Finite-element creep damage analyses of P91 pipes

In this paper, uniaxial and notched bar creep test data are used to establish the material behaviour models for two P91 steels of differing strength. The two steels are denoted here as Bar 257 steel, tested at 650 °C and A-369 steel, tested at 625 °C. Single-state variable and three-state variable creep damage constitutive models were used in the investigation.Methods for determining the material properties in the two sets of equations are briefly described. Finite-element analyses are performed using these material properties for a P91 pipe, subjected to internal pressure and end loading. The failure lives of the pipe were obtained, and on this basis, a preliminary assessment of using the two different sets of constitutive equations for failure predictions of high-temperature components under creep damage conditions can be made.     

Creep oxidation behaviour and creep strength prediction for Alloy 617

Creep experimental data was obtained by a series of creep tests with different stress levels at 950 °C for Alloy 617. Oxidation behaviour was investigated by observing the microstructures of fractured specimens after the creep tests. Oxidation thickness was measured quantitatively with the creep rupture times, and the oxidation microstructures were represented by a SEM image. In addition, the long-term creep strength for Alloy 617 was predicted by using a multi-constant method with two C instead of the conventional one with a unique C in the Larson-Miller (LM) parameter. For 10⁵ h at 950 °C, the creep strength for the conventional method was 7.2 MPa, but for the multi-constant method it was reduced to 4.7 MPa. The conventional method did not thoroughly match with the creep rupture data, and revealed an overestimation for the prediction of the long-term creep strength. On the other hand, the multi-constant method revealed a good agreement with the creep rupture data, and its method was thus more accurate than the conventional one. This multi-constant analysis can be used to accurately predict the long-term creep rupture of Alloy 617.     

High-temperature tensile and creep properties of a ferritic stainless steel for interconnect in solid oxide fuel cell

The purpose of this study is to investigate the high-temperature mechanical properties of a ferritic stainless steel (Crofer 22 APU) for use as an interconnect material in planar solid oxide fuel cells (pSOFCs). Tensile properties of the Crofer 22 APU steel are evaluated at temperatures of 25-800 °C. Creep properties are evaluated by constant-load tests at 650-800 °C. Several creep lifetime models are applied to correlate the creep rupture time with applied stress or minimum creep rate. Experimental results show the variation of yield strength with temperature can be described by a sigmoidal curve for different deformation mechanisms. The creep stress exponent, n, has a value of 5 or 6, indicating a power-law creep mechanism involving dislocation motion. The apparent activation energy for such a power-law creep mechanism is estimated as 393 kJ mol⁻¹ through some thermally activated relations. Creep rupture time of the Crofer 22 APU steel can be described by a Monkman-Grant relation with a time exponent, m = 1.11. The relation between creep rupture time and normalized stress is well fitted by a universal simple power law for all of the given testing temperatures. Larson-Miller relationship is also applied and shows good results in correlating the creep rupture time with applied stress and temperature for the Crofer 22 APU steel. Fractographic and microstructural observations indicate most of the creep cavities are nucleated along grain boundaries and a greater amount of cavities are formed under high stresses.     

Spectrally selective NbAlN/NbAlON/Si3N4 tandem absorber for high-temperature solar applications

A new spectrally selective NbAlN/NbAlON/Si₃N₄ tandem absorber was deposited on copper substrates using a reactive direct current magnetron sputtering system. A high solar absorptance (0.956) and a low emittance (0.07) were achieved by gradually decreasing the refractive index from the substrate to the surface. The tandem absorber was characterized using solar spectrum reflectometer and emissometer, X-ray photoelectron spectroscopy, phase-modulated spectroscopic ellipsometry, atomic force microscopy and micro-Raman spectroscopy techniques. In order to study the thermal stability of the tandem absorbers, they were subjected to heat treatment (in air and vacuum) at different durations and temperatures. The tandem absorber deposited on copper substrate exhibited high solar selectivity in the order of 13–15 even after heat treatment in air up to 500 °C for 2 h. These tandem absorbers also exhibited high thermal stability (450 °C) in air for longer durations (116 h). The onset of oxidation for the tandem absorber deposited on silicon substrates was 650 °C, indicating a high oxidation resistance. The results of the present study indicate the importance of NbAlN/NbAlON/Si₃N₄ tandem absorber for high-temperature solar selective applications.     

Alloy design and creep strength of advanced 9%Cr USC boiler steels containing high concentration of boron

Abstract

The research and development project of National Institute for Materials Science (NIMS) for advanced ferritic heat resistant steels for 650°C ultra super critical (USC) plants, revealed that the addition of >0·01 mass% boron to a 0·08C–9Cr–3W–3Co–V–Nb–,0·003N steel remarkably improves the long term creep strength. Boron enriched in M₂₃C₆ carbides near prior austenite grain boundaries suppresses the coarsening of carbides during creep deformation, leading to excellent microstructural stability and creep strength. If creep strength was further improved by the addition of nitrogen, it was found to enhance precipitation of fine MX. Addition of excess nitrogen to the high boron containing steel was found to reduce creep rupture lives and ductility. This results from a decrease in the amount of effective boron, which is dissolved in M₂₃C₆ and suppresses its coarsening, resulting from the formation of coarse BN at normalising temperature. The highest creep strength is obtained with steel of the following composition: 0·08C–9Cr–3W–3Co–0·2V–0·05Nb–0·008N–0·014B (mass%), which has an improved creep strength compared to P92. The 10⁵ h extrapolated creep rupture strength at 650°C is ～100 MPa. This steel also shows good creep ductility even in the long term. In conclusion, high boron bearing 9Cr–3W–3Co–V–Nb steel combined with the addition of 0·008 mass% nitrogen is a promising candidate for thick section components in the 650°C USC plants as it shows superior creep strength without impaired creep ductility.     

Creep strength of high chromium steel with ferrite matrix

Long-term creep strength of material in the low-stress regime below elastic limit is difficult to predict by an extrapolation of short-term creep strength in the high-stress regime above elastic limit. Long-term creep strength of fully annealed ferrite-pearlite microstructure of low alloy Cr–Mo steel is higher than that of martensite and bainite microstructures. It is explained by lower dislocation density of fully annealed microstructure. According to the above concept, creep strength of high chromium steel with ferrite matrix is investigated. Creep rupture life of 15Cr–Mo–W–Co steel with ferrite matrix which is longer than that of ASME Grade 92 steel is obtained at 650 °C by controlling the chemical composition and heat treatment condition.     

Microstructure evolution in HAZ and suppression of Type IV fracture in advanced ferritic power plant steels

The effect of boron and nitrogen on the microstructure evolution in heat affected zone (HAZ) of 9Cr steel during simulated heating and on the Type IV fracture in welded joints has been investigated at 650 °C. Gr.92 exhibits a significant decrease in time to rupture after thermal cycle to a peak temperature near A_C3, while the creep life of Gr.92N, subjected to only normalizing but no tempering, and 9Cr-boron steel is substantially the same as that of the base metals. In Gr.92 after A_C3 thermal cycle, very few precipitates are formed along PAGBs in the fine-grained microstructure. In the P92N and 9Cr-boron steel after A_C3 heat cycle, on the other hand, not only PAGBs but also lath and block boundaries are covered by M₂₃C₆ carbides in the coarse-grained microstructure. It is concluded that the degradation in creep life in Gr.92 after the A_C3 thermal cycle is not caused by grain refinement but that the reduction of boundary and sub-boundary hardening is the most important. Soluble boron is essential for the change in α/γ transformation behavior during heating and also for the suppression of Type IV fracture in welded joints. Newly alloy-designed 9Cr steel with 160 ppm boron and 85 ppm nitrogen exhibits much higher creep rupture strength of base metal than P92 and also no Type IV fracture in welded joints at 650 °C.     

Oxidation behaviour of an Alloy 617 in very high-temperature air and helium environments

The oxidation characteristics of Alloy 617, a candidate structural material for the key components in the very high-temperature gas-cooled reactor (VHTR), were investigated. High-temperature oxidation tests were conducted at 900 and 1100 °C in air and helium environments and the results were analysed. Alloy 617 showed parabolic oxidation behaviour at 900 °C, but unstable oxidation behaviour at 1100 °C, even in a low oxygen-containing helium environment. The SEM micrographs also revealed that the surface oxides became unstable and non-continuous as the temperature or the exposure time increased. According to the elemental analysis, Cr-rich oxides were formed on the surface and Al-rich discrete internal oxides were formed below the surface oxide layer. After 100 h in 1100 °C air, the Cr-rich surface oxide became unstable and non-continuous, and the matrix elements like Ni and Co were exposed and oxidized. Depletion of grain boundary carbides as well as matrix carbides was observed during the oxidation in both environments. When tensile loading was applied during high-temperature oxidation, the thickness of the surface oxide layer, the internal oxidation, and decarburization were enhanced because of the increase in diffusion of oxidizing agent and gaseous reaction products. Such enhancement would have detrimental effects on the high-temperature mechanical properties, especially the creep resistance of Alloy 617 for the VHTR application.     

Creep behaviour of porous metal supports for solid oxide fuel cells

The creep behaviour of porous iron–chromium alloy used as solid oxide fuel cell support was investigated, and the creep parameters are compared with those of dense strips of similar composition under different testing conditions. The creep parameters were determined using a thermo-mechanical analyser with applied stresses in the range from 1 to 15 MPa and temperatures between 650 and 800 °C. The Gibson–Ashby and Mueller models developed for uniaxial creep of open-cell foams were used to analyse the results. The influence of scale formation on creep behaviour was assessed by comparing the creep data for the samples tested in reducing and oxidising atmospheres. The influence of pre-oxidation on creep behaviour was also investigated. In-situ oxidation during creep experiments increases the strain rate while pre-oxidation of samples reduces it. Debonding of scales at high stress regime plays a significant role affecting the creep behaviour of the metal supports, in particular the stress exponent. The variation of the elastic modulus as function of temperature and oxidation conditions was also determined by a high temperature impulse excitation technique. Additionally nano-indentation testing was performed in the metal oxide interface to elucidate the mechanical properties of the oxide scales and qualitative information about the oxide scale-metal interfacial bonding.     

Thermal imaging of solid oxide fuel cell anode processes

A Si-charge-coupled device (CCD), camera-based, near-infrared imaging system is demonstrated on Ni/yttria-stabilized zirconia (YSZ) fragments and the anodes of working solid oxide fuel cells (SOFCs). NiO reduction to Ni by H₂ and carbon deposition lead to the fragment cooling by 5 ± 2 °C and 16 ± 1 °C, respectively. When air is flowed over the fragments, the temperature rises 24 ± 1 °C as carbon and Ni are oxidized. In an operational SOFC, the decrease in temperature with carbon deposition is only 4.0 ± 0.1 °C as the process is moderated by the presence of oxides and water. Electrochemical oxidation of carbon deposits results in a ΔT of +2.2 ± 0.2 °C, demonstrating that electrochemical oxidation is less vigorous than atmospheric oxidation. While the high temperatures of SOFCs are challenging in many respects, they facilitate thermal imaging because their emission overlaps the spectral response of inexpensive Si-CCD cameras. Using Si-CCD cameras has advantages in terms of cost, resolution, and convenience compared to mid-infrared thermal cameras. High spatial (0.1 mm) and temperature (0.1 °C) resolutions are achieved in this system. This approach provides a convenient and effective analytical technique for investigating the effects of anode chemistry in operating SOFCs.     

Manufacturing and testing of a gamma type Stirling engine

In this study, a gamma type Stirling engine with 276 cc swept volume was designed and manufactured. The engine was tested with air and helium by using an electrical furnace as heat source. Working characteristics of the engine were obtained within the range of heat source temperature 700–1000 °C and range of charge pressure 1–4.5 bar. Maximum power output was obtained with helium at 1000 °C heat source temperature and 4 bar charge pressure as 128.3 W. The maximum torque was obtained as 2 N m at 1000 °C heat source temperature and 4 bar helium charge pressure. Results were found to be encouraging to initiate a Stirling engine project for 1 kW power output.     

Improved approach for predicting weld creep strength factors of ferritic steels

Abstract

The cross-weld (CW) creep strength of ferritic steels is typically lower than that for parent metal (PM), and in the past the ratio of CW to PM creep strength (weld strength factor – WSF) was assumed to be limited to ～80%. For newer Cr steels WSF can be significantly lower for a typical design life of 100 000 h or more. The possibility of low WSF is also accommodated in the current design codes such as EN 13445, but no suggested WSF values are given for guidance. Assuming a too high WSF for such welds obviously results in an unsafe (too long) predicted creep life. Unfortunately, as a further complication the WSF of the newer Cr steels can decrease when the operating temperatures are increased for improved efficiency of future power plants. It is hence important that reliable and sufficiently high values of WSF can be guaranteed. However, there is often much less extensive data on the creep strength of welds than on parent steel, and also the extrapolation to long term values of WSF can add more relative uncertainty than what is expected in extrapolating the long term creep strength of parent steel. Here an improved approach is proposed to predict WSF using the Wilshire creep model to obtain the relationship between the CW creep strength and the corresponding parent material (PM) strength. The Wilshire model directly provides the WSF value for each CW data point, when the expected normalised stress is based on the CW time to rupture at stress and temperature. The corresponding master curve parameters are those for PM, when the PM hot tensile strength is also known. The WSF data points for each CW test can then be fitted for temperature and stress dependence. This approach avoids fitting distortion in WSF, unlike the traditional assessment where a master curve is first obtained for the CW creep strength. As an example, WSF of welded P91 steel at 100 000 h is here predicted in the temperature range of 550–650°C.     

Thermoelectric properties of porous SiC/C composites

We developed a porous SiC/C composite by oxidizing a SiC/C composite made from a mixed powder of wood charcoal and SiO₂ (32–45 μm) by pulse current sintering at 1600 and 1800 °C under a N₂ atmosphere. The microstructures of the porous SiC/C composites with oxidation and the SiC/C composites without oxidation were analyzed by Raman spectroscopy and scanning electron microscopy (SEM). Raman spectra revealed the disappearance of excess carbon and the presence of β-SiC. The porous microstructure was monitored by SEM observation as a function of the heat treatment temperature. The thermoelectric properties of porous SiC/C composites with oxidation and SiC/C composites without oxidation were investigated by measuring the Seebeck coefficient, the electrical conductivity and thermal conductivity. The Seebeck coefficient of all samples revealed n-type conduction, and the absolute value of the Seebeck coefficient for the porous SiC/C samples with oxidation was much larger than that for the SiC/C samples without oxidation. For the electrical conductivity the reverse is true. Only the thermal conductivity of the SiC/C sample heated to 1800 °C without oxidation was high initially and stayed rather high. In general, the thermoelectric properties improved at higher measurement temperatures indicating their suitability for high-temperature thermoelectric conversion. A maximum figure of merit of 2.01×10⁻⁵ K⁻¹ was obtained at 700 °C in porous SiC/C samples sintered at 1800 °C with oxidation.     

Manufacturing method for monolithic dye-sensitised solar cells permitting long-term stable low-power modules

A manufacturing technique for monolithic dye-sensitised solar cells is presented. Encapsulated modules designed for indoor low-power applications have been prepared using industrial methods and equipment. Under certain conditions (light intensity <5000 lx, temperature between –10°C and 50°C, and relative humidity of appr. 50%), the modules have performed well and shown excellent long-term stability. Moreover, modules withstand illumination in combination with storage at 100% relative humidity. However, a certain degradation of the module performance takes place at illuminations exceeding 5000 lx and temperatures exceeding 50°C.     

Torque and power characteristics of a helium charged Stirling engine with a lever controlled displacer driving mechanism

This study presents test results of a Stirling engine with a lever controlled displacer driving mechanism. Tests were conducted with helium and the working fluid was charged into the engine block. The engine was loaded by means of a prony type micro dynamometer. The heat was supplied by a liquefied petroleum gas (LPG) burner. The engine started to run at 118 °C hot end temperature and the systematic tests of the engine were conducted at 180 °C, 220 °C and 260 °C hot end external surface temperatures. During the test, cold end temperature was kept at 27 °C by means of water circulation. Variation of the shaft torque and power with respect to the charge pressure and hot end temperature were examined. The maximum torque and power were measured as 3.99 Nm and 183 W at 4 bars charge pressure and 260 °C hot end temperature. Maximum power corresponded to 600 rpm speed.     

Nanotube enhanced photoresponse of carbon modified (CM)-n-TiO2 for efficient water splitting

Carbon modified (CM)-n-TiO₂ nanotube arrays were successfully synthesized by anodization of Ti metal sheet in fluoride solution and subsequent annealing in air and natural gas flame oxidation. Both nanotube structure and carbon doping contributed to the enhancement of photoresponse of n-TiO₂. About two fold increase in photocurrent density was observed at undoped n-TiO₂ nanotube film compared to that at its undoped n-TiO₂ flat thin film. Also, about eight fold increase in photocurrent density was observed at carbon modified (CM)-n-TiO₂ nanotube film compared to that at undoped n-TiO₂ flat thin film. The sample prepared by anodization at 20 V cell voltage for 20 h followed by annealing in air at 500 °C for 1 h and natural gas flame oxidation at 820 °C for 18 min produced highest photocurrent density. It was found that the bandgap of n-TiO₂ was reduced to 2.84 eV and an additional intragap band was introduced in the gap at 1.30 eV above the valence band. The bandgap reduction and the new intragap band formation in CM-n-TiO₂ extended its utilization of solar energy up to the visible to infrared region.     

An assessment of the θ-projection method for the representation and extrapolation of creep data for a 1%Cr, , steel tested at 565°C

Constant stress creep data for a wrought 1%Cr, , steel obtained from six tests carried out at 565°C have been fitted and extrapolated using the θ-projection method. Creep curves for high stresses were fitted well, but curves extrapolated to stress levels below those used in the θ-projection did not represent well the available data for primary-secondary creep. To enable a satisfactory extrapolation of results, it was found necessary to redefine the failure condition to be less sensitive to the shape of the latter sections of the tertiary creep curve. This was achieved by defining lifetime as the point on the curve at which the strain rate reached a fixed multiple of the creep rate at half the rupture time. The extrapolated data compare well with the results of tests carried out independently on a cast 1%Cr, , steel. The extrapolation procedure not only predicts the ‘knee’ in the log stress-log lifetime curve but allows extrapolation of lifetimes by over a factor of thirty. In addition, acceptable predictions have been made of constant load experimental data.     

Accelerated aging tests of chromium containing amorphous hydrogenated carbon coatings for solar collectors

Chromium containing amorphous hydrogenated carbon films (a-C : H/Cr) have been prepared by simultaneous rf plasma activated chemical vapour deposition of methane and magnetron sputtering of a chromium target. During deposition the substrates were heated (up to 300°C) and DC biased (−200 and −600 V) in order to obtain films with high chemical stability. Constant temperature tests were performed at 250°C in air with coatings deposited on silicon substrates. The degradation of the coatings was monitored by Raman spectroscopy and reflectance and transmission measurements. The main degradation mechanisms are discussed and the relevant parameters which improve the durability of the coatings are presented. Furthermore, the durability of solar selective, multilayered coatings which were deposited on copper sheets was investigated. Based on accelerated aging tests at different temperature loads in air (at 220°C, 250°C and 300°C) and in a humid environment (80°C sample temperature in humid air with 85°C and 95% relative humidity) the service lifetime in a flat plate collector is predicted to amount to more than 25 years.     

Development of high strength ferritic steel for interconnect application in SOFCs

High-Cr ferritic model steels containing various additions of the refractory elements Nb and/or W were studied with respect to oxidation behaviour (hot) tensile properties, creep behaviour and high-temperature electrical conductivity of the surface oxide scales. Whereas W additions of around 2 wt.% had hardly any effect on the oxidation rates at 800 and 900 °C, Nb additions of 1% led to a substantially enhanced growth rate of the protective surface oxide scale. It was found that this adverse effect can be alleviated by suitable Si additions. This is related to the incorporation of Si and Nb into Laves phase precipitates which also contribute to increased creep and hot tensile strength. The dispersion of Laves phase precipitates was greatly refined by combined additions of Nb and W. The high-temperature electrical conductivity of the surface oxide scales was similar to that of the Nb/W-free alloys. Thus the combined additions of Nb, W and Si resulted in an alloy with oxidation resistance, ASR contribution and thermal expansion comparable to the commercial alloy Crofer 22 APU, but with creep strength far greater than that of Crofer 22 APU.     

Analysis of coke precursor on catalyst and study on regeneration of catalyst in upgrading of bio-oil

Catalyst HZSM-5 was used in bio-oil catalytic cracking upgrading. The precursor of coke on the catalyst was analyzed by means of TGA, FTIR and C13 NMR. Precursors of coke deposited in the pore of the molecular sieve were mainly aromatic hydrocarbon with the boiling point range from 350 °C to 650 °C. Those on the outer surface of the pellet precursor were identified as saturated aliphatic hydrocarbons with the boiling point below 200 °C. The activity of HZSM-5 was studied after regeneration. In terms of yield of organic distillate and formation rate of coke, results showed that catalytic activity change moderately during the first three times of regeneration.