösung von 100 µm x 100 µm erlaubt die Berücksichtigung der Heterogenität von Beton. Dabei lassen sich die Bindemittelmatrix und die Gesteinskörnung separat betrachten, wodurch sich die Aussagekraft der Ergebnisse und somit die Sicherheit der chemischen Zustandserfassung erhöht. Durch die stetige Weiterentwicklung von Komponenten wie Laser, Spektrometer und analytischer Auswerteroutinen sind mittlerweile automatisierte Systeme für die schnelle LIBS-Analyse auf dem Markt verfügbar. In diesem Vortrag wird der aktuelle Stand der Technik anhand von Praxisbeispielen präsentiert und entscheidende Vorteile gegenüber dem Standardverfahren herausgestellt. Aufgrund der Möglichkeit für eine simultane Multielementanalyse mit LIBS werden weitere Anwendungen, wie z.B. die Ermittlung der Karbonatisierungstiefe, Untersuchungen von Transportprozessen, Chlorideintrag entlang von Rissen oder Untersuchungen von Elementverteilungen im Kontext einer AKR vorgestellt.
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 ageing of the infrastructure facilities, a reliable assessment of the condition of concrete structures is of great interest to plan timely and appropriate measures. In concrete structures, pittingcorrosion of the reinforcement is the predominant deterioration mechanism affecting serviceability and eventually structural performance. Determination of quantitative chloride ingress is not only necessary to obtain valuable information on the current condition of a structure, but the data obtained can also be used to predict future developments and the associated risks. An overview of the progress and the possibilities of the application of laser-induced breakdown spectroscopy for concrete analysis in daily civil engineering practice is given. High-resolution 2D measurements of drill cores to determine the penetration of harmful species into concrete is presented. Furthermore, the application of a mobile LIBS system in a parking garage is shown. The system consists of a diode-pumped low-energy laser (3 mJ, 1.5 ns, 100 Hz) and a compact NIR spectrometer. A scanner allows two-dimensional element mapping. Progress towards the establishment of LIBS in a leaflet for the analysis of chlorine ingress into concrete in civil engineering is presented.
To conduct a reliable, repeatable and accurate LIBS analysis, the optimization of the experimental setup is an important task. Hardware parameters of lasers and spectrometers used in the setup as well as additionally required components such as optics or process gas pipes must be carefully aligned and adjusted because factors like (i) focal conditions of the optics, (ii) alignment of the sample, (iii) process purge gas (types, flow rate) or (iv) measurement settings (integration time, accumulation of pulses) have a big impact on the signal quality. Therefore, in most cases the effect of different factors is evaluated empirically due to changing one factor at a time while keeping the overall configuration the same. In the end, the optimal configuration is selected based on the best parameters for each influencing factor. During optimization, a configuration of the experimental setup is aimed at, which allows e.g. the highest signal intensity or the lowest variation. In most cases, cross-correlation, interference and interaction among the various factors are not considered. For this reason, the possibilities of using Design of Experiment (DoE) to optimize a LIBS experiment will be shown and advantages of (i) reduction of testing plans using a feature space, (ii) identifying and considering cross-correlations and interactions, (iii) evaluating individual impacts on the measurement (e.g. contour and surface plots) as well as (iv) multivariate models for prediction of impacts will be presented.
One of the most common causes of damage is the ingress of harmful ions into the concrete, which can lead to deterioration processes and affect structural performance. Therefore, the increasingly aging infrastructure is regularly inspected to assess durability. Regular chemical analysis can be useful to determine the extent and evolution of ion ingress and to intervene in a timely manner. This could prove more economical than extensive repairs for major damage, particularly for critical infrastructure. In addition to already established elemental analysis techniques in civil engineering such as potentiometric titration or X-ray fluorescence analysis, laser-induced breakdown spectroscopy (LIBS) can provide further important complementary information and benefits. The possibilities of LIBS are demonstrated using the example of a drill core taken from a parking garage.
Laser Induced Breakdown Spectroscopy – A Tool for Imaging the Chemical Composition of Concrete
(2022)
One of the most common causes of damage is the ingress of harmful ions into the concrete, which can lead to deterioration processes and affect structural performance. Therefore, the increasingly aging infrastructure is regularly inspected to assess durability. Regular chemical analysis can be useful to determine the extent and evolution of ion ingress and to intervene in a timely manner. This could prove more economical than extensive repairs for major damage, particularly for critical infrastructure. In addition to already established elemental analysis techniques in civil engineering such as potentiometric titration or X-ray fluorescence analysis, laser-induced breakdown spectroscopy (LIBS) can provide further important complementary information and benefits. The possibilities of LIBS are demonstrated using the example of a drill core taken from a parking garage.
The main application of LIBS in civil engineering is the detection of harmful ions in concrete, which can penetrate the component through the porous concrete structure. The advantages of LIBS over standard methods are the possibility of multi-element analysis, measurement speed, spatially resolved measurements, and minimal sample preparation. The spatially resolved measurements of LIBS allow the assessment of the heterogeneity of the concrete by measuring separately the chemical composition of the aggregates and the binder matrix. The latter is particularly relevant because the determined elemental distribution can be directly related to the binder matrix. This is not possible with standard methods, since the material is homogenized to powder during sample preparation stage and the determined concentration is thus related to the total mass. In addition to the use of LIBS for the specific analysis of individual harmful ions, LIBS can also be used to estimate the concrete composition and thus determine, for example, the type of cement used. Corresponding information are relevant for the estimation of the remaining service life and for the preparation of a maintenance concept. In recent years, LIBS has been increasingly used in civil engineering. Currently, however, it is primarily used in research institutions and only occasionally in building materials laboratories. Special commercial devices have also been developed, which greatly simplify the application due to the high degree of automation. Mobile LIBS systems allow on-site application. A central point, which limits the use of LIBS in the commercial sector, is the lack of norms and standards. Therefore, within the framework of a project funded by the German government, work has been carried out on the preparation of a leaflet on quantitative chlorine determination in concrete, which will be published this year. In interlaboratory comparisons the robustness and accuracy for the practical application was demonstrated. LIBS also has great potential in the recycling of construction waste in conjunction with hyperspectral sensors. This issue is currently being addressed in a national project. During the presentation, the state of the art of LIBS in civil engineering will be presented, next steps will be discussed, and future challenges will be outlined.
LIBS is a complementary method to XRF and can detect all elements without the need for vacuum conditions. Automated systems are already commercially available capable of scanning surfaces with a resolution of up to 0.1 mm within a few minutes. In addition to possible applications in R&D, LIBS is also used for practical applications in building materials laboratories and even on-site.
In view of ageing infrastructure facilities, a reliable assessment of the condition of concrete structures is of increasing interest. For concrete structures, the ingress of potential harmful ions is affecting the serviceability and eventually structural performance. Pitting corrosion induced by penetrating chlorides is the dominant deterioration mechanism. Condition assessment based on frequently performed chloride profiling can be useful to identify the extent and evolution of chloride ingress. This could prove to be more economical than extensive repairs, especially for important infrastructure facilities.
Currently the most common procedure for determining the chloride content is wet chemical analysis with standard resolution of 10 mm. The heterogeneity is not considered. LIBS is an economical alternative for determining the chloride content at depth intervals of 1 mm or less. It provides 2D distributions of multiple elements and can locate spots with higher concentrations. The results are directly correlated to the mass of binder and can also be performed on-site with a mobile LIBS-System.
The application of a LIBS-system is presented. Calibration is required for quantitative analysis. Concrete cores were drilled, sliced and analyzed to determine the 2D-distribution of harmful elements. By comparing the chloride ingress and the carbonation, the interaction of both processes can be visualized in a measurement that takes less than 10 minutes for a 50 mm x 100 mm drill core.
A leaflet on the use of LIBS for the chloride ingress assessment has been completed.
Responsible treatment of the environment and resources is a key element of sustainability. The building and construction industry is one of the largest consumers of natural resources. Consequently, there is a particular need for regulations and technologies that help to create closed material cycles. From the technological point of view, such efforts are complicated by the growing material diversity and the amount of composites contained in present and future construction and demolition waste (CDW). Nowadays, simple but proven techniques like manual sorting are mainly used. However, this practice not only poses health risks and dangers to the staff performing the work, but also relies on merely obvious, visually striking differences. Automated, sensor-based sorting of these building materials could complement or replace this practice to improve processing speed, recycling rates, sorting quality, and prevailing health conditions. The preliminary results for the identification of a wide variety of building materials with LIBS are presented.
Concrete structures often show severe damage during their lifetime. One such damage is pitting corrosion of the steel reinforcement caused by chloride ingress into the porous concrete structure. Laser-induced breakdown spectroscopy (LIBS) is a promising method in civil engineering, which is used for detection of chlorine in concrete structures in addition to conventional methods of wet chemistry. To assess LIBS as a trustful analytical technique, its accuracy and robustness is carefully tested. The presentation will outline the results of the interlaboratory comparison of chlorine quantification in cement paste samples, which was carried out by 12 laboratories in 10 countries. Two sets of samples with chloride content ranging from 0.06-1.95 wt.% in the training set and 0.23-1.51 wt.% in the test sample set (“unknowns”), with additional variations in the type of cement and chlorine source (salt type) were sent to the laboratories. The overall result demonstrates that LIBS is suitable for the quantification of the investigated sample compositions: average relative bias was mostly below 15 %. Considering that the laboratories did not receive instructions on how to perform the analysis or how to process the data, the results can be evaluated as a true status quo of the LIBS technique for this type of analysis.
Concrete structures experience severe damage during service, for example due to pitting corrosion of rebars caused by the ingress of chlorine (Cl) into the porous concrete structure. The ingress can be monitored using laser-induced breakdown spectroscopy (LIBS), a recently introduced civil engineering technique used to detect Cl in concrete structures in addition to conventional wet chemistry methods. The key advantages of LIBS are high spatial resolution, which is important when analyzing heterogeneous concrete samples, as well as the almost complete absence of sample preparation. To assess LIBS as a reliable analytical method, its accuracy and robustness must be carefully tested. This paper presents the results of an interlaboratory comparison on the analysis of Cl in cement paste samples conducted by 12 laboratories in 10 countries. Two sets of samples were prepared with Cl content ranging from 0.06 to 1.95 wt% in the training set and 0.23–1.51 wt% in the test set, with additional variations in the type of cement and Cl source (salt type). The overall result shows that LIBS is suitable for the quantification of the studied samples: the average relative error was generally below 15%. The results demonstrate the true status quo of the LIBS method for this type of analysis, given that the laboratories were not instructed on how to perform the analysis or how to process the data.
The Boltzmann plot method is widely used to determine the temperature of laser induced plasma. It involves the use of individual lines that are not easy to find in complex spectra and/or in the spectral range available. If the number of such lines is not enough to build a reliable Boltzmann plot, overlapping lines are often used, which are separated by software. However, line separation is a rather imprecise procedure, which, in addition, requires significant computational costs. This study proposes an extension of the Boltzmann plot method that allows a specific group of unresolved lines to be included in a Boltzmann plot without the need to separate them. This group of lines are multiplets, lines of the same element with similar upper and lower transition states. The multiplet lines along with the individual lines are included in the algorithm, which also includes a correction for self-absorption and is used to determine the plasma temperature. The algorithm is tested on synthetic spectra which are consistent with the model of a homogeneous isothermal plasma in local thermodynamic equilibrium and is shown to be superior to the standard Boltzmann plot method both in more accurate determination of the plasma temperature and in a significant reduction in the computational time. The advantages and disadvantages of the method are discussed in the context of its applications in laser induced breakdown spectroscopy.
Geschlossene Materialkreisläufe und sortenreine Materialfraktionen sind erforderlich, um hohe Verwertungs und Recyclingquoten in der Bauindustrie zu erreichen Beim Recycling von Bau und Abbruchabfällen wurden bisher bevorzugt einfache, aber bewährte Techniken eingesetzt, um große Mengen Bauschutt in kurzer Zeit zu verarbeiten Dies steht im Gegensatz zu den immer komplexer werdenden Verbundwerkstoffen in der Mineralbaustoffindustrie Die aktuell oft praktizierte händische Klaubung bürgt viele Risiken und Gefahren für das ausführende Personal und basiert lediglich auf offensichtlichen, visuell erkennbaren Unterschieden zur Trennung Eine automatisierte, sensorgestützte Sortierung dieser Baustoffe könnte diese Praxis ergänzen oder ersetzen, um die Verarbeitungsgeschwindigkeit, die Recyclingraten, die Sortierqualität und die vorherrschenden Gesundheitsbedingungen zu verbessern.
Geschlossene Materialkreisläufe und sortenreine Materialfraktionen sind erforderlich, um hohe Verwertungs und Recyclingquoten in der Bauindustrie zu erreichen Beim Recycling von Bau und Abbruchabfällen wurden bisher bevorzugt einfache, aber bewährte Techniken eingesetzt, um große Mengen Bauschutt in kurzer Zeit zu verarbeiten Dies steht im Gegensatz zu den immer komplexer werdenden Verbundwerkstoffen in der Mineralbaustoffindustrie Die aktuell oft praktizierte händische Klaubung bürgt viele Risiken und Gefahren für das ausführende Personal und basiert lediglich auf offensichtlichen, visuell erkennbaren Unterschieden zur Trennung Eine automatisierte, sensorgestützte Sortierung dieser Baustoffe könnte diese Praxis ergänzen oder ersetzen, um die Verarbeitungsgeschwindigkeit, die Recyclingraten, die Sortierqualität und die vorherrschenden Gesundheitsbedingungen zu verbessern.
Laser-induced breakdown spectroscopy (LIBS) is a spectroscopic method for detecting the chemical composition of optically accessible surfaces. In principle, the measurement of all elements of the periodic table is possible. System calibrations allow the quantification of element concentrations. In combination with scanner systems, the two-dimensional element distribution can be determined. Even rough surfaces can be measured by online adjustment of the laser focus. To detect element ingress into the concrete, typically cores are taken, cut in half, and LIBS measurements are performed on the cross-section. The high spatial resolution as well as the simultaneous multi-element analysis enables a separate evaluation of the binder-matrix and aggregates. Therefore, the element concentrations can be determined directly related to the cement paste. LIBS measurements are applicable in the laboratory, on-site and also over a distance of several meters.
Common applications include the investigation of material deterioration due to the ingress of harmful ions and their interaction in porous building materials. LIBS is able to provide precise input parameters for simulation and modelling of the remaining lifetime of a structure. Besides the identification of materials, also their composition can be determined on hardened concrete, such as the type of cement or type of aggregate. This also involves the identification of environmentally hazardous elements contained in concrete. Another possible application is the detection of the composition of material flows during dismantling. Non-contact NDT for “difficult to assess” structures as an example application through safety glass or in combination with robotics and automation are also possible.
This work presents the state of the art concerning LIBS investigations on concrete by showing exemplary laboratory and on-site applications.
Laser-induced breakdown spectroscopy (LIBS) is a spectroscopic method for the analysis of the chemical composition of sample materials. Generally, the measurement of all elements of the periodic table is possible. In particular, light elements such as H, Li, Be, S, C, O, N and halogens can be measured. Calibration with matrix-matching standards allows the quantification of element concentrations. In combination with scanner systems, the two-dimensional element distribution can be determined. Even rough surfaces can be measured by online adjustment of the laser focus. LIBS can also be used on-site with mobile systems. Hand-held systems are available for point measurements.
Common applications include the investigation of material deterioration due to the ingress of harmful ions and their interaction in porous building materials. Due to the high spatial resolution of LIBS and the consideration of the heterogeneity of concrete, the determination of precise input parameters for simulation and modelling of the remaining lifetime of a structure is possible. In addition to the identification of materials, it is also possible to assess the composition for example of hardened concrete, which involves the cement or aggregate type used. Other important fields of application are the detection of environmentally hazardous elements or the material classification for sorting heterogeneous material waste streams during dismantling. Non-contact NDT for “difficult to assess” structures as an example application through safety glass or in combination with robotics and automation are also possible.
In this work, an overview of LIBS investigations on concrete is given based on exemplary laboratory and on-site applications.
The electron density and temperature of a laser-induced plasma can be determined from the width and intensity of the spectral lines, provided that the corresponding optical transitions are optically thin. However, the lines in laser induced plasma are often self-absorbed. One of the methods of correction of this effect is based on the use of the Planck function and an iterative numerical calculation of the plasma temperature. In this study, the method is further explored and its inherent errors and limitations are evaluated. For this, synthetic spectra are used that fully correspond to the assumed conditions of a homogeneous isothermal plasma at local thermodynamic equilibrium. Based on the error analysis, the advantages and disadvantages of the method are discussed in comparison with other methods of self-absorption correction.
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.
This technical note highlights the fact that CF-LIBS algorithms work in mole fractions, while results of spectrochemical analysis are usually reported in mass fractions or mass percent. Ignoring this difference and not converting mole fractions to mass fractions can lead to errors in reported concentrations determined by the CF-LIBS method and inadequate comparison of these concentrations with certified concentrations. Here, the key points of the CF-LIBS algorithm are reproduced and the formulae for converting a mole fraction to a mass fraction and vice versa are given. Several numerical examples are also given, which show that the greater the difference between the molar mass of an individual element in a sample and the average molar mass, the greater the discrepancy between the mole and mass fractions.