Tempered martensite embrittlement in Fe-Mo-C and Fe-W-C steel

A study on the phenomenon of tempered martensite embrittlement (TME) has been made in experimental Fe-Mo-C and Fe-W-C steel. Charpy impact testing was conducted to evaluate the impact toughness, sensitive to TME. Retained austenite was observed by an analytical transmission electron microscopy in both steels. Both steels represented TME. TME was correlated with the formation of the interlath cementite, resulting from the decomposition of interlath retained austenite. TME occurred in a limited range of test temperatures where the interlath cementite could act as a source of embrittling cracks. Therefore, both the interlath cementite resulting from the decomposition of the interlath retained austenite, and the level of matrix toughness, enabling the interlath cementite to act as an effective embrittler, are necessary to produce TME.     

Correlation of microstructure and tempered martensite embrittlement in two 4340 steels

This study is concerned with a correlation between the microstructure and fracture behavior of two AISI 4340 steels which were vacuum induction melted and then deoxidized with aluminum and titanium additions. This allowed a comparison between microstructures that underwent large increases in grain size and those that did not. When the steels were tempered at 350°C,K _Ic and Charpy impact energy plots showed troughs which indicated tempered martensite embrittlement (TME). The TME results of plane strain fracture toughness are interpreted using a simple ductile fracture initiation model based on large strain deformation fields ahead of cracks, suggesting thatK _Icscales roughly with the square root of the spacing of cementite particles precipitated during the tempering treatment. The trough in Charpy impact energy is found to coincide well with the amount of intergranular fracture and the effect of segregation of phosphorus on the austenite grain boundaries. In addition, cementite particles are of primary importance in initiating the intergranular cracks and, consequently, reducing the Charpy energy. These findings suggest that TME in the two 4340 steels studied can be explained quantitatively using different fracture models.     

The effects of heat treatment on fracture toughness and fatigue crack growth Rates in 440C and BG42 steels

The fatigue crack growth rates,da/dN, and the fracture toughness, K_Ic have been measured in two high-carbon martensitic stainless steels, 440C and BG42. Variations in the retained austenite contents were achieved by using combinations of austenitizing temperatures, refrigeration cycles, and tempering temperatures. In nonrefrigerated 440C tempered at 150 °C, about 10 vol pct retained austenite was transformed to martensite at the fracture surfaces duringK _Ic testing, and this strain-induced transformation contributed significantly to the fracture toughness. The strain-induced transformation was progressively less as the tempering temperature was raised to 450 °C, and at the secondary hardening peak, 500 °C, strain-induced transformation was not observed. In nonrefrigerated 440C austenitized at 1065 °C,K _Ic had a peak value of 30 MPa m^1/2 on tempering at 150 °C and a minimum of 18 MPa m^1/2 on tempering at 500 °C. Refrigerated 440C retained about 5 pct austenite, and did not exhibit strain-induced transformation at the fracture surfaces for any tempering temperature. TheK _Ic values for corresponding tempering temperatures up to the secondary peak in refrigerated steels were consistently lower than in nonrefrigerated steels. All of the BG42 specimens were refrigerated and double or quadruple tempered in the secondary hardening region; theK _Ic values were 16 to 18 MPa m^1/2 at the secondary peak. Tempered martensite embrittlement (TME) was observed in both refrigerated and nonrefrigerated 440C, and it was shown that austenite transformation does not play a role in the TME mechanism in this steel. Fatigue crack propagation rates in 440C in the power law regime were the same for refrigerated and nonrefrigerated steels and were relatively insensitive to tempering temperatures up to 500 °C. Above the secondary peak, however, the fatigue crack growth rates exhibited consistently lower values, and this was a consequence of the tempering of the martensite and the lower hardness. Nonrefrigerated steels showed slightly higher threshold values, ΔK_th, and this was ascribed to the development of compressive residual stresses and increased surface roughening in steels which exhibit a strain-induced martensitic transformation.     

Retained Austenite and Tempered Martensite Embrittlement in Medium Carbon Steels

Electron microscopy, diffraction and microanalysis, X-ray diffraction, and auger spectroscopy have been used to study quenched and quenched and tempered 0.3 pct carbon low alloy steels. Some in situ fracture studies were also carried out in a high voltage electron microscope. Tempered martensite embrittlement (TME) is shown to arise primarily as a microstructural constraint associated with decomposition of interlath retained austenite into M₃C films upon tempering in the range of 250 °C to 400 °C. In addition, intralath Widmanstätten Fe₃C forms from epsilon carbide. The fracture is transgranular with respect to prior austenite. The situation is analogous to that in upper bainite. This TME failure is different from temper embrittlement (TE) which occurs at higher tempering temperatures (approximately 500 °C), and is not a microstructural effect but rather due to impurity segregation (principally sulfur in the present work) to prior austenite grain boundaries leading to intergranular fracture along those boundaries. Both failures can occur in the same steels, depending on the tempering conditions.     

Retained austenite and tempered martensite embrittlement in medium carbon steels

Electron microscopy, diffraction and microanalysis, X-ray diffraction, and auger spectroscopy have been used to study quenched and quenched and tempered 0.3 pct carbon low alloy steels. Somein situ fracture studies were also carried out in a high voltage electron microscope. Tempered martensite embrittlement (TME) is shown to arise primarily as a microstructural constraint associated with decomposition of interlath retained austenite into M₃C filM_s upon tempering in the range of 250 °C to 400 °C. In addition, intralath Widmanstätten Fe₃C forms from epsilon carbide. The fracture is transgranular with respect to prior austenite. The sit11Ation is analogous to that in upper bainite. This TME failure is different from temper embrittlement (TE) which o°Curs at higher tempering temperatures (approximately 500 °C), and is not a microstructural effect but rather due to impurity segregation (principally sulfur in the present work) to prior austenite grain boundaries leading to intergranular fracture along those boundaries. Both failures can o°Cur in the same steels, depending on the tempering conditions.     

Effects of silicon additions and retained austenite on stress corrosion cracking in ultrahigh strength steels

A study has been made of the effects of silicon additions and of retained austenite on the stress-corrosion cracking (SCC) behavior of commercial ultrahigh strength steels (AISI 4340 and 300-M) tested in aqueous solutions. By comparing quenched and tempered structures of 4340 and 300-M i) at equivalent strength and ii) at their respective optimum and commercially-used heat-treated conditions, the beneficial role of silicon addition on SCC re-sistance is seen in decreased Region II growth rates, with no change in K’_ISCC. The beneficial role of retained austenite is demonstrated by comparing isothermally transformed 300-M, containing 12 pct austenite, with conventionally quenched and tempered structures of 300-M and 4340, containing less than 2 pct austenite, at identical yield strength levels. Here, the isothermally transformed structure shows an order of magnitude lower Region II SCC growth rates than quenched and tempered 300-M and nearly two orders of magnitude lower Region II growth rates than 4340, K ISCC values remaining largely unchanged. The results are discussed in terms of hydrogen embrittlement mechanisms for SCC in martensitic high strength steels in the light of the individual roles of hydrogen diffusivity and carbide type.     

Transmission electron microscopy examination of hardening and toughening phenomena in Aermet 100

The effect of tempering on the microstructure and mechanical properties of ultrahigh strength Aermet 100 steel was examined. In the as-quenched condition, the steel contained a dispersion of relatively fine, undissolved, (CrTiFeMo)C and (CrFeMo)₂₃C₆ carbides in a martensitic matrix. Upon tempering at 427 °C, the martensite decomposed to form a high density of cementite particles concomitant with a significant drop in toughness. Tempering at 454 °C resulted in peak strength (yield strength ∼ 1756 MPa) due to the precipitation of coherent zones of fine carbides. The peak in toughness (170 MPa√m), attained at a tempering temperature of 482 °C, was attributed to both the absence of cementite and the formation of reverted, stable austenite. Tempering at higher temperatures resulted in loss of both strength and toughness, which was suggested to be the result of precipitate coarsening and formation of unstable austenite, respectively. The details of the electron microscopy studies and mechanism of strengthening and toughening are discussed in light of the current understanding of this subject.     

Tempering of Martensite in Dual-Phase Steels and Its Effects on Softening Behavior

The isothermal and nonisothermal tempering of martensite in dual-phase (DP) steels was investigated mainly by analytical transmission electron microscopy, and the effect on softening behavior was studied. The isothermal tempering resulted in coarsening and spheroidization of cementite and complete recovery of laths. However, nonisothermal tempering manifested fine quasi-spherical intralath and platelike interlath cementite, decomposition of retained austenite, and partial recovery of laths. The distinct characteristic of nonisothermal tempering was primarily attributed to the synergistic effect of delay in cementite precipitation and insufficient time for diffusion of carbon due to rapid heating that delays the third stage of tempering. The finer size and platelike morphology of cementite coupled with partial recovery of lath resulted in reduced softening in nonisothermal tempering compared to severe softening in isothermal tempering due to large spheroidized cementite and complete recovery of lath substructure. The substitutional content of precipitated cementite in nonisothermal tempering was correlated to the richness of particular steel chemistry. Softening resistance during nonisothermal tempering was related to DP steel chemistry, i.e., Cr and Mn content. Fine cementite and less decomposed martensite in rich chemistry confer high resistance to softening compared to leaner chemistries, which indicated severe decomposition of martensite with coarser cementite.     

Tempered martensite embrittlement in SAE 4340 steel

The toughness of SAE 4340 steel with low (0.003 wt pct) and high (0.03 wt pct) phosphorus has been evaluated by Charpy V notch (CVN) impact and compact tension plane strain fracture toughness (K _1c) tests of specimens quenched and tempered up to 673 K (400°C). Both the high and low P steel showed the characteristic tempered martensite embrittlement (TME) plateau or trough in room temperature CVN impact toughness after tempering at temperatures between 473 K (200°C) and 673 K (400°C). The CVN energy absorbed by low P specimens after tempering at any temperature was always about 10 J higher than that of the high P specimens given the same heat treatment. Interlath carbide initiated cleavage across the martensite laths was identified as the mechanism of TME in the low P 4340 steel, while intergranular fracture, apparently due to a combination of P segregation and carbide formation at prior austenite grain boundaries, was associated with TME in the high P steel.K _IC values reflected TME in the high P steels but did not show TME in the low P steel, a result explained by the formation of a narrow zone of ductile fracture adjacent to the fatigue precrack during fracture toughness testing. The ductile fracture zone was attributed to the low rate of work hardening characteristic of martensitic steels tempered above 473 K (200°C).     

Characterization of the Carbon and Retained Austenite Distributions in Martensitic Medium Carbon, High Silicon Steel

The retained austenite content and carbon distribution in martensite were determined as a function of cooling rate and temper temperature in steel that contained 1.31 at. pct C, 3.2 at. pct Si, and 3.2 at. pct noniron metallic elements. Mössbauer spectroscopy, transmission electron microscopy (TEM), transmission synchrotron X-ray diffraction (XRD), and atom probe tomography were used for the microstructural analyses. The retained austenite content was an inverse, linear function of cooling rate between 25 and 560 K/s. The elevated Si content of 3.2 at. pct did not shift the start of austenite decomposition to higher tempering temperatures relative to SAE 4130 steel. The minimum tempering temperature for complete austenite decomposition was significantly higher (>650 °C) than for SAE 4130 steel (～300 °C). The tempering temperatures for the precipitation of transition carbides and cementite were significantly higher (>400 °C) than for carbon steels (100 °C to 200 °C and 200 °C to 350 °C), respectively. Approximately 90 pct of the carbon atoms were trapped in Cottrell atmospheres in the vicinity of the dislocation cores in dislocation tangles in the martensite matrix after cooling at 560 K/s and aging at 22 °C. The 3.2 at. pct Si content increased the upper temperature limit for stable carbon clusters to above 215 °C. Significant autotempering occurred during cooling at 25 K/s. The proportion of total carbon that segregated to the interlath austenite films decreased from 34 to 8 pct as the cooling rate increased from 25 to 560 K/s. Developing a model for the transfer of carbon from martensite to austenite during quenching should provide a means for calculating the retained austenite. The maximum carbon content in the austenite films was 6 to 7 at. pct, both in specimens cooled at 560 K/s and at 25 K/s. Approximately 6 to 7 at. pct carbon was sufficient to arrest the transformation of austenite to martensite. The chemical potential of carbon is the same in martensite that contains 0.5 to 1.0 at. pct carbon and in austenite that contains 6 to 7 at. pct carbon. There was no segregation of any substitutional elements.     

Retained austenite and tempered martensite embrittlement

The problems of detecting the distribution of small amounts (5 pct or less) of retained austenite films around the martensite in quenched and tempered experimental medium carbon Fe/c/x steels are discussed and electron optical methods of analysis are emphasized. These retained austenite films if stable seem to be beneficial to fracture toughness. It has been found that thermal instability of retained austenite on tempering produces an embrittlement due to its decomposition to interlath films of M₃C carbides. The fractures are thus intergranular with respect to martensite but transgranular with respect to the prior austenite. The temperature at which this occurs depends upon alloy content. The effect is not found in Fe/Mo/C for which no retained austenite is detected after quenching, but is present in all other alloys investigated.     

Effect of molybdenum on tempered martensite embrittlement of medium carbon Si-Mn steels

This paper reports a study of the effects of molybdenum on tempered martensite embrittlement (TME) of medium carbon Si-Mn steels. The study employed standard U-notch impact tests, scanning electron fractography, transmission electron microscopy, Auger electron spectroscopy, and dilatometric measurements. It is shown that the addition of molybdenum to Si-Mn steels does not eliminate TME, but molybdenum acts to decrease the ductile-brittle transition temperature (DBTT), thus making the impact test temperature for revealing TME lowered. Furthermore, the deferring role of molybdenum on TME is observed. In the molybdenum doped steels the TME embrittlement trough is displaced to a higher tempering temperature. The embrittlement is found to be concurrent with the replacement of ?-carbide by cementite during tempering. In the molybdenum doped steels the displacement of TME to a higher tempering temperature is seen to be associated with the role of molybdenum retarding cementite precipitation.     

Influence of the Initial Microstructure on the Reverse Transformation Kinetics and Microstructural Evolution in Transformation-Induced Plasticity–Assisted Steel

The reverse transformation behavior upon heating to intercritical temperature was studied in Fe-0.21C-2.2Mn-1.5Si (wt pct) alloy with three initial microstructures. One is the cold-rolled (CR) structure and two others are martensite having different fractions of retained austenite. The CR structure exhibits slower reverse transformation kinetics than martensite due to the lesser population of potent nucleation sites and coarse cementite particles. The film type of retained austenite at the martensite lath boundary contributes to the earlier start of the reverse transformation, because it can proceed as the growth of pre-existing retained austenite, which makes the nucleation process less critical. Besides, the growth of interlath austenite plays an essential role in the evolution of fine lath-type reverse-transformed microstructure, which was difficult to obtain from similar initial microstructures of martensite having negligible fraction of interlath austenite.     

The influence of precipitated austenite on hydrogen embrittlement in 5.5Ni steel

This work was undertaken to test the influence of precipitated austenite on transgranular hydrogen embrittlement in 5.5Ni steel. Prior work has shown that the mechanism of transgranular hydrogen embrittlement in this steel is interlath separation. Since the austenite that forms during the tempering of 5.5Ni steel precipitates on the martenite lath boundaries, it was hypothesized that the austenite might have a beneficial effect. The experimental results show, however, that the precipitated austenite decreases the toughness in the presence of hydrogen. The apparent mechanism is straightforward. The precipitated austenite transforms to martensite in the strain field ahead of the crack tip. Interlath cracks appear at the periphery of the fresh martensite particles. They are apparently caused by the volume change that accompanies the martensite transformation, which imposes a tension across the lath boundary. The interlath cracks link together to form the macroscopic fracture.     

Fracture toughness of aisi M2 high-speed steel and corresponding matrix tool steel

The influence of microstructural variations on the fracture toughness of two tool steels with compositions 6 pct W-5 pct Mo-4 pct Cr-2 pct V-0.8 pct C (AISI M2 high-speed steel) and 2 pct W-2.75 pct Mo-4.5 pct Cr-1 pct V-0.5 pct C (VASCO-MA) was investigated. In the as-hardened condition, the M2 steel has a higher fracture toughness than the MA steel, although the latter steel is softer. In the tempered condition, MA is softer and has a higher fracture toughness than M2. When the hardening temperature is below 1095 °C (2000 °F), tempering of both steels causes embrittlement,i.e., a reduction of fracture toughness as well as hardness. The fracture toughness of both steels was enhanced by increasing the grain size. The steel samples with intercept grain size of 5 (average grain diameter of 30 microns) or coarser exhibit 2 to 3 MPa√m (2 to 3 ksi√in.) higher fracture toughness than samples with intercept grain size of 10 (average grain diameter of 15 microns) or finer. Tempering temperature has no effect on the fracture toughness of M2 and MA steels as long as the final tempered hardness of the steels is constant. Retained austenite has no influence on the fracture toughness of as-hardened MA steel, but a high content of retained austenite appears to raise the fracture toughness of as-hardened M2 steel. There is a temperature of austenitization for each tool steel at which the retained austenite content in the as-quenched samples is a maximum. The above described results were explained through changes in the microstructure and the fracture modes. CHONGMIN KIM, formerly with Climax Molybdenum Company of Michigan, Ann Arbor, MI.     

The micro-mechanisms of tempered martensite embrittlement in 4340-type steels

A study of the micro-mechanisms of tempered martensite embrittlement was made on a series of 4340-type steels in which the contents of manganese, silicon, and trace impurities, especially phosphorus and sulfur, were varied. One plain-carbon steel was also examined. The study employed Charpy impact tests and four-point slow-bend tests coupled with an elastic-plastic stress analysis, as well as scanning electron fractography, Auger electron spectroscopy, transmission electron microscopy of extraction replicas, and magnetic measurements of the transformation of retained austenite. The results indicate that in these steels the TME phenomenon is an intergranular embrittlement problem caused by carbide precipitation on prior austenite grain boundaries which are already weakened by segregated phosphorus and sulfur. The transformation of intragranular retained austenite is concluded not to be of primary significance in the TME in these steels, although it may contribute to the magnitude of the TME toughness trough.     

The role of heat treating on the sour gas resistance of an X-80 steel for oil and gas transport

In this work, the role of the microstructure in the stress sulfide cracking (SSC) resistance of an API X-80 steel was investigated by exposure of as-received and heat-treated specimens to a H₂S-saturated aqueous National Association of Corrosion Engineers (NACE) solution. It was found that for similar corrosive environments and applied stress intensity factors of 30 to 46 MPa√m, crack growth in LEFM (linear elastic fracture mechanics) compact specimens is strongly influenced by heat treating. In the as-received alloy, crack growth in the direction normal to rolling was controlled by metal dissolution of the crack tip region in contact with the corrosive environment, with crack growth rates of the order of 1/W(da/dt)∼8.3×10⁻⁴ h⁻¹. Alternatively, crack growth in the direction parallel to the rolling direction did not show metal dissolution, but instead hydrogen embrittlement along segregation bands. In this case, crack growth rates of the order of 1.2×10⁻³ h⁻¹ were exhibited. In the martensitic condition, the rate of crack propagation was relatively fast (1/W(da/dt)∼4.5×10⁻² h⁻¹), indicating severe hydrogen embrittlement. Crack arrest events were found to occur in water-sprayed and quenched and tempered specimens, with threshold stress intensity values (K _ISSC) of 26 and 32 MPa√m, respectively. Apparently, in the water-sprayed condition, numerous microcracks developed in the crack tip plastic zone. Crack growth occurred by linking of microcracks, which were able to reach the main crack tip. In particular, preferential microcrack growth occurred across carbide regions, but their growth was severely limited in the ferritic matrix. Quenching and tempering (Q&T) resulted in a tempered martensite microstructure characterized by fine distribution carbides, most of which were cementite. In this case, the crack path continually shifted to follow the ferrite interlath boundaries, which contained mostly fine cementite precipitates. As a result, the crack was tortuous with numerous bifurcations along ferrite grain boundaries. Most of the tests were carried out in NaCl-free NACE solutions; the only exception was the as-received condition where 5 wt pct NaCl was added to the sour environment. In this case, crack growth did not occur after exposing the specimen to the salt-free NACE solution for 30 days, but addition of 5 pct NaCl promoted crack propagation.     

The evaluation of tempered martensite embrittlement in 4130 steel by instrumented charpy V-notch testing

Tempered martensite embrittlement (TME) was studied in vacuum-melted 4130 steel with either 0.002 or 0.02 wt pct P. TME was observed as a severe decrease in Charpy V-notch impact energy, from 46 ft-lb. at 200 °C to 35 ft-lb. at 300 °C in the low P alloy. The impact energy of the high P alloy was consistently lower than that of the low P alloy in all tempered conditions. Fracture was transgranular for all specimens; therefore, segregation of P to the prior austenitic grain boundaries was not a factor in the o°Currence of TME. Analysis of load-time curves obtained by instrumented Charpy testing revealed that the embrittlement is associated with a drop in the pre-maximum-load and post-unstable-fracture energies. In specimens tempered at 400 °C the deleterious effect of phosphorus on impact energy became pronounced, a result more consistent with classical temper embrittlement rather than TME. A constant decrease in pre-maximum-load energy due to phosphorus content was observed. The pre-maximum-load energy decreases with increasing tempering temperature in the range of 200 °C to 400 °C, a result explained by the change in work hardening rate. Carbon extraction replicas of polished and etched as-quenched specimens revealed the presence of Fe₂MoC and/or Fe₃C carbides retained after austenitizing. Ductile crack extension close to the notch root was related to the formation of fine micro voids at the retained carbides. This paper is based on a presentation made at the “pcter G. Winchell Symposium on Tempering of Steel” held at the Louisville Meeting of The Metallurgical Society of AIME, October 12-13, 1981, under the sponsorship of the TMS-AIME Ferrous Metallurgy and Heat Treatment Committees.     

Role of Tungsten in the Tempered Martensite Embrittlement of a Modified 9 Pct Cr Steel

The effect of tempering on the mechanical properties and fracture behavior of two 3 pct Co-modified 9 pct Cr steels with 2 and 3 wt pct W was examined. Both steels were ductile in tension tests and tough under impact tests in high-temperature tempered conditions. At T ≤ 923 K (650 °C), the addition of 1 wt pct W led to low toughness and pronounced embrittlement. The 9Cr2W steel was tough after low-temperature tempering up to 723 K (450 °C). At 798 K (525 °C), the decomposition of retained austenite induced the formation of discontinuous and continuous films of M₂₃C₆ carbides along boundaries in the 9Cr2W and the 9Cr3W steels, respectively, which led to tempered martensite embrittlement (TME). In the 9Cr2W steel, the discontinuous boundary films played a role of crack initiation sites, and the absorption energy was 24 J cm^?2. In the 9Cr3W steel, continuous films provided a fracture path along the boundaries of prior austenite grains (PAG) and interlath boundaries in addition that caused the drop of impact energy to 6 J cm^?2. Tempering at 1023 K (750 °C) completely eliminated TME by spheroidization and the growth of M₂₃C₆ carbides, and both steels exhibited high values of adsorbed energy of ≥230 J cm^?2. The addition of 1 wt pct W extended the temperature domain of TME up to 923 K (650 °C) through the formation of W segregations at boundaries that hindered the spheroidization of M₂₃C₆ carbides.     

The Evaluation of Tempered Martensite Embrittlement in 4130 Steel by Instrumented Charpy V-Notch Testing

Tempered martensite embrittlement (TME) was studied in vacuum-melted 4130 steel with either 0.002 or 0.02 wt pct P. TME was observed as a severe decrease in Charpy V-notch impact energy, from 46 ft-lb. at 200 °C to 35 ft-lb. at 300 °C in the low P alloy. The impact energy of the high P alloy was consistently lower than that of the low P alloy in all tempered conditions. Fracture was transgranular for all specimens; therefore, segregation of P to the prior austenitic grain boundaries was not a factor in the occurrence of TME. Analysis of load-time curves obtained by instrumented Charpy testing revealed that the embrittlement is associated with a drop in the pre-maximum-load and post-unstable-fracture energies. In specimens tempered at 400 °C the deleterious effect of phosphorus on impact energy became pronounced, a result more consistent with classical temper embrittlement rather than TME. A constant decrease in pre-maximum-load energy due to phosphorus content was observed. The pre-maximum-load energy decreases with increasing tempering temperature in the range of 200 °C to 400 °C, a result explained by the change in work hardening rate. Carbon extraction replicas of polished and etched as-quenched specimens revealed the presence of Fe₂MoC and/or Fe₃C carbides retained after austenitizing. Ductile crack extension close to the notch root was related to the formation of fine microvoids at the retained carbides.