Steel for nitrocarburizing, and component

Information

  • Patent Grant
  • 11242593
  • Patent Number
    11,242,593
  • Date Filed
    Thursday, November 30, 2017
    6 years ago
  • Date Issued
    Tuesday, February 8, 2022
    2 years ago
Abstract
Provided is a steel for nitrocarburizing that can ensure hardened case depth by suppressing precipitation of Cr, V, and Nb in a part of the surface layer very close to the surface. The provided steel comprises: a specific chemical composition satisfying 9.5≤([Cr]/52+[V]/50.9+[Nb]/92.9+M)×103≤18.5, with the balance being Fe and inevitable impurities; and a steel microstructure in which an area ratio of bainite phase with respect to the entire microstructure is more than 50%.
Description
TECHNICAL FIELD

The present disclosure relates to steel for nitrocarburizing, and is intended to provide steel for nitrocarburizing that has certain machinability by cutting before nitrocarburizing treatment and can obtain excellent fatigue resistance after the nitrocarburizing treatment and that is suitable for use in components of vehicles and construction machines. The present disclosure also relates to a component obtainable by subjecting the steel for nitrocarburizing to nitrocarburizing treatment.


BACKGROUND

Machine structural components such as automobile gears are required to have excellent fatigue resistance, and thus are usually subjected to surface hardening treatment. As such surface hardening treatment, carburizing treatment, induction quench hardening treatment, nitriding treatment, and the like are well known.


Carburizing treatment is a process of infiltrating and diffusing C in a high-temperature austenite region, so that deep case depth is obtained. Carburizing treatment is thus effective in improving fatigue resistance. However, since carburizing treatment causes heat treatment distortion, it is difficult to apply carburizing treatment to components that, from the perspective of noise or the like, require high dimensional accuracy.


Induction quench hardening treatment is a process of quenching the surface layer by high frequency induction heating, which causes heat treatment distortion, too. Induction quench hardening treatment is therefore problematic in terms of dimensional accuracy, as with carburizing treatment.


Nitriding treatment is a process of infiltrating and diffusing nitrogen in a relatively low temperature range not higher than Ac1 transformation temperature, to increase surface hardness. With nitriding treatment, there is no possibility of heat treatment distortion mentioned above. However, nitriding treatment takes a long treatment time of 50 hr to 100 hr, and requires removal of a brittle compound layer in the surface layer after the treatment.


In view of this, nitrocarburizing treatment with approximately the same treatment temperature as and shorter treatment time than nitriding treatment has been developed and widely used for machine structural components and the like in recent years. Nitrocarburizing treatment is a process of infiltrating and diffusing N and C simultaneously in a temperature range of 500° C. to 600° C. to harden the surface, and can reduce the treatment time by more than half as compared with the conventional nitriding treatment.


However, while carburizing treatment can increase core hardness by quench hardening, core hardness does not increase with nitrocarburizing treatment because the treatment is performed at a temperature of not higher than the transformation temperature of steel. This causes lower fatigue resistance of nitrocarburized material than carburized material.


To enhance the fatigue resistance of nitrocarburized material, quenching-tempering treatment is typically performed before nitrocarburizing treatment to increase core hardness. The resultant fatigue resistance is, however, insufficient. Besides, production costs increase, and machinability decreases inevitably.


To solve such problems, JP H5-59488 A (PTL 1) proposes a steel for nitrocarburizing that contains Ni, Cu, Al, Cr, Ti, and the like to achieve high bending fatigue resistance after nitrocarburizing treatment. By subjecting the steel to nitrocarburizing treatment, the core is age-hardened by Ni—Al and Ni—Ti intermetallic compounds or Cu compounds, and the surface layer is hardened by precipitating nitrides or carbides of Cr, Al, Ti, and the like in the nitrided layer, thus improving bending fatigue resistance.


JP 2002-69572 A (PTL 2) proposes a steel for nitrocarburizing that contains 0.5% to 2% Cu and is extend-forged by hot forging and then air-cooled to form a microstructure mainly composed of ferrite in which Cu is dissolved. Nitrocarburizing treatment at 580° C. for 120 min causes precipitation hardening by Cu and also precipitation hardening by Ti, V, and Nb carbonitrides, to achieve excellent bending fatigue resistance after the nitrocarburizing treatment.


JP 2010-163671 A (PTL 3) proposes a steel for nitrocarburizing in which Ti—Mo carbides and carbides containing these elements and further containing one or more of Nb, V, and W are dispersed.


JP 5567747 B2 (PTL 4) proposes a steel material for nitriding that contains V and Nb and whose microstructure before nitriding is mainly composed of bainite so that the precipitation of V and Nb carbonitrides is suppressed before nitriding and induced during the nitriding, thus achieving excellent fatigue resistance with improved core hardness.


CITATION LIST
Patent Literatures

PTL 1: JP H5-59488 A


PTL 2: JP 2002-69572 A


PTL 3: JP 2010-163671 A


PTL 4: JP 5567747 B2


SUMMARY
Technical Problem

However, the steel for nitrocarburizing described in PTL 1 improves bending fatigue resistance by precipitation hardening by Ni—Al and Ni—Ti intermetallic compounds, Cu, and the like, but does not ensure sufficient workability. The steel for nitrocarburizing described in PTL 2 requires high production costs, because Cu, Ti, V, and Nb need to be added in relatively large amounts. The steel for nitrocarburizing described in PTL 3 is also costly, because Ti and Mo need to be added in large amounts in order to form sufficient fine precipitates.


The steel material for nitriding described in PTL 4 contains Cr, V, and Nb, for precipitation hardening of the nitrided layer. These elements are effective in hardening the nitrided layer. However, in the case where these elements are added excessively, precipitation hardening occurs only in a part of the surface layer very close to the surface, and the hardened case is formed only in a shallow part in the surface layer.


It could therefore be helpful to provide a steel for nitrocarburizing that can ensure hardened case depth by suppressing precipitation of Cr, V, and Nb in a part of the surface layer very close to the surface. It could also be helpful to provide a component having improved fatigue resistance by increasing core hardness as a result of nitrocarburizing treatment after machining.


Solution to Problem

Through intensive study on the influences of the chemical composition and microstructure of steel, we discovered the following: Steel that has a chemical composition containing a relatively large amount of inexpensive C and appropriate amounts of Cr, V, and Nb and a microstructure including bainite phase in an area ratio of more than 50% can ensure excellent machinability because precipitation of Cr, V, and Nb is suppressed. Moreover, in a nitrocarburized component obtained as a result of nitrocarburizing treatment on the steel, fine precipitates containing Cr, V, and Nb are dispersion-precipitated in the core, so that core hardness increases and excellent fatigue resistance is obtained. Further, with appropriate contents of Cr, V, Nb, W, Co, Hf, Zr, and Ti, carbonitride forming elements which prevent N and C from diffusing inwardly from the surface during nitrocarburizing treatment decrease, and the thickness of the hardened case formable by nitrocarburizing treatment increases, which contributes to higher surface fatigue strength.


The present disclosure is based on these discoveries and further studies. We thus provide:


1. A steel for nitrocarburizing, comprising:


a chemical composition containing (consisting of), in mass %,


C: 0.010% or more and 0.100% or less,


Si: 1.00% or less,


Mn: 0.50% or more and 3.00% or less,


P: 0.020% or less,


S: 0.060% or less,


Cr: 0.30% or more and 0.90% or less,


Mo: 0.005% or more and 0.200% or less,


V: 0.02% or more and 0.50% or less,


Nb: 0.003% or more and 0.150% or less,


Al: 0.005% or more and 0.200% or less,


N: 0.0200% or less,


Sb: 0.0005% or more and 0.0200% or less,


W: 0.3% or less inclusive of 0%,


Co: 0.3% or less inclusive of 0%,


Hf: 0.2% or less inclusive of 0%, and


Zr: 0.2% or less inclusive of 0%, and


Ti: 0.1% or less inclusive of 0%,


with the balance being Fe and inevitable impurities; and


a steel microstructure in which an area ratio of bainite phase with respect to the entire microstructure is more than 50%,


wherein the chemical composition satisfies the following Formula (1):

9.5≤([Cr]/52+[V]/50.9+[Nb]/92.9+M)×103≤18.5  (1)

where M is a sum total of [W]/183.8, [Co]/58.9, [Hf]/178.5, [Zr]/91.2, and [Ti]/47.9, and parentheses [ ] represent a content of a corresponding element in the parentheses in mass %.


2. The steel for nitrocarburizing according to 1., wherein the chemical composition further contains, in mass %, one or more selected from the group consisting of


B: 0.0100% or less,


Cu: 0.3% or less, and


Ni: 0.3% or less.


3. The steel for nitrocarburizing according to 1. or 2., wherein the chemical composition further contains, in mass %, one or more selected from the group consisting of


Pb: 0.2% or less,


Bi: 0.2% or less,


Zn: 0.2% or less, and


Sn: 0.2% or less.


4. A component comprising:


a core having the chemical composition and the steel microstructure according to any of 1. to 3.; and


a surface layer having a chemical composition in which contents of nitrogen and carbon are higher than in the chemical composition of the core,


wherein Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase.


Advantageous Effect

It is thus possible to provide a steel for nitrocarburizing excellent in machinability with an inexpensive chemical composition. By subjecting the steel for nitrocarburizing to nitrocarburizing treatment, a component according to the present disclosure having fatigue resistance higher than or equal to that of JIS SCr420 material subjected to carburizing treatment can be obtained. The steel for nitrocarburizing according to the present disclosure is therefore very useful as raw material for producing machine structural components of vehicles and the like. The component according to the present disclosure is very useful as machine structural components of vehicles and the like.





BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:



FIG. 1 is a diagram illustrating a roller pitching test piece;



FIG. 2 is a graph illustrating the influence of the value of ([Cr]/52+[V]/50.9+[Nb]/92.9+M)×103 on the surface fatigue strength; and



FIG. 3 is a diagram illustrating a typical production process of a nitrocarburized component.





DETAILED DESCRIPTION

Detailed description will be given below.


The reasons for limiting the chemical composition to the foregoing range in the present disclosure will be described below. Herein, “%” representing the chemical composition denotes “mass %” unless otherwise specified.


C: 0.010% or more and 0.100% or less


C is necessary to form bainite phase (described later) and ensure strength. If the C content is less than 0.010%, a sufficient amount of bainite phase cannot be obtained, and also the amounts of V and Nb precipitates after nitrocarburizing treatment are insufficient, which makes it difficult to ensure strength. The C content is therefore limited to 0.010% or more. If the C content is more than 0.100%, the hardness of the bainite phase formed increases, and machinability decreases. The C content is therefore limited to 0.010% or more and 0.100% or less. The C content is preferably 0.060% or more and 0.090% or less.


Si: 1.00% or less


Si is effective in not only deoxidation but also bainite phase formation. If the Si content is more than 1.00%, Si dissolves in ferrite and bainite phases, and causes solid solution hardening to thus decrease machinability and cold workability. The Si content is therefore limited to 1.00% or less. The Si content is preferably 0.50% or less, and more preferably 0.30% or less. For effective contribution to deoxidation, the Si content is preferably 0.010% or more.


Mn: 0.50% or more and 3.00% or less


Mn has an effect of enhancing the quench hardenability of the steel and enabling stable formation of bainite phase. Mn also improves bending impact resistance which is important for automotive components. In general, an effective way of enhancing fatigue resistance is to increase the C content and enhance core hardness in the component (hereafter referred to as “core hardness”). Simply increasing the C content, however, causes a decrease in bending impact resistance. If the Mn content is 0.50% or more, such a decrease in bending impact resistance caused by increasing the C content can be prevented. If the Mn content is less than 0.50%, this effect is insufficient. Besides, the amount of MnS formed is insufficient, so that machinability by cutting decreases. The Mn content is therefore limited to 0.50% or more. If the Mn content is more than 3.00%, machinability and cold workability decrease. The Mn content is therefore limited to 3.00% or less. The Mn content is preferably 1.50% or more and 2.50% or less, and more preferably 1.50% or more and 2.00% or less.


P: 0.020% or less


P is an element that enters into the steel as an impurity, and segregates to austenite grain boundaries and decreases grain boundary strength, thus causing lower strength and toughness. Hence, the P content is desirably as low as possible, yet up to 0.020% P is allowable. Reducing the P content to less than 0.001% requires high costs, and accordingly the P content may be 0.001% or more in industrial terms.


S: 0.060% or less


S is an element that enters into the steel as an impurity. If the S content is more than 0.060%, the toughness of the steel decreases. The S content is therefore limited to 0.060% or less. The S content is preferably 0.040% or less. Meanwhile, S is useful as it forms MnS in the steel and improves machinability by cutting. To achieve the effect of improving machinability by cutting by S, the S content is preferably 0.002% or more.


Cr: 0.30% or more and 0.90% or less


Cr is added as it is effective in bainite phase formation. If the Cr content is less than 0.30%, the amount of bainite phase formed is insufficient, and V and Nb precipitates form before nitrocarburizing treatment, so that the hardness before nitrocarburizing increases. Besides, the absolute amounts of V and Nb precipitates after nitrocarburizing treatment decrease, so that the hardness after nitrocarburizing treatment decreases. This makes it difficult to ensure strength. The Cr content is therefore limited to 0.30% or more. If the Cr content is more than 0.90%, the effective hardened case depth decreases, as described later. The Cr content is therefore limited to 0.90% or less. The Cr content is preferably in a range of 0.50% to 0.90%.


Mo: 0.005% or more and 0.200% or less


Mo has an effect of finely precipitating V and Nb precipitates and improving the strength of the nitrocarburized material, and is an important element in the present disclosure. Mo is also effective in bainite phase formation. To improve the strength, the Mo content needs to be 0.005% or more. However, since Mo is an expensive element, the component cost increases if the Mo content is more than 0.200%. The Mo content is therefore limited to a range of 0.005% to 0.200%. The Mo content is preferably in a range of 0.010% to 0.200%, and more preferably in a range of 0.040% to 0.200%.


V: 0.02% or more and 0.50% or less


V is an important element that, as a result of a temperature increase in nitrocarburizing, forms fine precipitates with Nb and increases core hardness, thus improving strength. If the V content is less than 0.02%, the desired effect is unlikely to be achieved. If the V content is more than 0.50%, precipitates coarsen, and the strength improvement is saturated. Besides, proeutectoid ferrite precipitates during continuous casting, which facilitates cracking. The V content is therefore limited to a range of 0.02% to 0.50%. The V content is preferably in a range of 0.03% to 0.30%, and more preferably in a range of 0.03% to 0.25%.


Nb: 0.003% or more and 0.150% or less


Nb is very effective in improving fatigue resistance because, as a result of a temperature increase in nitrocarburizing, Nb forms fine precipitates with V and increases core hardness. If the Nb content is less than 0.003%, the desired effect is unlikely to be achieved. If the Nb content is more than 0.150%, precipitates coarsen, and the strength improvement is saturated. Besides, proeutectoid ferrite precipitates during continuous casting, which facilitates cracking. The Nb content is therefore limited to a range of 0.003% to 0.150%. The Nb content is preferably in a range of 0.020% to 0.120%.


Al: 0.005% or more and 0.200% or less


Al is an element useful in improving surface hardness and effective hardened case depth after nitrocarburizing treatment, and is accordingly added intentionally. Al is also useful in improving toughness by inhibiting the growth of austenite grains during hot forging to yield a finer microstructure. In view of this, the Al content is limited to 0.005% or more. If the Al content is more than 0.200%, the effects are saturated, and rather the component cost increases. The Al content is therefore limited to 0.200% or less. The Al content is preferably 0.020% or more and 0.100% or less, and more preferably 0.020% or more and 0.040% or less.


N: 0.0200% or less


N is a useful element that forms carbonitrides in the steel and improves the strength of the nitrocarburized material. Accordingly, the N content is preferably 0.0020% or more. If the N content is more than 0.0200%, coarser carbonitrides form, causing a decrease in the toughness of the steel material. Moreover, surface cracking occurs in the cast steel, and cast steel quality decreases. The N content is therefore limited to 0.0200% or less.


Sb: 0.0005% or more and 0.0200%


Sb has an effect of facilitating bainite phase formation. If the Sb content is less than 0.0005%, the effect is insufficient. If the Sb content is more than 0.0200%, the effect is saturated, and not only the component cost increases but also the toughness of base metal decreases due to segregation. The Sb content is therefore limited to a range of 0.0005% to 0.0200%. The Sb content is preferably in a range of 0.0010% to 0.0100%.


W: 0.3% or less (inclusive of 0%), Co: 0.3% or less (inclusive of 0%), Hf: 0.2% or less (inclusive of 0%), Zr: 0.2% or less (inclusive of 0%), Ti: 0.1% or less (inclusive of 0%)


W, Co, Hf, Zr, and Ti are each an element effective in improving the strength of the steel. These elements may be added, or omitted (the content may be 0%). To improve the strength of the steel, the W content is preferably 0.01% or more, the Co content is preferably 0.01% or more, the Hf content is preferably 0.01% or more, the Zr content is preferably 0.01% or more, and the Ti content is preferably 0.001% or more. These elements may be added in any combination. If the W content is more than 0.3%, if the Co content is more than 0.3%, if the Hf content is more than 0.2%, if the Zr content is more than 0.2%, or if the Ti content is more than 0.1%, the toughness of the steel decreases. Accordingly, the contents of these elements are limited to the foregoing ranges. Preferable ranges are W: 0.01% to 0.25%, Co: 0.01% to 0.25%, Hf: 0.01% to 0.15%, Zr: 0.01% to 0.15%, and Ti: 0.001% to 0.01%.


Of the elements described above, if the contents of carbonitride forming elements such as Cr, V, Nb, W, Co, Hf, Zr, and Ti are increased, N and C precipitate excessively in a part of the surface layer very close to the surface, as a result of which the hardened case depth decreases. To avoid this, it is important to satisfy the following Formula (1):

9.5≤([Cr]/52+[V]/50.9+[Nb]/92.9+M)×103≤18.5  (1)

where M is a sum total of [W]/183.8, [Co]/58.9, [Hf]/178.5, [Zr]/91.2, and [Ti]/47.9, and the parentheses [ ] represent the content of the corresponding element in the parentheses (mass %).


An experiment that led to finding Formula (1) will be described below.


Steel ingots of 100 kg each having a chemical composition containing C: 0.05%, Si: 0.1%, Mn: 1.5%, Cr: (0 to 1.5) %, V: (0 to 0.3) %, Nb: (0 to 0.3) %, Mo: 0.1%, and N: 0.0100% with the balance being Fe and inevitable impurities were obtained by steelmaking. Each of the steel ingots was hot forged to obtain a steel bar of 33 mmφ. The obtained steel bar was held at 1200° C. for 1 hr, and then allowed to naturally cool, to obtain a hot-forged-equivalent material. A roller pitching test piece of 26 mmφ×130 mm illustrated in FIG. 1 was collected from the hot-forged-equivalent material. The test piece was subjected to nitrocarburizing treatment at 570° C. for 3 hr, and then a roller pitching test was performed. The roller pitching test was performed under the same conditions as the fatigue resistance evaluation described in the EXAMPLES section below.



FIG. 2 illustrates the results of the roller pitching test. As illustrated in FIG. 2, the surface fatigue resistance was particularly excellent in the case where the value of ([Cr]/52+[V]/50.9+[Nb]/92.9+M)×103 was 9.5 or more and 18.5 or less. For a roller pitching test piece produced in the same way as above, the hardened case depth after nitrocarburizing treatment was measured under the same conditions as the fatigue resistance evaluation described in the EXAMPLES section below. As a result, the hardened case depth was shallower in the case where the value of ([Cr]/52+[V]/50.9+[Nb]/92.9+M)×103 was more than 18.5 than in the case where the value was 18.5 or less. This is considered to be the reason why the surface fatigue resistance was lower in the case where the value was more than 18.5. Moreover, the surface hardness was lower in the case where the value was less than 9.5 than in the case where the value was 9.5 or more. This is considered to be the reason why the surface fatigue resistance was lower in the case where the value was less than 9.5.


To increase the hardened case depth, the contents of carbonitride forming elements such as Cr, V, Nb, W, Co, Hf, Zr, and Ti need to be reduced. To increase the hardened case depth after nitrocarburizing treatment, the contents (mass %) of these carbonitride forming elements need to satisfy the foregoing Formula (1).


The basic chemical composition according to the present disclosure has been described above. In addition, one or more of the following elements may be optionally added.


B: 0.0100% or less


B has an effect of improving quench hardenability and facilitating the formation of bainite microstructure. Hence, the B content is preferably 0.0003% or more. If the B content is more than 0.0100%, B precipitates as BN, and not only the quench hardenability improving effect is saturated but also the component cost increases. Accordingly, in the case of adding B, the B content is limited to 0.0100% or less. The B content is more preferably 0.0005% or more and 0.0080% or less.


Cu: 0.3% or less


Cu is a useful element that forms intermetallic compounds with Fe and Ni during nitrocarburizing treatment and improves the strength of the nitrocarburized material by precipitation hardening. Cu is also effective in bainite phase formation. If the Cu content is more than 0.3%, hot workability decreases. The Cu content is therefore limited to 0.3% or less. The Cu content is preferably in a range of 0.05% to 0.25%.


Ni: 0.3% or less


Ni has an effect of increasing quench hardenability and reducing low-temperature brittleness. If the Ni content is more than 0.3%, hardness increases, and as a result machinability by cutting decreases. This is also disadvantageous in terms of cost. The Ni content is therefore limited to 0.3% or less. The Ni content is preferably in a range of 0.05% to 0.25%.


Pb: 0.2% or less, Bi: 0.2% or less, Zn: 0.2% or less, Sn: 0.2% or less


Pb, Bi, Zn, and Sn are each an element that has an effect of improving the machinability by cutting of the steel. In the case of adding any of these elements, the content of the element is preferably 0.02% or more. If the content is more than 0.2%, strength and toughness decrease. Accordingly, the content is limited to this range. Preferable ranges are Pb: 0.02% to 0.1%, Bi: 0.02% to 0.1%, Zn: 0.02% to 0.1%, and Sn: 0.02% to 0.1%.


The balance of the steel composition other than the above-described elements is Fe and inevitable impurities. The balance preferably consists of Fe and inevitable impurities.


The reasons for limiting the steel microstructure of the steel for nitrocarburizing according to the present disclosure to the foregoing range will be described below.


Bainite phase: 50% in area ratio with respect to entire microstructure


The present disclosure is intended to cause V and Nb precipitates to be dispersion-precipitated in the core other than the surface layer nitrided portion after nitrocarburizing treatment, to increase core hardness and improve fatigue resistance after the nitrocarburizing treatment. Here, the presence of Cr, V, and Nb precipitates before the nitrocarburizing treatment is normally disadvantageous in terms of machinability by cutting during cutting work performed before the nitrocarburizing treatment. In bainite transformation, Cr, V, and Nb precipitates are unlikely to form in the matrix phase, as compared with ferrite-pearlite transformation. Hence, the steel microstructure of the steel for nitrocarburizing according to the present disclosure, i.e. the steel microstructure before the nitrocarburizing treatment, is mainly composed of bainite phase. Specifically, the area ratio of bainite phase with respect to the entire microstructure is more than 50%. The area ratio of bainite phase with respect to the entire microstructure is preferably more than 60%, and more preferably more than 80%. The area ratio of bainite phase with respect to the entire microstructure may be 100%. Microstructures other than bainite phase are, for example, ferrite phase and pearlite phase. The area ratios of these other microstructures are preferably as low as possible.


The area ratio of each phase can be calculated as follows. A test piece is collected from the obtained steel for nitrocarburizing. A section (L section) in parallel with the rolling direction of the test piece is surface polished, and then etched by natal. The types of phases are identified using an optical microscope through cross-sectional microstructure observation (optical microscope microstructure observation at 200 magnifications), and the area ratio of each phase is calculated.


It is also preferable that the amount of solute Cr, the amount of solute V, and the amount of solute Nb in the steel are respectively 0.27% or more, 0.05% or more, and 0.02% or more, and the proportion of the amount of solute Cr to the original content is 90% or more, the proportion of the amount of solute V to the original content is 75% or more, and the proportion of the amount of solute Nb to the original content is 50% or more. As mentioned above, the present disclosure is intended to cause Cr, V, and Nb to precipitate finely in nitrocarburizing treatment to thus improve fatigue resistance after the nitrocarburizing treatment. In terms of ensuring machinability by cutting, too, it is desirable to suppress the formation of Cr, V, and Nb precipitates. Accordingly, the amount of solute Cr, the amount of solute V, and the amount of solute Nb are preferably limited to these ranges.


When the above-described steel for nitrocarburizing is subjected to typical nitrocarburizing treatment, a component having greater hardened case depth than a component produced from conventional steel for nitrocarburizing can be obtained. Specifically, as a result of subjecting the above-described steel for nitrocarburizing to nitrocarburizing treatment at 560° C. for 3.5 hr in an atmosphere of NH3:N2:CO2=50:45:5, an effective hardened case depth (described later) of 0.2 mm or more can be achieved.


A production method of producing a nitrocarburized component from steel for nitrocarburizing will be described below.



FIG. 3 illustrates a typical process of producing a nitrocarburized component using the steel for nitrocarburizing (steel bar) according to the present disclosure. The method includes production of a steel bar (steel for nitrocarburizing) as raw material (S1), conveyance (S2), and component (nitrocarburized component) production (S3).


First, in the steel bar production (S1), a steel ingot is hot rolled and/or hot forged to obtain a steel bar, and the steel bar is shipped after quality inspection. In the nitrocarburized component finishing (S3) after the conveyance (S2), the steel bar is cut to predetermined dimensions, hot forged or cold forged, and optionally subjected to cutting work such as drill boring or lathe turning to form a desired shape (e.g. the shape of a gear component or a shaft component). After this, nitrocarburizing treatment is performed to obtain a product.


A hot-rolled material may be directly finished into a desired shape by cutting work such as lathe turning or drill boring, and then subjected to nitrocarburizing treatment to obtain a product. In the case of performing hot forging, the hot forging may be followed by cold straightening. The final product may be subjected to coating treatment such as painting or plating.


In the method of producing the steel for nitrocarburizing according to the present disclosure, hot working before nitrocarburizing treatment is performed under specific conditions of heating temperature and working temperature, to yield the above-described microstructure mainly composed of bainite phase and ensure the amounts of solute Cr, V, and Nb. The hot working mainly denotes hot rolling or hot forging, but hot rolling may be followed by hot forging. Alternatively, hot rolling may be followed by cold forging. In the case where the hot working immediately before the nitrocarburizing treatment is hot rolling, that is, in the case where hot rolling is not followed by hot forging, the following conditions are satisfied in the hot rolling.


Hot rolling heating temperature: 950° C. to 1250° C.


In the hot rolling, carbides remaining from the time of melting are dissolved in order to prevent fine precipitates from forming in the rolled material (the steel bar as the raw material of the component by cold forging and/or cutting work) and impairing forgeability.


If the rolling heating temperature is less than 950° C., carbides remaining from the time of melting are unlikely to dissolve. If the rolling heating temperature is more than 1250° C., crystal grains coarsen, and forgeability tends to decrease. The rolling heating temperature is therefore limited to 950° C. to 1250° C.


Rolling finish temperature: 800° C. or more


If the rolling finish temperature is less than 800° C., ferrite phase forms. This is disadvantageous in terms of forming bainite phase in an area ratio of more than 50% with respect to the entire microstructure of the steel for nitrocarburizing. Besides, the rolling load increases. The rolling finish temperature is therefore limited to 800° C. or more. The upper limit is preferably about 1100° C.


Cooling rate at least in temperature range of 700° C. to 550° C. after rolling: more than 0.4° C./s


To prevent fine precipitates from forming before the finishing into the desired shape and impairing workability, that is, to ensure the above-described amounts of solute Cr, Nb, and V, the cooling rate after the rolling is limited to more than 0.4° C./s which is the critical cooling rate at which the above-described solute amounts can be ensured, at least in a temperature range of 700° C. to 550° C. which is the precipitation temperature range of fine precipitates. The upper limit is preferably about 200° C./s.


In the case where the hot working before the nitrocarburizing treatment is hot forging, that is, in the case where only hot forging is performed or hot rolling is followed by hot forging, the following conditions are satisfied in the hot forging. In the case where hot rolling is performed before the hot forging, the hot rolling conditions described above need not necessarily be satisfied.


Hot Forging Conditions


In the hot forging, the heating temperature in the hot forging is limited to 950° C. to 1250° C., the forging finish temperature is limited to 800° C. or more, and the cooling rate after the forging at least in a temperature range of 700° C. to 550° C. is limited to more than 0.4° C./s, in order to obtain bainite phase in an area ratio of more than 50% with respect to the entire microstructure and to prevent fine precipitates from forming and making it impossible to ensure solute Cr, V, and Nb in terms of cold straightening after the hot forging and machinability by cutting. The upper limit of the cooling rate is preferably about 200° C./s.


The resultant rolled material or forged material is then subjected to cutting work to form a component shape, and then subjected to nitrocarburizing treatment. The nitrocarburizing treatment may be performed under typical conditions. Specifically, the typical conditions are a treatment temperature of 550° C. to 700° C. and a treatment time of 10 min or more. As a result of the nitrocarburizing treatment with such treatment temperature and treatment time, Cr, V, and Nb in the solid solution state precipitate finely, and consequently the strength of the core increases. The hardened case obtained by the typical nitrocarburizing treatment conditions has greater hardened case thickness than that obtained from conventionally known steel for nitrocarburizing. If the treatment temperature is less than 550° C., a sufficient amount of precipitates cannot be obtained. If the treatment temperature is more than 700° C., the temperature is in the austenite region, and surface hardening treatment without phase transformation is difficult. Transformation expansion occurs, and distortion associated with surface hardening treatment increases. Such treatment can no longer be regarded as nitrocarburizing treatment, and the advantages of the nitrocarburizing treatment cannot be ensured. The nitrocarburizing treatment temperature is preferably in a range of 550° C. to 630° C.


The nitrocarburizing treatment infiltrates and diffuses N and C simultaneously into the steel. Accordingly, the nitrocarburizing treatment may be performed in a mixed atmosphere of a nitrogenous gas such as NH3 or N2 and a carburizing gas such as CO2 or CO, e.g. an atmosphere of NH3:N2:CO2=50:45:5.


The component according to the present disclosure is obtained as a result of this production process. The obtained component includes a core having the same chemical composition and steel microstructure as the steel for nitrocarburizing and a surface layer having a chemical composition in which the contents of nitrogen and carbon are higher than in the chemical composition of the core. In the component according to the present disclosure, precipitates containing Cr, V, and Nb are dispersion-precipitated in the bainite phase.


Chemical Composition of Core and Chemical Composition of Surface Layer


When the steel for nitrocarburizing having the above-described chemical composition is subjected to the nitrocarburizing treatment, nitrogen and carbon from the surface infiltrate and diffuse into the surface layer. On the other hand, the diffusion of nitrogen and carbon does not reach the core. That is, the part in which C and N are not diffused is the core. Hence, in the resultant component, the core has the same chemical composition as the steel for nitrocarburizing, whereas the surface layer has a chemical composition in which the contents of nitrogen and carbon are higher than in the core. If nitrogen and carbon are not infiltrated and diffused in the surface layer of the component, that is, if the contents of nitrogen and carbon are not higher in the surface layer than in the core, a hard layer is not formed in the surface layer, and sufficient improvement in fatigue strength cannot be expected.


Steel Microstructure of Core


In the component produced by subjecting the steel for nitrocarburizing according to the present disclosure to the nitrocarburizing treatment, the steel microstructure of the steel for nitrocarburizing remains in the core. In detail, the steel microstructure of the core in the component after the nitrocarburizing treatment includes bainite in an area ratio of more than 50% with respect to the entire microstructure. The steel microstructure of the core in the component is the same as the steel microstructure of the steel for nitrocarburizing. Accordingly, the area ratio of bainite phase with respect to the entire microstructure is preferably more than 60% and more preferably more than 80%, as mentioned above. The area ratio of bainite phase with respect to the entire microstructure may be 100%. Microstructures other than bainite phase are, for example, ferrite phase and pearlite phase. The area ratios of these other microstructures are preferably as low as possible.


Dispersion Precipitation of Cr-Containing Precipitates, V-Containing Precipitates, and Nb-Containing Precipitates in Bainite Phase


When Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase of the core, the core hardness increases, and the fatigue resistance of the component after the nitrocarburizing treatment increases significantly. Herein, the dispersion precipitation of Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates means their total dispersion precipitation state in which 500 or more particles of precipitates with a particle size of (preferably) less than 10 nm are dispersion-precipitated per unit area of 1 μm2. Such dispersion precipitation is preferable in terms of strengthening by precipitation for the component after the nitrocarburizing treatment. The measurement limit of the precipitate particle size, i.e. the minimum measurable particle size, is 1 nm.


The component with the above-described structure has deep effective hardened case depth (described later) and high surface hardness and core hardness. Specifically, the component has an effective hardened case depth of 0.2 mm or more, a surface hardness of 700 HV or more, and a core hardness of 200 HV or more.


Effective Hardened Case Depth: 0.2 mm or More


The effective hardened case depth herein is the depth of the effective hardened case that is a region having hardness greater than or equal to a specific value. Specifically, the depth (mm) from the surface with HV 550 is taken to be the effective hardened case depth. It is difficult to achieve high fatigue strength unless the effective hardened case depth is 0.2 mm or more. The effective hardened case depth is therefore preferably 0.2 mm or more. The effective hardened case depth is more preferably 0.25 mm or more.


The component according to the present disclosure preferably has a surface hardness of 700 HV or more and a core hardness of 200 HV or more. The component satisfying these hardness conditions has favorable fatigue resistance.


EXAMPLES

Examples will be described below.


Steels (steel samples No. 1 to 42) having the compositions shown in Table 1 were each formed into cast steel of 300 mm×400 mm in cross section by a continuous casting machine. Whether the cast steel had cracks at the surface was examined. The cast steel was soaked at 1250° C. for 30 min, and then hot rolled to obtain a billet with a rectangular section of 140 mm on a side. The billet was hot rolled to obtain a steel bar (raw material as hot rolled) of 60 mmφ. The heating temperature of the billet in the hot rolling, the rolling finish temperature, and the cooling rate in a range of 700° C. to 550° C. after the hot rolling are shown in Table 2.


Some of the raw materials as hot rolled were each hot forged at the heating temperature and the forging finish temperature shown in Table 2, to obtain a steel bar of 30 mmφ. After this, the steel bar was cooled to room temperature at the cooling rate in a range of 700° C. to 550° C. shown in Table 2, to obtain a hot forged material.
























TABLE 1




















(mass %)


Steel

















sample













Formula



No.
C
Si
Mn
P
S
Cr
Mo
V
Nb
Al
N
Sb
Others
1*)
Category






























1
0.043
0.05
1.75
0.014
0.015
0.61
0.070
0.08
0.063
0.035
0.0090
0.0005

14.0
Example


2
0.056
0.11
1.45
0.012
0.019
0.32
0.006
0.14
0.074
0.031
0.0044
0.0006

 9.7
Example


3
0.061
0.25
2.42
0.012
0.017
0.55
0.105
0.12
0.051
0.028
0.0053
0.0007

13.5
Example


4
0.021
0.35
1.65
0.015
0.015
0.45
0.123
0.09
0.149
0.123
0.0048
0.0007

12.0
Example


5
0.033
0.65
1.75
0.010
0.016
0.36
0.051
0.12
0.132
0.013
0.0055
0.0012

10.7
Example


6
0.016
0.06
1.76
0.012
0.015
0.56
0.190
0.20
0.083
0.006
0.0053
0.0018

15.6
Example


7
0.061
0.07
1.55
0.008
0.016
0.56
0.185
0.18
0.034
0.007
0.0045
0.0009

14.7
Example


8
0.091
0.06
1.76
0.012
0.015
0.61
0.124
0.20
0.084
0.097
0.0123
0.0052

16.6
Example


9
0.098
0.07
1.64
0.008
0.016
0.34
0.090
0.34
0.123
0.064
0.0045
0.0185

14.5
Example


10
0.033
0.86
1.82
0.010
0.023
0.46
0.183
0.21
0.111
0.025
0.0056
0.0056

14.2
Example


11
0.064
0.05
1.77
0.012
0.017
0.52
0.084
0.04
0.124
0.023
0.0046
0.0098

12.1
Example


12
0.037
0.06
1.69
0.008
0.015
0.55
0.126
0.18
0.004
0.013
0.0036
0.0008
B: 0.0005
14.2
Example


13
0.033
0.12
2.26
0.015
0.016
0.61
0.193
0.13
0.148
0.037
0.0192
0.0010
Cu: 0.1
15.9
Example


14
0.068
0.31
1.69
0.018
0.033
0.32
0.180
0.15
0.039
0.031
0.0054
0.0006
Cu: 0.1,
 9.5
Example















Ni: 0.15




15
0.043
0.02
1.85
0.012
0.018
0.65
0.050
0.10
0.049
0.025
0.0060
0.0040
W: 0.2
16.6
Example


16
0.095
0.05
1.51
0.010
0.020
0.55
0.103
0.15
0.148
0.031
0.0120
0.0060
Co: 0.3
15.1
Example


17
0.092
0.20
1.98
0.015
0.017
0.54
0.123
0.18
0.050
0.028
0.0130
0.0008
Hf: 0.2,
17.8
Example















Zr: 0.2




18
0.088
0.03
1.86
0.013
0.015
0.49
0.089
0.12
0.147
0.130
0.0097
0.0070
Pb: 0.1
13.4
Example


19
0.094
0.75
1.75
0.010
0.016
0.33
0.051
0.15
0.133
0.137
0.0090
0.0012
Bi: 0.2
10.7
Example


20
0.045
0.02
1.54
0.012
0.013
0.33
0.062
0.45
0.110
0.045
0.0150
0.0040
Zn: 0.2
16.4
Example


21
0.011
0.05
2.98
0.009
0.045
0.65
0.080
0.17
0.034
0.034
0.0157
0.0009
Sn: 0.2
16.2
Example


22

0.005

0.04
2.12
0.013
0.014
0.49
0.070
0.21
0.040
0.026
0.0132
0.0012

14.0
Comparative Example


23

0.153

0.09
1.65
0.014
0.024
0.66
0.142
0.14
0.069
0.045
0.0065
0.0012

16.2
Comparative Example


24
0.084

1.26

1.65
0.012
0.024
0.55
0.111
0.16
0.078
0.035
0.0073
0.0053

14.6
Comparative Example


25
0.053
0.25

0.48

0.013
0.019
0.45
0.074
0.15
0.101
0.037
0.0047
0.0008

12.7
Comparative Example


26
0.061
0.09

3.24

0.018
0.025
0.36
0.068
0.21
0.049
0.135
0.0052
0.0009

11.6
Comparative Example


27
0.036
0.13
1.61

0.028

0.018
0.35
0.079
0.13
0.064
0.088
0.0063
0.0012

10.0
Comparative Example


28
0.051
0.13
2.13
0.018

0.075

0.54
0.195
0.25
0.063
0.153
0.0124
0.0013

16.0
Comparative Example


29
0.095
0.13
1.61
0.018
0.022

0.25

0.094
0.10
0.057
0.132
0.0032
0.0006

7.4
Comparative Example


30
0.090
0.13
1.61
0.018
0.022

1.37

0.118
0.11
0.054
0.157
0.0032
0.0012


29.1

Comparative Example


31
0.065
0.05
1.64
0.016
0.015
0.70

0.004

0.12
0.075
0.053
0.0056
0.0010

16.6
Comparative Example


32
0.036
0.22
1.73
0.014
0.034
0.56
0.096

0.01

0.052
0.024
0.0152
0.0009

11.5
Comparative Example


33
0.034
0.31
1.48
0.011
0.008
0.55
0.132

0.55

0.069
0.024
0.0065
0.0007


22.1

Comparative Example


34
0.045
0.06
1.66
0.015
0.026
0.34
0.062
0.14

0.002

0.097
0.0088
0.0014

9.3
Comparative Example


35
0.035
0.06
1.66
0.008
0.015
0.46
0.059
0.06

0.156

0.065
0.0051
0.0011

11.7
Comparative Example


36
0.085
0.06
1.66
0.012
0.026
0.60
0.057
0.13
0.054

0.004

0.0088
0.0009

14.7
Comparative Example


37
0.088
0.06
1.66
0.015
0.026
0.54
0.063
0.09
0.046

0.211

0.0103
0.0015

12.6
Comparative Example


38
0.086
0.05
1.65
0.015
0.014
0.59
0.070
0.20
0.075
0.022

0.0251

0.0010

16.1
Comparative Example


39
0.035
0.13
1.92
0.016
0.028
0.87
0.164
0.11
0.045
0.030
0.0059
0.0008


19.4

Comparative Example


40
0.083
0.02
0.95
0.011
0.025
0.35
0.149
0.12
0.012
0.018
0.0052
0.0010

9.2
Comparative Example


41
0.050
0.03
1.46
0.010
0.016
0.56
0.101
0.15
0.146
0.037
0.0123

0.0002


15.3
Comparative Example


42

0.206

0.33
0.81
0.014
0.021

1.15


0.001


0.01


0.001

0.027
0.0130



Conventional Example





*1Underlines indicate outside application range.


*)Formula 1: ([Cr]/52 + [V]/50.9 + [Nb]/92.9 + [M]) × 103


















TABLE 2










Hot rolling conditions
Hot forging conditions




















Heating
Hot rolling
Cooling rate
Heating
Hot forging
Cooling rate




Steel
Billet
temperature
finish
after hot
temperature in
finish
after hot




sample
surface
in hot rolling
temperature
rolling
hot forging
temperature
forging



No.
No.
cracking*4
(° C.)
(° C.)
(° C.)
(° C.)
(° C.)
(° C./s)
Remarks



















1
1
A
1150
970
0.8
1200
1100
0.8
Example


2
2
A
1150
970
0.7
1200
1100
0.8
Example


3
3
A
1150
970
0.8
1200
1100
0.8
Example


4
4
A
1150
970
0.7
1200
1100
0.8
Example


5
5
A
1150
970
0.8
1200
1100
0.7
Example


6
6
B
1150
970
0.8
1200
1100
0.8
Example


7
7
B
1150
970
0.6
1200
1100
0.8
Example


8
8
A
1150
970
0.8
1200
1100
0.8
Example


9
9
A
1150
970
0.8
1200
1100
0.5
Example


10
10
A
1150
970
0.5
1200
1100
0.8
Example


11
11
A
1050
900
0.8
1200
1100
0.6
Example


12
12
A
1150
970
0.8
1200
1100
0.8
Example


13
13
B
1050
910
0.8
1200
1100
0.5
Example


14
14
A
1080
920
0.8
1200
1100
0.8
Example


15
15
A
1150
970
0.8
1200
1100
0.8
Example


16
16
A
1150
970
0.7
1200
1100
0.8
Example


17
17
A
1150
970
0.5
1200
1100
0.5
Example


18
18
B
1150
970
0.8
1200
1100
0.8
Example


19
19
B
1150
970
0.8
1200
1100
0.8
Example


20
20
B
1150
970
0.8
1200
1100
0.6
Example


21
21
B
1150
970
0.8
1200
1100
0.8
Example


22
1
A
1150
970
0.8
960
840
0.8
Example


23
1
A
1150
970
0.8
1250
1050
0.8
Example


24
1
A
1150
970
0.8



Example


25
1
A
960
810
0.8



Example


26
1
A
1250
1050
0.8



Example


27
1
A
930
815
0.8



Comparative Example


28
1
A
1150
750
0.8



Comparative Example


29
1
A
1150
970
0.3



Comparative Example


30
1
A
1150
970
0.4



Comparative Example


31
1
A
1150
970
0.8
900
1100
0.8
Comparative Example


32
1
A
1150
970
0.8
1200
750
0.8
Comparative Example


33
1
A
1150
970
0.8
1200
1100
0.3
Comparative Example


34
1
A
1150
970
0.8
1200
1100
0.4
Comparative Example


35

22

A
1150
970
0.8
1200
1100
0.8
Comparative Example


36

23

B
1150
970
0.8
1200
1100
0.8
Comparative Example


37

24

B
1150
970
0.8
1200
1100
0.8
Comparative Example


38

25

A
1150
970
0.8
1200
1100
0.8
Comparative Example


39

26

C
1150
970
0.8
1200
1100
0.8
Comparative Example


40

27

C
1150
970
0.8
1200
1100
0.8
Comparative Example


41

28

C
1150
970
0.8
1200
1100
0.8
Comparative Example


42

29

A
1150
970
0.8
1200
1100
0.8
Comparative Example


43

30

B
1150
970
0.8
1200
1100
0.8
Comparative Example


44

31

A
1150
970
0.8
1200
1100
0.8
Comparative Example


45

32

A
1150
970
0.8
1200
1100
0.8
Comparative Example


46

33

C
1150
970
0.8
1200
1100
0.8
Comparative Example


47

34

A
1150
970
0.8
1200
1100
0.8
Comparative Example


48

35

C
1150
970
0.8
1200
1100
0.8
Comparative Example


49

36

A
1150
970
0.8
1200
1100
0.8
Comparative Example


50

37

C
1150
970
0.8
1200
1100
0.8
Comparative Example


51

38

C
1150
970
0.8
1200
1100
0.8
Comparative Example


52

39

A
1150
970
0.8
1200
1100
0.8
Comparative Example


53

40

A
1150
970
0.8
1200
1100
0.8
Comparative Example


54

41

C
1150
970
0.8
1200
1100
0.8
Comparative Example


55

42

B
1150
970
0.8
1200
1100
0.8
Conventional Example





*1Underlines indicate outside application range.


*4Cast steel surface cracking A: no cracks, B: 1 to 4 cracks/m2, C: 5 or more cracks/m2






The machinability by cutting (tool life) of each of the resultant raw materials as hot rolled and hot forged materials was evaluated by an outer periphery turning test. As the test material, the raw material as hot rolled or the hot forged material was cut to a length of 200 mm. As the cutting tool, CSBNR 2020 produced by Mitsubishi Materials Corporation was used as the folder and SNGN 120408 UTi20 high-speed tool steel produced by Mitsubishi Materials Corporation was used as the tip. The conditions of the outer periphery turning test were as follows: cutting depth: 1.0 mm, feed rate: 0.25 mm/rev, cutting rate: 200 m/min, and no lubricant. As an evaluation item, the tool life was defined as the time until the tool wear (flank wear) reached 0.2 mm.


In addition, microstructure observation and hardness measurement were performed on each of the raw materials as hot rolled and the hot forged materials. A test piece for evaluation was collected from a center portion of the raw material as hot rolled or the hot forged material. In the microstructure observation, the types of phases were identified and the area ratio of each phase was calculated by the above-described method. In the hardness measurement, hardness at one-fourth the diameter from the surface was measured at five locations with a test load of 2.94 N (300 gf) using a Vickers hardness meter in accordance with JIS Z 2244, and the average value was taken to be hardness HV. The measurement results and evaluation results are shown in Table 3.











TABLE 3








Steel properties (before nitrocarburizing treatment)




















Amount of







Bainite
Amount of
solute/





Core
Steel
phase
solute
amount
Tool




hardness
micro-
area ratio
(mass %)
added (%)
life



















No.
HV
structure
(%)
Cr
V
Nb
Cr
V
Nb
(s)
Remarks





















1
253
Mainly B
92
0.60
0.07
0.034
98
84
55
630
Example


2
301
Mainly B
98
0.30
0.12
0.044
93
83
59
510
Example


3
317
Mainly B
97
0.53
0.10
0.027
97
81
53
471
Example


4
282
Mainly B
95
0.43
0.07
0.089
95
78
60
559
Example


5
280
Mainly B
96
0.33
0.09
0.067
90
75
51
563
Example


6
285
Mainly B
98
0.53
0.15
0.049
94
76
60
550
Example


7
279
Mainly B
94
0.52
0.14
0.020
93
75
59
564
Example


8
284
Mainly B
96
0.60
0.17
0.048
98
84
57
552
Example


9
252
Mainly B
55
0.32
0.29
0.067
95
84
55
632
Example


10
291
Mainly B
93
0.42
0.17
0.059
91
79
53
534
Example


11
281
Mainly B
60
0.48
0.03
0.064
92
83
51
561
Example


12
277
Mainly B
97
0.49
0.14
0.002
89
78
50
570
Example


13
290
Mainly B
96
0.56
0.11
0.081
91
83
55
538
Example


14
275
Mainly B
80
0.29
0.12
0.021
91
81
54
575
Example


15
296
Mainly B
95
0.58
0.08
0.026
90
78
52
625
Example


16
363
Mainly B
100 
0.52
0.12
0.079
94
80
53
483
Example


17
335
Mainly B
92
0.49
0.14
0.028
90
78
56
543
Example


18
280
Mainly B
96
0.44
0.10
0.081
89
79
55
1205
Example


19
301
Mainly B
98
0.31
0.13
0.078
93
84
59
1360
Example


20
256
Mainly B
97
0.31
0.35
0.064
94
78
58
1230
Example


21
237
Mainly B
95
0.60
0.14
0.020
92
82
59
750
Example


22
249
Mainly B
88
0.56
0.07
0.037
92
84
59
640
Example


23
256
Mainly B
96
0.56
0.06
0.035
92
81
56
623
Example


24
252
Mainly B
96
0.60
0.07
0.036
98
82
57
632
Example


25
239
Mainly B
87
0.57
0.06
0.032
94
76
51
665
Example


26
233
Mainly B
75
0.60
0.06
0.035
98
80
55
680
Example


27
189
F + P + B

42

0.49
0.06
0.026
80
71
41
405
Comparative Example


28
222
F + P + B
24
0.46
0.05
0.025
75
64
40
309
Comparative Example


29
210
F + P + B

38

0.46
0.05
0.023
76
67
37
186
Comparative Example


30
215
F + P + B

45

0.46
0.06
0.030
75
73
48
213
Comparative Example


31
195
F + P + B

45

0.45
0.06
0.030
74
72
47
299
Comparative Example


32
256
F + P + B

24

0.42
0.05
0.025
69
67
40
126
Comparative Example


33
220
F + P + B

41

0.45
0.06
0.026
73
70
41
133
Comparative Example


34
231
F + P + B

48

0.48
0.06
0.025
78
74
40
136
Comparative Example


35
154
F + B

32

0.46
0.19
0.028
94
89
70
1250
Comparative Example


36
389
Mainly B
95
0.59
0.11
0.036
89
77
52
126
Comparative Example


37
356
Mainly B
85
0.51
0.13
0.046
92
83
58
374
Comparative Example


38
321
F + P

32

0.33
0.11
0.032
73
70
32
133
Comparative Example


39
363
M + B
96
0.33
0.17
0.028
92
83
58
224
Comparative Example


40
298
Mainly B
96
0.32
0.11
0.038
92
84
59
517
Comparative Example


41
281
Mainly B
95
0.49
0.20
0.035
90
80
55
561
Comparative Example


42
285
F + P + B

23

0.18
0.07
0.018
71
69
31
169
Comparative Example


43
401
M + B
56
1.29
0.09
0.029
94
79
54
122
Comparative Example


44
202
F + P + B

18

0.48
0.06
0.029
69
49
38
162
Comparative Example


45
191
Mainly B
96
0.55
0.01
0.028
98
78
53
510
Comparative Example


46
320
Mainly B
97
0.54
0.46
0.040
99
83
58
312
Comparative Example


47
223
Mainly B
95
0.31
0.11
0.001
90
80
55
505
Comparative Example


48
280
Mainly B
96
0.41
0.05
0.085
90
79
54
493
Comparative Example


49
307
Mainly B
94
0.57
0.11
0.031
95
82
57
495
Comparative Example


50
292
Mainly B
87
0.50
0.07
0.026
93
82
57
533
Comparative Example


51
290
Mainly B
90
0.53
0.17
0.045
90
83
60
434
Comparative Example


52
306
Mainly B
94
0.79
0.09
0.027
91
84
59
498
Comparative Example


53
285
Mainly B
93
0.34
0.09
0.006
98
77
52
551
Comparative Example


54
278
Mainly B
90
0.53
0.11
0.075
95
77
52
568
Comparative Example


55
220
F + P







265
Conventional Example





*1Underlines indicate outside application range.


*2Symbols for microstructure represent the following phases: F: ferrite, P: pearlite, B: bainite, M: martensite






Furthermore, from each of the raw materials as hot rolled and the hot forged materials, a roller pitching test piece having a parallel portion of 26 mmφ×28 mm long and grip portions of 24.3 mmφ×51 mm on both sides as illustrated in FIG. 1 was collected in the longitudinal direction. The test piece was subjected to nitrocarburizing treatment under two types of conditions: at the treatment temperature shown in Table 4 for 3.5 hr; and at 560° C. for 3.5 hr. The nitrocarburizing treatment was performed in an atmosphere of NH3:N2:CO2=50:45:5. For comparison, the hot forged material of steel sample No. 35 was subjected to carburizing-quenching-tempering of carburizing at 930° C. for 3 hr, holding at 850° C. for 40 min, then oil quenching, and further tempering at 170° C. for 1 hr.


For each of the nitrocarburized materials obtained as a result of the nitrocarburizing treatment at the nitrocarburizing treatment temperature shown in Table 4 and the carburized-quenched-tempered materials, microstructure observation, hardness measurement, precipitate observation, measurement of the amounts of solute Cr, solute V, and solute Nb, and fatigue resistance evaluation were performed.


In the microstructure observation, the types of phases were identified and the area ratio of each phase was calculated by the above-described method, as in the microstructure observation before the nitrocarburizing treatment.


In the hardness measurement, for each of the nitrocarburized materials obtained as a result of the nitrocarburizing treatment at the nitrocarburizing treatment temperature shown in Table 4 and the carburized-quenched-tempered materials, the hardness of the surface layer was measured at a depth of 0.05 mm from the surface of the parallel portion, and the hardness of the core of the parallel portion was measured at one-fourth the diameter from the surface. The surface layer hardness and the core hardness were both measured at six locations with a test load of 2.94 N (300 gf) using a Vickers hardness meter in accordance with JIS Z 2244, and the respective average values were taken to be surface layer hardness HV and core hardness HV. As the hardened case depth, the depth (effective hardened case depth) from the surface with HV 550 was measured. The hardened case depth was also measured for the test pieces subjected to nitrocarburizing treatment at 560° C. for 3.5 hr.


In the precipitate observation, from the position of one-fourth the diameter from the surface of the parallel portion of each of the nitrocarburized materials at the nitrocarburizing temperature shown in Table 4 and the carburized-quenched-tempered materials, a test piece for transmission electron microscope (TEM) observation was prepared by twin-jet electropolishing, and precipitates in the test piece were observed using a transmission electron microscope with an acceleration voltage of 200 V. Further, the compositions of the observed precipitates were determined with an energy-dispersive X-ray spectrometer (EDX).


In the measurement of the amounts of solute Cr, solute V, and solute Nb, a test piece of 10 mm×10 mm×40 mm was collected from a position of one-fourth the diameter from the surface of the above-described hot-forged steel bar of 30 mmφ, and constant-current electrolysis was applied using a 10% acetylacetone-1% tetramethylammonium-methanol electrolytic solution. The extracted precipitates were collected using a filter having a pore size of 0.2 mm. The precipitates were decomposed and formed into a solution using a mixed acid, and then analyzed by ICP optical emission spectrometry to measure the amount of precipitates. The amount of precipitates was then subtracted from the original content to obtain the solute amount.


In the fatigue resistance evaluation, roller pitching test pieces (see FIG. 1) after the nitrocarburizing treatment at the nitrocarburizing temperature shown in Table 4 or the carburizing-quenching-tempering and not subjected to any of the microstructure observation, the hardness measurement, and the precipitate observation were used in a roller pitching test, and the number of repetitions up to damage under a load surface pressure of 2600 MPa was counted. The parallel portion of 26 mmφ of the roller pitching test piece was a portion serving as a ralling contact surface, and was as nitrocarburized (without polishing) or as carburized-quenched-tempered (without polishing). As the roller pitching test conditions, the slip rate was 40%, automatic transmission oil (Mitsubishi ATF SP-III) was used as the lubricating oil, and the oil temperature was 80° C. As large rollers to be brought into contact with the ralling contact surface, carburized-quenched products of SCM420H with crowning R of 150 mm were used.












TABLE 4









Component properties (after rntrocarburizing treatment)

















Nitro-

Effective



Number of




carburizing

hardened
Core

Bainite
repetitions




treatment
Surface
case depth
hard-
Steel
phase
up to roller




temperature
hardness
(HV550)
ness
micro-
area ratio
damage × 103



No.
(° C.)
HV
(mm)
HV
structure
(%)
(2600MPa)
Remarks


















1
575
816
0.27
263
Mainly B
92
2534
Example


2
580
813
0.26
312
Mainly B
98
1936
Example


3
600
826
0.30
326
Mainly B
97
3132
Example


4
590
831
0.29
302
Mainly B
95
3080
Example


5
595
823
0.29
298
Mainly B
96
2663
Example


6
580
815
0.30
301
Mainly B
98
2673
Example


7
575
819
0.28
304
Mainly B
94
3122
Example


8
570
817
0.26
305
Mainly B
96
2360
Example


9
570
820
0.25
256
Mainly B
55
3056
Example


10
570
823
0.28
310
Mainly B
93
2858
Example


11
570
843
0.29
299
Mainly B
60
2826
Example


12
570
826
0.30
288
Mainly B
97
2332
Example


13
570
821
0.27
306
Mainly B
96
2944
Example


14
570
812
0.27
295
Mainly B
80
2305
Example


15
590
834
0.22
356
Mainly B
95
2592
Example


16
595
815
0.28
370
Mainly B
100 
3025
Example


17
585
812
0.27
299
Mainly B
92
2942
Example


18
570
800
0.26
350
Mainly B
96
2672
Example


19
565
811
0.24
265
Mainly B
98
2251
Example


20
570
825
0.25
280
Mainly B
97
2289
Example


21
570
821
0.27
257
Mainly B
95
2930
Example


22
570
823
0.31
260
Mainly B
88
2997
Example


23
570
819
0.30
263
Mainly B
96
2837
Example


24
560
825
0.30
269
Mainly B
96
2663
Example


25
570
823
0.28
251
Mainly B
87
2766
Example


26
570
805
0.27
249
Mainly B
75
3246
Example


27
570
786
0.27
223
F + P + B

42

910
Comparative Example


28
570
789
0.27
205
F + P + B

24

884
Comparative Example


29
570
796
0.27
208
F + P + B

38

510
Comparative Example


30
570
803
0.28
216
F + P + B

45

576
Comparative Example


31
570
650
0.23
278
F + P + B

45

90
Comparative Example


32
570
812
0.28
401
F + P + B

24

340
Comparative Example


33
570
788
0.29
202
F + P + B

41

145
Comparative Example


34
570
801
0.26
215
F + P + B

48

345
Comparative Example


35
570
810
0.26
155
F + B

32

1120
Comparative Example


36
570
812
0.28
401
Mainly B
95
1376
Comparative Example


37
570
825
0.30
345
Mainly B
85
2247
Comparative Example


38
570
788
0.25
371
F + P

32

1976
Comparative Example


39
570
803
0.32
370
M + B
96
2951
Comparative Example


40
570
805
0.26
316
Mainly B
96
786
Comparative Example


41
570
814
0.27
301
Mainly B
95
347
Comparative Example


42
570
657
0.32
262
F + P + B

23

685
Comparative Example


43
570
825
0.12
398
Tempered
56
61
Comparative Example







M + B





44
570
792
0.23
211
F + P + B

18

1127
Comparative Example


45
570
816
0.20
178
Mainly B
96
954
Comparative Example


46
570
810
0.14
326
Mainly B
97
37
Comparative Example


47
570
680
0.24
222
Mainly B
95
879
Comparative Example


48
570
810
0.25
295
Mainly B
96
1799
Comparative Example


49
570
702
0.14
321
Mainly B
94
22
Comparative Example


50
570
845
0.36
324
Mainly B
87
3128
Comparative Example


51
570
800
0.35
207
Mainly B
90
512
Comparative Example


52
570
804
0.17
275
Mainly B
94
71
Comparative Example


53
570
689
0.22
270
Mainly B
93
143
Comparative Example


54
570
816
0.24
272
Mainly B
90
375
Comparative Example


55
—*3
730
1.02
344
Tempered M

3710
Conventional Example





*1Underlines indicate outside application range.


*2Symbols for microstructure represent the following phases: F: ferrite, P: pearlite, B: bainite, M: martensite


*3Carburizing treatment was performed.






The test results are shown in Table 4. Examples No. 1 to 26 are examples according to the present disclosure, No. 27 to 54 are comparative examples, and No. 55 is a conventional example produced by subjecting steel equivalent to JIS SCR420 to carburizing-quenching-tempering.


As is clear from Table 4, Examples No. 1 to 26 all had excellent tool life before nitrocarburizing treatment (i.e. as steel for nitrocarburizing treatment). Examples No. 1 to 26 all had slightly lower fatigue resistance than carburized-quenched-tempered Conventional Example No. 55 after nitrocarburizing treatment (equivalent to a nitrocarburized component), but exhibited excellent fatigue strength as a nitrocarburized material. In Examples No. 1 to 26, those with a nitrocarburizing treatment temperature of 560° C. all had an effective hardened case depth of 0.2 mm or more, although the description of detailed measurement results is omitted here. As a result of determining the composition of precipitates using an energy-dispersive X-ray spectrometer (EDX) as described above, 500 or more precipitates of Cr-based precipitates, V-based precipitates, and Nb-based precipitates with a particle size of less than 10 μm were dispersion-precipitated per unit area of 1 m2 in all of Examples No. 1 to 26.


In Comparative Examples No. 27 to 54, the chemical composition or the resultant steel microstructure was outside the range according to the present disclosure, so that cracking occurred in continuous casting or fatigue resistance or machinability by cutting was poor.


In No. 27, the heating temperature in hot rolling was low. Consequently, precipitates formed during continuous casting did not dissolve sufficiently, and fatigue resistance after nitrocarburizing treatment was low. Besides, since the total microstructure proportion of ferrite and pearlite was high, machinability by cutting after hot rolling was low.


In No. 28, the hot rolling finish temperature was excessively low. Consequently, the proportion of bainite in the microstructure was low, and machinability by cutting was low. Besides, since the total microstructure proportion of ferrite and pearlite was high, the amounts of solute Cr, Nb, and V were small before nitrocarburizing treatment, as a result of which fine precipitates did not form after nitrocarburizing treatment, and fatigue resistance was low.


In No. 29 and 30, the cooling rate after hot rolling was low. Consequently, an appropriate amount of bainite was not obtained. Moreover, the amounts of solute Cr, Nb, and V were small before nitrocarburizing treatment, as a result of the amount of fine precipitates formed after nitrocarburizing treatment was small, causing insufficient strengthening by precipitation. Thus, fatigue resistance was low as compared with Examples. Machinability by cutting was also low.


In No. 31, the heating temperature in hot forging was low. Consequently, precipitate did not dissolve sufficiently, and fatigue resistance was low. Besides, since the total microstructure proportion of ferrite and pearlite was high, machinability by cutting after hot rolling was low.


In No. 32, the hot forging finish temperature was excessively low. Consequently, the proportion of bainite in the microstructure was low, and machinability by cutting was low. Besides, since the total microstructure proportion of ferrite and pearlite was high, the amounts of solute Cr, Nb, and V were small before nitrocarburizing treatment, as a result of which fine precipitates did not form after nitrocarburizing treatment, and fatigue resistance was low.


In No. 33 and 34, the cooling rate after hot forging was low. Consequently, an appropriate amount of bainite phase was not obtained. Moreover, the amounts of solute Cr, Nb, and V were small before nitrocarburizing treatment, and the amount of fine precipitates formed as a result of nitrocarburizing treatment was small, causing insufficient strengthening by precipitation. Thus, fatigue resistance was low as compared with Examples. Machinability by cutting was also low. In No. 35, the C content was less than the appropriate range, so that core hardness after nitrocarburizing treatment was low, and fatigue resistance was low as compared with Examples.


In No. 36, the C content was more than the appropriate range, so that the hardness of the hot forged material before nitrocarburizing treatment increased, causing low machinability by cutting.


In No. 37, the Si content was more than the appropriate range, so that the hardness of the hot forged material before nitriding treatment increased, causing low machinability by cutting.


In No. 38, the Mn content was less than the appropriate range, so that the steel microstructure of the hot forged material before nitrocarburizing treatment was mainly composed of ferrite phase and pearlite phase. Hence, V and Nb precipitates formed in the microstructure, as a result of which hardness before nitrocarburizing treatment increased, causing low machinability by cutting.


In No. 39, the Mn content was more than the appropriate range, so that cracking occurred in continuous casting. Moreover, martensite phase formed before nitrocarburizing treatment, causing low machinability by cutting.


In No. 40, the P content was more than the appropriate range, so that cracking occurred in continuous casting. Besides, fatigue resistance was low.


In No. 41, the S content was more than the appropriate range, so that cracking occurred in continuous casting. Besides, fatigue resistance was low.


In No. 42, the Cr content was less than the appropriate range, so that the steel microstructure of the hot forged material before nitrocarburizing treatment was mainly composed of ferrite phase and pearlite phase. Hence, coarse V and Nb precipitates formed in the microstructure, as a result of which hardness before nitrocarburizing treatment increased, causing low machinability by cutting. Moreover, the amounts of solute Cr, Nb, and V were small before nitrocarburizing treatment, and the amount of fine precipitates formed as a result of nitrocarburizing treatment was small, causing insufficient strengthening by precipitation. Thus, fatigue resistance was low as compared with Examples.


In No. 43, the Cr content was more than the appropriate range, so that cracking occurred in continuous casting. Besides, hardness after hot forging was high, causing low machinability by cutting.


In No. 44, the Mo content was less than the appropriate range. Accordingly, quench hardenability decreased, and the formation of bainite phase was insufficient. As a result, the amounts of Cr, Nb, and V were small before nitrocarburizing treatment, and the amount of fine precipitates formed as a result of nitrocarburizing treatment was small, causing insufficient strengthening by precipitation. Thus, fatigue resistance was low.


In No. 45, the V content was less than the appropriate range. Accordingly, the amount of solute V before nitrocarburizing treatment was small, and the amount of fine precipitates formed as a result of nitrocarburizing treatment was small, so that sufficient core hardness was not obtained. Thus, fatigue resistance was low.


In No. 46, the V content was more than the appropriate range, so that cracking occurred in continuous casting.


In No. 47, the Nb content was less than the appropriate range. Accordingly, the amount of solute Nb before nitrocarburizing treatment was small, and the amount of fine precipitates formed as a result of nitrocarburizing treatment was small, so that sufficient core hardness was not obtained. Thus, fatigue resistance was low.


In No. 48, the Nb content was more than the appropriate range, so that cracking occurred in continuous casting.


In No. 49, the Al content was less than the appropriate range. Accordingly, surface hardness after nitrocarburizing treatment was low, and fatigue resistance was low.


In No. 50, the Al content was more than the appropriate range, so that cracking occurred in continuous casting.


In No. 51, the N content was more than the appropriate range, so that cracking occurred in continuous casting.


In No. 52, Formula (1) was not satisfied, so that hardened case depth after nitrocarburizing treatment was shallow, and fatigue resistance was low.


In No. 53, Formula (1) was not satisfied, so that surface hardness after nitrocarburizing treatment was low, and fatigue resistance was low.


In No. 54, the Sb content was less than the appropriate range, so that cracking occurred in continuous casting.

Claims
  • 1. A steel for nitrocarburizing, comprising: a chemical composition containing, in mass %,C: 0.010% or more and 0.100% or less,Si: 1.00% or less,Mn: 0.50% or more and 3.00% or less,P: 0.020% or less,S: 0.060% or less,Cr: 0.30% or more and 0.90% or less,Mo: 0.005% or more and 0.200% or less,V: 0.02% or more and 0.50% or less,Nb: 0.003% or more and 0.150% or less,Al: 0.005% or more and 0.200% or less,N: 0.0200% or less,Sb: 0.0005% or more and 0.0200% or less,Ti: 0.1% or less, andone or more selected from the group consisting of:W: 0.01% or more and 0.3% or less,Co: 0.01% or more and 0.3% or less,Hf: 0.01% or more and 0.2% or less, andZr: 0.01% or more and 0.2% or less,with the balance being Fe and inevitable impurities; anda steel microstructure in which an area ratio of bainite phase with respect to the entire microstructure is more than 50%,wherein the chemical composition satisfies the following Formula (1): 9.5≤([Cr]/52+[V]/50.9+[Nb]/92.9+M)×103≤18.5  (1)
  • 2. The steel for nitrocarburizing according to claim 1, wherein the chemical composition further contains, in mass %, one or more selected from the group consisting of B: 0.0100% or less,Cu: 0.3% or less, andNi: 0.3% or less.
  • 3. The steel for nitrocarburizing according to claim 2, wherein the chemical composition further contains, in mass %, one or more selected from the group consisting of Pb: 0.2% or less,Bi: 0.2% or less,Zn: 0.2% or less, andSn: 0.2% or less.
  • 4. A component comprising: a core having the chemical composition and the steel microstructure according to claim 3; anda surface layer having a chemical composition in which contents of nitrogen and carbon are higher than in the chemical composition of the core,wherein Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase.
  • 5. The component according to claim 4, wherein the component has an effective hardened case depth with HV 550 of 0.2 mm or more.
  • 6. A component comprising: a core having the chemical composition and the steel microstructure according to claim 2; anda surface layer having a chemical composition in which contents of nitrogen and carbon are higher than in the chemical composition of the core,wherein Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase.
  • 7. The component according to claim 6, wherein the component has an effective hardened case depth with HV 550 of 0.2 mm or more.
  • 8. The steel for nitrocarburizing according to claim 1, wherein the chemical composition further contains, in mass %, one or more selected from the group consisting of Pb: 0.2% or less,Bi: 0.2% or less,Zn: 0.2% or less, andSn: 0.2% or less.
  • 9. A component comprising: a core having the chemical composition and the steel microstructure according to claim 8; anda surface layer having a chemical composition in which contents of nitrogen and carbon are higher than in the chemical composition of the core,wherein Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase.
  • 10. The component according to claim 9, wherein the component has an effective hardened case depth with HV 550 of 0.2 mm or more.
  • 11. A component comprising: a core having the chemical composition and the steel microstructure according to claim 1; anda surface layer having a chemical composition in which contents of nitrogen and carbon are higher than in the chemical composition of the core,wherein Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase.
  • 12. The component according to claim 11, wherein the component has an effective hardened case depth with HV 550 of 0.2 mm or more.
  • 13. The steel for nitrocarburizing according to claim 1, wherein the chemical composition consists of, in mass %, C: 0.010% or more and 0.100% or less,Si: 1.00% or less,Mn: 0.50% or more and 3.00% or less,P: 0.020% or less,S: 0.060% or less,Cr: 0.32% or more and 0.65% or less,Mo: 0.006% or more and 0.193% or less,V: 0.02% or more and 0.50% or less,Nb: 0.003% or more and 0.150% or less,Al: 0.005% or more and 0.200% or less,N: 0.0200% or less,Sb: 0.0005% or more and 0.0200% or less,Ti: 0.1% or less, andone or more selected from the group consisting of:W: 0.01% or more and 0.3% or less,Co: 0.01% or more and 0.3% or less,Hf: 0.01% or more and 0.2% or less, andZr: 0.01% or more and 0.2% or less,
  • 14. A component comprising: a core having the chemical composition and the steel microstructure according to claim 13; anda surface layer having a chemical composition in which contents of nitrogen and carbon are higher than in the chemical composition of the core,wherein Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase.
  • 15. The component according to claim 14, wherein the component has an effective hardened case depth with HV 550 of 0.2 mm or more.
  • 16. The steel for nitrocarburizing according to claim 1, wherein the chemical composition consists of, in mass %, C: 0.011% or more and 0.098% or less,Si: 0.02% or more and 1.00% or less,Mn: 1.45% or more and 2.98% or less,P: 0.008% or more and 0.018% or less,S: 0.013% or more and 0.045% or less,Cr: 0.32% or more and 0.65% or less,Mo: 0.006% or more and 0.193% or less,V: 0.04% or more and 0.45% or less,Nb: 0.004% or more and 0.149% or less,Al: 0.006% or more and 0.137% or less,N: 0.0036% or more and 0.0192% or less,Sb: 0.0005% or more and 0.0185% or less,Ti: 0.1% or less, andone or more selected from the group consisting of:W: 0.01% or more and 0.3% or less,Co: 0.01% or more and 0.3% or less,Hf: 0.01% or more and 0.2% or less, andZr: 0.01% or more and 0.2% or less,
  • 17. A component comprising: a core having the chemical composition and the steel microstructure according to claim 16; anda surface layer having a chemical composition in which contents of nitrogen and carbon are higher than in the chemical composition of the core,wherein Cr-containing precipitates, V-containing precipitates, and Nb-containing precipitates are dispersion-precipitated in the bainite phase.
  • 18. The component according to claim 17, wherein the component has an effective hardened case depth with HV 550 of 0.2 mm or more.
Priority Claims (1)
Number Date Country Kind
JP2016-233423 Nov 2016 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2017/043211 11/30/2017 WO 00
Publishing Document Publishing Date Country Kind
WO2018/101451 6/7/2018 WO A
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Related Publications (1)
Number Date Country
20200149148 A1 May 2020 US