The present disclosure relates to a method for manufacturing a ferritic stainless steel product.
Conventionally, a surface modification method of stainless steel has been investigated. For example, a nitriding method has been known in which ferritic stainless steel is heated at a nitriding temperature in an inert atmosphere containing nitrogen gas.
The present disclosure provides a method for manufacturing a ferritic stainless steel product. The method includes forming a carburized layer on a workpiece made of ferritic stainless steel, and forming a nitrided layer on a surface of the workpiece by heating the workpiece at a temperature equal to or higher than a transformation point of the ferritic stainless steel in an atmosphere containing an N2 gas.
The above and other objects, features and advantages of the present disclosure will become more apparent from the following detailed description made with reference to the accompanying drawings in which:
For example, a nitrided layer may be formed on a surface of a ferritic stainless steel workpiece at a temperature lower than 1100 degrees Celsius (° C.) in a heating furnace whose inner wall is covered with carbon in order to stably form a nitrided layer.
However, in this method for forming a nitrided layer, a nitrided layer may not be sufficiently formed on a workpiece having a low carbon concentration. That is, in order to form a sufficient nitrided layer, a workpiece to be processed is limited. If the nitrided layer cannot be sufficiently formed, a martensite phase cannot be sufficiently formed, and hardness cannot be sufficiently improved by modifying the ferritic stainless steel.
(First Embodiment)
Embodiments of a method for manufacturing a ferritic stainless steel product will be described with reference to the drawings. In manufacturing the ferritic stainless steel product, the following carburizing step and the nitriding step are performed.
As illustrated in
As the workpiece 2 made of ferritic stainless steel, there is no particular limitation as long as the workpiece 2 is ferritic stainless steel, and various compositions can be used. The ferritic stainless steel material in the workpiece preferably has a carbon content of 0.3 mass % or less. In this case, a corrosion resistance is further improved. From the viewpoint of further enhancing the above effect, the carbon content of the ferritic stainless steel material is more preferably 0.12 mass % or less, and further preferably 0.01 mass % or less.
The carburizing step and the nitriding step can be performed, for example, in a heating furnace 4 as exemplified in
The carburized layer 21 can be formed in the carburizing step by, for example, gas carburizing, vacuum carburizing, or plasma carburizing. In those carburizing processes, carburizing gas can be used.
As the carburizing gas, a hydrocarbon gas such as a saturated hydrocarbon gas or an unsaturated hydrocarbon gas can be used. Preferably, an unsaturated hydrocarbon gas such as acetylene is used. In this case, a passive film present on the surface of the ferritic stainless steel is more easily broken, and the reactivity with the workpiece can be improved. As the carburizing gas, the above-mentioned hydrocarbon gas can be used alone, or a mixed gas of a hydrocarbon gas and, for example, an inert gas can be used.
As illustrated in
As illustrated in
The atmosphere containing the N2 gas may contain at least N2, and may further contain an inert gas. The atmosphere in the nitriding step may contain the carburizing gas remaining in the carburizing step. The amount of residual carburizing gas is preferably small. Preferably, the atmosphere containing the N2 gas is the N2 gas.
The transformation point is a temperature at which at least a part of a ferrite phase in a ferritic stainless steel material is transformed into an austenite phase. The transformation point differs depending on the composition of the material, but is, for example, 700 to 900° C.
The nitriding temperature is preferably 900° C. or higher, which is a decomposition temperature of nitrogen. In this case, the solid solution of nitrogen in the workpiece 2 is more likely to occur. In light of easier solid solution of nitrogen, the nitriding temperature is more preferably 1000° C. or higher, and more preferably 1050° C. or higher.
The nitriding temperature is preferably 1100° C. or less. In this case, coarsening of crystal grains in the workpiece can be reduced and a decrease in strength can be reduced. From the viewpoint of further reducing coarsening of the crystal grains, the nitriding temperature is more preferably 1050° C. or less.
As shown in
In the temperature increasing step (I) and the heat soaking step (II), for example, the inside of the heating furnace in which the workpiece 2 is installed is increased in temperature to the carburizing temperature and held. The carburizing temperature can be appropriately determined, and is, for example, 1000 to 1100° C.
In the carburizing gas introducing step (III), carburizing gas is supplied into, for example, a heating furnace in which the workpiece 2 is installed. As a result, the carburizing step of forming the carburized layer 21 on the workpiece 2 can be performed. An introduction time of the carburizing gas can be appropriately determined. The carburizing gas introduction time and the carburizing temperature may be appropriately determined so that, for example, a surface carbon concentration XC and a thickness LC of the carburized layer 21 shown in Experimental Example 2, which will be described later, have a desired relationship.
As illustrated in
As illustrated in
After the cooling step, it is preferable to perform a sub-zero process for cooling the workpiece 2 to a low temperature of, for example, 0° C. or less. The sub-zero process is also called a deep cooling process. With the above process, the residual austenite phase in the material of the workpiece 2 can be martensitized.
After the sub-zero process, tempering is preferably performed. In that case, the unstable structure inside the material can be stabilized.
In the present embodiment, the nitriding step is performed after the carburizing step as described above. As illustrated in
The nitrided layer 3 can cause martensitic transformation by, for example, cooling, and can form a martensite phase having excellent hardness. Therefore, according to the manufacturing method of the present embodiment, the ferritic stainless steel product 1 having high hardness can be manufactured.
In the nitriding step, as described above, after the formation of the carburized layer 21, heating is performed at a high temperature, which is equal to or higher than the transformation point temperature of the ferritic stainless steel. For that reason, in the nitriding step, carbon atoms in the carburized layer 21 can be diffused into the interior of the workpiece 2. In other words, in the nitriding step, not only the solid solution of nitrogen into the carburized layer 21 and the formation of the nitrided layer 3 but also the diffusion of carbon atoms can lower the surface carbon concentration of the workpiece 2. This decrease in the surface carbon concentration makes it possible to improve the corrosion resistance. Therefore, the ferritic stainless steel product 1 having excellent corrosion resistance can be manufactured.
As described above, with the execution of the nitriding step after the carburizing step, the ferritic stainless steel product 1 having the excellent corrosion resistance and the high hardness can be obtained. The ferritic stainless steel product 1 can be used for various applications requiring the corrosion resistance and the hardness. Examples include automobile engine control components, fuel system components, and exhaust system components.
(Second Embodiment)
The present embodiment is an example of manufacturing a disk-shaped ferritic stainless steel product 1 by performing a carburizing step and a nitriding step using a heating furnace 4 illustrated in
As illustrated in
A vacuum pump (P) 41 and a nitrogen gas cylinder 42 capable of pressurizing a nitrogen gas to an atmospheric pressure or higher are connected to both of the carbonitriding chamber 5 and the cooling chamber 6. A carburizing gas cylinder 51 containing at least a carburizing gas such as acetylene gas is connected to the carbonitriding chamber 5 through a mass flow controller 52. The mass flow controller is hereinafter referred to as MFC as appropriate. The heating furnace 4 is provided with a transport device capable of moving the ferritic stainless steel product 1 between the carbonitriding chamber 5 and the cooling chamber 6. In
In manufacturing the ferritic stainless steel product 1 using the heating furnace 4 according to the present embodiment, first, a disk-shaped workpiece 2 made of ferritic stainless steel and having a diameter Φ of 15 mm and a thickness of 2 mm is disposed in the carbonitriding chamber 5.
Next, the temperature rise in the carbonitriding chamber 5 is started by the heater (not shown). Then, the temperature in the carbonitriding chamber 5 is raised to, for example, the carburizing temperature of 1050° C. Next, while maintaining at this carburizing temperature for 10 minutes (heat soaking step), the inside of the carbonitriding chamber 5 is depressurized to a vacuum state by drawing a vacuum with the vacuum pump 41.
Next, acetylene gas is introduced into the carbonitriding chamber 5 as the carburizing gas from the carburizing gas cylinder 51 at a predetermined flow rate while adjusting the MFC 52 (carburizing gas introducing step). In the present embodiment, the carburizing gas was introduced for 1 minute. As a result, the carburized layer 21 is formed on the workpiece 2. From the viewpoint of improving productivity by shortening a formation time of the carburized layer 21, an introduction time of the carburizing gas is preferably 5 minutes or less, more preferably 3 minutes or less, and still more preferably 2 minutes or less.
Next, the nitrogen gas is introduced into the carbonitriding chamber 5 from the nitrogen gas cylinder 42, and the interior of the carbonitriding chamber 5 is maintained at the above-mentioned temperature of 1050° C. for another 120 minutes (high-temperature nitriding step). As a result, nitrogen is dissolved in a solid solution in the workpiece on which the carburized layer 21 is formed, and the nitrided layer 3 is formed. Further, in the high-temperature nitriding step, carbon in the carburized layer 21 diffuses from the surface side to the inside side of the workpiece 2.
Next, the heater is stopped, and the ferritic stainless steel product 1 on which the carburized layer 21 and the nitrided layer 31 are formed is transported from the nitriding chamber 5 to the cooling chamber 6 by the transport device (not shown). Further, in the cooling chamber 6, the ferritic stainless steel product 1 is immersed in the oil tank 61 by the lifting device (not shown) to perform the oil cooling. With the above oil cooling, martensitic transformation occurs in the nitrided layer 3 of the ferritic stainless steel, and a martensite phase is formed. After cooling the oil, the ferrite steel stainless steel product 1 is pulled up from the oil tank by the lifting device.
Next, after the sub-zero process has been performed, tempering process is performed to obtain the ferritic stainless steel product 1 of the present embodiment. The ferritic stainless steel product 1 thus obtained has both of the excellent corrosion resistance and the excellent hardness as shown in Experimental Example 1 to be described later.
(Experimental Example 1)
In this example, the corrosion resistance and the hardness of a ferritic stainless steel product (that is, an example product) produced by performing the nitriding step after the carburizing step and a ferritic stainless steel product (that is, a comparative example product) produced by performing the nitriding step without performing the carburizing step are evaluated. The example product is a ferritic stainless steel product produced in the same manner as in second embodiment described above. The comparative example product is the ferritic stainless steel product produced in the same manner as in second embodiment except that acetylene gas is not introduced.
<Evaluation on Corrosion Resistance>
A neutral salt spray test is conducted in accordance with JIS Z2371: 2000 to evaluate the corrosion resistance of the example product and the comparative example product. The spraying of the brine is carried out continuously. After the test, the presence or absence of discoloration of the surface is visually observed. The results of the example product are shown in
<Hardness Evaluation>
(1) Cross-Sectional Texture Observation
The disk-shaped example product and the disk-shaped comparative example product are cut so as to be bisected in a diameter direction, and the cross-sectional texture of those cut products is observed with an optical microscope at a magnification of 100-fold. A cross-sectional texture photograph of the example product is shown in
(2) Measurement of Vickers Hardness
A relationship between a distance L from the surface of the sample product and the comparative sample product and the Vickers hardness Hv 0.1 is examined. In the measurement of the Vickers hardness Hv, first, the disk-shaped ferritic stainless steel product 1 of the example product illustrated in
As illustrated in
Further, as illustrated in
On the other hand, as illustrated in
As described above, according to this example, the ferritic stainless steel product having both of the excellent corrosion resistance and the excellent hardness can be obtained by performing the nitriding step after the carburizing step.
(Experimental Example 2)
In this embodiment, a preferable relationship between a carbon concentration A mass % of the workpiece before forming the carburized layer, a surface carbon concentration XC mass % of the carburized layer after the carburizing step and before the nitriding step, a thickness LC mm of the carburized layer after the carburizing step and before the nitriding step, and a thickness LN mm of the carburized layer after the nitriding step is examined.
First, a relationship between the carbon concentration C (unit: mass %) of the ferritic stainless steel material and the corrosion resistance is examined. Specifically, the neutral salt spray test described above is performed. After the test, the surface of the material is observed, and an area ratio Sc of the discolored portion is measured. The discoloration portion is a corrosion portion.
As shown in
As shown in
Next, in the process of performing the carburizing step and the nitriding step on the disk-shaped workpiece similar to the second embodiment, the C-concentration distribution of the workpiece is measured by an electron-beam microanalyzer (i.e., EPMA) under the following measuring device and measuring condition. As a sample for measuring the EPMA, the semi-disk-shaped sample obtained by diametrically cutting the disk-shaped sample in the diameter direction is used. Then, the C concentration distribution is measured by measuring the C concentration in the thickness direction of the semi-disk-shaped sample.
Measurement Device: EPMA 1610 manufactured by Shimadzu Manufacturing Co., Ltd.
The measurement is performed at a portion where the carburized layer is formed to a sufficient depth after each step of the carburizing step and the nitriding step. Specifically, first, the carbon concentration distribution of the workpiece obtained after performing the carburizing step in the same manner as in second embodiment is measured. Next, the carbon concentration distribution of the workpiece obtained by further performing the nitriding step after the carburizing step is measured. An example of the measurement is shown in
Although the carbon concentration distribution after the carburizing step and the carbon concentration distribution after the nitriding step have different carbon concentrations on the outermost surface, that is, different heights, and the shapes of the curves until convergence to a material carbon concentration A are different from each other, a distribution curve similar to that illustrated in
In the carbon concentration distribution after the carburizing step and before the nitriding step, a mean value of the carbon concentration at a position corresponding to 10 points of the beam diameter from the outermost surface, that is, at a position 30 μm from the outermost surface is defined as a surface carbon concentration XC.
Further, as illustrated in
Further, as illustrated in
In addition, the material carbon concentration A of the workpiece is an original carbon concentration of the ferritic stainless steel material of the workpiece before the above-mentioned carburizing step or nitriding step is performed.
A relationship between the thickness of the carburized layer after the carburizing step (that is, the depth of carburizing) and the carbon concentration is shown in a diagram I, and a relationship between the thickness of the carburized layer diffused inside after the nitriding step and the carbon concentration is also shown in a diagram II in
In this example, the amount of carbon taken into the workpiece after the carburizing step is represented by a hatched area α in
Assuming that the surface carbon concentration of the workpiece after the nitriding step becomes 0.3 mass %, the carbon amount present in the workpiece in the nitriding step is represented by a hatched region β1 in
In other words, (XC−A)×LC×½≤(0.3−A)×LN×½ is preferable. This is synonymous with the preference for (XC−A)×LC≤(0.3−A)×LN. Therefore, in order to obtain a ferritic stainless steel product excellent in corrosion resistance, (XC−A)×LC≤(0.3−A)×LN is preferable.
Assuming that the surface carbon concentration of the workpiece after the nitriding step becomes 0.2 mass %, the carbon amount present in the workpiece in the nitriding step is represented by a hatched region β2 in
In other words, (0.2−A)×LN×½≤(XC−A)×LC×½ is preferable. This is synonymous with the preference for (0.2−A)×LN≤(XC−A)×LC. Therefore, in order to form the nitrided layer more stably to obtain a ferritic stainless steel product having higher hardness, (0.2−A)×LN≤(XC−A)×LC is preferable.
The various conditions can be adjusted so that the material carbon concentration A mass %, the surface carbon concentration XC mass % of the carburized layer after the carburizing step and before the nitriding step, the thickness LC mm of the carburized layer after the carburizing step and before the nitriding step, and the thickness LN mm of the carburized layer after the nitriding step satisfy the above-mentioned preferable relationship. That is, the carburizing temperature and the carburizing time in the carburizing step, the nitriding temperature and the nitriding time in the nitriding step, and the like can be controlled so as to satisfy the desired relationships described above. This makes it possible to obtain a ferritic stainless steel product having superior corrosion resistance and hardness.
Although the present disclosure is described based on the above embodiments, the present disclosure is not limited to the embodiments and the structures. Various changes and modification may be made in the present disclosure. Furthermore, various combination and formation, and other combination and formation including one, more than one or less than one element may be made in the present disclosure.
Optional aspects of the present disclosure will be set forth in the following clauses.
According to an aspect of the present disclosure, a method for manufacturing a ferritic stainless steel product includes: forming a carburized layer on a workpiece made of ferritic stainless steel; and forming a nitrided layer on a surface of the workpiece by heating the workpiece at a temperature equal to or higher than a transformation point of the ferritic stainless steel in an atmosphere containing an N2 gas after forming the carburized layer.
According to the aspect of the present disclosure, after the carburized layer is formed on the workpiece, the nitrided layer is formed. For that reason, even if the carbon concentration of the workpiece is low, the carbon concentration of the workpiece can be increased when the carburized layer is formed, so that the nitrided layer can be sufficiently formed when the nitrided layer is formed.
In addition, since the passive film existing on the surface of the ferritic stainless steel can be broken by the formation of the carburized layer, nitrogen easily dissolves in the ferritic stainless steel in the formation of the nitrided layer. For that reason, the nitrided layer can be sufficiently formed, and the nitrided layer can be formed from the surface of the workpiece to a sufficiently deep portion.
The nitrided layer can undergo a martensitic transformation, for example by cooling. As a result, a martensite phase having a high hardness can be formed. Therefore, according to the aspect of the present disclosure, a ferritic stainless steel product having a high hardness can be manufactured.
In forming the nitrided layer, heating is performed at a high temperature of not less than the transformation point temperature of the ferritic stainless steel after the carburized layer has been formed. For that reason, when the nitrided layer is formed, carbon atoms in the carburized layer can be diffused into the interior of the workpiece. That is, in forming the nitrided layer, not only the solid solution of nitrogen into the carburized layer and the formation of the nitrided layer but also the diffusion of carbon atoms can lower the surface carbon concentration of the workpiece. This decrease in the surface carbon concentration improves the corrosion resistance. In other words, the hardness can be improved without lowering the corrosion resistance. That is, a ferritic stainless steel product having excellent hardness and corrosion resistance can be manufactured.
According to the aspect of the present disclosure described above, a method for manufacturing a ferritic stainless steel product capable of forming a nitrided layer and improving hardness regardless of a carbon concentration of a material can be provided.
Number | Date | Country | Kind |
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2016-177568 | Sep 2016 | JP | national |
The present application is a continuation application of International Patent Application No. PCT/JP2017/032412 filed on Sep. 8, 2017, which designated the United States and claims the benefit of priority from Japanese Patent Application No. 2016-177568 filed on Sep. 12, 2016. The entire disclosures of all of the above applications are incorporated herein by reference.
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Number | Date | Country | |
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20190203331 A1 | Jul 2019 | US |
Number | Date | Country | |
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Parent | PCT/JP2017/032412 | Sep 2017 | US |
Child | 16294016 | US |