Chlorides

Chloride diffusivity in high performance concrete is influenced by the exposure environment, aside from the concrete mixture properties like, water to cementitious ratio (w/cm) and presence of add-on pozzolans. In this study, a set of concrete specimens (eleven-different concrete mixtures) were cast and exposed to three different environmental conditions (Tidal, Splash and Barge) in which the solution was seawater or brackish water. These exposures simulated environmental field conditions. After the specimens had been wet cured for 32 days (on average), the specimens were exposed to three different field simulation conditions for up to 54 months. The specimens under the field simulated conditions were cored at 6, 10, 18, 30 and 54 months at four elevations and then the chloride profiles were obtained from the cores. The apparent diffusivity values for each profile were calculated based on Fick’s 2nd law. Then, the aging factor “m” was calculated by regression analysis of the diffusivity values vs. time (days) plotted in the log10-log10 scale. This was done for samples exposed to the three different exposure conditions and then the results were compared side-by-side. First, the “m” values were calculated using the exposure duration. Then, to study the effect of including the curing time on “m” value, the curing time was added to the exposure time and a new calculation and “m” value was obtained and compared with the previous results. Moreover, upon inspecting the chloride diffusivity values vs. time plots, it was observed that in some cases, a number of data points showed significantly higher or lower values in comparison with the rest of the data points. It was decided to recalculate the “m” values for these cases, and to only use selected data points instead of all data points (i.e., remove outlier data points). In terms of chloride diffusivity value, it was found that in most cases the specimens with higher water to cementitious (w/cm) ratio showed higher diffusivity, as expected. Further, the presence of pozzolans had a noticeable impact on the chloride diffusivity by decreasing the diffusion rate due to microstructure changes that occurred with time. In terms of “m” values, the result for the field simulated conditions showed a range of “m” values dependent on the specimen’s mixture composition and the elevation at which the specimens were cored. It was observed that the chloride diffusivity declined with time and after a certain amount of time (in this research, almost after 30 months) the diffusivity reduction became small and a transition in the slope of the diffusivity trend appeared in a number of cases. After the transition, the diffusivity trend reached either a plateau zone or continued with a significantly lower slope, depending on the time, composition and exposure. It was found that the specimens under tidal and splash field simulation conditions that had only fly ash in their mixtures showed higher “m” values when compared with samples that contained fly ash and silica fume or fifty percent slag.

Critical chloride threshold, CT values for initiation of reinforced steel corrosion m
mortar typical of Florida coastal bridge substructures were determined in laboratory tests.
Previous research has reported CT values that vary by more than an order-of-magnitude,
making design life estimation for structures difficult. On this basis, experiments on
piling type specimens focused on [Cl-] contamination in the splash zone and coupling of
this steel to a large surface area submerged anode. The lower portion of simulated piling
was immersed and the region above the waterline periodically sprayed with NaCI
solution. Corrosion potential with respect to height above the waterline was monitored.
A temporary depolarization method for determining as to whether or not corrosion had
initiated is proposed. Chloride distribution at the reinforcement-concrete interface was
determined in piling using energy dispersive x-ray analysis and related to height with
respect to the waterline. Chloride threshold was related to corrosion potential.

The penetration of chloride ions through concrete can compromise the integrity of
a structure. The chloride concentration, [Cl-], at which the corrosion process initiates is
termed the critical chloride concentration or chloride threshold, [Cl-]th. One of the
purposes of this research was to determine the [Cl-]th for various reinforcing alloys.
Furthermore, the time-to-corrosion (TIC) was measured to determine the time at which
bars become active. Both parameters, [Cl-]th and TTC, were found to be distributed;
therefore, statistical analyses were performed to forecast the probability of activity. A
new experimental procedure was introduced to increase the TTC data set by electrically
isolating the top bars as they became active.
The research also compared the [Cl-] for core samples with those values obtained
from along the top rebar trace. In general, this analysis demonstrated that core sample
[Cr] was lower than at the rebar-trace.

The objective of this study was to determine whether the presence of undissolved calcium hydroxide at the steel interface helped maintain or delay the breakdown of passivity under adverse conditions, such as the presence of chlorides and carbonation. Saturated calcium hydroxide solution was used as an electrolyte in the test cell, and steel specimens were exposed to a range of chloride ion concentration and carbonation. The results indicate that undissolved calcium hydroxide has an important role in the passivation of reinforcing steel. Also, the critical chloride to hydroxide ratio may be more relevant in characterizing the breakdown of passivity than the threshold value of total or soluble chloride present in the electrolyte. It was noted that in the presence of undissolved calcium hydroxide, steel remained passive for as high a chloride ion concentration as 0.54% (by weight of electrolyte).

In order to identify the influence of chlorides and surface finish on pitting potential of high performance reinforcing steel, cyclic polarization scans were performed on types 304, 2201 and 3Cr12 stainless steels and MMFX-II in simulated pore solution to which chloride was incrementally added. Furthermore, the surface condition was investigated with regard to the pitting potential. Pitting potential distributions versus the chloride content and surface finish were obtained. Pitting resistance was lowered as chloride was added and as the surface became rougher. Furthermore, a critical chloride to hydroxide ratio as a function of potential was determined for each material. Finally, according to the results of this study, the MMFX reinforcing steel was considered to have a corrosion performance close to that of Type 2201 stainless steel for bridge use. MMFX-II specimens with a polished surface exhibited more positive pitting potentials than did ones with an as-received finish.

A study was performed of variables that affect the chloride threshold for corrosion of reinforcement, including pore water alkalinity, water-to-cement ratio, the use of Florida aggregate, and the addition of fly ash. To accomplish this, specimens were subjected to a periodic wet-dry ponding cycle using 15% by weight NaCl solution. Half cell potential and macrocell current measurements were taken to determine the time to corrosion. Upon active corrosion, the specimens were removed from the ponding cycle and dissected. Powder samples were collected from the concrete at the steel depth to ascertain the total chloride concentration. The determination of the pore water pH was attempted using a leaching method. To date only a portion of the specimens have displayed corrosion. The role of cement alkalinity and water-to-cement ratio in affecting corrosion resistance is reported and the results are discussed within the context of designing concrete structures for corrosion resistance.

Effects of (1) cement alkalinity (low, normal and high), (2) exposure conditions (RH and temperature), (3) rebar surface condition (as-received versus cleaned) and (4) density and distribution of air voids at the steel-concrete interface on the chloride threshold and time-to-corrosion for reinforcing steel in concrete have been studied. Also, experiments were performed to evaluate effects of RH and temperature on the diffusion of chloride in concrete and develop a method for ex-situ pH measurement of concrete pore water. Once specimens were fabricated and exposed to a corrosive chloride solution, various experimental techniques were employed to determine time-to-corrosion, chloride threshold, diffusion coefficient and void density along the rebar trace as well as pore water pH. Based upon the resultant data, several findings related to the above parameters have been obtained as summarized below. First, time for the corrosion initiation was longest for G109 concrete specimens with high alkalinity cement (HA). Also, chloride threshold increased with increasing time-to-corrosion and cement alkalinity. Consequently, the HA specimens exhibited the highest chloride threshold compared to low and normal alkalinity ones. Second, high temperature and temperature variations reduced time-to-corrosion of reinforcing steel in concrete since chloride diffusion was accelerated at higher temperature and possibly by temperature variations. The lowest chloride threshold values were found for outdoor exposed specimens suggesting that variation of RH or temperature (or both) facilitated rapid chloride diffusion. Third, an elevated time-to-corrosion and chloride threshold values were found for the wire brushed steel specimens compared to as-received ones. The higher ratio of [OH-]/[Fe n+] on the wire brushed steel surface compared to that of as-received case can be the possible cause because the higher ratio of this parameter enables the formation of a more protective passive film on the rebar. Fourth, voids at the steel-concrete interface facilitated passive film breakdown and onset of localized corrosion. This tendency for corrosion initiation increased in proportion to void size irrespective of specimen type. Also, [Cl -]th decreased with increasing void diameter. In addition, new ex-situ leaching method for determining concrete pore water alkalinity was developed.

The aim of this study was to investigate the diffusion of chloride ions into concrete samples that were exposed in scenarios that simulate the splash, tidal, atmospheric, and immersed portions of a marine structure. To study the atmospheric deposition, the project also investigated the relationship between chloride ion deposition on the wet candle and its accumulation into concrete samples. Results from the wet candle experiment indicated that between 2% and 45% of the chlorides deposited per square meter of exposed area could be found within the concrete samples. After 6 months, slag G1a blocks showed the most resistance to chloride penetration in the tidal and splash simulations. After 10 months of exposure, fly ash samples had the slowest rates of diffusion in the tidal simulation while the fly ash + silica fume samples and the slag samples measured similar rates of diffusion within the tidal zone. After 90 days of curing, cylinders composed of 20% fly ash & 8% silica fume measured the highest average resistivity values and were found to be less vulnerable to chloride ion penetration than the 20% fly ash and the 50% slag concrete through rapid migration tests.