Effect of temperature on the threshold fatigue crack growth behaviour of spheroidal graphite cast iron

The influence of temperature at various R ratio values on the fatigue crack propagation response of a ferritic spheroidal graphitic cast iron has been studied. It has been established that the influence of R ratio on ΔK_th is strongly dependent upon the test temperature. At elevated temperatures the influence of R ratio is significantly less than that at ambient temperature. At low to intermediate R ratio values temperature initially decreased, then, with increasing temperature, increased the ΔK_th levels, causing a minimum in ΔK_th to occur at 250–300°C. At high R ratio, however, ΔK_th exhibited a small but consistent increase with temperature. The influence of temperature on the ΔK_th at various R ratio values could be adequately explained in terms of crack closure. Much intergranular failure was observed on the fatigue fracture surfaces at ambient temperature, whereas at elevated temperatures there was little evidence of this particular failure.     

The near-threshold high R-ratio fatigue crack growth characteristics of SA508 cl III reactor pressure vessel steel

This paper describes the effect of frequency and environment on the near-threshold fatigue crack growth behaviour of SA508 cl III reactor pressure vessel (RPV) steel. The study has shown that in the near-threshold regime microstructure and environment markedly affect fatigue crack growth behaviour. In an aqueous environment, fatigue crack growth behaviour became even more sensitive to microstructure, and the fatigue crack growth rate increased by a factor of four in the case of the 3 Hz test, while that for the 0·3 Hz test was increased by a factor of approximately sixteen. This environmental enhancement manifested itself in the form of intergranular failure. For the 0·3 Hz test the percentage intergranular failure decreased from 18% to <1% with an increase in ΔK level. The transition from microstructure-sensitive to microstructure-insensitive occurs when the cyclic plastic zone size is of the order of the prior austenite grain size.     

Some formulae for the effective stress range ratio used in crack growth of 6063-T6 aluminium alloy

The influence of stress ratio R and stress intensity range (ΔK) on fatigue crack growth experiments were determined for 6063-T6 aluminium alloy and crack growth data were analysed with different formulae for the effective stress intensity range ratio U. The data covered R values from 0 to 0·3. A good correlation was obtained from da/dN and ΔK_eff using the equation for U as a function of R.     

Threshold fatigue crack extension characteristics of a low alloy steel: The influence of environment and microstructure

The present investigation is aimed at examining the influence of environment and microstructure on the fatigue crack extension behaviour of a low alloy steel. Significant environmental effects were recorded under low R-Ratio testing but not under high R-Ratio conditions, viz., the ΔK_th values recorded in salt solution were significantly larger than those for a dry air environment and a constant value of 10 MPa√m was recorded irrespective of microstructure (yield strength). Such effects were attributed to oxide induced closure effects.

Above threshold, environmental assisted cracking behaviour in the salt solutions was the result of the appearance of transgranular cleavage facets on the fatigue surfaces. The extent of this environmentally enhanced cracking was simply related to the extent of cleavage failure.     

Experimental observation of crack propagation in 6063-T6 al-alloy under constant amplitude loading

Crack propagation experiments were performed on 6063-T6 Al-alloy for various load ranges and stress ratios. Experimental results show that for a constant load range, the life of specimens decreased as stress ratio increased. At constant maximum load, the life of the specimen increased as the load ratio increased. The crack growth data were analysed in terms of ΔK_eff as a function of stress ratio R. The data covered R values from 0 to 0·5 and a good relationship was obtained for K_eff/K = 0·55 + 0·12 R². A crack growth rate equation was developed.     

Measurement of crack propagation velocity in nuclear pressure vessel steel (SA516 gr. 70)

An attempt has been made to develop a simple, reliable and cost-effective device for measuring the dynamic crack propagation velocity in a nuclear pressure vessel steel (SA516 gr. 70). The experimental method is described and a simple digital approach is proposed. The experimentally determined dynamic crack velocity has been utilized to obtain elastic dynamic stress intensity factors by INSAMCR (a two-dimensional dynamic finite element code which is a modified version of SAMCR developed by Dr Schwartz at the University of Maryland). A relationship between instantaneous crack tip velocities and dynamic stress intensity factors for pressure vessel steels is estimated using dynamic crack propagation velocities determined by a proposed measuring device. The relationship between the dynamic stress intensity factor and time history and the dynamic arrest toughness for each test are obtained using the generation mode dynamic finite element analysis. A function ƒ(å) = 1·356 − 2·672å + 6·494å² − 4·539å³ + 1·461å⁴ is suggested which may be useful to predict the relationship between the dynamic fracture toughness (K(å)) and the dynamic crack arrest toughness (K_Ia) for SA516 gr. 70 steel (say K(å) = K_Ia ƒ(å) where å is the dynamic crack propagation velocity).     

Instrumented drop-weight test results for normalised and tempered 9Cr1Mo steel

From instrumented drop-weight tests, the nil ductility transition temperature (T_NDT), and a conservative estimate of dynamic fracture toughness (K_Id), at T_NDT for normalised and tempered 9Cr---1Mo steel, are determined to be −25°C and 70 MPa√m, respectively. The latter value agrees well with that determined from pre-cracked Charpy tests. The K_Id/σ_Yd (σ_Yd is the dynamic yield stress) ratio at T_NDT is estimated to be 0·076 √m, in agreement with previous estimates. The uncertainties in crack profile measurement and effect of microstructural variation in the heat affected zone on fracture loads are also discussed.     

The influence of mean stress or R-Ratio on the fatigue crack threshold characteristics of steels—A review

The present review attempts to describe an assessment of the effects of the R-Ratio on ΔK_th values in steels and compares the predictions of the various approaches or models dealing with R-Ratio response, with experimentally determined threshold stress intensity range values. Essentially significant R-Ratio effects on ΔK_th have been observed and that the extent of such effects are highly dependent on microstructural considerations. The two classical approaches dealing with R-Ratio effects, viz., the Barsom and the Klesnil and Lukas models, can adequately describe the R-Ratio response when the data are considered in terms of microstructural characteristics. However, the other approaches of Mazumdar and Conrad and McEvily and Groeger fall short in predictive terms while the Musuva and Radon approach needs more detailed high R-Ratio ΔK_th data before it can be realistically assessed.     

Thermodynamic evaluation of water splitting by a cation-excessive (Ni, Mn) ferrite

Water-splitting potential by cation-excessive (Ni, Mn) Ferrite, Ni_{0.5(1 + )}Fe_{1.99(1 + )}O₄ was evaluated using the standard Gibbs free energy change (ΔG°) for the cation-excessive ferrite formation in different O₂ partial pressures. The cation-excessive degree ranged from 0.026 to 0.16 in pO₂ values of 7.9 × 10⁻⁷ to 1.0 × 10⁻¹. From the relation between value of (Ni, Mn) ferrite and oxygen partial pressure, equilibrium constant K(th) was determined. Furthermore ΔH°s for O₂ releasing and water-splitting reactions with cation-excessive (Ni, Mn) ferrite were evaluated from the van't Hoff plot and compared with that for magnetite-wüstite system; where ΔH°s were assumed to be the same values for both (Ni, Mn) ferrite and magnetite-wüstite system: +300 kJ for O₂ releasing and −35 −63 kJ for water-splitting. ΔG°s evaluated for water-splitting with cation-excessive (Ni, Mn) ferrite and wüstite were −38 kJ and −35 kJ, respectively, at 298K. It suggests that water splitting with cation-excessive (Ni, Mn) ferrite proceed easily compared with that with wüstite. ΔS°s for water-splitting are −0.93 kJ K⁻¹ for the former and −0.83 kJ K⁻¹ for the latter. H₂ generation rates by reaction with H₂O for (Ni, Mn) ferrite were studied at temperatures of 573 K-1073 K. It reached the maximum at 1000 K while it proceeds preferentially below 830 K from thermodynamics.     

Determination of the equilibrium constant and standard free energy of the over-potentially deposited hydrogen for the cathodic H2 evolution reaction at the Pt–Rh alloy electrode interface using the phase-shift method

The Langmuir adsorption isotherm of the over-potentially deposited hydrogen (OPD H) for the cathodic H₂ evolution reaction (HER) at the Pt–Rh (Pt:Rh; 80:20 wt%) alloy/0.5 MH₂SO₄ aqueous electrolyte interface has been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift (0°−φ90°) for the optimum intermediate frequency can be linearly related to that of the fractional surface coverage (1θ0) of the OPD H for the cathodic HER at the interface. The phase-shift profile (−φ vs. E) for the optimum intermediate frequency, i.e., the phase-shift method, can be used as a new electrochemical method to determine the Langmuir adsorption isotherm (θ vs. E) of the OPD H for the cathodic HER at the interface. At the Pt–Rh alloy electrode interface, the equilibrium constant (K) and the standard free energy (ΔG_ads) of the OPD H are 2.2×10⁻⁴ and 20.9 kJ/mol, respectively. At the steady state, the behaviors of the cyclic voltammogram and the Langmuir adsorption isotherm of the OPD H for the cathodic HER at the Pt–Rh alloy electrode interface are similar to those of the pure Pt electrode interfaces. At the steady state, the effect of Rh on the OPD H for the cathodic HER can be neglected at the Pt–Rh (Pt:Rh; 80:20 wt%) alloy/0.5 MH₂SO₄ aqueous electrolyte interface.     

Synthesis of LiCoO2 from cobalt—organic acid complexes and its electrode behaviour in a lithium secondary battery

Well-crystallized, layered LiCoO₂ has been prepared by heating cobalt—organic acid complexes (such as malic acid and succinic acid) at 900 °C in air after preheating at 400 °C (2 h) and at 650 °C (6 h). LiCoO₂ obtained by this method shows a high (003) peak intensity and low (104) or (101) intensities in X-ray diffraction (XRD). The first discharge capacity of LiCoO₂ obtained from this method in ester-based electrolyte is 132 mA h g⁻¹ on cycling between 4.3 and 3.7 V. The value is larger than that obtained by the conventional method. X-ray diffraction studies and open-circuit voltage curves show the presence of at least two types of reaction. A two-phase reaction occurs in the region of 0.71<χ <1.0 in Li_xCoO₂. The lithiation proceeds as a homogeneous reaction together with expansion of the c-axis in the region of 0.47<χ<0.71. The expansion of the c-axis againstΔχ at x=0.56 corresponds well with the voltage jump observed in the charge/discharge curves.     

Creep test of type 304 stainless steel tube containing a notch subjected to internal pressure

This paper summarises the results of experimental creep tests of type 304 stainless steel tube subjected to internal pressure at 650°C. The equipment used was especially developed for these tests.

The tubes without notches were tested at pressures of 9·32 and 7·36 MPa. Test results indicate that the rupture time of the tubes without notches is in good agreement with that of uniaxial specimens when the maximum stress is taken as the rupture criterion. The tubes containing axial and circumferential surface notches were tested at a pressure of 7·36 MPa. Test results indicate that the ductile fracture theory is applicable to the life prediction in the case of axial notches.

An electric potential method was very useful for monitoring the creep crack growth from the notch root. The relationship between the creep crack growth rate and the fracture mechanics parameter, σ_net or K₁, was investigated.     

Optical and electrochemical characteristics of niobium oxide films prepared by sol-gel process and magnetron sputtering A comparison

Electrochromic niobia (Nb₂0₅) coatings were prepared by the sot-gel spin-coating and d.c. magnetron sputtering techniques. Parameters were investigated for the process fabrication of sol-gel spin coated Nb₂0₅ films exhibiting high coloration efficiency comparable with that d.c. magnetron sputtered niobia films. X-ray diffraction studies (XRD) showed that the sot-gel deposited and magnetron sputtered films heat treated at temperatures below 450°C, were amorphous, whereas those heat treated at higher temperatures were slightly crystalline. X-ray photoelectron spectroscopy (XPS) studies showed that the stoichiometry of the films was Nb₂0₅. The refractive index and electrochromic coloration were found to depend on the preparation technique. Both films showed low absorption and high transparency in the visible range. We found that the n, k values of the sot-gel deposited films to be lower than for the sputtered films. The n and k values were n = 1.82 and k = 3 × 10⁻³, and n = 2.28 and K = 4 × 10⁻³ at 530 urn for sot-gel deposited and sputtered films, respectively. The electrochemical behavior and structural changes were investigated in 1 M LiC10₄/propylene carbonate solution. Using the electrochemical measurements and X-ray photoelectron spectroscopy, the probable electrode reaction with the lithiation and delithiation is Nb₂O₅ + x Li⁺ + x e⁻ ↔ Li_xNb₂0₅. Cyclic voltametric (CV) measurements showed that both Nb₂0₅ films exhibits electrochemical reversibility beyond 1200 cycles without change in performance. “In situ” optical measurement revealed that those films exhibit an electrochromic effect in the spectral range 300 < λ < 2100 nm but remain unchanged in the infrared spectral range. The change in visible transmittance was 40% for 250 nm thick electrodes. Spectroelectrochemical measurements showed that spin coated films were essentially electrochemically equivalent to those prepared by d.c. magnetron sputter deposition.     

Crack propagation rate as a function of crack tip characteristics

The dependence of crack growth rate on various crack tip parameters was studied. Experiments were performed on thin sheets of 6063-T6 Al-alloy having a central notch, to find crack tip opening displacement, total strain range, plastic strain range, crack opening stress and crack growth rate. Crack tip opening displacement and crack opening stress were measured, using a surface measurement technique, with small crack opening displacement gauges. The theoretical predictions of crack tip opening displacement compare fairly well with the experimental values. It is found that crack propagation rate vs total strain range-plastic strain range gives a straight-line fit on a log-log graph and, for positive stress ratios, the fatigue crack growth rates are found to be independent of R.

Experimental results show that the crack opening stress is not affected by the position of the gauge when it is mounted behind and near the crack tip.

The effect of mechanical properties and loading on crack growth were also studied. The specimens were fatigue cracked to a predetermined length and some specimens were annealed and again loaded cyclically. The application of cyclic loads to annealed specimens caused significant increase in crack propagation rates in comparison with the specimens having no heat-treatment. The load-displacement record was found to stabilize in about 10 cycles; the crack then extended slowly as a fatigue crack. Crack propagation rates for different values of R for annealed and work-hardened material were plotted against a crack tip parameter, ΔK*, based on notional crack lengths. Since the results of da/dN vs ΔK* for both states of material (as-received and annealed) seem to lie on the same straight line on a log-log graph, the study provides a hope that the results for a material tested in any state (annealed or work-hardened) for positive values of R (0·0≤R≤0·3) will lie on this line, thus eliminating fatigue tests on the same material under different work-hardening conditions for different values of R. Models for da/dN have been developed using various crack tip parameters.     

Kinetics of the NCO radical reacting with atoms and selected molecules

Rate constants for the reaction of isocyanate radicals (NCO) in its electronic ground state ( ²Π) with oxygen atoms were determined at 2.5 Torr total pressure in the temperature range 302–757 K. Excimer laser photolysis (ELP) of chlorine isocyanate (ClNCO) produced NCO radicals detected by laser-induced fluorescence (LIF). The reaction NCO + O exhibits a negative temperature dependence, described by the two-parameter equation: k_NCO+O(T) = (4.3_−2.2^+3.2) × 10⁻⁸ × T^{−1.14_−0.12+0.08} cm³ molecule⁻¹ s⁻¹. Measurements at 298 K and total pressures of 2.5 and 9.9 Torr, respectively, indicated a slight pressure dependence. For the reaction of NCO radicals with hydrogen atoms, the rate constant k_NCO+H = (2.2 ± 1.5) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹was obtained at 298 K and a total pressure of 2.6 Torr for the first time by a direct measurement. From a single measurement k = (3.8 ± 1.6) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ was determined at 548 K and 2.4 Torr total pressure. In addition, rate constants for the reactions of NCO radicals with molecular oxygen (O₂), carbon dioxide (CO₂), molecular hydrogen (H₂), and carbon monoxide (CO), which is a dissociation product of CO₂ in a microwave discharge, were measured at two different temperatures. At room temperature these reactions were slow and at the detection limit of the ELP/LIF technique. However, at elevated temperatures at least the rate constants of the reactions NCO + O₂ and NCO + H₂ become significantly larger and, therefore, should be taken into account, when modeling combustion processes under certain conditions.     

Preparation and properties of LiCoyMnxNi1−x−yO2 as a cathode for lithium ion batteries

The preparation of LiCo_yMn_xNi_1−x−yO₂ from LiOH·H₂O, Ni(OH)₂ and γ-MnOOH in air was studied in detail. Single-phase LiCo_yMn_xNi_1−x−yO₂ (0y0.3 and x=0.2) is obtained by heating at 830–900°C. The optimum heating temperatures are 850°C for y=0–0.1 and 900°C for y=0.2–0.3. Excess lithium (1z1.11 for y=0.2) and the Co doping level (0.05y0.2) do not significantly affect the discharge capacity of Li_zCo_yMn_0.2Ni_0.8−yO₂. The doping of Co into LiMn_0.2Ni_0.8O₂ accelerates the oxidation of the transition metal ion, and suppresses partial cation mixing. Since the valence of the manganese ion in LiMn_0.2Ni_0.8O₂ is determined to be 4, the formation of a solid solution between LiCo_yNi_1−yO₂ and Li₂MnO₃ is confirmed.     

The effect of a long post weld heat treatment on the integrity of a welded joint in a pressure vessel steel

The effect of a long post weld heat treatment on the microstructure and mechanical properties of a welded joint in a 0·2%C-1·4%Mn-0·5%Mo pressure vessel steel was studied. Multipass submerged-arc welds were made at a heat input of 1·2 and 4·3 kJ mm⁻¹. Individual microstructural regions observed in the heat-affected zone of the actual weld were simulated. These regions were brittle in the as-simulated condition. Post weld heat treatment for periods of up to 40 h at 620°C resulted in a significant improvement in the Charpy impact toughness. At the same time, a loss of the heat-affected zone and weld metal hardness and transverse weld strenghth occurred. A fracture toughness (J_Ic) of 134 kJ m⁻² was measured in the heat-affected zone of the 4·3 kJ mm⁻¹ welds after prolonged post weld heat treatment. The improvement in weldment toughness with post weld heat treatment was primarily attributed to softening of the structure.     

Energy-efficient conversion of propane to propylene and ethylene over a V2O5/CeO2/SA5205 catalyst in the presence of limited oxygen

Oxidative conversion of propane to propylene and ethylene over a V₂O₅/CeO₂/SA5205 (V:Ce=1:1) catalyst, with or without steam and limited O₂, has been studied at different temperatures (700–850 °C), C₃H₈/O₂ ratio (4.0), H₂O/C₃H₈ ratio (0.5) and space velocity (3000 cm³ g⁻¹ h⁻¹). The propane conversion, selectivity for propylene and net heat of reaction (ΔHr) are strongly influenced by the reaction temperature and presence of steam in the reactant feed. In the presence of steam and limited O₂, the process involves a coupling of endothermic thermal cracking and exothermic oxidative conversion reactions of propane which occur simultaneously. Because of the coupling of exothermic and endothermic reactions, the process operates in an energy-efficient and safe manner. The net heat of reaction can be controlled by the reaction temperature and concentration of O₂. The process exothermicity is found to be reduced drastically with increasing temperature. Due to the addition of steam in the feed, no coke formation was observed in the process.     

Membranes based on phosphotungstic acid and polybenzimidazole for fuel cell application

Composite membranes based on phosphotungstic acid (PWA) adsorbed on silica (SiO₂) and polybenzimidazole (PBI) have been prepared and their physico-chemical properties have been studied. The membranes with high tensile strength and thickness of less than 30 μm can be cast. They are chemically stable in boiling water and thermally stable in air up to 400°C. Proton conductivity is influenced by the temperature (range: 30–100°C), relative humidity and PWA loading in the membrane. Maximum conductivity of 3.0×10⁻³ S/cm is obtained at 100% relative humidity and 100°C with membrane containing 60 wt.% PWA/SiO₂ in PBI. Conductivity measurements performed at higher temperatures, in the range from 90°C to 150°C, give almost stable values of 1.4–1.5×10⁻³ S/cm at 100% relative humidity.