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Scripta Materialia 62 (2010) 286289 www.elsevier.com/locate/scriptamat

Modeling of the yield strength of a stainless maraging steel

R. Schnitzer,a,* S. Zinnerb and H. Leitnera,c
a

Christian Doppler Laboratory for Early Stages of Precipitation, University of Leoben, Franz-Josef-Strae 18, A-8700 Leoben, Austria b Bo hler Edelstahl GmbH & Co KG, Mariazeller Strae 25, A-8605 Kapfenberg, Austria c Department of Physical Metallurgy and Materials Testing, University of Leoben, Franz-Josef-Strae 18, A-8700 Leoben, Austria
Received 28 October 2009; revised 13 November 2009; accepted 13 November 2009 Available online 18 November 2009

In the present study, the yield strength of a maraging steel was modeled using data gained by atom probe tomography. The inuence of reverted austenite on the strength was considered as tensile tests on samples consisting of pure austenite were performed and subtracted from the overall curves. Furthermore, a new approach which considers the distribution of the particles sizes was used to describe the age-hardening phenomena. This leads to signicantly improved agreement with the experimental data. 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Maraging steel; Reverted austenite; Tensile testing; Atom probe tomography; Modeling

Various age-hardening models based on thermodynamics and dislocation mechanics have been developed for precipitation-hardened materials over recent decades [15]. The mechanism thought to be responsible for strengthening in age-hardened materials is that of second-phase precipitates acting as obstacles to dislocation movement. Models exist for age-hardened alloys which give a mathematical relation between process variables such as aging temperature and time and the nal alloy strength or hardness. These models are based straightforwardly on physical principles, including thermodynamics, kinetic theory and dislocation mechanism [1]. Such models oer considerable advantages as well as help to optimize the processes and properties of materials. The contributions to the overall yield strength rYS for a precipitation-hardened material can be expressed as follows: rYS rm rss rGS rd rp 1 where rm, rss, rGS, rd and rp are the contributions from the matrix, solid solution strengthening, grain boundary hardening, dislocation hardening and precipitation hardening, respectively. The sum of (rm + rss + rGS+ rd) is equal to the value of rYS in the solution annealed (SA) state. However, it was found that precipitation hardening plays the most important role in strengthening of the material [2,3]. Successful implementation

* Corresponding author. Tel.: +43 3842 4024214; fax: +43 3842 4024202; e-mail: ronald.schnitzer@unileoben.ac.at

and use of precipitation hardening models have already been achieved for Al alloys by Starink and Wang [2], Rometsch and Schaer [6] and Esmaeili et al. [7]. However, application of models to maraging steels showed low accuracy [8]. This seems to be caused by their complex microstructure, as the age-hardening characteristic of maraging steels is also determined by the high reversion tendency of martensite to austenite during aging, which signicantly inuences the strength. The aim of the present work is to model the yield strength of a maraging steel by considering the inuence of austenite and the size distribution of the precipitates. The PH 138 Mo steel investigated belongs to the group of corrosion-resistant maraging alloys which are hardened by the precipitation of the b-NiAl phase [9,10]. The precipitates in the present study were characterized by APT, and strength values were obtained by tensile testing. Precipitates act as obstacles to the glide of dislocations and thus reduce their mobility. Depending on precipitate size and coherency, dislocations have two ways of overcoming these obstacles: (i) by shearing the precipitates; or (ii) by bowing around them (Orowan mechanism). For maraging steels, the following models were proposed to be applicable to describe their precipitation hardening [8,11,12]. The increase in material strength when precipitates are sheared by dislocations follows the Friedel formula and is given by [3]: p 1 2S cxr r3=2 f DsFriedel p 2 r b pxq S

1359-6462/$ - see front matter 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.scriptamat.2009.11.020

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The dislocation line tension S is calculated from S = Gb2/2, where G is the shear modulus of the matrix, and b is the Burgers vector of the dislocation. In this study, a value of 78 GPa was used for G and a value of 0.203 nm for b. The constants xr and xq, derived from particle statistics, have values of 0.82 and 0.75, respectively [3]. The variable r denotes the radius, f the volume fraction, and c the antiphase boundary energy of the sheared particles. A value of 0.256 J m2 for c was used, according to Ref. [13]. Orowan established a relation between the yield strength and the distance L between the particles when the particles are circumvented by dislocation, leaving loops around them. The strength in maraging steels was modeled by the following form of the Orowan relationship [8,11]: DsOrowan 2Gb/ L 2r ln 12pL 2r 2b 3

Table 1. Heat treatments applied in the present study. Aging treatment None 575 C/3 h 575 C/5 h 575 C/10 h 575 C/100 h Volume fraction of austenite (vol.%) 0 7 9 16 30 Hardness (hrc) 31 42 40 39 33

The distance L between particles was calculated according to L = (1.23(2p/(3f))1/2 2(2/3)1/2)r [14,15]. The constant u is related to Poissons ratio m of the matrix by u = (1 + 1/1 m)/2, where m was set to 0.3, as commonly used for metals. In the above-mentioned models, the average precipitate size typically is used for the calculations of the strength. Ansell and Lenel [5] examined the Orowan theory in more detail, and came to the conclusion that yielding will not occur unless the particles plastically deform or fracture. This assumption is dierent from the abovementioned Orowan criterion, where yielding occurs when the dislocations move past the dispersed particles, leaving residual loops surrounding the particles. In this model, the deformation of the particles is considered and, therefore the shear modulus of the precipitates is taken into account according to Eq. (4). In contrast to the other models, this assumption further uses only the volume fraction of the precipitates.   G0 f 1=3 DsAnsellLenel 2=3 4 4C 0:82 f 1=3 The shear modulus of the NiAl precipitates G0 amounts to 49.65 GPa [16], and C = 30 is a constant. The yield strength of a precipitation-hardened material rYS can be calculated according to: rYS r0 M Ds 5 where r0 is the yield strength of the SA material, M is the Taylor factor, which is $3 for body centered cubic materials [17], and Ds is the increase in the shear stress associated with particle hardening and can be derived from one of the above equations. The chemical composition of the investigated PH 13 8 Mo maraging steel is Fe0.03C12.7Cr8.1Ni2.2Mo 1.1Al (all values in wt.%). The alloy was commercially produced and provided by Bo hler Edelstahl GmbH & Co KG as a rolled bar. The material was subjected to solution annealing at 900 C for 1.5 h and subsequently cooled in air. Aging was performed at 575 C for various times. The dierent aging treatments are listed in Table 1, together with the corresponding hardness and phase fraction of austenite. Tensile tests were conducted

on cylindrical specimens 8 mm in diameter, according to standard EN 10 002. In this study, the terms stress and strain refer to engineering stress and engineering strain. The determination of the austenite phase fraction was made by X-ray diraction (XRD) measurements on a Siemens D500 instrument, using Cu Ka radiation. For evaluation of the diraction scans, the method of direct comparison of the integrated intensities of the martensite and austenite peaks was applied [18]. For atom probe tomography (APT), small rods were cut from the bulk material and then etched to sharp needles by a standard two-step electropolishing technique [19]. The second polishing step was conducted in 2% perchloric acid in 2-butoxyethanol. APT was performed on a LEAPe 3000X HR atom probe at a base temperature of 20 K. For the measurements, the laser mode was used, as the evaporation is gentler and allows a larger sample volume to be measured, even in low ductility materials. The laser energy was adjusted to 0.2 nJ, and the repetition rate was set to 200 kHz. Data reconstruction was conducted using the software package IVASe from Imago Scientic Instruments Corporation (Madison, WI, USA). The engineering stressstrain curves obtained by tensile testing of dierently aged samples at 575 C are illustrated in Figure 1. A strong inuence of the aging time on the curve progression can be clearly seen. The short-aged samples show moderate work hardening followed by a continuous stress drop towards failure. With increasing aging time, an increasing work hardening rate can be observed. The SA sample possesses a yield

Figure 1. Engineering stressstrain curves of the maraging steel PH 138 Mo in the SA state and aged at 575 C for dierent times and for the test alloy consisting of austenite.

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R. Schnitzer et al. / Scripta Materialia 62 (2010) 286289 Table 3. Results for the NiAl precipitates obtained by atom probe data analysis. Aging treatment 575 C/3 h 575 C/5 h 575 C/10 h 575 C/100 ha
a

strength of 742 MPa and a tensile strength of 1058 MPa. As expected, a signicant increase in strength was detected after aging. The sample with the shortest aging time of 3 h exhibits a yield strength of 1223 MPa and a tensile strength of 1249 MPa. These values are well under the peak aged strength of the investigated alloy. After aging for 100 h, the tensile strength amounts to $1000 MPa. The elongation at fracture increases from 12% after aging for 3 h to 20% after aging for 100 h. The SA state possesses nearly the same strength level as the 100 h aged sample, whereas the ductility of the SA material is as high as in the 3 h aged sample. As the intermetallic precipitates interact with dislocations, they are the main strengthening mechanism in maraging steels. However, growth of precipitates during aging, which results in loss of strength, is accompanied by an increase in the phase fraction of reverted austenite. To judge the individual inuence of these two eects, tensile tests on material consisting of 100% reverted austenite were performed. The chemical composition of the nanometer-sized reverted austenite was measured by APT and published elsewhere [20]. The result of one such tensile test is also shown in Figure 1. A yield strength of 217 MPa and an elongation at fracture of almost 64% was evaluated. By assuming a linear mixture rule for describing the elastic behavior of a two-phase alloy [12,21], the inuence of reverted austenite was subtracted based on the results obtained. In this way, the yield strength, which corresponds solely to a martensitic matrix with precipitates, was obtained. The measured and corrected yield strengths are summarized in Table 2. In situ XRD under tensile loading showed that reverted austenite was not stable during deformation. However, the amount of transformed austenite in the elastic regime is very small and thus can be neglected [22]. As the mechanical properties of maraging steels strongly depend on precipitates, characterization of their shape, size and distribution is of key interest for describing age-hardening phenomena. APT was performed on samples after dierent heat treatments, as listed in Table 1. The evaluated radius, number density and volume fraction of the precipitates after dierent aging conditions are summarized in Table 3. A detailed analysis of the precipitates is given elsewhere [20]. An increase in the radius from 3.4 to 9.4 nm and a decrease in the number density from 2 1023 to 1 1022 with prolonged aging time are observed, where the volume fraction of the precipitates remains approximately constant.

Radius (nm) 3.4 1.1 4.0 1.6 5.2 2.1 9.4

Number density (1 m3) 1.98E+23 1.16E+23 6.2E+22 1.1E+22

vol.% 3.3 3.2 3.5 3.5

Values with higher uncertainty because of poor statistics.

In a rst step, the models mentioned above were used to estimate the yield strengths after dierent aging times, using the data of the precipitates listed in Table 3. Figure 2 shows the calculated yield strengths together with the experimental values. It can be seen that the age hardening of the investigated steel grade cannot be suciently described by the classical theories of shearing or bypassing of precipitates or by their combination when bypassing is assumed above the maximum of the yield strength. While shearing follows the experimental data up to the maximum, the bypassing model follows the same trend as the experimental data above the maximum. However, the values obtained by classical bypassing are too high. The best agreement of the established models is from the AnsellLenel model, which predicts an almost constant strength. This is due to the approximately constant volume fraction of the precipitates, which is the decisive factor in this model. However, the inadequate factor of the models for shearing and bypassing is thought to be due to the assumption of an average particle size. In all real materials, a distribution of precipitate sizes exists and, therefore, in the case of NiAl precipitates, which are coherent with the matrix [10], it is assumed that precipitates below a critical radius are sheared by dislocations, and larger precipitates are circumvented. Thus, it is most likely that both mechanisms occur in material with a broad precipitate size distribution, as is the case for the material investigated. In this work, the critical radii for the precipitates after dierent aging times were calculated by iterative chang-

Table 2. Eect of aging time on the measured 0.2rYS and the corresponding calculated 0.2rYS matrix with precipitates, where the inuence of the volume fraction of austenite is subtracted. Aging treatment Volume 0.2rYS (MPa) fraction of austenite (vol.%) 0 7 9 16 30 742 1223 1153 1045 795
measured

0.2rYS (MPa)

matrix with precipitates

None 575 C/3 h 575 C/5 h 575 C/10 h 575 C/100 h

742 1299 1246 1203 1043

Figure 2. Measured and calculated yield strength from dierent models and the present approach.

R. Schnitzer et al. / Scripta Materialia 62 (2010) 286289 Table 4. Calculated 0.2rYS after dividing the particle size distribution into sheared and bypassed precipitates. Aging treatment 575 C/3 h 575 C/5 h 575 C/10 h 575 C/100 h rcrit (nm) 6.78 6.78 6.80 6.80 xCutting (%) 100 90 80 0 xBypassing (%) 0 10 20 100 rCutting (nm) 3.4 3.7 4.5 rBypassing (nm) 7.2 8 9.4 0.2rYS (MPa) 1217 1219 1257
Cutting

289

0.2rYS (MPa) 895 944 1013

Bypassing

0.2rYS (MPa) 1217 1219 1257 1013

our approach

ing of the particle radius, unless the stresses obtained by Eqs. (2) and (3) delivered the same value. The results obtained for the critical radii are shown in Table 4. Based on these values, the particle size distributions gained by APT were divided into sheared precipitates (radius smaller than the critical radius) and bypassed precipitates (radius larger than the critical radius). The averaged particle sizes and the corresponding volume fractions of the sheared and bypassed precipitates (Table 4) were used to calculate the yield strengths according to Eqs. (2) and (3). Then it was assumed that major strength contribution derives from the mechanism which provides the higher strengthening value. These values were compared with the experimental data (Fig. 2). Good agreement was obtained for the long-aged samples, and slightly higher dierences are visible for the shortaged samples, up to 10 h of aging. However, it is obvious that dividing the particle size distribution results in the highest accuracy. The small dierences for the short-aged samples can be explained in terms of the high inuence of the antiphase boundary energy, as shearing of precipitates is the dominant mechanism in these aging states. Values in the literature for the NiAl phase scatter in a broad range, where measured energies show by trend lower values than energies from rst-principle calculations [13,2327]. However, there can be also a high inuence of alloying elements on the antiphase boundary energy. In particular, Fe is incorporated in high amounts in NiAl precipitates [20,28], but this inuence is a matter of debate in the literature [29,30]. At longer aging times, when bypassing of precipitates is the dominant mechanism, the experimental values show excellent agreement with the calculated ones from the bypassing model. Small dierences might be due to poor statistics, as only a small number of large precipitates are measured in APT. Therefore, information from complementary methods, e.g., transmission electron microscopy or small angle neutron scattering, which provide analysis of larger sample volume, would be very benecial. In the course of the present work, the yield strength of a PH 138 Mo maraging steel was modeled using the classical theories of shearing and bypassing of precipitates, with the AnsellLenel model and by a new approach. The inuence of reverted austenite was considered by performing tensile tests on samples consisting fully of austenite. The experimental values of the pure martensitic matrix with precipitates were compared with the yield strengths, which were calculated from already known models, using data for the precipitates obtained by APT. It was shown that the age hardening of maraging steels cannot be described adequately by the classical theories of shearing and bypassing of precipitates and by the AnsellLenel model. It was fur-

ther shown that dividing the particle size distribution based on a critical radius leads to a signicantly improved model.
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