Corrosion and anti-corrosives

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.

This research proposed to characterize any microbial induced degradation of carbon fiber/polyetheretherketone (PEEK) composites from acid-producing bacteria (APB) and sulfate-reducing bacteria (SRB). Electrochemical impedance spectroscopy (EIS) was used to provide a measure of degradation of the composite system as a function of exposure time. In addition, mechanical testing and microscopic evaluation of the specimens were utilized to determine if changes in the EIS spectra as a function of exposure time correlated to changes in the mechanical properties. Results from most EIS scans were consistent with a well-consolidated and undamaged composite system. Changes in the EIS response of specimens exposed to the SRB environment were not matched by a reduction in the flexural strength. Mechanical testing also indicated no reduction in the flexural strength in any of the other exposure environments. Environmental scanning electron microscopy (ESEM)/energy dispersive x-ray spectroscopy (EDS) were inconclusive, though changes in the EDS spectra were seen. No definitive degradation was seen to occur in this composite system.

Experiments were conducted to investigate the effectiveness of ion vapor deposited (IVD) aluminum as a base coat for polyurethane topcoat systems in marine environments. Three test environments were used including marine atmospheric atmosphere, quiescent filtered seawater open to laboratory air and aerated seawater. Visual observation and electrochemical impedance spectroscopy techniques were primary testing methods; other characterizations included adhesion tape test, coating thickness measurements, holiday detection, optical microscopy, open circuit potential measurements and potentiodynamic polarization. It was found that IVD aluminum was a good candidate for replacement of environmentally sensitive coatings on AA2219-T87 and AISI 4340 steel substrates, respectively. The IVD aluminum coating provided good sacrificial protection and served as a good base for polyurethane topcoat systems. Electrochemical impedance spectroscopy was a suitable method to predict coating performance in the early stages of exposure.

Experiments were conducted to determine the effectiveness of localized cathodic polarization for reducing corrosion of simulated prestressed concrete piles containing admixed calcium chloride and exposed to a simulated sea water tidal cycle. The specimens contained both continuous and segmented steel tendons, the purpose of the latter being to facilitate measurement of cathodic protection current. Conductive rubber in an impressed current system was used as the anode material. The specimens were initially freely corroded and then cathodically polarized at a constant current ranging from 0.5 to 1 mA/m$\sp2$ which corresponded to potentials (current-on) which ranged from $-$0.500 to $-$1.100 V(sce) in the anode region. The magnitude of impressed current and its distribution along the embedded steel was monitored as a function of exposure time, level of polarization and water levels. Current-on and instant-off potential distribution for both the continuous and segmented tendons were also measured. The level of cathodic polarization was assessed as a function of position along the specimens by the depolarization method. The results were evaluated within the context of marine bridge substructure cathodic protection technology.

The objective of this study was to determine the influences of chlorides, pH and surface films on the corrosion of reinforcing steel in alkaline solutions. Anodic and linear polarization experiments were conducted on 1018 steel specimens exposed to these environments. The results indicate that there is a threshold amount of [Cl-] beyond which passivity is compromised. The i-passive in the electrolyte of pH 12.24 was approximately 0.01 of that in the electrolyte of pH 10.13. At least a one day period was necessary for the effect of the excess crystals of Ca(OH)2 to be felt. Corrosion rates of specimen with a Ca(OH)2 surface film were lower than without this film. [Cl-] /[OH-] in the range 2.5 to 3.5 appeared to be the threshold for breakdown of passivity.

Study of selected candidate steels for offshore application was undertaken to observe the effects of cathodic protection and cyclic frequency on corrosion fatigue life. Keyhole Compact Tension Fatigue experiments under constant amplitude sinusoidal loading and stress ratio of 0.5 were performed on 25.4 mm thick specimens in natural sea water and also in air upon three different steels (Y.S. 500-563 MPa). These steels represented different strengthening techniques, namely precipitation hardening, direct quenching--a thermomechanical control process (TMCP), and controlled rolling. Cathodic polarization was in the range between freely corroding and -1.10 Volts (SCE). The tests were performed at a frequency of 0.3 and 1.0 Hz. The results are presented in the S-N and potential versus cycles to initiation format. No effect of frequency (1.0-0.3 Hz) was observed at cathodic protection of -1.10 V (SCE). The steels showed an increase in fatigue life to an optimum potential, and excessive potentials were detrimental. The fatigue life in dry air was greater than in laboratory air (~50% RH).

Two models for pipeline bracelet anodes depletion with time were analyzed: one with uniform corrosion and the other with localized corrosion. The potential of the pipeline was determined to become more positive with time due to corrosion of the anode. The pipeline protected by the anode with localized corrosion had more a positive potential than the one protected by the anode with uniform corrosion. A method based upon the equations of Sunde was developed for determining resistance of linear and rectangular anode arrays. Accuracy of this approach was evaluated using Boundary Element Modeling (BEM). The difference between the two methods was defined as Error. A corrected function of Sunde's equation was developed in order to get a more accurate resistance of a 1 x N anode array. The influence on resistance of a M x N (M < N) anode array of anode size, separation distance and array number was analyzed. Error increased with increasing anode size and decreased with increasing number of anodes and separation distance. The application and limitations of commonly used anode resistance formulas are discussed.

Tests in a cyclic chamber and in real atmospheric conditions resulted in the development of an improved corrosion coulometer sensor. First tests showed that it responded well in a reproduced environment but not satisfactorily in a real one, although it seemed to present a good correlation with the weather observations. However, these tests allowed a small time step data analysis of atmospheric corrosion and therefore an improved knowledge of this process. Also discussed are the possible ways of retrieving the corrosion coulometer data wirelessly, thus allowing a real-time analysis of atmospheric corrosion on steel structures. Ideas are proposed for improving both the sensor and the electronic package to make the system an efficient monitor of atmospheric corrosion.

Near-threshold fatigue crack growth rate data were generated for six high strength steels at stress ratios of 0.5 and 0.8 under different environmental conditions, which included air, freely corroding in seawater, and cathodically polarized in seawater to -0.80v, -0.95v and -1.10v (vs SCE). The influence of stress ratio, loading frequency, magnitude of cathodic polarization and initial DeltaK on fatigue crack growth behavior for these high strength steels was experimentally characterized. The results disclosed general trends of fatigue crack growth under conditions relevant to offshore structure applications and circumscribed variables that are primarily influential with regard to service performance. The rate controlling processes and cracking mechanisms of near-threshold fatigue crack growth, particularly under cathodic polarization in seawater, were also studied in conjunction with crack mouth opening displacement measurements, fractographic observation and crack profile examination. The data and observations suggest that calcareous deposit induced closure was the rate-controlling factor for near-threshold fatigue crack growth under cathodic polarization in seawater although the cracking involved a brittle failure mechanism as a result of hydrogen embrittlement. With different FCGR determining procedures which included natural K-decreasing, enhanced K-decreasing, natural K-increasing and constant DeltaK, the FCGR under cathodic polarization in seawater was found to be time-dependent and, as such, was not a unique function of DeltaK but depended upon K-history or experimental procedures. These observations were consistent with results of a theoretical analysis which involved kinetics modeling of the interaction between fatigue crack growth and calcareous deposit thickening. The model also predicted the existence of an upper limit transition DeltaK, DeltaK Upp/T, between the Paris and threshold regions and it was found that the predicted DeltaK Upp/T was in agreement with the experimental one. The basis for applying this critical parameter (DeltaK Upp/T) to offshore structure designs was addressed in conjunction with experimental results.

A study of the corrosion protection afforded by epoxy coatings on reinforcing steel was performed. To accomplish this bars were acquired from ten sources and coatings were characterized in terms of defects, thickness, solvent extraction weight loss and hardness. Testing involved exposure in various aqueous solutions at both ambient temperature and 80$\sp\circ$C and in chloride-contaminated concrete slabs under outdoor exposure. Direct pull-off adhesion testing was performed on tested and virgin epoxy coated reinforcing steels (ECRs). Electrochemical impedance spectroscopy (EIS) scans were made periodically, and a curve fitting technique was employed to analyze coating parameters. Conventional electrochemical measurements were also made, and corrosion morphology of ECR specimens was examined. It was found that the density and size of coating defects was the primary factor affecting ECR performance. The circuit analysis indicated that poorly performing defect-free coatings absorbed water and oxygen; and these species reached the coating/substrate interface and electrochemical reactions at the interface caused coating degradation. By way of contrast, the impedance response for well-performing ECR specimens showed no signs of active degradation at the interface although diffusional processes similar to those noted for poorly performing bars occurred here also. Experimental results indicated a relationship between corrosion behavior and bar source. Weight loss upon solvent extraction correlated with impedance reduction from hot water exposure. Coating defects developed during most of the tests, especially in high pH solutions containing chloride ions. ECRs with excessive coating defects, either initially present or ones which developed in service, performed poorly in every test category regardless of source. Forms of coating failure were extensive rusting at defects, blistering, wet adhesion loss, cathodic delamination, underfilm corrosion and coating cracks. These occurred sequentially or concurrently, depending on the condition of the ECR and nature of the environment.