Restoration of charpy toughness for “in service” temper embrittled steels

This paper describes a detailed examination which could be conducted during a planned outage. It is concerned with assessing reverse temper embrittlement of CrMoV steel turbine bolts after 120 000 h of service. A small section of material was removed from a non-critical location of all the 92 IP and HP bolts. From this section, the chemical composition, average hardness and average prior austenite grain size were measured. The toughness of the bolts was measured by Charpy impact testing and/or Auger electron spectroscopy. From the various parameters investigated, it was established that grain size and phosphorus level were the only factors which consistently identified whether a bolt was embrittled or non-embrittled. Indeed, at a phosphorus level of 0.01%, bolts with grain sizes less than 20 μm were not embrittled while those with larger grain sizes suffered reverse temper embrittlement during service. An embrittlement estimative diagram was established by plotting grain size versus phosphorus level (%P). This portrayed two distinct regimes, an embrittled and non-embrittled regime which were separated by a critical embrittled-non-embrittled interface which could be described by d × (%P) = 0.18 where d is the grain size in μm. Such an embrittlement estimate diagram represent a cogent and practical route in the identification of in-service embrittled bolts.     

Geminal bis-ureas as gelators for organic solvents: gelation properties and structural studies in solution and in the gel state

Several geminal bis-urea compounds were synthesised by means of an acid-catalysed condensation of various benzaldehydes with different monoalkylureas. Many of these compounds form thermoreversible gels with a number of organic solvents at very low concentrations (<3mM) and which are stable to temperatures higher than 100 degrees C. Electron microscopy revealed a three-dimensional (3D) network of intertwined fibres, which are several tens of micrometers long and have a width ranging from approximately 30 to 300 nm. The possible aggregate forms and aggregate symmetries were evaluated by means of molecular mechanics calculations. 1H NMR, 2D NMR, 13C NMR and 13C-CP/MAS NMR techniques were used to obtain information about the aggregation and possible aggregate symmetry of geminal bis-ureas in solution, in the gel state, and in the solid state.     

Long-range sigma-pi interactions in tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes). Photo-electron spectroscopy, ab initio SCF MO calculations, and natural bond orbital analyses

Long-range sigma-pi interactions in tetrahydro4H-thiopyran end-capped oligo(cyclohexylidenes) were identified by He(I) photoelectron spectroscopy (PES) and ab initio RHF/6-31G* calculations. The vertical ionization energies Ivj of the highest occupied molecular orbitals (MO's) were assigned using Koopmans' theorem (Iv,j = -epsilonj) and by correlation with the ionizations of related reference compounds. The experimental (PES) and theoretical (RHF/6-31G*) results are in good agreement. For tercyclohexylidene derivatives which contain two nonconjugated pi-bonds splittings deltaIv,j of the pi-bands in the range from approximately 0.5 to 0.7 eV (delta-epsilonj approximately 0.6 to 0.9 eV). For the bi- and tercyclohexylidene compounds containing two sulfur atoms at their alpha- and omega-end positions the pi-type sulfur lone pair bands [Lppi(S)] split significantly by deltaIvj approximately 0.3 to 0.4 eV (delta-epsilonj approximately 0.3 to 0.4 eV), i.e. sigma-pi interactions over distances of ca. 8 and 12 A, respectively, occur. The magnitude of the interactions and the observed splittings are independent of the anti and syn conformations of the oligo(cyclohexylidene) hydrocarbon skeletons. RHF/6-31G* Natural Bond Orbital analyses reveal that the Hax-C-C-Hax precanonical MO's (PCMO's) centered on the cyclohexyl-type rings are paramount for the relay of the through-bond sigma-pi interactions; no through-space sigma-pi interactions were identified.     

Design and synthesis of aromatic inhibitors of anthranilate synthase

Anthranilate synthase catalyses the conversion of chorismate to anthranilate, a key step in tryptophan biosynthesis. A series of 3-(1-carboxy-ethoxy) benzoic acids were synthesised as chorismate analogues, with varying functionality at C-4, the position of the departing hydroxyl group in chorismate. Most of the compounds were moderate inhibitors of anthranilate synthase, with inhibition constants between 20-30 microM. The exception was 3-(1-carboxy-ethoxy) benzoic acid, (C-4 = H), for which K(I)= 2.4 microM. These results suggest that a hydrogen bonding interaction with the active site general acid (Glu309) is less important than previously assumed for inhibition of the enzyme by these aromatic chorismate analogues.     

Effect of humidity and R-ratio on the near threshold fatigue crack growth of two granular bainitic microstructures

The present report has shown that in ferrite-martensite microstructures, the relative humidity of an air environment can affect both the near threshold fatigue crack growth behaviour and the intermediate Stage II fatigue characteristics. The magnitude of the threshold stress intensity, ΔK_th, was not affected by relative humidity and the significant effect of R-ratio on ΔK_th was suitably demonstrated.The relative humidity affected the nature of both the subcritical static failure mode and the final stage III static failure mode. A direct relationship between the degree of fatigue crack growth enhancement and the extent of transgranular cleavage was evidenced.     

Reverse temper embrittlement — environmentally assisted cracking interactions in ferritic low alloy steels

Assessed in this study are the relationships that were recorded between the magnitude of the environmental assisted crack (EAC), growth contribution and the fatigue fractographic details observed in steels under ambient conditions. Four discrete static failure modes were observed on the fatigue surfaces; they are primarily transgranular cleavage and intergranular decohesion with a few instances of fan-shaped growth and macrofacet formation. All static failure modes could be explained by Beacham's model for hydrogen assisted cracking. It was established that the extent of EAC growth was uniquely related to the amount of static failure mode and that the relationship agreed well with the predictions of Congleton's model for EAC growth expressed in terms of the ratio of crack growth rate (da/dN)^* in environments of humid air and saline solution to da/dN in dry air for a given stress intensity factor range ΔK.     

Molecular distribution of some commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Nonylphenol ethoxylates (NPEs) belong to a group of nonionic surfactants that are collectively referred to as alkylphenol ethoxylates (APEs). APEs find widespread use in heavy-duty commercial and household cleaning formulations, shampoos, and industrial processing, i.e. textile manufacture. Their environmental impact depends on the molecular distribution and the extent of their biodegradation in municipal sewage systems, waterways and rivers. We have established two sample preparation methods that have enabled the determination of the molecular distributions of six commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). In both methods, alpha-cyano-4-hydroxycinnamic acid, dissolved in acetonitrile/tetrahydrofuran, was used as the matrix. In one set of experiments, the NPEs were dissolved in an acetonitrile/tetrahydrofuran solvent system prior to mixing with the matrix solution, and the resulting MALDI-TOF mass spectra produced mostly sodiated molecules [M + Na](+). The NPEs, all having the formula 4-(C(9)H(19))-C(6)H(4)-(OCH(2)CH(2))(n)-OH, are Surfonic (R)N-95, N-100, N-102, N-120, N-150 and N-300. Surfonic N-95 and N-100 gave n values of 5-20; Surfonic N-102, N-120, N-150, and N-300 gave n values of 5-21, 5-22, 8-25 and 15-40, respectively. In order to develop a sample preparation method that could be used with less polar NPEs, we dissolved the NPEs (except N-300) in pentane prior to mixing with the matrix solution, and found that the MALDI spectral quality was unaffected by the solvent systems. Copyright 1999 John Wiley & Sons, Ltd.     

Fractographic analysis of fatigue cracking in spheroidal graphite cast irons

This paper is concerned with the influence of R-ratio on the fatigue threshold ΔK_th, in two spheroidal graphite cast irons. The microstructures, viz, ferritic and pearlitic, exhibited significant and consistent R-ratio effects on ΔK_th. Intergranular failure facets were observed and they tended to reach a maximum amount when the reversed plastic zone size approached grain size dimensions. Reasonable correlation of experimental data required the increment of crack closure effects in the analytical model. At R-ratio values approaching zero, both microstructures showed ΔK_th, values that were markedly greater than those recorded for steels even when the data was corrected or normalised to a constant yield stress and grain size for a specific microstructure. The presence of graphite nodules may cause an increase in crack closure which in turn promoted high ΔK_th values.