The work described here was in part financed by the Swiss Federal Roads Office (research project AGB2012/010). We greatly acknowledge the financial support.

<ol><li>Bertolini, L., Elsener, B., Pedeferri, P., Redaelli, E., Polder, R. B. <a target="_blank" href="http://www.researchandmarkets.com/reports/2330648/corrosion_of_steel_in_concrete_prevention.pdf">Corrosion of Steel in Concrete: Prevention, Diagnosis, Repair. 2nd edn</a>. , WILEY-VCH. (2013).</li>
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<li>Breit, W., et al. <a target="_blank" href="http://onlinelibrary.wiley.com/doi/10.1002/best.201100007/references">Zum Ansatz eines kritischen Chloridgehaltes bei Stahlbetonbauwerken.</a> Beton- und Stahlbetonbau. (5), 290-298 (2011).</li>
<li><a target="_blank" href="https://www.evs.ee/products/evs-en-14629-2007">European Standard EN14629: Products and systems for the protection and repair of concrete structures - Test methods - Determination of chloride content in hardened concrete.</a> European Committee for Standardization. , (2007).</li>
<li><a target="_blank" href="https://www.astm.org/Standards/C1152.htm">ASTM C1152 Standard Test Method for Acid-Soluble Chloride in Mortar and Concrete.</a> ASTM International. , (2012).</li>
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<li>Draft, <a target="_blank" href="https://trid.trb.org/view.aspx?id=1005306">Draft recommendation for repair strategies for concrete structures damaged by reinforcement corrosion.</a> Mater Struct. 27, RILEM TC 124-SRC 415-436 (1994).</li>
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<li>Richartz, W. Die Bindung von Chlorid bei der Zementerhärtung. Zement-Kalk-Gips. 10, (in German) 447-456 (1969).</li>
<li>Vassie, P. <a target="_blank" href="http://www.icevirtuallibrary.com/doi/abs/10.1680/iicep.1985.929?journalCode=jpric">Reinforcement corrosion and the durability of concrete bridges.</a> Proc. Inst. Civ. Eng. Part 1. 76, 713-723 (1984).</li>
<li>Angst, U. M., et al. <a target="_blank" href="https://link.springer.com/article/10.1617/s11527-017-1010-1">The steel-concrete interface.</a> Mater. Struct. 50 (2), 143(2017).</li>
<li>Polder, R. B., Peelen, W. H. A., Courage, W. M. G. <a target="_blank" href="http://onlinelibrary.wiley.com/doi/10.1002/maco.201206725/abstract">Non-traditional assessment and maintenance methods for aging concrete structures - technical and non-technical issues.</a> Mater. Corros. 63 (12), 1147-1153 (2012).</li>
<li><a target="_blank" href="https://www.astm.org/Standards/C876.htm">Standard Test Method for Corrosion Potentials of Uncoated Reinforcing Steel in Concrete.</a> ASTM International. , ASTM C876 (2015).</li>
<li>Planung, <a target="_blank" href="http://shop.sia.ch/normenwerk/ingenieur/sia%202006-c1/d/D/Product">SIA 2006:2013 Planung Durchführung und Interpretation der Potenzialmessung an Stahlbetonbauten.</a> Schweizerischer Ingenieur- und Architektenverein SIA. , (in German) (2013).</li>
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<li>B2: Merkblatt zur zerstörungsfreien Betondeckungsmessung und Bewehrungsortung an Stahl- und Spannbetonbauteilen. Deutsche Gesellschaft für Zerstörungsfreie Prüfung DGZfP. , (in German) (2014).</li>
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<li><a target="_blank" href="http://shop.bsigroup.com/ProductDetail/?pid=000000000030164918">European Standard EN 12504-1:2009 - Testing concrete in structures. Cored specimens. Taking, examining and testing in compression.</a> European Committee for Standardization. , (2009).</li>
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<li><a target="_blank" href="https://www.en-standard.eu/csn-en-14630-products-and-systems-for-the-protection-and-repair-of-concrete-structures-test-methods-determination-of-carbonation-depth-in-hardened-concrete-by-the-phenolphthalein-method/">European Standard EN 14630: Products and systems for the protection and repair of concrete structures - Test methods - Determination of carbonation depth in hardened concrete by the phenolphthalein method.</a> European Committee for Standardization. , (2006).</li>
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<li>Angst, U., Wagner, M., Elsener, B., Leemann, A., Nygaard, P. v Method to determine the critical chloride content of existing reinforced structures. VSS report no. 677. , Swiss Federal Roads Office. (in German) (2016).</li>
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<li>Angst, U. M., Elsener, B., Larsen, C. K., Vennesland, Ø <a target="_blank" href="http://www.sciencedirect.com/science/article/pii/S0010938X11000473">Chloride induced reinforcement corrosion: Electrochemical monitoring of initiation stage and chloride threshold values.</a> Corros. Sci. 53 (4), 1451-1464 (2011).</li>
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<li>Boubitsas, D., Tang, L. <a target="_blank" href="https://link.springer.com/article/10.1617/s11527-014-0343-2">The influence of reinforcement steel surface condition on initiation of chloride induced corrosion.</a> Mater Struct. 48 (8), 2641-2658 (2015).</li>
<li>Pacheco, J. <a target="_blank" href="https://repository.tudelft.nl/islandora/object/uuid:bc726ead-0999-4fe4-bad1-5c26c0e50405/?collection=research">Corrosion of steel in cracked concrete - chloride microanalysis and service life predictions.</a> TU Delft. , The Netherlands. (2015).</li>
<li>Li, L., Sagüés, A. A. <a target="_blank" href="http://corrosionjournal.org/doi/10.5006/1.3287721?code=nace-prem-site">Chloride corrosion threshold of reinforcing steel in alkaline solutions - Effect of specimen size.</a> Corros. 60 (2), 195-202 (2004).</li>
<li>Angst, U., Rønnquist, A., Elsener, B., Larsen, C. K., Vennesland, Ø <a target="_blank" href="http://www.sciencedirect.com/science/article/pii/S0010938X10004488">Probabilistic considerations on the effect of specimen size on the critical chloride content in reinforced concrete.</a> Corros. Sci. 53 (1), 177-187 (2011).</li>
</ol>

The authors have nothing to disclose.

The most critical steps for the success of the suggested experimental protocol to determine Ccrit are those including the measures taken to prevent false corrosion initiation and other steel bar end effects. In this regard, a variety of approaches were tested, among which the here reported protocol was found to yield the best results28. In further tests, this approach permitted decreasing the rate of false initiation to below 10%. On the one hand, this is owing to coating the border area of the exposed concrete surface with epoxy resin, which increases the length of transport of chlorides through the concrete to the steel bar ends considerably. On the other hand, replacing the original concrete around the steel bar at its ends with a dense, highly alkaline cementitious slurry significantly enhances the corrosion resistance in these areas. Such systems, i.e., coating the steel bar ends with a layer of a polymer-modified cementitious material, have proven successful also in other studies29,30.
Another important aspect is the criterion for corrosion initiation. This criterion is based on RILEM technical committee TC-235 that aimed to recommend a test method for the measurement of Ccrit in samples manufactured in the laboratory31. The rationale is that it is well known that onset of corrosion of unpolarized steel embedded in concrete might take place over a long period of time rather than a well-defined instant30,32. Steel may start corroding at relatively low chloride concentrations but if these are not able to sustain the corrosion process, repassivation will occur, which becomes apparent by a potential increase back to the initial passive level. Such depassivation-repassivation events are typically observed in similar studies30,33,34. The chloride concentration measured at a time of stable corrosion is more relevant for practice than the time at which the very first signs of potential deviations from the passive level become apparent. With the suggested criterion, Ccrit represents the chloride concentration at which corrosion initiates and also stably propagates.
A limitation of the method is that the samples are relatively small, which may have an influence on the results35,36. In order to counteract this, it is suggested to use a relatively high number of samples (ideally 10). The level of confidence depends on the statistical distribution of Ccrit in the actual test area. For more details in this regard, refer to reference36. An additional limitation is that the moisture conditions in the laboratory exposure may differ from those of an actual structure. Finally, the detection of corrosion initiation may be difficult in cases where the potential is generally negative, such as in slag cements or other sulfide containing binders.
To the best of our knowledge, this is the first method of Ccrit determination in engineering structures at a stage prior to corrosion initiation. In contrast to empirical experience from structures, which is by definition obtained after corrosion initiation, this method can be used to measure Ccrit for specific structures or structural members before corrosion degradation occurs; the results can thus be used to assess the risk of (future) corrosion and to predict the remaining time to corrosion initiation (service life modeling). Thus, this method has the potential to be used in material testing, similar to established methods used for mechanical testing (compressive strength, etc.)
The method is currently applied to a number of different concrete infrastructures in Switzerland. This will broaden the severely limited5 knowledge about statistical distributions of Ccrit in structures. Moreover, it will reveal the influence of different factors such as the age of structures, the construction materials used, etc., and thus provide important information for civil engineers and for decision-makers in infrastructure management.

Corrosion of steel in concrete, triggered by the penetration of chlorides through the concrete, is the most frequent cause of the premature degradation of reinforced and pre-stressed concrete structures, and thus presents one of the most important challenges in civil engineering1,2,3,4. Industrialized countries typically have a large inventory of aging concrete infrastructures, built in the second half of the last century, and thus with a history of several decades of exposure to marine climate or deicing salts used on roads. Being able to reliably assess the condition of these structures, i.e., the risk for corrosion, forms the basis for planning maintenance work and for infrastructure management, in general.
The established approach in engineering for managing chloride-induced steel corrosion in concrete is based on a chloride threshold value (also termed critical chloride content, Ccrit)1,5,6. According to this concept, corrosion initiation is thought to occur as soon as the chloride concentration in the concrete at the steel surface exceeds the Ccrit threshold. Thus, assessing the condition of existing structures and estimating the remaining service life typically rely on determining the chloride content at different depths in the concrete, particularly at the depth of the embedded reinforcing steel. A number of reliable and standardized methods exist to measure this chloride concentration in samples of concrete7,8. Comparing the results to Ccrit provides the basis for the assessment of corrosion risk, and planning the type and the extent of repair measures. However, this approach requires knowledge of Ccrit.
Different international standards and recommendations, as well as text books, stipulate values for Ccrit1,3,9,10,11. These are typically around 0.4% chloride by weight of cement, based on long-term experience or early studies12,13. However, it is well known that the actual resistance against Ccrit of a certain structure or structural member is strongly influenced by the materials used, by the age of the structure, and by exposure history and conditions1,5. Thus, it is generally accepted that experience from one structure should only be applied to other structures with caution.
Despite this, it is common engineering practice to use tabulated Ccrit values, independent of the actual structure. This can be explained by the huge scatter of Ccrit in the literature and by the lack of reliable methods to determine Ccrit on-site and in the laboratory5. The approach of using tabulated threshold values in durability assessments is in contrast to structural considerations in condition assessments of aging concrete structures. In the latter case, there exist a number of standardized test methods to determine mechanical properties, such as the strength of the materials in the structure (concrete, reinforcing steel), to be used in the calculations of the structural behavior.
In this work, an experimental protocol to determine Ccrit on samples taken from engineering structures is presented. The approach is based on drilling cores of reinforced concrete in parts of concrete structures where corrosion has not yet initiated. These samples are transferred to the laboratory where they are subjected to an accelerated corrosion test in order to study the conditions for corrosion initiation. The main advantage of the proposed method is that the samples stem from structures and thus exhibit real conditions concerning a number of parameters that are well known to greatly influence Ccrit and which cannot be representatively mimicked in laboratory-produced samples. This includes the type and the age of the concrete (young laboratory concrete versus mature site-produced concrete), the type and surface condition of the reinforcing steel used at the time of construction, and in general the properties of the steel-concrete interface14. Together with the accuracy of laboratory measurement methods, this approach permits the reliable determination of Ccrit for specific structures or structural members.
Application of the suggested protocol in engineering practice will - compared with the common practice of using a constant value for Ccrit - enhance the accuracy of condition assessments and the predictive power of models to analyze the remaining service life. The expected strong increase in repair works of our built infrastructure over the coming decades15 poses an urgent need for such an improvement in engineering of corroding infrastructures.

<table><tbody><tr><td>Stranded wire</td><td></td><td></td><td>cross section at least 0.50 mm&amp;sup2;; ideally copper wire, tin plated</td></tr><tr><td>Self-tapping metal screw</td><td></td><td></td><td>any suitable self-tapping screw, typically of length 4 - 5 mm and diameter around 2.5 mm</td></tr><tr><td>Ring cable lug</td><td></td><td></td><td>suitable to connect screw and cable</td></tr><tr><td>SikaTop Seal-107</td><td>Sika</td><td></td><td>two-part polymer modified cementitious waterproof mortar slurry</td></tr><tr><td>Epoflex 816 L</td><td>Adisa</td><td></td><td>epoxy coating</td></tr><tr><td>Exposure tank</td><td></td><td></td><td>any suitable tank (&lt;em&gt;e.g.&lt;/em&gt; rako box) with a lid;&amp;nbsp; sufficiently large for exposing the samples</td></tr><tr><td>Reference electrode</td><td></td><td></td><td>Any stable reference electrode suitable for continuous immersion in sodium chloride solution</td></tr><tr><td>Tap water</td><td></td><td></td><td></td></tr><tr><td>Sodium chloride</td><td></td><td></td><td></td></tr><tr><td>Data logger</td><td></td><td></td><td>any device able to monitor the potentials of all samples vs. the reference electrode at the specified interval (input impedance &gt;10E7 Ohm)</td></tr></tbody></table>

experimental protocol to determine the chloride threshold value for corrosion in samples taken from reinforced concrete structures

The aging of reinforced concrete infrastructure in developed countries imposes an urgent need for methods to reliably assess the condition of these structures. Corrosion of the embedded reinforcing steel is the most frequent cause for degradation. While it is well known that the ability of a structure to withstand corrosion depends strongly on factors such as the materials used or the age, it is common practice to rely on threshold values stipulated in standards or textbooks. These threshold values for corrosion initiation (Ccrit) are independent of the actual properties of a certain structure, which clearly limits the accuracy of condition assessments and service life predictions. The practice of using tabulated values can be traced to the lack of reliable methods to determine Ccrit on-site and in the laboratory.
Here, an experimental protocol to determine Ccrit for individual engineering structures or structural members is presented. A number of reinforced concrete samples are taken from structures and laboratory corrosion testing is performed. The main advantage of this method is that it ensures real conditions concerning parameters that are well known to greatly influence Ccrit, such as the steel-concrete interface, which cannot be representatively mimicked in laboratory-produced samples. At the same time, the accelerated corrosion test in the laboratory permits the reliable determination of Ccrit prior to corrosion initiation on the tested structure; this is a major advantage over all common condition assessment methods that only permit estimating the conditions for corrosion after initiation, i.e., when the structure is already damaged.
The protocol yields the statistical distribution of Ccrit for the tested structure. This serves as a basis for probabilistic prediction models for the remaining time to corrosion, which is needed for maintenance planning. This method can potentially be used in material testing of civil infrastructures, similar to established methods used for mechanical testing.

Figure 7 displays typical steel potentials monitored during chloride exposure in the laboratory. Both examples show that the potential may drop significantly within a very short time, but that the corrosion process may not yet stably propagate, which becomes apparent through an increase of the potential towards its initial passive level. In this protocol, the time of corrosion initiation, i.e., the time at which exposure is stopped and Ccrit is determined, is defined by a marked potential drop followed by 10 days of negative potentials (see section 3.5.2 and the Discussion for more details).
It is common that it may take several months until stable corrosion initiation occurs. This also depends on the initial chloride content already present in the concrete when the samples are taken from the structures. In some cases of the experiments so far conducted, it took more than 1 year until corrosion initiated.
Figure 8 shows an example of Ccrit measured in 11 samples taken from a more than 40 years old road tunnel in the Swiss alps. All these samples were taken from within an area of 1 - 2 m2, thus presumably identically produced and exposed. In this example, the chloride content at the steel surface at the time of sampling was negligible. Additionally, the carbonation front was still far from the steel surface.
Figure 9 shows two examples where the steel potential decreased strongly upon exposure to the chloride-free solution. In one of these specific cases, it was during the subsequent (destructive) examination of the sample found that the concrete at the steel depth was already carbonated. Upon arrival of water at the steel surface, the corrosion process thus immediately started. In the other case, false corrosion initiation occurred at one of the steel bar ends.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56229/56229fig1.jpg" /> 
Figure 1. Schematic Drawing of the Sample Taken from a Structure and Treated in the Laboratory: (a) concrete core with an embedded piece of reinforcing steel; (b) reducing the concrete cover on the exposed side and on the back side by water-cooled diamond cutting; (c) steel bar end protection by means of removing some concrete around the steel and replacing it with a dense cement paste/mortar and subsequent epoxy coating; and (d) epoxy-coating on lateral faces and on end zones of the exposed concrete surface. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56229/56229fig2.jpg" /> 
Figure 2. Schematic Drawing of the Setup for the Corrosion Test in the Laboratory. This shows the placement of the samples in the exposure tank. Spacers are used to ensure contact to exposure solution from the bottom sample surface. All samples are connected to a data logger, measuring the potential of each sample vs. a reference electrode placed in the exposure solution. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56229/56229fig3.jpg" /> 
Figure 3. Schematic Drawing of Possible Time-evolutions of the Steel Potential that Illustrates the Criterion for Corrosion Initiation. At point 1, a potential drop by less than 150 mV from the initial &#34;passive level&#34; occurs; at point 2, a potential drop by at least 150 mV occurs, which is followed by repassivation; at point 3, a potential drop of at least 150 mV occurs (within a max. of 5 days) and the achieved negative potential level is sustained over 10 days. At tini, withdraw the sample from the exposure solution. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig3large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/56229/56229fig4.jpg" /> 
Figure 4. Schematic Drawing Illustrating the Cutting and Splitting of the Concrete Sample after Detection of Corrosion Initiation. First, a &#34;trench&#34; is cut from the rear side, in parallel to the steel bar. By inserting a chisel or a similar tool, the trench can be used to split the sample as indicated by the arrows. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig4large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/56229/56229fig5.jpg" /> 
Figure 5. Photographs Illustrating Sample Analysis After Corrosion Initiation. (a) The two halves of the sample after splitting, and (b) a rust spot is visible at the steel surface after corrosion initiation. Photographs from different samples. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig5large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/56229/56229fig6.jpg" /> 
Figure 6. Schematic Drawing Illustrating the Sampling for the Chloride Analysis After Corrosion Initiation: (a) removal of epoxy-coated parts of the split concrete core (purple = cutting planes); (b) removal of the concrete cover down to 2 mm from the steel surface (purple = cutting plane); (c) grinding over a depth interval of +/-2 mm of the steel bar cover depth (red = sampled volume). <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig6large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/56229/56229fig7.jpg" /> 
Figure 7. Representative Examples of Measured Potential vs. Time Curves. The typically pronounced potential drops that may be followed by a potential increase (repassivation) until stable corrosion initiation according to the suggested criterion finally initiates. (a) Shows a case where the potential stabilizes on the negative level, and (b) is an example where the potential continues decreasing over the studied period of 10 days. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig7large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 8" class="xfigimg" src="/files/ftp_upload/56229/56229fig8.jpg" /> 
Figure 8. Example of Ccrit Measured in 11 Samples Taken from Within a Small Concrete Area in a More than 40 Years Old Road Tunnel in the Swiss Alps. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig8large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 9" class="xfigimg" src="/files/ftp_upload/56229/56229fig9.jpg" /> 
Figure 9. Examples of Marked Potential Decreases Immediately upon Exposure in Chloride-free Solution. In one case, the concrete at the steel depth was already carbonated, thus upon arrival of water at the steel surface, the corrosion process immediately started, leading to a sharp decrease in potential. In the other case, false corrosion initiation occurred at one of the steel bar ends, which here led to a more gradual potential decrease. <a href="https://cloudflare.jove.com/files/ftp_upload/56229/56229fig9large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

Watch this Scientific Journal Video about Experimental Protocol to Determine the Chloride Threshold Value for Corrosion in Samples Taken from Reinforced Concrete Structures at JoVE.com

Experimental Protocol to Determine the Chloride Threshold Value for Corrosion in Samples Taken from Reinforced Concrete Structures

We propose a method to measure a parameter that is highly relevant for corrosion assessments or predictions of reinforced concrete structures, with the main advantage of permitting testing of samples from engineering structures. This ensures real conditions at the steel-concrete interface, which are crucial to avoid artifacts of laboratory-made samples.

The aging of reinforced concrete infrastructure in developed countries imposes an urgent need for methods to reliably assess the condition of these ...

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15.3K Views.  ETH Zurich. Wij stellen een methode voor het meten van een parameter die is zeer relevant voor corrosie evaluaties of voorspellingen van gewapend beton-structuren, met het belangrijkste voordeel van het toestaan van testen van monsters van kunstwerken. Dit zorgt voor reële omstandigheden op de staal-beton-interface, die cruciaal zijn om te voorkomen dat artefacten van laboratorium-en-klare monsters.

Video: Experimental Protocol to Determine the Chloride Threshold Value for Corrosion in Samples Taken from Reinforced Concrete Structures

Potentiodynamic Corrosion Testing

Different metallic materials have different polarization characteristics as dictated by the open circuit potential, breakdown potential, and passivation potential of the material. The detection of these electrochemical parameters identifies the corrosion factors of a material. A reliable and well-functioning corrosion system is required to achieve this.
Corrosion of the samples was achieved via a potentiodynamic polarization technique employing a three-electrode configuration, consisting of reference, counter, and working electrodes. Prior to commencement a baseline potential is obtained. Following the stabilization of the corrosion potential (Ecorr), the applied potential is ramped at a slow rate in the positive direction relative to the reference electrode. The working electrode was a stainless steel screw. The reference electrode was a standard Ag/AgCl. The counter electrode used was a platinum mesh. Having a reliable and well-functioning in vitro corrosion system to test biomaterials provides an in-expensive technique that allows for the systematic characterization of the material by determining the breakdown potential, to further understand the material's response to corrosion. The goal of the protocol is to set up and run an in vitro potentiodynamic corrosion system to analyze pitting corrosion for small metallic medical devices.

Here, we present a protocol to set up and run an in vitro potentiodynamic corrosion system to analyze pitting corrosion for small metallic medical devices.

Different metallic materials have different polarization characteristics as dictated by the open circuit potential, breakdown potential, and passivation ...

Environment

Dynamic Electrochemical Measurement of Chloride Ions

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver chloride electrode is used extensively for potentiometric measurement of chloride ions concentration in electrolyte. In this measurement, long-term and continuous monitoring is limited due to the inherent drift and the requirement of a stable reference electrode. We utilized the chronopotentiometric approach to minimize drift and avoid the use of a conventional reference electrode. A galvanostatic pulse is applied to an Ag/AgCl electrode which initiates a faradic reaction depleting the Cl&#713; ions near the electrode surface. The transition time, which is the time to completely deplete the ions near the electrode surface, is a function of the ion concentration, given by the Nernst equation. The square root of the transition time is in linear relation to the chloride ion concentration. Drift of the response over two weeks is negligible (59 &#181;M/day) when measuring 1 mM [Cl&#713;]using a current pulse of 10 Am-2. This is a dynamic measurement where the moment of transition time determines the response and thus is independent of the absolute potential. Any metal wire can be used as a pseudo-reference electrode, making this approach feasible for long-term measurement inside concrete structures.

Dynamic measurement of chloride ions is presented. Transition time of an Ag/AgCl electrode, during a chronopotentiometric technique, can give the concentration of chloride ions in electrolyte. This method does not require a stable conventional reference electrode.

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver ...

Chemistry

Metal Corrosion and the Efficiency of Corrosion Inhibitors in Less Conductive Media

Material corrosion can be a limiting factor for different materials in many applications. Thus, it is necessary to better understand corrosion processes, prevent them and minimize the damages associated with them. One of the most important characteristics of corrosion processes is the corrosion rate. The measurement of corrosion rates is often very difficult or even impossible especially in less conductive, non-aqueous environments such as biofuels. Here, we present five different methods for the determination of corrosion rates and the efficiency of anti-corrosion protection in biofuels: (i) a static test, (ii) a dynamic test, (iii) a static test with a reflux cooler and electrochemical measurements (iv) in a two-electrode arrangement and (v) in a three-electrode arrangement. The static test is advantageous due to its low demands on material and instrumental equipment. The dynamic test allows for the testing of corrosion rates of metallic materials at more severe conditions. The static test with a reflux cooler allows for the testing in environments with higher viscosity (e.g., engine oils) at higher temperatures in the presence of oxidation or an inert atmosphere. The electrochemical measurements provide a more comprehensive view on corrosion processes. The presented cell geometries and arrangements (the two-electrode and three-electrode systems) make it possible to perform measurements in biofuel environments without base electrolytes that could have a negative impact on the results and load them with measurement errors. The presented methods make it possible to study the corrosion aggressiveness of an environment, the corrosion resistance of metallic materials, and the efficiency of corrosion inhibitors with representative and reproducible results. The results obtained using these methods can help to understand corrosion processes in more detail to minimize the damages caused by corrosion.

The testing of processes associated with material corrosion can often be difficult especially in non-aqueous environments. Here, we present different methods for short-term and long-term testing of corrosion behavior of non-aqueous environments such as biofuels, especially those containing bioethanol.

Material corrosion can be a limiting factor for different materials in many applications. Thus, it is necessary to better understand corrosion processes, ...

Determining the Chemical Composition of Corrosion Inhibitor/Metal Interfaces with XPS: Minimizing Post Immersion Oxidation

An approach for acquiring more reliable X-ray photoelectron spectroscopy data from corrosion inhibitor/metal interfaces is described. More specifically, the focus is on metallic substrates immersed in acidic solutions containing organic corrosion inhibitors, as these systems can be particularly sensitive to oxidation following removal from solution. To minimize the likelihood of such degradation, samples are removed from solution within a glove box purged with inert gas, either N2 or Ar. The glove box is directly attached to the load-lock of the ultra-high vacuum X-ray photoelectron spectroscopy instrument, avoiding any exposure to the ambient laboratory atmosphere, and thus reducing the possibility of post immersion substrate oxidation. On this basis, one can be more certain that the X-ray photoelectron spectroscopy features observed are likely to be representative of the in situ submerged scenario, e.g. the oxidation state of the metal is not modified.

A protocol to avoid the oxidation of metallic substrates during sample transfer from an inhibited acidic solution to an X-ray photoelectron spectrometer is presented.

An approach for acquiring more reliable X-ray photoelectron spectroscopy data from corrosion inhibitor/metal interfaces is described. More specifically, ...

Detecting the Water-soluble Chloride Distribution of Cement Paste in a High-precision Way

To improve the accuracy of the chloride distribution along the depth of cement paste under cyclic wet-dry conditions, a new method is proposed to obtain a high-precision chloride profile. Firstly, paste specimens are molded, cured, and exposed to cyclic wet-dry conditions. Then, powder samples at different specimen depths are grinded when the exposure age is reached. Finally, the water-soluble chloride content is detected using a silver nitrate titration method, and chloride profiles are plotted. The key to improving the accuracy of the chloride distribution along the depth is to exclude the error in the powderization, which is the most critical step for testing the distribution of chloride. Based on the above concept, the grinding method in this protocol can be used to grind powder samples automatically layer by layer from the surface inward, and it should be noted that a very thin grinding thickness (less than 0.5 mm) with a minimum error less than 0.04 mm can be obtained. The chloride profile obtained by this method better reflects the chloride distribution in specimens, which helps researchers to capture the distribution features that are often overlooked. Furthermore, this method can be applied to studies in the field of cement-based materials, which require high chloride distribution accuracy.

A protocol for obtaining a water-soluble chloride profile by using a high precision milling method is presented.

To improve the accuracy of the chloride distribution along the depth of cement paste under cyclic wet-dry conditions, a new method is proposed to obtain a ...

Applicability Analysis of Assessment Methods for Morphological Parameters of Corroded Steel Bars

The irregular and uneven residual sections along the length of a corroded steel bar substantially change its mechanical properties and significantly dominate the safety and performance of an existing concrete structure. As a result, it is important to measure the geometry and amount of corrosion of a steel bar in a structure properly to assess the residual bearing capacity and service life of the structure. This paper introduces and compares five different methods for measuring the geometry and amount of corrosion of a steel bar. A single 500 mm long and 14 mm diameter steel bar is the specimen that is subjected to accelerated corrosion in this protocol. Its morphology and the amount of corrosion were carefully measured before and after using mass loss measurements, a Vernier caliper, drainage measurements, 3D scanning, and X-ray micro-computed tomography (XCT). The applicability and suitability of these different methods were then evaluated. The results show that the Vernier caliper is the best choice for measuring the morphology of a non-corroded bar, while 3D scanning is the most suitable for quantifying the morphology of a corroded bar.

This paper measures the geometry and the amount of corrosion of a steel bar using different methods: mass loss, calipers, drainage measurements, 3D scanning, and X-ray micro-computed tomography (XCT).

The irregular and uneven residual sections along the length of a corroded steel bar substantially change its mechanical properties and significantly ...

Determining Tribocorrosion Rate and Wear-Corrosion Synergy of Bulk and Thin Film Aluminum Alloys

The increasing complexity and severity of service conditions in areas, such as aerospace and marine industries, nuclear systems, microelectronics, batteries, and biomedical devices, etc., impose great challenges on the reliable performance of alloys exposed to extreme conditions where mechanical and electrochemical attack co-exist. Finding ways for alloys to mitigate the combined attack of wear and corrosion (i.e., tribocorrosion) under such extreme conditions is thus highly critical for improving their reliability and service lifetime when used in such conditions. The challenge lies in the fact that wear and corrosion are not independent of each other, but rather work synergistically to accelerate the total material loss. Thus, a reliable method to evaluate the tribocorrosion resistance of metals and alloys is needed. Here, a protocol for measuring the tribocorrosion rate and wear-corrosion synergy of Al-based bulk and thin film samples in a corrosive environment under room temperature is presented.

Here, we present a protocol to measure the tribocorrosion rate and wear-corrosion synergy of thin film and bulk Al alloys in simulated sea water at room temperature.

The increasing complexity and severity of service conditions in areas, such as aerospace and marine industries, nuclear systems, microelectronics, ...

Tests on Fresh Concrete

Source:&#160;Roberto Leon, Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA
Concrete consists of two phases, a cement paste phase comprised of cement, water, and air, and an aggregate phase comprised of coarse and fine aggregates. There are two key considerations when designing a concrete mix. First, the concrete must be workable and easy to cast in the forms in its fresh condition, even when the forms are packed with steel reinforcement. In this condition, it is the rheology of concrete that is important. Second, the mix must produce a hardened concrete of specified strength at 28 days (or similar specified time) that is durable and provides good serviceability.
In this laboratory exercise, a method of concrete mixture proportioning, named the trial batch method, will be explored. The concrete produced will be used in conducting typical tests to determine the principal characteristics of fresh concrete, including slump, flowability, air content, and density. The trial batch method is a simple, empirical approach to mixture design.
The objectives of this experiment are fourfold: (1) to use the trial batch mix method to determine optimum proportions of aggregates, cement, and water for concrete to meet specified slump requirements, (2) to learn concrete mixing practice in a laboratory environment, (3) to observe the characteristic properties of fresh concrete, and (4) to prepare 4&#34;x8&#34; concrete cylinders for subsequent evaluation.

Testing Fresh Concrete by the Trial Batch Method

Source:&#160;Roberto Leon, Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA
Concrete consists of two phases, a cement ...

JoVE Science Education

Structural Engineering

Tests of Hardened Concrete in Tension

Source:&#160;Roberto Leon, Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA
In a previous laboratory focused on concrete in compression, we observed that concrete can withstand very large stresses under uniaxial compressive forces. However, the failures observed were not compressive failures but failures along shear planes where maximum tensile forces occur. Thus, it is important to understand the behavior of concrete in tension and particularly its maximum strength as that will govern both its ultimate and service behavior. From the ultimate standpoint, combinations of tension and shear stresses will lead to cracking and immediate and catastrophic failure. For that reason, concrete is seldom if ever used in an unreinforced condition in structural applications; most concrete members will be reinforced with steel so that these cracks can be stopped and the crack widths limited. The latter is important from the serviceability standpoint because controlling crack widths and distribution is the key to durability, as this will impede deicing salts and similar chemicals from penetrating and corroding the reinforcing steel.
The objectives of this experiment are threefold: (1) to conduct tensile split cylinder tests to determine concrete tensile strength, (2) to conduct beam tests to determine concrete tensile strength, and (3) to demonstrate the influence of steel reinforcement on behavior by comparing the behavior of lightly reinforced beam with an unreinforced one.

Split Tension Test and Beam Tension Test for Hardened Concrete

Source:&#160;Roberto Leon, Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA
In a previous laboratory focused on concrete ...

Corrosion of Reinforcement

The corrosion of steel reinforcement within concrete is a process influenced by the material&#39;s inherent properties and external factors. The high pH level of around 13, provided by calcium hydroxide present in concrete, initially protects the steel reinforcement by promoting the formation of a passive iron oxide layer on its surface.
However, over time and under certain conditions like carbonation, chloride ingress, and cracking this protective state can be compromised. Steel has areas with different electrochemical potentials, known as anodic and cathodic regions. The hydrated cement paste, containing salts, acts as an electrolyte that connects these regions. At the anodic regions, iron from the steel dissolves as positively charged ions into the electrolyte, while at the cathodic regions, electrons are consumed in reactions that involve water and oxygen from the surrounding concrete to produce hydroxyl ions.
These hydroxyl ions combine with the dissolved iron to create ferric hydroxide, which further oxidizes to become rust. The presence of chloride ions exacerbates this process, leading to localized pitting corrosion by forming hydrochloric acid that attacks the protective iron oxide layer. This corrosion can expand the steel, causing the concrete to crack and spall.
Preventative measures against the corrosion of steel reinforcement include using protective coatings such as epoxy or zinc on the steel itself or improving the concrete&#39;s quality to reduce its permeability, thereby hindering the ingress of corrosive agents.

Inside a concrete mass, high alkalinity of calcium hydroxide with a pH of around 13 shields steel reinforcement from corrosion by creating a protective ...

Experimental Protocol to Determine the Chloride Threshold Value for Corrosion in Samples Taken from Reinforced Concrete Structures

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