Gordon R. Holcomb

Corrosion prevention and remediation strategies for reinforced concrete coastal bridges

Abstract Oregons coastal highway includes over 120 bridges, most of which are reinforced concrete bridges. Twelve are historic structures. Over 40,000 m 2 of bridge surface has been repaired and is protected from further corrosion damage using thermal-sprayed zinc anodes in impressed current and galvanic cathodic protection (CP) systems. In addition, thermal-sprayed titanium, thermal-sprayed Al–12Zn–0.2In, and zinc-hydrogel anodes are being evaluated in demonstration projects on coastal bridges. Thermal-sprayed zinc anodes are estimated to have a service life exceeding 25 yr but exhibit increasing anode polarization with electrochemical age. Humectants such as lithium nitrate and lithium bromide can reduce anode polarization and extend anode service life. Catalyzed thermal-sprayed titanium anodes develop no significant anode polarization and exhibit stable long-term performance. Zinc-hydrogel galvanic anodes produce a stable protection current with no evidence of aging effects. One of the more powerful and economical tools available for assessing potential corrosion problems in a structure and for characterizing the corrosivity of bridge microclimates is chloride profiling. Current Oregon DOT specifications call for the use of stainless steel reinforcing bar in deck, beams, and precast prestressed girders, and of microsilica concrete in all future coastal bridge construction. Stainless steel bar adds a 10% premium to total project cost compared to black iron bar but is expected to reduce cumulative costs by 50% over the 120+ yr bridge life.

Steam oxidation and chromia evaporation in ultrasupercritical steam boilers and turbines

U.S. Department of Energy’s goals include power generation from coal at 60% efficiency, which requires steam conditions of up to 760 °C and 340 atm, so-called ultra-supercritical (USC) conditions. Evaporation of protective chromia scales is expected to be a primary corrosion mechanism. A methodology to calculate Cr evaporation rates from chromia scales was developed and combined with Cr diffusion calculations within the alloy (with a constant flux of Cr leaving the alloy from evaporation) to predict Cr concentration profiles and to predict the time until breakaway oxidation. At the highest temperatures and pressures, the time until breakaway oxidation was predicted to be quite short for the turbine blade, and of concern within the steam pipe and the higher temperature portions of the superheater tube. Alloy additions such as Ti may allow for a reduction in evaporation rate with time, mitigating the deleterious effects of chromia evaporation.

Dual-environment effects on the oxidation of metallic interconnects

Metallic interconnects in solid oxide fuel cells are exposed to a dual environment: fuel on one side (i.e., H2 gas) and oxidizer on the other side (i.e., air). It has been observed that the oxidation behavior of thin stainless steel sheet in air is changed by the presence of H2 on the other side of the sheet. The resulting dual-environment scales are flaky and more friable than the single-environment scales. The H2 disrupts the scale on the air side. A model to explain some of the effects of a dual environment is presented where hydrogen diffusing through the stainless steel sheet reacts with oxygen diffusing through the scale to form water vapor, which has sufficient vapor pressure to mechanically disrupt the scale. Experiments on preoxidized 316L stainless steel tubing exposed to air-air, H2-air, and H2-Ar environments are reported in support of the model.

Thermal sprayed titanium anode for cathodic protection of reinforced concrete bridges

Stable operation of cobalt catalyzed thermal sprayed titanium anodes for cathodic protection (CP) of bridge reinforcing steel was maintained in accelerated tests for a period equivalent to 23 years service at Oregon Department of Transportation (Oregon DOT) bridge CP conditions with no evidence that operation would degrade with further aging. The cobalt catalyst dispersed into the concrete near the anodeconcrete interface with electrochemical aging to produce a more diffuse anode reaction zone. The titanium anode had a porous heterogeneous structure composed of α-titanium containing interstitial oxygen and nitrogen, and a fee phase thought to be Ti(O,N). Splat cooling rates were 10 to 150 K/s, and microstructures were produced by equilibrium processes at the splat solidification front. Nitrogen gas atomization during thermal spraying produced a coating with more uniform composition, less cracking, and lower resistivity than using air atomization.

Effect of manganese addition on reactive evaporation of chromium in Ni-Cr alloys

Chromium is used as an alloy addition in stainless steels and nickel-chromium alloys to form protective chromium oxide scales. Chromium oxide undergoes reactive evaporation in high-temperature exposures in the presence of oxygen and/or water vapor. Deposition of gaseous chromium species onto solid oxide fuel-cell electrodes can reduce the efficiency of the fuel cell. Manganese additions to the alloy can reduce the activity of chromium in the oxide, either from solid solution replacement of chromium with manganese (at low levels of manganese) or from the formation of manganese-chromium spinels (at high levels of manganese). This reduction in chromium activity leads to a predicted reduction in chromium evaporation factors as much as 35 at 800 °C and 55 at 700 °C. Quantifying the effects of manganese additions on chromium evaporation should aid alloy development of metallic interconnects and balance-of-plant alloys.

Determination of the Initiation and Propagation Mechanism of Fireside Corrosion

A variety of deposit compositions were examined in short-term laboratory tests with the aim of determining the corrosion mechanisms of fireside corrosion for a range of chromia-forming alloys in various combustion systems. The deposits formed in boilers are complex, and despite decades of study, the propagation mechanism of fireside corrosion is not well understood. Alkali iron trisulfates, which are stabilized by SO3 in the gas atmosphere, have been cited to be the major corrosive species for many years. The propagation mechanism for fireside corrosion was investigated using T92 (a typical ferritic boiler steel) and a model austenitic Fe–Ni–Cr alloy in contact with synthetic coal ash deposits. The metal loss, corrosion product morphologies, and compositions were carefully characterized to define a propagation mechanism. The corrosive species responsible for degradation was a (Na,K)2SO4–Fe2(SO4)3 solution and not alkali iron trisulfates. The formation of the liquid deposit is similar to Type II hot corrosion of components in gas turbine engines. The mechanism is a synergistic dissolution process, where simultaneous basic and acidic dissolution of protective Cr2O3 and Fe2O3 disrupts protective oxide formation and locally produces negative solubility gradients at the oxide/salt interface. The dissolved Fe2O3 and Cr2O3 precipitate where there is lower solubility, creating the observed corrosion products. The effect of the deposit composition was examined with respect to the proposed fireside corrosion mechanism. These measurements were found to be consistent with the proposed mechanism based on synergistic fluxing.

On the Relation Between Oxide Ridge Evolution and Alloy Surface Grain Boundary Disorientation in Fe-22 wt % Cr Alloys

cNational Energy Technology Laboratory, Albany, Oregon 97321-2198, USA Oxide ridges formed during the transient stage oxidation of the scale evolution in iron alloys containing 22 wt % Cr that were held at 800°C in dry air. The surface oxidation process was imaged in situ through a confocal scanning laser microscope, and the results were correlated with postexperiment characterization through scanning electron microscopy and the DualBeam system focus ion beam and electron beam analysis combined with three-dimensional reconstruction. The oxide ridges that formed on top of the Cr oxide scale overlapped the intersections of the underlying alloy grain boundaries with the Cr oxide scale. Ridges were generally very small on grain boundaries with disorientation angles of less than 15°, and it was suggested that the boundaries of the surface grains in the alloy may serve as bottlenecks for the transport of scale-forming elements. The effects of La 120 and 290 ppm and Ce 270 and 610 ppm additions during melt-stage processing were also investigated.

PERFORMANCE OF ZINC ANODES FOR CATHODIC PROTECTION OF REINFORCED CONCRETE BRIDGES

Operation of thermal spray zinc (Zn) anodes for cathodic protection (CP) of reinforced concrete structures was investigated in laboratory and field studies conducted by the Albany Research Center (ARC) in collaboration with the Oregon Department of Transportation. The purposes of the research presented in this report were: evaluate the need for preheating concrete to improve the adhesion of the anode; estimate the service life of thermal spray Zn CP anodes; determine the optimum thickness for Zn CP anodes; characterize the anode-concrete interfacial chemistry; and correlate field and laboratory results. Laboratory studies involved accelerated electrochemical aging of thermal sprayed Zn anodes on concrete slabs, some of which were periodically wetted while others were unwetted. Concrete used in the slabs contained either 1.2 or 3 kg NaCl /m3 (2 or 5 lbs NaCl /yd3) as part of the concrete mix design. The Zn anodes were applied to the slabs using the twin wire arc-spray technique. Half of the slabs were preheated to 120-160 C (250-320 F) to improve the initial Zn anode bond strength and the other half were not. Accelerated aging was done at a current density of 0.032 A/m2 (3 mA/ft2), 15 times that used on Oregon DOT Coastal bridges, i.e, . 0.0022 A/m2 (0.2 mA/ft2) Cores from the Cape Creek Bridge (OR), the Richmond San Rafael Bridge (CA), and the East Camino Underpass (CA) were used to study the anode-concrete interfacial chemistry, to relate the chemistry to electrochemical age at the time of sampling, and to compare the chemistry of the field anodes to the chemistry of anodes from the laboratory studies. Cores from a CALTRANS study of a silane sealant used prior to the application of the Zn anodes and cores with galvanized rebar from the Longbird Bridge (Bermuda) were also studied. Aged laboratory and field anodes were characterized by measuring some or all of the following parameters: thickness, bond strength, anode-concrete interfacial chemistry, bulk chemistry, anode resistance, circuit resistance, electrochemical age, and air and water permeability. Models are presented for the operation of periodically-wetted and unwetted thermal spray Zn anodes from the initial energizing of the anode to the end of its service life. The models were developed in terms of bond strength, circuit resistance, anode-concrete interfacial chemistry, electrochemical age, and anode condition. The most significant results of the research are: (1) preheating concrete surfaces prior to coating with Zn is unnecessary; (2) anodes generally fail due to loss of bond strength rather than Zn consumption; (3) Unwetted anodes fail more quickly than periodically-wetted anodes; (4) 0.47-0.60 mm (12-15 mil) anode thickness is adequate for most Oregon DOT coastal impressed current CP (ICCP) installations; (5) based on bond strength, thermal spray Zn ICCP anode service life is approximately 27 years at 0.0022 A/m2 (0.2 mA/ft2); (6) anode reaction products alter the anode-concrete interface by rejecting Ca from the cement paste, by replacing it with Zn, and by the accumulation of a Zn mineral layer that includes chloride and sulfur compounds; (7) CP system circuit resistance provides an effective means for monitoring the condition of Zn ICCP anodes as they age.

High-temperature stability of silver nanoparticles geometrically confined in the nanoscale pore channels of anodized aluminum oxide for SERS in harsh environments

We report the ability of nanoscale pore channels of anodized aluminum oxide (AAO) to endow entrapped silver nanoparticles (Ag NPs) within with structural and oxidation stability for potential surface-enhanced Raman scattering (SERS) at elevated temperatures. AAO was prepared via two-step anodization of high purity aluminum foil in phosphoric acid. Ag NPs of controlled size and coverage were obtained via in situ seeded growth from aqueous AgNO3 solution inside the AAO pore channels. The structural and chemical characteristics and the SERS activity of the Ag NPs before and after environmental exposure in air at up to 600 °C for as long as 5 days were evaluated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. We show that the Ag NPs entrapped in the AAO pore channels exhibit enhanced structural and oxidation stability and thus retain significant SERS activity upon high-temperature treatment, indicating the intricate role of geometric confinement in retarding Ostwald ripening, evaporation loss, as well as oxidation of Ag NPs.

State-of-the-art review of electrochemical noise sensors

There are a number of different techniques capable of being used to measure corrosion within equipment. The most simple, the use of metal coupons, usually causes the process to be shut down, is manpower intensive, and has a time delay in getting the required corrosion information. Electrical Resistance (ER) techniques are often used but their response is very sensitive to temperature and they cannot differentiate between general and localized corrosion. Electrochemical techniques, such as linear polarization resistance (LPR), electrochemical noise (EN), electrochemical impedance spectroscopy (EIS), harmonic distortion analysis (HDA), and electrochemical frequency modulation (EFM), have the capability of solving most of those drawbacks. Electrochemical probes can be mounted permanently in most equipment, give regular measurements of the intensity of corrosion, and some can detect localized corrosion. Of all of the electrochemical techniques, EN has the most potential for being used successfully to measure general and localized corrosion rates of equipment. The EN technique was studied in the late 1970s and early 80s as a means of detecting localized (stochastic) corrosion phenomena, such as occurs with pitting, crevice and cavitation attack. EN measurements are based on fluctuations in electrochemical potential and corrosion current that occur during corrosion. Electrochemical potential is related to the driving force (thermodynamics) of the reaction, while corrosion current is related to the rate of reaction (kinetics) of the reaction. The idea is that random electrochemical events on the surface of a corroding metal will generate noise in the overall potential and current signals. Each type of corrosion (for example general corrosion, pitting corrosion, crevice corrosion, and stress corrosion cracking) will have a characteristic “fingerprint” or “signature” in the signal noise. This “fingerprint” can be used to predict the type and severity of corrosion that is occurring. By comparison, conventional electrochemical techniques such as LPR, EIS, HDA and EFM rely on a steady-state analogy for the determination of general corrosion rates. Early studies were carried out using potential EN measurements, using time domain, statistical and frequency domain analyses to characterise the electrochemical response of systems undergoing localised corrosion. Current EN measurements followed quickly using zero resistance ammetry to study the current noise between two identical electrodes. For general corrosion processes, EN has been demonstrated independently by several workers to provide information similar to LPR. Noise technology has been used to study systems undergoing very low to very high rates of corrosion, for example, coatings performance, passive systems undergoing pit initiation/propagation, condensing systems, systems undergoing stress corrosion cracking, and general corrosion through to the very high corrosion rates experienced during chemical cleaning processes. This review will describe: state of the art methods and probes used to measure EN, data acquisition requirements, theory to analyze the signal and to relate the signal to corrosion rates and types, the results of EN field trials, and laboratory results in environments similar to gaspipelines.