Effects of impurities in steels on mechanical properties and corrosion behaviour

In steels produced and utilized in the Fed. Rep. of Germany the elements P and Sn may occur as impurities. Both these elements tend to enrich (segregate) at grain boundaries. The equilibria of grain boundary segregation in iron and the effects of alloying elements have been studied for P and Sn by Auger-electron-spectroscopy and were thermodynamically described. For a 3.5% NiCrMoV-turbine steel the grain boundary segregation of P and its effect on ductility have been studied in detail, with the results that the long-term embrittlement of this steel during application at temperatures around 400°C can be predicted and the maximum bulk concentration of P can be given. The effect of Sn on the creep of a 1% CrMoNiV steel at 550°C has been investigated, Sn favours cavity nucleation and growth, therefore tertiary creep starts earlier and premature failure occurs with increasing Sn content. Therefore, the Sn content should be kept as low as possible in heat resistant steels. Since carbon also segregates to grain boundaries and can displace P and Sn if there is enough free C in a steel, plain carbon steels are not subjected to embrittlement by P and Sn. The susceptibility to intergranular stress corrosion cracking in nitrates and other electrolytes is somewhat enhanced by P, however, only in a restricted range of potentials. In the range of maximum susceptibility the impurities have no effect, all carbon steels are susceptible to IGSCC, independently of their purity. So stress corrosion cracking cannot be suppressed by diminishing the content of phosphorus – only by avoiding the critical corrosion conditions concerning electrolyte and potential.     

Structure and mechanical properties of Fe-Cr-Mo-C alloys with and without boron

A study of the structure and mechanical properties of Fe-Cr-Mo-C martensitic steels with and without boron addition has been carried out. Nonconventional heat treatments have subsequently been designed to improve the mechanical properties of these steels. Boron has been known to be a very potent element in increasing the hardenability of steel, but its effect on structure and mechanical properties of quenched and tempered martensitic steels has not been clear. The present results show that the as-quenched structures of both steels consist mainly of dislocated martensite. In the boron-free steel, there are more lath boundary retained austenite films. The boron-treated steel shows higher strengths at all tempering temperatures but with lower Charpy V-notch impact energies. Both steels show tempered martensite embrittlement when tempered at 350 °C for 1 h. The properties above 500 °C tempering are significantly different in the two steels. While the boron-free steel shows a continuous increase in toughness when tempered above 500 °C, the boron-treated steel suffers a second drop in toughness at 600 °C tempering. Transmission electron microscopy studies show that in the 600 °C tempered boron-treated steel large, more or less continuous cementite films are present at the lath boundaries, which are probably responsible for the embrittlement. The differences in mechanical properties at tempering temperatures above 500 °C are rationalized in terms of the effect of boron-vacancy interactions on the recovery and recrystallization behavior of these steels. Although boron seems to impair room temperature impact toughness at low strength levels, it does not affect this property at high strength levels. By simple nonconventinal heat treatments of the present alloys, martensitic steels may be produced with quite good strength-toughness properties which are much superior to those of existing commercial ultra-high strength steels. It is also shown that very good combinations of strength and toughness can be obtained with as-quenched martensitic steels.     

Embrittlement of 4130 steel by low-pressure gaseous hydrogen

A study has been made of the embrittlement of fully hardened 4130 steel in low-pressure, <760 torr, gaseous hydrogen. It was found that the embrittlement was caused by hydrogen-induced, slow crack growth. In the range of temperature from 80° to 25°C, the crack growth rate increased with decrease in temperature; in the range from 0° to ?80°C, the rate decreased with decrease in temperature. It was also found that the crack growth rate had a different pressure dependence at high temperatures than at low temperatures. From a consideration of these experimental data as well as data from earlier investigations, it was determined that gaseous-hydrogen embrittlement and the embrittlement of hydrogen-charged steels are basically the same phenomenon. The data are discussed in terms of a surface-reaction model that adequately explains both gaseous-hydrogen embrittlement and the embrittlement of hydrogencharged steels.     

Effect of microstructure on creep and creep crack growth behaviour of titanium alloy

Creep and creep crack growth behaviour of a near α titanium alloy has been investigated at 600°C which is affected by primary α content. The alloy was heat treated at different temperatures so as to obtain different levels of equiaxed primary α in the range from 5 to 24 %. Constant load creep tests were carried out at 600°C in the stress range 250 to 400 MPa till rupture of the specimens. Creep crack growth tests were carried out at 600°C. Creep data reveals with increase in primary α content leads to creep weakening. On similar lines maximum creep crack growth resistance is associated with the alloy with lowest primary α content. Microstructural and fractographic examination has revealed that creep fracture occurs by nucleation, growth and coalescence of microvoids nucleated at primary β / transformed β (matrix) interfaces. On the other hand, creep crack growth occurs by surface cracks nucleated by fracture of primary α particles as well as by growth and coalescence of microvoids nucleated at primary β / transformed β (matrix) interfaces in the interior of the specimen.     

Finite element modelling of the creep deformation of T91 steel weldments at 600°C

Finite element modelling of the creep deformation of T91 steel weldments, welded using the manual metal arc (MMA) and submerged arc (SA) welding processes, was carried out to predict creep curves for both of the weldments under different stresses and compared with the experimental data. The stress and strain redistribution across the length of the transverse-weld specimens has also been predicted. Data of creep tests at 600°C at stresses between 90-130 MPa for the base metal, the MMA and SA weld metals, and the simulated heat-affected zone were used to determine Garofalo's equation for creep strain. Finite element meshes for both of the weldments were constructed after calculating the HAZ locations using Rosenthal's heat flow equation.     

Effect of microstructure on hydrogen embrittlement of weld-simulated HSLA-80 and HSLA-100 steels

HSLA-80 and HSLA-100 steels have been subjected to weld-simulated grain-coarsened heat-affected zone (GCHAZ) and grain-refined heat-affected zone (GRHAZ) treatments at peak temperatures of 1350 °C and 950 °C, respectively, followed by varying cooling rates to approximate the weld heat inputs of 10 to 50 kJ/cm. Subsequent slow strain rate testing in synthetic seawater has been employed to assess the hydrogen embrittlement (HE) propensity of the materials. It is indicated that in spite of an increase in strength after weld simulation, further ductility deterioration, compared to the base material under similar testing conditions, did not occur in GCHAZ HSLA-100 steel and for low heat input condition of GRHAZ HSLA-80. This has been attributed to their HE resistant microstructures. Predominant acicular ferrite or lath martensite or a combination of both imparts resistance to HE, as observed in the case of grain-coarsened HSLA-100 and for the low heat input grain-refined HSLA-80 steels. The deleterious effect of bainitic-martensitic microstructure has been reflected in the ductility values of grain-coarsened HSLA-80, which is in agreement with the observation of higher susceptibility of the as-received HSLA-100 steel having a similar structure. However, contrary to its beneficial effect in the as-received HSLA-80, an acicular ferrite structure has shown vulnerability toward HE for high heat input grain-refined HSLA-80. This has been attributed to the presence of polygonal ferrite and to the development of an HE susceptible substructure on GRHAZ weld simulation.     

New approach to predict the long-term creep behaviour and evolution of precipitate back-stress of 9–12% chromium steels

Modern advanced 9–12 % Cr steels are complex alloys with excellent creep strength even at high temperatures up to 620°C. The mechanical properties of these steels are significantly influenced by the presence and stability of various precipitate populations. Numerous secondary phases grow, coarsen and, sometimes, dissolve again during heat treatment and service, which leads to a varying obstacle effect of these precipitates on dislocation movement. In this work, the experimentally observed creep rupture strength of an modified 9–12% Cr steel developed in the European COST Group is compared to the calculated maximal obstacle effect (Orowan stress) caused by the precipitates present in these steels for different heat treatment conditions. It is shown that the differences in creep rupture strength caused by different heat treatments disappear after long time service. This observation is discussed on the basis of the calculated evolution of the precipitate microstructure. The concept of boosting long-term creep rupture strength by maximizing the initial creep strength with optimum quality heat treatment parameters for precipitation strengthening is critically assessed.     

Structure and elevated temperature properties of carbon-free ferritic alloys strengthened by a laves phase

A Laves phase, Fe₂Ta, was utilized to obtain good elevated temperature properties in a carbon-free iron alloy containing 1 at. pct Ta and 7 at. pct Cr. Room temperature embrittlement resulting from the precipitation of the Laves phase at grain boundaries was overcome by spheroidizing the precipitate. This was accomplished by thermally cycling the alloys through theα →γ transformation. The short-time yield strength of the alloys decreased very slowly with increase in test temperature up to 600°C, but above this temperature, the strength decreased rapidly. Results of constant load creep and stress rupture tests conducted at several temperatures and stresses indicated that the rupture and creep strengths of spheroidized 1 Ta−7 Cr alloy were higher than those of several commercial steels containing chromium and/or molybdenum carbides but lower than those of steels containing substantial amounts of tungsten and vanadium. When molybdenum was added to the base FeTa-Cr alloy, the rupture and creep strengths were considerably increased. Formerly with Lawrence Berkeley Laboratory.     

Indentation loading studies of acoustic emission from temper and hydrogen embrittled A533B steel

Isothermal tempering at 500 °C (within the region rendering low alloy steels susceptible to reversible temper embrittlement) induced acoustic emission activity in A533B steel during indentation loading. Samples, when sectioned, were found to contain small (∼10 μm long) MnS inclusions, some of which had debonded from the matrix material when they were near the indentations. Hydrogen charging prior to testing greatly enhanced the acoustic emission activity. It also resulted in the formation of small (∼20 to 200 μm) microcracks in samples tempered at 500 °C. These microcracks, when examined by optical metallography, appear to have propagated along prior austenite grain boundaries, consistent with fractographic observations of temper embrittlement in other low alloy steels. Many were nucleated by MnS inclusion debonding and all were confined to within a few hundred micrometers of the sample surface and within two or three indenter diameters from the indent. It is proposed that trace impurities (P, As, Sb, Sn) diffuse during the 500 °C temper to both the MnS inclusion interfaces and the prior austenite grain boundaries, reducing local cohesive strength. The tensile field created by the indenter debonds inclusions to form crack nuclei. Moderate acoustic emission results. In the absence of hydrogen these void nuclei may grow but do not coalesce to form observable cracks. The prior austenite grain boundaries, which in contrast to the dispersed inclusions can provide continuous crack paths, are not sufficiently temper embrittled to fracture without the assistance of hydrogen at these stresses. Hydrogen charging induces a high hydrogen concentration in a surface layer of the sample. This reduces further the grain boundary cohesion, and cracks initiated at inclusions are able to propagate along continuous grain boundary paths, generating additional energetic acoustic emission signals. This process can continue after unloading the indenter due to hydrogen diffusion to the residual stress field.     

Structure and elevated temperature properties of carbon-free ferritic alloys strengthened by a laves phase

A Laves phase, Fe₂Ta, was utilized to obtain good elevated temperature properties in a carbon-free iron alloy containing 1 at. pct Ta and 7 at. pct Cr. Room temperature embrittlement resulting from the precipitation of the Laves phase at grain boundaries was overcome by spheroidizing the precipitate. This was accomplished by thermally cycling the alloys through the α→γ transformation. The short-time yield strength of the alloys decreased very slowly with increase in test temperature up to 600°C, but above this temperature, the strength decreased rapidly. Results of constant load creep and stress rupture tests conducted at several temperatures and stresses indicated that the rupture and creep strengths of spheroidized 1 Ta-7 Cr alloy were higher than those of several commercial steels containing chromium and/or molybdenum carbides but lower than those of steels containing substantial amounts of tungsten and vanadium. When molybdenum was added to the base Fe-Ta-Cr alloy, the rupture and creep strengths were considerably increased. M. Dilip Bhandarkar, formerly with Lawrence Berkeley Laboratory.     

Effect of heat input and preheating on hydrogen assisted weld joint cracking of a 0.13% C, 1.5% Mn, 0.032% Nb high strength steel of 50 mm plate thickness in the IRC test

The effects of preheating and heat input on hydrogen assisted weld joint cracking are investigated at a restraint intensity of 32 kN mm^?2 of a 0.13% C, 1.5% Mn, 0.032% Nb high strength steel of 50 mm thickness in the IRC test, using a high hydrogen experimental electrode of 530 N mm^?2 yield strength. For a heat input ranging from 0.6 to 1.05 kJ mm^?1 a critical preheating temperature of 140°C for almost complete crack prevention, for a range from 1.5 to 2.05 kJ mm^?1, 120°C were found respectively. Nominal stresses at the ends of the 70-80 mm long welds at the start of extensive cracking increase with heat input and preheat, the crack propagating from the HAZ into the weld metal quickly. Under conditions without or close to cracking, however, final stresses after 18 h are reduced with heat inputs. Consequently, crack critical combinations of preheating and heat input are linked to stresses decreasing with heat input but increasing with preheat. From the established IRC-test diagram required combinations of local preheat and heat input for either avoiding hydrogen cracking or overstressing of the weld metal can be determined. Currently used cracking prediction procedures do not consider the effect of heat input and preheat on stress sufficiently and, therefore, may provide unsafe conclusions.     

The influences of impurity content,tensile strength,and grain size on in-service temper embrittlement of CrMoV steels

The influences of impurity levels, grain size, and tensile strength on in-service temper embrittlement of CrMoV steels have been investigated. The samples for this study were taken from several steam turbine CrMoV rotors which had operated for 15 to 26 years. The effects of grain size and tensile strength on embrittlement susceptibility were separated by evaluating the embrittlement behavior of two rotor forgings, which were made from the same ingot, after giving an extended step-cooling treatment. The results reveal that among the residual elements in the steels, only P produces a significant embrittlement. The variation of P and tensile strength of the steels in the ranges investigated has no effect on in-service temper embrittlement susceptibility, as measured by the shift in fracture appearance transition temperature (FATT). However, the prior austenite grain size plays a major role on in-service embrittlement. The fine grain steels with a grain size of ASTM No. 9 or higher are virtually immune to in-service embrittlement. In steels having duplex grain sizes, the embrittlement susceptibility is controlled by the size of coarser grains. For a given steel chemistry, the coarse grain steel is more susceptible to in-service embrittlement, and a decrease in ASTM grain size number from 4 to 0/1 increases the shift in FATT by 61°C (110°F). It is demonstrated that long-term service embrittlement can be simulated, except in very coarse grain steels, by using the extended step-cooling, treatment. The results of step-cooling studies also show that the coarse grain rotor steels take longer time during service to reach a fully embrittled state than the fine grain rotor steels. This difference in the kinetics of embrittlement is believed to be related to the variations in Mo content in the matrix and the grain size of the steels.     

Hot workability of steels for forgings

Sufficient hot ductility is one of the prerequisites for the successful forming and heat treatment of steels. The influence of chemical composition (including trace elements), of soaking and deformation temperatures, strain rate and duration of deformation was to be studied in hot tensile testing. To distinguish the different embrittling mechanisms from each other, a great number of steels with systematically varied composition were examined. Test conditions were chosen so as to give maximum agreement with actual hot working operations. In the temperature range from 1 200–600°C, which was covered by this study, hot embrittlement was only found on steels containing at least one of the elements N, Nb, Pb or Bi. Embrittlement due to MnS precipitations did not occur, as the soaking temperature was limited to max. 1 315°C and the Mn/S ratio was at least 30. Nitrogen is the main cause of hot embrittlement in commercial steels. The fact that also unalloyed, aluminium-free steels embrittle with sufficiently low strain rate shows that nitrogen in solid solution may cause embrittlement even in the absence of nitride formers. The nitride formers accelerate the embrittling process, provided the nitrides are dissolved at soaking temperature. Aluminium, however, has a retarding effect in the presence of vanadium. Embrittlement is attributed to nitrogen atoms entering into multiple voids and micropores, where they recombine to form molecules which impede the slip of dislocations, thus leading to embrittlement. A sufficient length of the deformation operation and recrystallisation being impeded by precipitations are the prerequisites for this type of embrittlement. Titanium, by binding nitrogen at an early stage, prevents precipitation. Also in the case of embrittlement by lead and bismuth, the most conclusive explanation is that atoms of these elements accumulate in voids. Embrittlement by niobium, however, is attributed to deformation-induced precipitation, as it only occurs on cooling from soaking to test temperature and not on direct heating to test temperature.     

Stress and temperature dependence of creep in Alloy 600 in primary water

The stress and temperature dependence of creep of commercial nickel-base Alloy 600 was investigated through constant load, step-load, and step-temperature creep tests in deaerated primary water containing 40 to 60 cc/kg hydrogen. To analyze creep rates for Alloy 600 in the mill-annealed (MA) condition, effective stresses were estimated using applied stresses and instantaneous strains. The apparent activation area was determined to be 7b ² by the multiple regression analysis of creep rates. The apparent activation energy for creep has a weak stress dependence and was determined to lie between 188 and 281 kJ/mole for the effective stress range of 117 to 232 MPa. Creep rates were better correlated with effective stress than applied stress and the stress exponent of Alloy 600 MA was determined to be 2.2 at 337 °C and 5.1 at 360 °C. The magnitudes of the stress exponent, activation energy, and activation area can be interpreted to support a creep mechanism controlled by dislocation-climb and nonconservative motion of jogs in commercial Alloy 600 MA. The activation area agreed with that determined from carbon in solution, implying thermally activated dislocation glide as another possible creep mechanism.     

Creep Rupture Strength and Microstructure of Low C-10Cr-2Mo Heat-Resisting Steels with V and Nb

The new ferritic heat-resisting steels of 0.05C-10Cr-2Mo-0.10V-0.05Nb (Cb) composition with high creep rupture strength and good ductility have already been reported. The optimum amounts of V and Nb that can be added to the 0.05C-10Cr-2Mo steels and their effects on the creep rupture strength and microstructure of the steels have been studied in this experiment. The optimum amounts of V and Nb are about 0.10 pct V and 0.05 pct Nb at 600 °C for 10,000 h, but shift to 0.18 pct V and 0.05 pct Nb at 650 °C. Nb-bearing steels are preferred to other grades on the short-time side, because NbC precipitation during initial tempering stages delays recovery of martensite. On the long-time side, however, V-bearing steels have higher creep rupture strength. By adding V to the steels, electron microscopic examination reveals a stable microstructure, retardation during creep of the softening of tempered martensite, fine and uniform distribution of precipitates, and promotion of the precipitation of Fe₂Mo.     

The effect of fine precipitate particles on the creep behaviour of ferritic model steels – II. Analysis of creep results

In view of efforts to develop ferritic creep resistant steels for applications above 600°C the effect of fine precipitate particles on the creep behaviour of ferritic model steels (20% Cr, up to 0.9 % Nb and 0.1 % C) was studied between 600 and 800°C as a function of stress, temperature and particle distribution. The analysis of the experimental results leads to the conclusion that the observed secondary creep rate can be described completely as dislocation creep by means of a modified power law: the temperature dependence is determined by that of the diffusion coefficient and of the shear modulus, the stress dependence is given by (σ-σ_th)³where σ = applied stress and σ_th = threshold stress, and the effect of the particles is described exclusively by the threshold stress which is of the order of the Orowan stress.     

Thermal and Irradiation Creep Behavior of a Titanium Aluminide in Advanced Nuclear Plant Environments

Titanium aluminides are well-accepted elevated temperature materials. In conventional applications, their poor oxidation resistance limits the maximum operating temperature. Advanced reactors operate in nonoxidizing environments. This could enlarge the applicability of these materials to higher temperatures. The behavior of a cast gamma-alpha-2 TiAl was investigated under thermal and irradiation conditions. Irradiation creep was studied in beam using helium implantation. Dog-bone samples of dimensions 10 × 2 × 0.2 mm³ were investigated in a temperature range of 300 °C to 500 °C under irradiation, and significant creep strains were detected. At temperatures above 500 °C, thermal creep becomes the predominant mechanism. Thermal creep was investigated at temperatures up to 900 °C without irradiation with samples of the same geometry. The results are compared with other materials considered for advanced fission applications. These are a ferritic oxide-dispersion-strengthened material (PM2000) and the nickel-base superalloy IN617. A better thermal creep behavior than IN617 was found in the entire temperature range. Up to 900 °C, the expected 10⁴ hour stress rupture properties exceeded even those of the ODS alloy. The irradiation creep performance of the titanium aluminide was comparable with the ODS steels. For IN617, no irradiation creep experiments were performed due to the expected low irradiation resistance (swelling, helium embrittlement) of nickel-base alloys.     

Stress corrosion cracking mechanisms of alloy 600 polycrystals and single crystals in primary water—Influence of hydrogen

This article investigates the mechanisms governing the process of alloy 600 stress corrosion cracking (SCC). Several critical points have been selected. First, the deleterious influence of cathodic polarization on alloy 600 SCC resistance has been assessed by slow strain rate tests (SSRTs) in primary water at 360 °C. The effects on crack initiation and propagation have been distinguished. Second, a global hydrogen embrittlement of alloy 600 has also been studied at different temperatures from 25 °C to 360 °C. Finally, the use of alloy 600 single crystals allowed clear separation of the crack initiation and crack propagation mechanisms. Transgranular SCC propagation has been precisely observed and described. The possible mechanisms for SCC initiation and propagation on polycrystals are then discussed.     

Crack susceptibility of medium and high alloyed tool steels under continuous casting conditions

Hot tensile tests after partial melting of the specimens were carried out on medium and high alloyed tool steels and their mechanical properties (maximum force and reduction of area) were determined in the temperature range between liquidus and 900°C. Cooling conditions and strain rates were varied in this range. The temperature ranges of reduced ductility were determined, the metallurgical reasons for embrittlement were investigated by means of metallographic and microprobe analysis. The crack susceptibility is related to an enrich-ment of carbon and carbide forming elements in cold and hot working steels, and to the high S content in the segregated zone of the laminate forming steels. The crack susceptibility can be minimized by low strain rates combined with a strong secondary cooling.