Optimisation of long-term creep strength of martensitic steels

Besides the reduction of greenhouse gases the increase of thermal efficiency is one of the major goals in modern material development for process and power plants. Increasing the steam inlet temperatures and pressures is at present the favoured method to increase the thermal efficiency. For the realization of 700°C power plants, new creep resistant ferritic-martensitic 9–12 wt. % Cr steels are required to be applied in the 650°C temperature range. An important task for the optimization of long term creep properties is the characterization of the changes in the microstructure during creep exposure. A sufficient long term creep strength is based on a small initial size and slow coarsening of the M₂₃C₆ precipitates as well as the dynamic precipitation of small V(C, N) particles along with the absence of Z-phase. The paper describes the R&D activities of the MPA University of Stuttgart in the frame work of national and international research projects aimed at the development and long term characterisation of optimised martensitic steels with higher long term creep strength.     

Strength and toughness of Fe-10ni alloys containing C,Cr, Mo,and Co

The effects of C (0.10 to 0.20 pct), Cr (0 to 3 pct), Mo (0 to 2 pct), and Co (0 to 8 pct) on the yield strength, toughness (Charpy shelf energy), and tempering behavior of martensitic lONiCr-Mo-Co steels have been investigated. Variations in the carbon content between 0.10 and 0.20 pct result in yield strengths between 160 and 210 ksi (1.1 and 1.45 GN/m²) when these steels are tempered at 900° to 1000°F (480° to 540°C) for times of 1 to 100 h. These steels exhibit a secondary-hardening peak at 900° to 1000° F (480° to 540°C) where coarse Fe₃C carbides are gradually replaced by a fine, dislocation-nucleated dispersion of (Mo, Cr)₂C carbides. Maximum toughness at a given yield strength in these steels is only obtained when they are tempered for sufficiently long times so that the coarse Fe₃C carbides are completely dissolved. Molybdenum is primarily responsible for the secondary-hardening peak observed in these steels. However, chromium additions do result in lower secondaryhardening temperatures and promote coarsening of the secondary-hardening carbide. Best combinations of strength and toughness are obtained with steels containing 2 pct Cr and 1 pct Mo. Cobalt increases the yield strength of these steels over the entire tempering range and results in a higher secondary-hardening peak. This effect of cobalt is attributed to 1) a retardation in the rate of recovery of the dislocation substructure of the martensite, 2) the formation of a finer dispersion of secondary-hardening carbides, and 3) solid-solution strengthening. The finer dispersion of secondary-hardening carbides in steels containing cobalt is favored by the finer dislocation substructure in these steels since the (Mo, Cr)₂C carbide is dislocation-nucleated. This fine dispersion of (Mo, Cr)₂C carbide combined with the high nickel content accounts for the excellent combination of strength and toughness exhibited by these steels.     

Mechanical Performance of Ferritic Martensitic Steels for High Dose Applications in Advanced Nuclear Reactors

Ferritic/martensitic (F/M) steels are considered for core applications and pressure vessels in Generation IV reactors as well as first walls and blankets for fusion reactors. There are significant scientific data on testing and industrial experience in making this class of alloys worldwide. This experience makes F/M steels an attractive candidate. In this article, tensile behavior, fracture toughness and impact property, and creep behavior of the F/M steels under neutron irradiations to high doses with a focus on high Cr content (8 to 12) are reviewed. Tensile properties are very sensitive to irradiation temperature. Increase in yield and tensile strength (hardening) is accompanied with a loss of ductility and starts at very low doses under irradiation. The degradation of mechanical properties is most pronounced at <0.3T _M (T _M is melting temperature) and up to 10 dpa (displacement per atom). Ferritic/martensitic steels exhibit a high fracture toughness after irradiation at all temperatures even below 673 K (400 °C), except when tested at room temperature after irradiations below 673 K (400 °C), which shows a significant reduction in fracture toughness. Creep studies showed that for the range of expected stresses in a reactor environment, the stress exponent is expected to be approximately one and the steady state creep rate in the absence of swelling is usually better than austenitic stainless steels both in terms of the creep rate and the temperature sensitivity of creep. In short, F/M steels show excellent promise for high dose applications in nuclear reactors.     

Effect of Co on Creep Behavior of a P911?Steel

The microstructure and creep behavior of a 3 pct Co modified P911 steel and standard P911 steel were examined. It was shown that the nanoscale M₂₃C₆ carbides and MX carbonitrides in the 3 pct Co modified P911 steel are not susceptible to significant coarsening under creep conditions. Also, coarsening simulations of M₂₃C₆ particles were performed for both steels. The rates of lath and particle coarsening in the P911 + 3 pct Co steel are remarkably lower than those in the P911. Increased stability of a tempered martensite lath structure in the 3 pct Co modified P911 steel provides enhanced creep resistance at an exceptionally high temperature of 923 K (650 °C).     

Characterization of Microstructures across the Heat-Affected Zone of the Modified 9Cr-1Mo Weld Joint to Understand Its Role in Promoting Type IV Cracking

In the postweld heat-treated (PWHT) fusion welded modified 9Cr-1Mo steel joint, a soft zone was identified at the outer edge of the heat-affected zone (HAZ) of the base metal adjacent to the deposited weld metal. Hardness and tensile tests were performed on the base metal subjected to soaking for 5 minutes at temperatures below Ac₁ to above Ac₃ and tempering at the PWHT condition. These tests indicated that the soft zone in the weld joint corresponds to the intercritical region of HAZ. Creep tests were conducted on the base metal and cross weld joint. At relatively lower stresses and higher test temperatures, the weld joint possessed lower creep rupture life than the base metal, and the difference in creep rupture life increased with the decrease in stress and increase in temperature. Preferential accumulation of creep deformation coupled with extensive creep cavitation in the intercritical region of HAZ led to the premature failure of the weld joint in the intercritical region of the HAZ, commonly known as type IV cracking. The microstructures across the HAZ of the weld joint have been characterized to understand the role of microstructure in promoting type IV cracking. Strength reduction in the intercritical HAZ of the joint resulted from the combined effects of coarsening of dislocation substructures and precipitates. Constrained deformation of the soft intercritical HAZ sandwich between relatively stronger constitutes of the joint induced creep cavitation in the soft zone resulting in premature failure.     

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.     

Short‐term Creep Behavior of an X 37 Cr Mo V 5‐1 Hot‐work Tool Steel with almost Bainitic and fully Martensitic Microstructures

In this study two different heat treatments were conducted on an X 37 Cr Mo V 5‐1 hot‐work tool steel, resulting either in a tempered fully martensitic matrix or a matrix almost consisting of tempered bainite. Short‐term creep tests were performed at a high stress level of 800 MPa and at temperatures in the range from 450 °C to 500 °C. Creep specimens consisting of a tempered fully martensitic microstructure exhibited a three times longer creep‐to‐rupture time, than those consisting of a tempered almost bainitic microstructure. Microstructural investigations of creep specimens were performed by transmission electron microscopy. Results of these investigations revealed that due to a lower cooling rate, which is necessary to form bainite, the tempered bainitic microstructure consists of large former bainitic plates, whereas tempered martensite shows fine former martensitic laths. Tempered bainite also exhibits a higher number density of large M₃C, M₇C₃ and MC carbides than tempered martensite. Small M₂C carbides appear in both microstructures in the same quantity, however, nanometer‐sized MC carbides could only be found in tempered martensite. Thus poor short‐term creep behavior of the tempered almost bainitic microstructure can be explained by the lesser amount of strengthening relevant precipitates, a smaller size‐effect due to distance of bainitic interfaces as well as lower solid solution hardening.     

The effect of an intercritical heat treatment on temper embrittlement of a Ni-Cr-Mo-V rotor steel

The effect of an intercritical heat treatment on tempor embrittlement has been investigated for a rotor steel containing 0.25 pct C, 3.5 pct Ni, 1.7 pct Cr, 0.5 pct Mo, 0.1 pct V, and deliberate additions of phosphorus, tin, or antimony. Both martensitic and bainitic steels were held at the intercritical temperature of 1380°F (750°C) for times up to 40 h and were then quenched or cooled to obtain martensitic or bainitic transformation. The steels were then tempered, followed by water quenching or step cooling from the tempering temperature. The residual ferrite maintained a fine plate-like shape even after 40 h at the intercritical temperature. Embrittlement induced by step cooling from the final tempering was mark edly reduced by the intercritical treatment as compared to the embrittlement observed after conventional heat treatment; for example, AFATT, the increase in the Charpy V-notch 50 pct shear fracture transition temperature caused by step cooling, was reduced by at least 80°F (45°C) as a result of the intercritical treatment of steels containing 0.02 pct P. Molybdenum effectively reduced AFATT in intercritlcally heat-treated steels as well as in conventionally treated steels. Possible mechanisms for reducing temper embrittlement with the intercritical treatment are discussed.     

The rapid heat treatment of steel

The technique of austenitizing steel by heating rapidly through the Ac₁ to Ac₃ range, limiting the maximum temperature to the minimum required for complete austenitization and quenching immediately is discussed. Rapid austenitizing refines the austenite grain size if the initial microstructure is a fine aggregate, such as martensite or tempered martensite. Additional grain refinement usually results from two or more cycles and most steels hardenable by heat treatment become ultrafine grained and hence exhibit increased strength and toughness. Rapid austenitizing can also be applied, particularly to high-carbon steels, to develop a unique microstructure comprised of a uniform dispersion of very small carbide particles in an ultrafine grained martensitic matrix. This paper is based on a presentation made at a symposium on Altering the Time Cycle of Heat Treatment, held at the Philadelphia meeting of The Metallurgical Society of AIME, October 14, 1969, under the sponsorship of the IMD Heat Treatment Committee.     

Effect of Tungsten on Long-Term Microstructural Evolution and Impression Creep Behavior of 9Cr Reduced Activation Ferritic/Martensitic Steel

The present study describes the changes in the creep properties associated with microstructural evolution during thermal exposures to near service temperatures in indigenously developed reduced activation ferritic-martensitic steels with varying tungsten (1 and 1.4 wt pct W) contents. The creep behavior has been studied employing impression creep (IC) test, and the changes in impression creep behavior with tungsten content have been correlated with the observed microstructures. The results of IC test showed that an increase in 0.4 pct W decreases the creep rate to nearly half the value. Creep strength of 1.4 pct W steel showed an increase in steels aged for short durations which decreased as aging time increased. The microstructural changes include coarsening of precipitates, reduction in dislocation density, changes in microchemistry, and formation of new phases. The formation of various phases and their volume fractions have been predicted using the JMatPro software for the two steels and validated by experimental methods. Detailed transmission electron microscopy analysis shows coarsening of precipitates and formation of a discontinuous network of Laves phase in 1.4 W steel aged for 10,000 hours at 823 K (550 °C) which is in agreement with the JMatPro simulation results.

     

Microstructure Evolution and Pinning of Boundaries by Precipitates in a 9 pct Cr Heat Resistant Steel During Creep

Structural changes in a 9 pct Cr martensitic steel during a creep test at 923 K (720 °C) under the applied stress of 118 MPa were examined. The tempered martensite lath structure (TMLS) was characterized by M₂₃C₆-type carbide particles with an average size of about 110 nm and MX-type carbonitrides with a size of 40 nm. The M₂₃C₆ particles were located on the packet/block/lath boundaries, whereas the MX precipitates were distributed homogeneously throughout TMLS. TMLS in the grip portion of the crept specimen changed scarcely during the tests. In contrast, the structural changes in the gauge section of the samples were characterized by the evolution of relatively large subgrains with remarkably lowered density of interior dislocations within former martensite laths. The formation of a well-defined subgrain structure in the gauge section was accompanied by the coarsening of M₂₃C₆ carbides and precipitations of Laves phase during creep. The most pronounced structural changes occurred just at the beginning of the tertiary creep regime, which was interpreted as a result of the change in the mechanism of grain boundary pinning by precipitates.     

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.     

Tempering behaviour of a dual-phase low-alloy steel

The tempering behaviour of a dual phase steel of 0.08% C, 1.21% Mn, 1.00% Si, 0.42% Cr, and 0.41% Mo composition with two different martensite contents of 30 and 52%. (obtained by intercritical treatments at 820 and 860°C, respectively) has been studied. The ultimate tensile strength decreased and percentage elongation increased continuously with increasing tempering temperature up to 600°C for both intercritical treatments. The yield strength has, however, increased up to 300°C, beyond which it decreased for the steel with 30% martensite. In contrast it remained almost constant for 52% martensite up to 300°C, beyond which it decreased. The martensite of dual-phase steel for both the intercritical treatments has undergone microstructural changes on tempering that are akin to those of fully martensitic low carbon steels. The SEM fractographs from the as-quenched specimens indicate that the tensile specimens failed by microvoid coalescence with the martensite areas appearing facetted and featureless while those for 600°C tempered condition by the formation of equiaxed dimples.     

Effects of Heating and Cooling Rates on Phase Transformations in 10 Wt Pct Ni Steel and Their Application to Gas Tungsten Arc Welding

10 wt pct Ni steel is a high-strength steel that possesses good ballistic resistance from the deformation induced transformation of austenite to martensite, known as the transformation-induced-plasticity effect. The effects of rapid heating and cooling rates associated with welding thermal cycles on the phase transformations and microstructures, specifically in the heat-affected zone, were determined using dilatometry, microhardness, and microstructural characterization. Heating rate experiments demonstrate that the Ac₃ temperature is dependent on heating rate, varying from 1094 K (821 °C) at a heating rate of 1 °C/s to 1324 K (1051 °C) at a heating rate of 1830 °C/s. A continuous cooling transformation diagram produced for 10 wt pct Ni steel reveals that martensite will form over a wide range of cooling rates, which reflects a very high hardenability of this alloy. These results were applied to a single pass, autogenous, gas tungsten arc weld. The diffusion of nickel from regions of austenite to martensite during the welding thermal cycle manifests itself in a muddled, rod-like lath martensitic microstructure. The results of these studies show that the nickel enrichment of the austenite in 10 wt pct Ni steel plays a critical role in phase transformations during welding.     

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.     

Nanoscale Analyses of High-Nickel Concentration Martensitic High-Strength Steels

Austenite reversion in martensitic steels is known to improve fracture toughness. This research focuses on characterizing mechanical properties and the microstructure of low-carbon, high-nickel steels containing 4.5 and 10 wt pct Ni after a QLT-type austenite reversion heat treatment: first, martensite is formed by quenching (Q) from a temperature in the single-phase austenite field, then austenite is precipitated by annealing in the upper part of the intercritical region in a lamellarization step (L), followed by a tempering (T) step at lower temperatures. For the 10 wt pct Ni steel, the tensile strength after the QLT heat treatment is 910 MPa (132 ksi) at 293 K (20 °C), and the Charpy V-notch impact toughness is 144 J (106 ft-lb) at 188.8 K (?84.4 °C, ?120 °F). For the 4.5 wt pct Ni steel, the tensile strength is 731 MPa (106 ksi) at 293 K (20 °C) and the impact toughness is 209 J (154 ft-lb) at 188.8 K (?84.4 °C, ?120 °F). Light optical microscopy, scanning electron and transmission electron microscopies, synchrotron X-ray diffraction, and local-electrode atom-probe tomography (APT) are utilized to determine the morphologies, volume fractions, and local chemical compositions of the precipitated phases with sub-nanometer spatial resolution. The austenite lamellae are up to 200 nm in thickness, and up to several micrometers in length. In addition to the expected partitioning of Ni to austenite, APT reveals a substantial segregation of Ni at the austenite/martensite interface with concentration maxima of 10 and 23 wt pct Ni for the austenite lamellae in the 4.5 and 10 wt pct Ni steels, respectively. Copper-rich and M₂C-type metal carbide precipitates were detected both at the austenite/martensite interface and within the bulk of the austenite lamellae. Thermodynamic phase stability, equilibrium compositions, and volume fractions are discussed in the context of Thermo-Calc calculations.     

Creep Strength of Dissimilar Welded Joints Using High B-9Cr Steel for Advanced USC Boiler

The commercialization of a 973 K (700 °C) class pulverized coal power system, advanced ultra-supercritical (A-USC) pressure power generation, is the target of an ongoing research project initiated in Japan in 2008. In the A-USC boiler, Ni or Ni-Fe base alloys are used for high-temperature parts at 923 K to 973 K (650 °C to 700 °C), and advanced high-Cr ferritic steels are planned to be used at temperatures lower than 923 K (650 °C). In the dissimilar welds between Ni base alloys and high-Cr ferritic steels, Type IV failure in the heat-affected zone (HAZ) is a concern. Thus, the high B-9Cr steel developed at the National Institute for Materials Science, which has improved creep strength in weldments, is a candidate material for the Japanese A-USC boiler. In the present study, creep tests were conducted on the dissimilar welded joints between Ni base alloys and high B-9Cr steels. Microstructures and creep damage in the dissimilar welded joints were investigated. In the HAZ of the high B-9Cr steels, fine-grained microstructures were not formed and the grain size of the base metal was retained. Consequently, the creep rupture life of the dissimilar welded joints using high B-9Cr steel was 5 to 10 times longer than that of the conventional 9Cr steel welded joints at 923 K (650 °C).     

Effect of Nitrogen Content on Grain Refinement and Mechanical Properties of a Reversion-Treated Ni-Free 18Cr-12Mn Austenitic Stainless Steel

Martensite reversion treatment was utilized to obtain ultrafine grain size in Fe-18Cr-12Mn-N stainless steels containing 0 to 0.44 wt pct N. This was achieved by cold rolling to 80 pct reduction followed by reversion annealing at temperatures between 973 K and 1173 K (700 °C and 900 °C) for 1 to 10⁴ seconds. The microstructural evolution was characterized using both transmission and scanning electron microscopes, and mechanical properties were evaluated using hardness and tensile tests. The steel without nitrogen had a duplex ferritic-austenitic structure and the grain size refinement remained inefficient. The finest austenitic microstructure was achieved in the steels with 0.25 and 0.36 wt pct N following annealing at 1173 K (900 °C) for 100 seconds, resulting in average grain sizes of about 0.240 ± 0.117 and 0.217 ± 0.73 µm, respectively. Nano-size Cr₂N precipitates observed in the microstructure were responsible for retarding the grain growth. The reversion mechanism was found to be diffusion controlled in the N-free steel and shear controlled in the N-containing steels. Due to a low fraction of strain-induced martensite in cold rolled condition, the 0.44 wt pct N steel displayed relatively non-uniform, micron-scale grain structure after the same reversion treatment, but it still exhibited superior mechanical properties with a yield strength of 1324 MPa, tensile strength of 1467 MPa, and total elongation of 17 pct. While the high yield strength can be attributed to strengthening by nitrogen alloying, dislocation hardening, and slight grain refinement, the moderate strain-induced martensitic transformation taking place during tensile straining was responsible for enhancement in tensile strength and elongation.     

Thermally Stable Ni-rich Austenite Formed Utilizing Multistep Intercritical Heat Treatment in a Low-Carbon 10 Wt Pct Ni Martensitic Steel

Austenite reversion and its thermal stability attained during the transformation is key to enhanced toughness and blast resistance in transformation-induced-plasticity martensitic steels. We demonstrate that the thermal stability of Ni-stabilized austenite and kinetics of the transformation can be controlled by forming Ni-rich regions in proximity of pre-existing (retained) austenite. Atom probe tomography (APT) in conjunction with thermodynamic and kinetic modeling elucidates the role of Ni-rich regions in enhancing growth kinetics of thermally stable austenite, formed utilizing a multistep intercritical (Quench-Lamellarization-Tempering (QLT)-type) heat treatment for a low-carbon 10 wt pct Ni steel. Direct evidence of austenite formation is provided by dilatometry, and the volume fraction is quantified by synchrotron X-ray diffraction. The results indicate the growth of nm-thick austenite layers during the second intercritical tempering treatment (T-step) at 863 K (590 °C), with austenite retained from first intercritical treatment (L-step) at 923 K (650 °C) acting as a nucleation template. For the first time, the thermal stability of austenite is quantified with respect to its compositional evolution during the multistep intercritical treatment of these steels. Austenite compositions measured by APT are used in combination with the thermodynamic and kinetic approach formulated by Ghosh and Olson to assess thermal stability and predict the martensite-start temperature. This approach is particularly useful as empirical relations cannot be extrapolated for the highly Ni-enriched austenite investigated in the present study.