This report summarizes the work completed in Phase 1 and Phase 2 of PRCI SCC-2-12 project: Effect of Pressure Fluctuations on Growth Rate of Near-Neutral pH SCC. The following two insights from the two-phase PRCI SCC 2-12 project can be proven to be the most important: 1) The identification of three types of pressure fluctuations and their different susceptibility to crack growth; 2) The importance of load interaction effects during variable amplitude pressure fluctuations in the prediction of crack growth rate. The work has enabled us to divide near-neutral pH SCC cracking into the following two governing processes: the dissolution growth process for crack initiation and early stage crack growth and the hydrogen facilitated fatigue growth after crack initiation and dormancy. The first process features very high rate of dissolution at the pipe surface caused by various forms of galvanic processes and reduced crack growth in the depth direction leading to crack dormancy. The hydrogen facilitated fatigue growth process has been determined to be predominant for the crack growth after crack initiation and dormancy. Depending on the location of pipeline sections, the pressure fluctuations could be characterized into three types based on the relative pressure levels of the large loading events and the minor cycles. It has been determined from extensive experimental investigations that crack growth under Type I pressure fluctuations with frequent underload cycles, which is often found within 30 km downstream of a compressor station, can be enhanced significantly because of effects of load interactions of variable amplitude of cyclic loading. The load-interactions during SCC of pipeline steels in near-neutral pH environments are complex, which include both the time independent load-history interactions and the time dependent load interactions related to the rate of diffusion of hydrogen and hydrogen embrittlement in response to various scenarios of pressure fluctuations. Based on the experimental findings obtained, strategies for mitigating near-neutral pH crack initiation and crack growth during field operations have been proposed. The experimental findings have also been integrated into a software, namely the Pipe-Online, for making crack growth and remaining life prediction. For the purpose of capturing all the crack-growth contributing events of pressure fluctuations for life predictions, a method of recording pressure fluctuations has also been developed.
Pipelines are designed to operate below a maximum operating pressure in service. However, there are pressure fluctuations during operation. The presence of pressure fluctuations creates a drive for crack growth in steel pipes. In order to prevent catastrophic failure of pipelines, there is need for better understanding of the contribution of pressure fluctuations to crack growth rate in steel pipelines. Analysis of pressure fluctuation data in oil and gas pipelines shows that there are different types of fluctuations in a pipe due to friction loss with distance from the pump or compressor station. All these fluctuation types show a form of variable amplitude loading classified in this research as underload, mean load and overload. Studies of some structural systems shows that underload can cause acceleration of crack growth while retardation of crack growth is observed after an overload. This research aims to apply pressure fluctuations to manage integrity of steel pipelines through a novel approach of load sequence involving underload and overload in near neutral pH environment. Clear knowledge of the effect of load interaction involving load sequence of underload and overload is vital to control crack growth in steel pipelines under near neutral pH environment. The result of crack growth rate under different load sequence on X65 steel indicate that increase in overload ratio of 2, 3 and 4 caused an increase in crack growth rate of 1.68E−3, 1.89E−3 and 2.31E−3 mm/block respectively. These results are compared with results from other tests under variable amplitude without load sequence. Analyses were carried out on the morphology of the crack tip and the fracture surface after the test.
Ce or CeO2 is often added to Fe–Cr–Ni base alloys to enhance protective Cr2O3 ceramic scale formation. In high-temperature carbonaceous reducing environments, however, it is still unsolved that Ce-containing alloys often exhibited increased carburization and coke formation. This research is aimed at understanding the mechanism of Ce-enhanced coke formation. It was found that CeO2 can cause catalytic activation of chromium carbide for carbon growth by first forming CeCrO3 and then decomposing CeCrO3 into CeO2 and active nanosize chromium carbide particles; the latter has proven to be conducive to coke formation. These findings can be helpful for the design of alloys with better ceramic coating resistant to carbonaceous degradation and for the growth of graphitic nanostructures using Cr-related catalysts.
High pH Stress Corrosion Cracking (HpHSCC) is a significant threat to the buried pipelines, which are protected through simultaneous coating and cathodic protection strategies. In the past decades, extensive research has been devoted to assessing the influence of environmental and metallurgical factors on the susceptibility to HpHSCC. With reference to mechanical factors, previous studies employed either slow strain rate or constant amplitude testing methods. However, the pressure fluctuation data extracted from pipeline operations has indicated that pipelines experience highly variable amplitude loading conditions during their service. Accordingly, an important consideration in managing HpHSCC is load interaction. Statistics show a higher probability of HpHSCC failures within the 30 km downstream from pump/compressor stations where the pipeline steels experience elevated service temperatures, with incipient higher susceptibility to HpHSCC. However, the pipeline sections within the 30 km downstream from pump/compressor stations also experience the underload-type of pressure fluctuations that feature a maximum pressure close to the design limit, frequent and large amplitudes of depressurization, resulting in low stress ratio, R (minimum stress/maximum stress), and many smaller pressure fluctuations (minor cycles) with R ratio closer to +1.0. It has been well characterized that the underload-minor-cycle-type of pressure fluctuations has the significant acceleration effect on crack growth rates in near-neutral pH (NNpH) environments. However, the effect of the underload-type of pressure schemes on HpHSCC crack growth has not been well developed. In this research work, a cathodically protected X65 steel specimen in the developed high pH solution, composed of 1N Na2CO3 and 1N NaHCO3, was subjected to different loading conditions. These loading waveforms simulate underload cycles (R = 0.5), minor cycles (R = 0.9) and variable amplitudes consisting of both underload and minor cycles, respectively. The HpHSCC test results showed that the highest and lowest crack growth rates were obtained in high and low R ratio constant amplitude loading conditions, respectively. Furthermore, an intermediate crack growth rate was obtained under variable amplitude loading condition. These results indicate that the underload cycles retard crack growth rate in high pH environments.
The development of inexpensive carbon fiber precursors is necessary to meet the future demands of carbon fibers. This work shows how asphaltenes, which are obtained as a by-product in bitumen production, can play an important role as such inexpensive carbon fiber precursors. To synthesize carbon fibers from asphaltene, stabilization by means of oxidizing acids (HNO3 and H2SO4) was developed. Stabilization could not be achieved by a non-oxidizing acid (HCl). The reactions leading to fiber stabilization was investigated for nitric acid treatment, which led to oxidation and the incorporation of nitro-groups. Further thermal treatment caused an increase in C/H ratio that was related to decomposition of nitro-groups, which facilitated air oxidation and other reactions leading to the loss of volatile hydrogen-rich products, such as light hydrocarbons. Additionally, the influence of the acid concentration during treatment on fiber properties, such as fiber diameter, composition, tensile strength and elastic modulus, has been examined. The application of the acid treatment leads to carbon fibers with good tensile properties, with a tensile strength and elastic modulus of 811 MPa and 32.7 GPa, respectively. The overall yield of carbon fibers is 37 – 38 wt.%.
A three-dimensional ultralong-CNTA-supported Pd-based anode (Pd/CNTA) has been designed for ethanol oxidation. Nano-size Pd particles were uniformly attached to the surface of CNTs within CNTA by using pulse electrodeposition technique. The as-prepared Pd/CNTA anode is featured with low ion diffusion resistance, vertical electron conduction, and large surface area, which offer enhanced active sites for ethanol oxidation reaction and allow fast ion adsorption/desorption from the electrode. The performance of the Pd/CNTA anode is tested and compared with that of Pd/C and Pd/MWCNT (multiwall carbon nanotube) electrodes for ethanol oxidation in alkaline media. The mass activity of the current Pd/CNTA electrode was 17.5 and 10.3 times higher than that of Pd/C and Pd/MWCNT electrodes, respectively. This novel electrode can provide efficient ethanol oxidation and may form a new promising platform for both fundamental investigation of the effects of electrode structure and the development of high-performance alkaline direct ethanol fuel cells.
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