Hartt, William H.

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.

Development of a baseline design protocol for cathodic protection retrofits of offshore structures is becoming an increasingly important topic in light of the large number of structures operating beyond their original cp system design life. One of the critical steps in this development is determination of the total anode mass which is required to continue sufficient cathodic protection for which structure current demand must be established. Three current demand determination methods were investigated including the Gaussian ammeter, the Potential method, which utilizes the driving potential and anode resistance in its current calculation, and the IR Drop method. To this end, three anodes were deployed at the Naval Research Laboratory, Key West, Fl., and current output determinations were made upon these. Each of the three current measurement methods was evaluated on the basis of accuracy, reliability and feasibility in field use.

Twenty-four test cells arranged in a pipe flow setup were assembled to
investigate the effect of seawater velocity on the polarization behavior of
galvanically polarized mild steel. Each 1023 steel pipe specimen of 10.8 em ID
was coupled via a current limiting resistor to a mercury activated aluminum
anode and exposed to a velocity of either 0.03, 0.09 or 0.30 m/s. The resistors
were sized such that polarization was controlled according to one of six slope
parameters. Steady state potential and maintenance current density values were
determined, and a steady state potential vs. current density curve was
established for specimens in each velocity. Some specimens experienced a rise in
cathode potential and current density after an apparent steady state had been
reached. This was probably related to the influence of velocity on the
protectiveness of the calcareous deposit. Of the specimens that experienced a
rise in steady state potential and current density, a few were later observed to
decrease in potential and current density and reach steady state. Steady state
current density vs. velocity plots of specimens at steady state potentials of -0.78,
-0.88 and -0.98 V showed that current density was directly proportional to
velocity as well as relatively insensitive to potential. Ficks' first law was utilized in conjunction with an empirically derived dimensionless correlation that
characterizes the behavior between fluid velocity and mass transfer of molecular
species from the bulk solution to the cathode surface in turbulent seawater pipe
flow. Calcareous deposit porosity constants were calculated and it was surmised
that as velocity increased by a factor of three, the porosity of the deposits near 0.78
and -0.89 V increased by multiples of about two on average. Porosity at the
above potentials increased with decreasing potential by a factor of a little over
two. SEM micrographs were made and EDX analyses were performed on the
calcareous deposits of selected specimens.

Qualification criteria for cathodic protection of pre-tensioned tendon wires in concrete were studied with regard to the risks of embrittlement due to chromium microalloying and existing corrosion damage. The selected materials included two microalloyed (with 0.23 and 0.24 w% chromium) and one non-microalloyed, high carbon prestressing steels. The slow strain rate testing technique was used to evaluate the effects of polarization to -0.90 and -1.30 VSCE upon strength and ductility of the steels. Fractographic analysis was performed using scanning electron microscopy. Based upon statistical analysis, an attempt was made to relate the remaining strength of the corroded wire to the extent of corrosion damage for different corrosion morphologies.

Experiments and analyses were performed to better define the limits of concern regarding hydrogen embrittlement in association with application of cathodic protection to prestressed concrete. To accomplish this, prestressed concrete specimens were locally corroded to different levels by anodic polarization and then polarized to -1.30 V SCE. A procedure of examination was developed using strain gauges to determine the level of prestrain. Relatively few brittle failures of wires resulted due, at least in part, to a relatively low prestrain of the pretensioned tendons. A model was developed which, coupled with data from parallel research, permitted definition of the minimum cross section for brittle failure as a function of the magnitude of prestrain and corrosion morphology of the wire. These results were tabulated in a format that can be used during field inspection to identify structural elements for which fracture could occur upon application of cathodic protection.

A pH determination technique of concrete pore water by means of leaching OH- ions from powdered samples was developed. This method was then evaluated in terms of sample size, extent of dilution, leaching period, the type of leaching, calcium hydroxide error, and titration scatter. Based upon variations of the above parameters it was concluded that a maximum amount of hydroxide ions was released into solution for samples with the smallest particle size within a 24 hours static leaching period. A 50ml dilution volume proved optimum with regard to filtration and titration. Under the above circumstances calcium hydroxide dissolution did not seem to pose a significant source of error. Furthermore, repeatability of the measurements was good and titration scatter was determined to be about 0.05 pH units. This method was used to determine the pH of samples containing different amounts of fly ash or silica fume additions as well as plain cement (control) samples. A drop in OH- concentration, that is pH, was detected with increasing pozzolanic addition. The results are discussed with the context of the degree of corrosion mitigation afforded by these pozzolans.

Hollow, cylindrical mortar specimens of 0.4 water-cement ratio were prepared without reinforcement and exposed to flowing natural sea water for periods up to one year. Direct currents of 2, 10 and 50 mA were impressed between a mixed metal-oxide titanium substrate electrode positioned within each of these two zones, with a different electrolyte supply and exhaust for the cylinder core and exterior surface. Linear expansion of the specimens was evaluated as a function of exposure duration from the output of embedded strain gages and from dimensional measurement of cylinder length and diameter. It was found that expansion of specimens exposed to direct current exceeded baseline ones (no current). Also, the expansion was anisotropic in that different magnitudes and trends were apparent for the diameter versus length directions. The expansion under free exposure (no current) was determined to be a function of specimen size and of the direction of measurement relative to the cast specimen face.

Experiments were conducted to evaluate occurrence of any deterioration of prestressing steel tendon to concrete bond as a consequence of cathodic polarization. Pretensionned concrete specimens were cathodically polarized with current densities ranging from 50 to 5000 m^2 of steel while exposed to a constant flow of natural sea water. The concrete and steel dimensional changes were monitored by strain gages mounted on the tendons and embedded in the concrete. Contractions of the steel of 25 to 50 percent of the initial tensioning were recorded after 17 to 36 MC/m^2 were transferred to the tendons on specimens polarized at the highest currents. This corresponds to 54 to 114 years of polarization at 10mA/m^2 if bond loss was solely dependent on the charge transfer. It was noticed that the smaller the current, the more the charge that was transferred before steel contraction began. These results imply that cathodic polarization should impose no threat to the prestressing steel-to-concrete bond on typical structures over their expected lifetime.

Cathodic protection is currently recognized as the most practical mean for arresting corrosion of reinforcing steel tendons in existing concrete structures, however, its appropriateness in the case of prestressed concrete is questioned because prestressing steels are relatively susceptible to environmental cracking (hydrogen embrittlement). For the purpose of studying embrittlement tendencies a series of experiments using the slow strain rate technique were performed. The susceptibility to environmental cracking was compared for different steels corresponding to ASTM grades 270 and 250 polarized at $-$900 and $-1300$ mV (SCE) in deaerated saturated Ca(OH)$\sb2$ solutions. The influence of different notch and pit geometries was studied to simulate the behavior of corroded tendons and investigate the transition between smooth and severely notched specimen behavior. Also evaluated was the evolution of the mechanical properties of tendons after excessive polarization. The different cracking processes are discussed based on test data, fractography and exposures conditions associated with concrete structures.

Dimensional changes of thin cement paste specimens were monitored during exposure to distilled water, hydrochloric acid, alkaline and FeCl$\sb2$ solutions; and comparison was made with the experimental results obtained by other authors. Post experimental examination of reaction products formed on the specimen surface exposed to FeCl$\sb2$ was conducted using X-Ray diffraction. The data resulting from the measured dimensional changes were input to a finite element model to project the stresses that should occur in association with localized corrosion of embedded steel and wetting of adjacent cement by aqueous FeCl$\sb2$. Implications of the findings with regard to cement and concrete cracking in association with embedded metal corrosion are discussed.