The cyclic oxidation behavior of a Ni-Mo-Cr alloy was studied in air at 900 degrees C for exposure periods of up to 1000 h. The morphology, microstructure and composition of the oxide scale was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. Oxidation kinetics was determined by weight gain measurements. The results show that steady state oxidation was achieved within I h of exposure. During transient oxidation, the alloy grain boundaries intersecting the alloy surface became depleted in Ni and enriched in Mo and Cr. The scale initially formed at the surface was NiO which grew outwardly. However, a protective Cr2O3 layer developed, rapidly retarding the rate of oxidation. Formation of NiMoO4 was also observed. The presence of Mo in the alloy facilitated the formation of a Cr2O3 layer at an early stage of oxidation. The alloy exhibited considerable oxide spalling during prolonged exposure. (c) 2006 Elsevier Inc. All rights reserved.

This paper demonstrates the effect of materials selection and design on the performance of engineering products, with the help of two case studies. In each case, the process constituted production of Hydrogen (H2) gas by cracking of methane (CH4) using a catalytic steam reformer. The failed component was outlet manifold pipe of the steam reformer. In the first case, a heat-resistant steel casting grade HP+Nb was used while wrought INCOLOY alloy 800H tubing was employed in the second case. Dimensions of the pipe varied in each case depending on the type of material used. This variation in material and design resulted in significant difference in service performance such that the pipe in case 1 failed after only 22,000h of service while that in case 2 remained in operation for 83,000h.

An investigation was conducted to determine the role of Pt in a thermal barrier coating system deposited on a nickel-base superalloy. Three coating systems were included in the study using a layer of yttria-stabilized zirconia as a model top coat, and simple aluminide, Pt-aluminide, and Pt bond coats. Thermal exposure tests at 1,150 °C with a 24-h cycling period to room temperature were used to compare the coating performance. Additional exposure tests at 1,000, 1,050, and 1,100 °C were conducted to study the kinetics of interdiffusion. Microstructural features were characterized by scanning electron microscopy and transmission electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction. Wavelength dispersive spectroscopy was also used to qualitatively distinguish among various refractory transition metals. Particular emphasis was placed upon: (i) thermal stability of the bond coats, (ii) thickening rate of the thermally grown oxide, and (iii) failure mechanism of the coating. Experimental results indicated that Pt acts as a “cleanser” of the oxide-bond coat interface by decelerating the kinetics of interdiffusion between the bond coat and superalloy substrate. This was found to promote selective oxidation of Al resulting in a purer Al2O3 scale of a slower growth rate increasing its effectiveness as “glue” holding the ceramic top coat to the underlying metallic substrate. However, the exact effect of Pt was found to be a function of the state of its presence within the outermost coating layer. Among the bond coats included in the study, a surface layer of Pt-rich γ′-phase (L12 superlattice) was found to provide longer coating life in comparison with a mixture of PtAl2 and β-phase.

A large number of radiant tubes belonging to an ethylene furnace of a petrochemical plant failed during service. All tubes exhibited severe carburisation, while some of them lost their structural integrity and sagged. The tube material was based on a Fe-Ni-Cr alloy system with three varying compositions. Scanning electron microscopy and energy dispersive X-ray spectroscopy were used to characterize the microstructure and elemental composition of the tube material. Microhardness was tested to determine their mechanical strength. Experimental results indicated that the sagged tubes exhibited a higher degree of carburisation as compared to other tubes. The microstructure of these tubes also revealed coarser Cr-carbide precipitation and a continuous carbide lattice at austenite grain boundaries. It was concluded that exposure to excessive temperature during service was responsible for the degradation of all tube materials. Based on the above results, it is recommended that better control of furnace temperature should be employed in order to avoid overheating during service.

Transfer line tubes of an ethane pyrolysis furnace, operating at 850 +/- 20 degrees C and 1.0 atm pressure, developed longitudinal cracks after less than one third of their expected service life. The tubes were constructed of Fe-based USN N08810 alloy with a wall thickness of 10 mm. Metallurgical evaluation revealed that the mode of failure was high-temperature carburization attack leading to intergranular cracking. The cause of failure was overheating, likely to have occurred during decoking operations. Better control of furnace temperature was recommended to avoid overheating. Alternatively, a wrought alloy capable of developing highly protective aluminum oxide (Al2O3)-base scale such as Ni-based UNS N07214 could be used as a replacement.

In this paper, the procedure for conducting quantitative elemental analysis by ZAF correction method using wavelength dispersive X-ray spectroscopy (WDS) in an electron probe microanalyzer (EPMA) is elaborated. Analysis of a thermal barrier coating (TBC) system formed on a Ni-based single crystal superalloy is presented as an example to illustrate the analysis of samples consisting of a large number of major and minor elements. The analysis was performed by known standards and measured peak-to-background intensity ratios. The procedure for using separate set of acquisition conditions for major and minor element analysis is explained and its importance is stressed.

An outlet transfer line tube of an ethylene-cracking furnace failed after five years of service. The tube, made from Incoloy alloy 800H, developed cracks that penetrated the entire thickness. Optical and scanning electron microscopy, X-ray diffraction, and microhardness tests were used to evaluate the failed tube. It was found that the tube was considerably embrittled by high-temperature carburization, leading to intergranular fracture at the inner surface. Carburization appeared to have been caused by high-temperature exposure to the carbonrich atmosphere associated with the coke adhered to the inner surface. Additionally, the decrease in heat transfer due to the coke deposits caused the wall temperature to increase during service. However, at the outer surface, the tube fractured by a fatigue process that could result from the use of a counterweight to prevent sagging of the tube as a result of the coke deposition. Based on the results obtained, a short-term solution was to modify various process parameters to reduce the extent of coke deposition and/or increase the frequency of decoking and to discontinue the use of a counterweight. However, the long-term solution is to replace alloy 800H.

PurposeTo determine if the interim use of liquid waste as a fuel in a catalytic steam reformer unit had any deleterious effect on the long‐term life of the reformer tubes.Design/methodology/approachStandard metallographic techniques were used to prepare representative samples obtained from various sections of the reformer tubes for metallurgical evaluation. Microstructural characterization was carried out in a scanning electron microscope equipped with an energy dispersive X‐ray spectrometer. Imaging and elemental analysis was used for the identification of the alloy material, corrosion products and other microstructural features.FindingsHydrogen was produced in a catalytic steam reformer by cracking methane using natural gas as a fuel. Corrosion of reformer tubes occurred when natural gas fuel was replaced with a liquid waste. Use of liquid fuel waste accelerated the rate of oxidation at the outer tube surface. However, foreign species from the fuel were not transported into the tube material. The heat‐resistant steel casting used for this application was susceptible to precipitation of Si‐stabilized Ni‐Nb Laves phase, thus reducing rupture life of the component. Voids at grain boundaries indicative of creep damage were observed.Practical implicationsAlthough, the interim use of liquid waste fuel appeared not to have damaged the tubes, it was concluded that the expected service life of the tubes may not be realized because of the susceptibility of the material to precipitation of Laves phase. An Fe‐base superalloy UNS N08810 or UNS N08811 was recommended as a replacement material for this application.Originality/valueThis paper provides an account of a failure analysis study. It identifies incorrect materials selection for a particular application and suggests better alternative along with its justification. The information is deemed useful for plant designers and engineers working in the related industry.

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VINYL-CHLORIDE monomer and poly-vinyl chloride are extensively used as raw materials by the plastic industry. Petrochemical plants that produce these raw materials are often highly structured units employing a wide variety of engineering materials in their construction and design. The selection of a particular material is based on the performance of a component required under specific conditions. This paper describes the materials' evaluation of a dryer support component used in the drying unit of a PVC plant.The component was made of 304-type stainless steel and was fractured after a relatively-short period of service. Various techniques used for materials analysis included scanning-electron microscopy combined with energy dispersive X-ray spectroscopy and diffraction. The dryer support appeared to fail by hydrogen-induced cracking (HIC). Based upon the results obtained, it was recommended to use an alloy more resistant to hydrogen-induced cracking such as the 309-type stainless steel.

The oxidation behaviour of a wrought Ni‐Mo‐Cr alloy was studied under thermal cyclic conditions in air at 800°C for exposure periods of up to 1,000 h. The morphologies, microstructures and compositions of the oxide scales were characterized by scanning electron microscopy, energy dispersive X‐ray spectroscopy and X‐ray diffraction. Oxidation kinetics were determined by weight gain measurements. Results show that steady‐state oxidation was achieved within 1 h of exposure while partial scale spalling was observed after 400 h. The alloy grain boundaries intersecting the alloy surface showed preferential oxidation. They became depleted in Ni and enriched in Mo and Cr during transient oxidation. The scale initially formed at the surface was NiO which grew outwardly and laterally to cover the entire alloy. Upon continued oxidation, the scale developed into an outer NiO layer and an inner Cr2O3 layer while the presence of NiMoO4 was also observed within the scale.

A number of weld joints between carbon steel (CS) pipe and type 304 stainless steel (SS) elbows constituting a gas piping system of a petrochemical unit developed cracks after a relatively short period of usage, resulting in leakage. The gas flowing through the pipe, was hydrogen rich at a temperature of 45 °C and a pressure of 16 kg/cm2. Light optical metallography and scanning electron microscopy, combined with energy dispersive X-ray spectroscopy, inductively coupled plasma and microhardness testing were used to determine the most probable cause of failure. Analysis showed that the cracks originated at the interface between the CS pipe and the SS root weld. A narrow band between the CS pipe and SS weld exhibited a hardness of Rockwell C 60 suggesting the formation of martensite due to C segregation at welding temperature and subsequent quenching during cooling. The ferritic region of CS adjacent to the weld was decarburized and was devoid of pearlite; corroborating C diffusion. The weld region was diluted comprising mainly of Fe with small amounts of Cr and Ni. Cracking is thought to have initiated at the hardened region. However, the failure might have been aided by hydrogen rich medium and soft C-depleted ferrite region.

An investigation was carried out to determine the performance of a thermal barrier coating system consisting of (ZrO2-8% Y2O3)/(Pt) on two single-crystal Ni-base superalloys. Coating/alloy behavior was studied with reference to: (i) initial microstructural features, (ii) oxidation properties, (iii) thermal stability characteristics, and (iv) failure mechanism. All thermal exposure tests were carried out at 1150°C in still air with a 24-h cycling period to room temperature. Failure of the coating system was indicated by macroscopic spallation of the ceramic top coat. Scanning electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction were used to characterize the microstructure.

The weather in the Arabian Gulf region constitutes an environment that is corrosive to carbon steel. In the Gulf region, atmospheric corrosion is aggravated further by the high salinity of Gulf sea‐water. In addition, sulphur dioxide and deposits from combustion products tend to make the atmosphere in the Gulf region even more corrosive. Various inhibitors are reported in the literature that can help in the prevention of metal corrosion in aqueous environments. Among these, sodium dihydrogen orthophosphate, sodium benzoate, sodium nitrite and sodium nitrate were obtained and the effectiveness of certain corrosion inhibitors on carbon steel specimens was examined in a simulated atmospheric corrosion environment containing 2% NaCl and 1% Na2SO4 with various inhibitor concentrations. Test specimens were prepared from locally produced carbon steel reinforcing bars. It was found as a result of the test programme that treatment of the steel with 10 or 100mM sodium dihydrogen orthophosphate for one day at room temperature resulted in the best inhibition of corrosion. The results also demonstrated that inhibitors such as sodium benzoate and sodium nitrite were only similarly effective, as was sodium nitrate. Plans further study to examine the inhibition performance of sodium dihydrogen orthophosphate under actual atmospheric conditions.

An investigation was carried out to determine the comparative performance of selected bond coats representing the diffusion aluminides and overlays in thermal barrier coating systems. Emphasis was placed upon oxidation behavior, thermal stability, and failure mechanism. Isothermal oxidation tests were carried out attemperatures in the range of 1000 °C to 1150 °C. Scanning electron microscopy combined with energy dispersive x-ray spectroscopy, x-ray diffraction, and transmission electron microscopy were used to characterize the coating microstructure. Among the bond coats examined, overlays exhibited the best performance followed by Pt-aluminides and simple alunimides for a given alloy substrate. However, for all types of bond coats, failure of the coating system occurred by decohesion of the oxide scale at the oxide-bond coat interface. All bond coats examined were found to be degraded by oxidation and interdiffusion with the alloy substrate permitting the formation of non-protective oxide scale near the bond coat surface. Platinum as well as active elements such as Hf and Y were identified as key elements in improving the performance of thermal barrier coating systems.

An investigation was carried out to determine the failure mechanism of a thermal barrier coating system on an Ni-base superalloy. The coating system consisted of an outer layer of yttria-stabilized zirconia (top coat), and an inner layer of Pt-aluminide (bond coat). Specimens were exposed at 1010 and 1150 °C with a 24-h cycling period to room temperature. Scanning electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction were used in microstructural characterization. Spallation of the oxide scale developed by the bond coat was found to be the mode of failure. Experimental results indicated that the breakdown of oxide was affected by internal oxidation of Hf diffusing from the alloy substrate into the bond coat surface developing localized high levels of stress concentration at the oxide–bond coat interface. It was concluded that the cause of failure was degradation of thermal stability of the bond coat accelerating its oxidation rate and permitting outward diffusional transport of elements from the substrate.

The literature on the analysis of biological fluids by ion chromatography is reviewed herein. It has been demonstrated that ion chromatography is the method of choice for the determination of anions such as chloride, nitrite, bromide, phosphate, nitrate, sulfate, oxalate, thiocyanate, thiosulfate, citrate, isocitrate, carbonate, and similar species. Cations such as sodium, ammonium, potassium, magnesium, and calcium in various biological solutions have also been successfully identified and quantified. The technique fulfils several requirements of a reliable microanalytical method by providing sufficient speed, automation, case of use, and accuracy. For many types of analyses, very little or even no sample preparation is required. Because of this, as presented in this review, ion chromatography is widely used not only to obtain reliable clinical data, but also to study ion chemistry. It has been an invaluable tool in nephrolithiasis and dental research. This review should provide a useful reference for analysts and researchers involved in clinical studies. The review is presented in four sections: (1) introduction, (2) methods of analysis, (3) ion chemistry and (4) critical comments and concluding remarks. Section 1, as usual, deals with the general introduction of the subject and objectives. Section 2 includes the review of the literature on ion chromatography (IC) methods developed for routine analysis of various analytes present in biological fluids. Section 3 deals with the applications of IC used in the understanding of ion chemistry of biological fluids. Specifically, it deals with the physical chemistry aspects related to nephrolithiasis and dental research, such as speciation, driving force for crystals formation and crystallization, and pathophysiology. Section 4 contains critical comments and concluding remarks.

It is the objective of this paper to compare the thermal stability characteristics and isothermal oxidation behavior of an aluminide coating and a Pt-aluminide coating of the same Al content on a Ni-base superalloy. Addition of Pt to an aluminide coating was found to improve its thermal stability as well as its capability for selective oxidation of Al resulting in a purer scale of slower growth rate. This was correlated with the greater diffusional stability of the Pt-aluminide coating restricting the transport of substrate elements into the outer coating layers.

X-ray photoelectron spectroscopy (XPS) has been applied to the characterization of barium-impregnated MFI high-silica zeolites which are used for the conversion of methanol to light alkenes. X-ray photoelectron spectroscopy provided information about the degree of the dispersion of the various barium loadings on the silicalite structure, and this information helped in elucidating the observed relationship between the activity/selectivity of the catalysts and the barium loading. The XPS results also helped in predicting that the performance of the catalyst would be optimized at 4 wt% Ba loading which was found to agree with the catalytic conversion of methanol to light alkenes.