Patent Application
20240268927
The present invention relates to a base material for a screw or a screw and a producing method thereof, particularly a base material for a medical screw or a medical screw and a producing method thereof, more particularly a base material for a medical anchor screw or a medical anchor screw and a producing method thereof, most particularly, a base material for an orthodontic anchor screw or an orthodontic anchor screw and a producing method thereof.
A medical screw made of titanium has become important in medical implants. Most of them are made of alloy titanium (Ti64). Titanium alloys (for example, Ti-6Al-4V) have had problems with allergies, especially due to vanadium, since vanadium is one of the alloying elements.
In industrial products, for example, during the step of cleaning a substrate in which special acids and solutions are used, that require cleanliness and corrosion resistance, and during the step of producing a film in which the film is subjected to vacuum or special gas environments in the semiconductor industry, a screw made of pure titanium has been used, since titanium alloys such as Ti-6Al-4V are inferior to pure titanium in corrosion resistance, and also since elution of aluminum and vanadium, which are additive elements of titanium alloys, occurs and thus titanium alloys may cause contamination with impurities. On the other hand, since pure titanium has low strength, it is necessary to make up for the lack of strength by increasing the size of the screw or increasing the number of screws, and thus there is a need to improve the strength of pure titanium itself.
As a method for improving the strength of pure titanium, for example, Patent Documents 1 and 2 disclose that titanium or a titanium alloy as an implant was swaged to improve mechanical properties. Further, Patent Document 3 discloses appropriate processing conditions and processing ratio. However, Patent Documents 1 to 3 show the advantages of general working strengthening common to metal plastic working. They also show that the processing ratio is preferably 20 to 80%, and thus that if it is greater than 80%, it becomes brittle and cracks occur during processing.
More, Patent Document 4 discloses the characteristics of the processing mode of swaging, but it is only qualitative and cannot be said to be sufficient from the point of view of reliability.
Patent Document 5 discloses a technique for improving the mechanical properties of titanium by methods such as warm rolling, extrusion, and die forging. The method involves using the cyclic shear deformation method (ECAP), which is one of the crystal refinement and strengthening methods of titanium, to create a material by controlling the temperature while heating from the surroundings, and then performs rolling, which is the main secondary processing, to enhance the effect. The features of Patent Document 5 reside in grain refinement and improved crystal isotropy.
Further, Patent Document 6 discloses that after refining titanium by a Multi-Directional Forging process (MDF), it is subjected to rolling and rod processing, wherein the processing temperature at that time is 70° C. or less, to realize increased strength.
More, Non-Patent Document 1 discloses that for pure titanium Grades 1 to 4, starting from materials that have been refined by structural changes due to heat treatment such as quenching, they are further strengthened by processing.
Although pure titanium is the metal with the lowest allergy risk, it lacks the tensile strength and torsional rupture strength required for medical screws compared to titanium alloys. Since minimal invasiveness is required, it is not preferable to increase the strength by increasing the size, and thus the strength of the material itself is required.
Conventional technology tried to use the work hardening and fine strengthening characteristics of pure titanium to improve mechanical properties, but the technology was insufficient. Recently, after making a special grain refining strengthened material through bulk ultrafine grained (UFG) processing, the material is subjected to rolling processing, to make a cylindrical shape (bar material or wire material) for medical screws. Therefore, the process is complicated, and there are restrictions on the shape and volume of the material subjected to huge strain, and thus a low-cost method having excellence in productivity has been needed.
On the other hand, commercial pure titanium (CP titanium), which is commercially available as a bar or wire, is easily available. However, since crystal grains of CP titanium are as large as several tens of microns and thus CP titanium does not have sufficient strength, and since there are some variations in internal structure thereof, it has been necessary to have quality control to achieve stable production and high reliability even when using CP titanium.
Accordingly, an object of the present invention is to provide a base material for a screw or a screw, particularly a base material for a medical screw or a medical screw, more particularly a base material for a medical anchor screw or a medical anchor screw, most particularly a base material for an orthodontic anchor screw or an orthodontic anchor screw, each of which is made of pure titanium, and has sufficient strength comparable to that of a titanium alloy.
Another object of the present invention is, in addition to or other than the above objects, to provide a method for producing a base material made of pure titanium for a screw, or a screw made of pure titanium, or the like.
Specifically, an object of the present invention is to provide an enable production from commercially available pure titanium bars or wires without going through a special process such as bulk ultrafine grained processing, and to provide a method capable of producing the above-described base material made of pure titanium for a screw, or the above-described screw made of pure titanium, or the like, by using a stable production method and a highly reliable management method.
The Present Inventors have Found the Following Inventions:
The present invention can provide a base material for a screw or a screw, particularly a base material for a medical screw or a medical screw, more particularly a base material for a medical anchor screw or a medical anchor screw, most particularly a base material for an orthodontic anchor screw or an orthodontic anchor screw, each of which is made of pure titanium, and has sufficient strength comparable to that of a titanium alloy.
Further, other than or in addition to the above effect, the present invention can provide a method for producing a base material made of pure titanium for a screw, or a screw made of pure titanium, or the like.
Specifically, the present invention can provide an enable production from commercially available pure titanium bars or wires without going through a special process such as bulk ultrafine grained processing, and to provide a method capable of producing the above base material made of pure titanium for a screw, or a screw made of pure titanium, or the like, by using a stable production method and a highly reliable management method.
The invention described in the present application (hereinafter sometimes abbreviated as “the present invention”) will be described hereinafter.
The present application provides a base material for a screw which is made of pure titanium and has substantially cylindrical shape, a screw which is made of pure titanium and has substantially cylindrical shape, a method for producing the base material for the screw, and a method for producing the screw.
They will be described in order, hereinafter.
The present application provides a base material for a screw which is made of pure titanium and has substantially cylindrical shape, wherein the base material has 3 or more, preferably 4 or more, more preferably 5 or more of a maximum specific intensity of the orientation in the (1 0-1 0) plane in the axial direction of the substantially cylindrical shape. Further, the maximum specific intensity of the orientation may be 15 or less, preferably 12 or less, more preferably 10 or less.
Furthermore, the term “(1 0-1 0)” used herein is usually represented by following (X). However, in the present specification, the term “(1 0-1 0)” is used for convenience.
The “substantially cylindrical shape” includes not only a cylindrical shape but also a so-called truncated cone shape in which the side surface is inclined along the axial direction of the cylindrical shape.
One “made of pure titanium” is not limited to one that does not contain any impurities, but may be pure titanium Grade 1, pure titanium Grade 2, pure titanium Grade 3, or pure titanium Grade 4 according to JIS standard. Further, it may be pure titanium with crystal grains refined to 1 μm or less.
Furthermore, the material of “pure titanium” is preferably selected from the group consisting of pure titanium Grade 2, pure titanium Grade 3, pure titanium Grade 4, and pure titanium with crystal grains refined to 1 μm or less.
The base material for the screw according to the present invention has 3 or more of a maximum specific intensity of the orientation in the (1 0-1 0) plane in the axial direction of the substantially cylindrical shape. Further, the maximum specific intensity may be preferably 4 or more, more preferably 5 or more. More, the maximum specific intensity of the orientation may be 15 or less, preferably 12 or less, more preferably 10 or less.
The term “axial direction” has the same definition as the length direction of the substantially cylindrical shape.
Pure titanium is usually isotropic (or equiaxed crystal), but can be oriented by processing. The orientation imparts properties that cannot be obtained with an isotropic structure (or equiaxed crystal), to the screw base material. A specific crystal plane is preferentially aligned in the axial direction by a force applied perpendicularly to the outer peripheral surface of the raw material toward the center of the raw material for obtaining a base material for a screw having substantially cylindrical shape with a circular cross section. As a result, the strength in the axial direction is generally increased, and the tensile strength of the base material for the screw and the screw formed from the base material can be improved.
Conventionally, the orientation of pure titanium has been treated as a qualitative factor related to mechanical properties, rather than being treated quantitatively, although the orientation is a fundamental property along with crystallites. In order quantitatively to evaluate the orientation, X-ray diffraction (XRD) is used to quantitatively treat a specific crystal plane of pure titanium in the direction of interest as the maximum value of the ratio of intensity to average intensity, to find out treating the orientation quantitatively.
The present inventors found that, with respect to the characteristic crystal plane (1 0-1 0) of pure titanium having a close-packed hexagonal crystal, a pole figure in the direction (axial direction) perpendicular to the cross section of a material having substantially cylindrical shape is created, and that the maximum specific intensity in the pole figure, which is the “maximum value of the specific intensity of the orientation in the (1 0-1 0) plane in the axial direction of the substantially cylindrical shape”, is obtained.
A pole figure shows how specific crystal planes of a material are distributed in a cross section of the material, and its intensity is generally indicated by a contour map or shading. The maximum specific intensity is the ratio of the intensity of the darkest part to the average. The higher the specific intensity is, the higher the orientation (also referred to as anisotropy) is. The value closer to 1 means the less orientation and the isotropic or random distribution.
The maximum value of specific intensity can be obtained by using X-ray diffraction (XRD), as described above. As a specific method of determination, D8 ADVANCE manufactured by BRUKER is used as an X-ray diffraction device, cobalt is used for the tube, and the output is set at a voltage of 35 kV and a current of 40 mA. A two-dimensional detector is used with a divergence slit diameter of 0.3 mm and a collimator diameter of 0.3 mm.
In creating the pole figure, the in-plane direction angle Φ of the sample is measured in 72 steps in 5 degree increments around 360 degrees, and the range of the tilt angle Y is determined by measuring the starting point at 15 degrees and the ending point at 45 degrees. The obtained measurement data are analyzed using the analysis software DIFFRAC.TEXTURE MRDB V4.1 (manufactured by BRUKER), to create the pole figure of (1 0-1 0) showing the characteristic behavior in the orientation of pure titanium. As a result, it is set so that the direction in which the crystal planes are most oriented can be understood by the color density. The maximum value of the relative intensities to the average intensity, which is obtained from the entire pole figure and is defined as 1, is defined as the maximum specific intensity. If the material is isotropic (no orientation) there will be less color shading, and orientation will produce darker areas at certain angles and higher relative intensities at those angles. The angle at which the intensity reaches the maximum value can also be found using a contour map.
According to the present invention, as described above, the “maximum value of the specific intensity in the orientation in the (1 0-1 0) plane in the axial direction of the substantially cylindrical shape” may be 3 or more, preferably 4 or more, and more preferably 5 or more.
High strength and high toughness are required for a screw, especially a medical screw. The characteristics are also required for a base material for a screw.
Regarding the strength, the tensile strength in the axial direction of the screw, that is, the axial direction of the base material for the screw is important.
The tensile strength may be 800 MPa or higher, preferably 860 MPa or higher, more preferably 920 MPa or higher.
It may be preferably 820 MPa or more in order to make it nearly equivalent to alloy titanium (for example, Ti-6% Al-4% V). Depending on the application, it may be more preferably 950 MPa.
Tensile strength can be measured with an Amsler universal testing machine.
Further, torsional shear strength is required when screwing a screw, especially a medical screw. The torsional shear strength is roughly proportional to the hardness of the material.
Therefore, the Vickers hardness may be 200 HV or higher, preferably 220 HV or higher, more preferably 240 HV or higher.
Hardness can be measured with a Vickers hardness tester.
More, a screw is required to have high toughness (non-brittle property), and is generally required to have a sufficient necking at break, that is, to have a sufficient reduction of area.
Therefore, the reduction of area may be 45% or more, preferably 50% or more, and more preferably 60% or more, considering subsequent workability such as headability.
The term “reduction of area” used herein means plastic workability in the axial direction (longitudinal direction) of a substantially cylindrical shape.
The reduction of area can be measured by the evaluation value of the necking at the time of tensile breakage, and specifically can be tested and measured with an Amsler universal testing machine.
In order to create a structure suitable for a screw, especially a medical screw, and in order to obtain the reliability of actual products, evaluation methods are important. Phenomena that occur in pure titanium result from a very complicated interplay of recrystallization, strain accumulation, crystal twinning and the like. Thus, since the crystal grains themselves become complicated, conventional evaluation methods such as measurement and evaluation using an optical microscope are difficult. Further, also in determining crystal grain size using transmission electron microscopy, complicated procedures such as setting the angle (inclination) are required. More, the method is not easily suitable as a process inspection/evaluation method during production.
Therefore, by using the crystallite size that exists as the original crystal unit in the complex crystal grains, an effective index is given to the above-mentioned complicated structure, and thus, screws of interest, in particular, medical screws have been found to have desirable mechanical properties.
A crystallite is a minimum unit that contributes to X-ray diffraction, unlike a crystal grain size, and is a portion of a crystal grain that can be regarded as a single crystal.
The crystallite size is a smaller value (or unit) than the crystal grain size determined from the apparent size of the crystal. In addition, in a pure single crystal, the grain size and the crystallite size can be considered to be almost the same, but if the crystal loses its regularity under various conditions due to processing, there is not necessarily a correlation between the grain size and the crystallite size.
It is decided to use the crystallite size as an index of whether pure titanium has desired properties, in particular mechanical properties, regardless of the presence or absence of processing and the processing ratio.
Crystallite size can be identified by X-ray diffraction (XRD) and can be also used as a production process check.
An X-ray diffractometer (D8 ADVANCE) manufactured by BRUKER is used, and Kα rays of cobalt are used as X-rays. The output of the cobalt tube is 35 kV and the current is 40 mA.
In the present specification, the crystallite size is obtained by measuring the diffraction X-ray of the crystal plane (1 0-1 0) of pure titanium.
The X-ray scanning range is 2θ=35.0° to 48.0°, the divergence slit diameter is 0.3 mm, and the collimator diameter is 0.3 mm. Analysis of the measurement data is performed using BRUKER's analysis software DIFFRAC. EVA.
The crystallite size Lvol can be obtained from the Scherrer equation represented by the following Equation 1, wherein the crystallite size is Lvol [Å], the measurement wavelength is λ [Å], the integrated width ß [rad] of the peak excluding the influence of the apparatus, and the angular position θ [rad] of the peak.
Furthermore, for details of the crystallite size, refer to Waseda, Matsubara, Shinoda (2008), Basics of Exercise X-ray Structural Analysis (Uchida Rokakuho) pp. 103-108 (all of which are incorporated herein by reference).
According to the present invention, the crystallite size may be 280 Å or less, preferably 270 Å or less, more preferably 260 Å or less.
The screw according to the present invention may be formed from the base material for the screw described above. Therefore, the screw according to the present invention should have the same properties as the base material for the screw described above.
That is, the screw according to the present invention may be made of pure titanium and may have a substantially cylindrical shape, and the maximum value of the specific intensity of the orientation of the (1 0-1 0) plane in the axial direction of the substantially cylindrical shape may be 3 or more, preferably 4 or more, more preferably 5 or more.
Further, the crystallite size of pure titanium may be 280 Å or less, preferably 270 Å or less, more preferably 260 Å or less.
More, the screw according to the present invention may have at least one, two, or three of the following mechanical properties i) to iii):
Further, the screw according to the present invention may be made of pure titanium. The pure titanium may be selected from the group consisting of pure titanium Grade 2, pure titanium Grade 3, pure titanium Grade 4, and pure titanium with crystal grains refined to 1 μm or less, and the pure titanium may be preferably pure titanium Grade 4.
More, the screw according to the present invention may have a combination of A) the desired maximum value of the orientation specific intensity and B) the desired crystallite size. Alternatively, the screw according to the present invention may have a combination of B) desired crystallite size and C) at least one, two or three of mechanical properties i) to iii). Alternatively, the screw according to the present invention may have a combination of A) the desired maximum value of the orientation specific intensity, B) the desired crystallite size, and C) the at least one, two or three of mechanical properties i) to iii).
The base material for screws according to the present invention may be a base material for a medical screw, in particular a base material for a medical anchor screw. The base material for the medical anchor screw may be a base material for an orthodontic anchor screw.
Further, the screw according to the present invention may be a medical screw, in particular a medical anchor screw. The medical anchor screw may be an orthodontic anchor screw.
The base material for the screw can be produced by the following producing method:
The method comprises the steps of:
The step of processing pure titanium material adopts “swaging”, and the reason why the step adopts “swaging” is as follows:
Deformation (plastic deforming) of the metal material converts approximately 90% of the strain energy introduced by the deformation into heat (processing heat), thereby increasing the temperature of the metal material itself. In general, the heat generated during processing is considered to around 100° C., depending on the processing method. Therefore processing does not utilize the heat generated solely during processing. On the contrary, molds are cooled during processing, in order to suppress the disadvantage of the heat generated.
Titanium has a low thermal conductivity, which suppresses the diffusion of heat throughout the titanium material, and the heat stays in the part where the material undergoes plastic deformation, and thus a temperature of titanium material rises more. If the processing conditions are the same, the thermal conductivity of titanium is less than half that of steel, and thus, it is thought that the temperature of the processed portion of titanium material will rise about twice than that of iron material, that is, around 200° C.
Further, increased processing speed (or strain rate) leads to the high-speed processing region above a certain speed, and can locally generate a large amount of heat through a mechanism different from the above-described processing heat. In swaging, for example, it is also possible to achieve impact processing speeds of the surface of approximately 50 meters/second, because of the availability of high speed rotation of the peripheral rollers. The strain rate at that time is about 10 to 100/s, which is almost in the region of high-speed processing.
If the contact time between the mold and the titanium material is instantaneous, there is almost no heat flow to the mold, and thus the heat is trapped inside the material. Swaging has such properties, so that swaging is a preferred processing method, which increases the temperature of the material itself by the heat generated due to processing.
In this way, the combination of titanium's low thermal conductivity and high-speed processing can raise the temperature of the titanium material to 300° C. or higher without heating up from the surroundings. Specifically, properly setting of the rotation speed for high-speed processing, the insertion speed of the workpiece, the contact time with the die, the amount of lubricant applied, the processing ratio per time (the processing ratio in a single process), and the total processing ratio (total of the processing ratio in a single process) can control the strain speed while maintaining the internal temperature of the material at 300 to 400° C., making it possible to create an appropriate balanced state (equilibrium state) between the introduction of working strain and the generation of recrystallization.
By utilizing the processing heat of the material itself in this way, it is possible to control the state of the crystals and their orientation, and the strength and toughness of the material, to form an appropriate structure for the screw having the above-described properties.
According to this method, it is possible to continue processing without performing intermediate annealing (softening heat treatment to give ductility to the material), up to the final material diameter by reducing the material diameter by repeating the single process several times to several tens of times. In this way, since the ductility is spontaneously improved by recrystallization that occurs during processing, it is possible to increase the total processing ratio (sum of single steps) to 80 to 95% or more beyond the conventional case.
Since it is possible to obtain an extremely high total processing ratio, it is possible to absorb variations in the state of the structure of the material before processing.
When such a method is used, it is possible that desired properties can be imparted to the medical screw even by using a bar or wire made of pure titanium Grades 1 to 4 without using a material that has been grain refining, such as a material made by repeated shear deformation processing (ECAP) or multi-axis forging (MDF), as a pre-processing material.
The present invention provides a method for producing a base material for a screw, comprising the steps of:
Alternatively, the present invention provides a method for producing a base material for a screw, comprising the steps of:
The term “true strain” used herein means an index indicating the processing ratio, and the true strain ε can be expressed by the following equation 2 from the cross-sectional area A0 before processing and the cross-sectional area A1 after processing.
The term “processing ratio” used herein means literally an index indicating the processing ratio, and the processing ratio e can be expressed by the following equation 3 from the cross-sectional area A0 before processing and the cross-sectional area A1 after processing.
For example, when the processing ratio e is 80%, the true strain ε is 1.61, when the processing ratio e is 90%, the true strain ε is 2.3, and when the processing ratio e is 95%, the true strain ε is 3.0.
According to the present invention, the true strain ε may be 2 or more (processing ratio of 86% or more), preferably 2.5 or more (processing ratio of 92% or more), more preferably 3 or more (processing ratio of 95% or more).
The base material for the screw obtained by the method according to the present invention has the same definition and the same properties as described above.
The swaging conditions are not particularly limited as long as the above-described true strain ε and/or the above-described processing ratio e can be achieved.
For example, swaging conditions may include, but are not limited to, setting conditions such that the surface temperature of the workpiece being worked is 250° C. or higher.
Further, the present invention also provides a method for producing a screw.
The present invention also provides a method for producing a screw, the method further comprising the step of:
In the above-described producing method, the terms “true strain” and “processing ratio” have the same definitions as described above.
As pure titanium materials, i) pure titanium Grade 2 with a wire diameter of 5.8 mm (CP-T2) (manufactured by Toho Tech Co., Ltd.), and ii) pure titanium Grade 4 with a wire diameter of 6.0 mm (CP-T4) (manufactured by Toho Tech Co., Ltd.) were prepared. Further, iii) a block-shaped material (manufactured by Kawamoto Heavy Industries, Ltd.) was prepared by refining a pure titanium Grade 2 with crystals to less than 1 μm meter by bulk ultrafine grained processing (UFG), and the block-shaped material was cut out, to prepare a bar material (FTi2) with a wire diameter of 6.0 mm.
These materials were swaged several times at room temperature using a 15HP-SD type (four-way) swaging device manufactured by Yoshida Kinen Co., Ltd. The true strain of each single swaging step was set to 0.15 to 0.25, followed by repeating the step several times, to prepare four to five processed base materials each having a rod shape with the true strain ranging from 0 to about 3.7 in total (processing ratio: about 97%).
Furthermore, in each swaging step, the surface temperature of the material was measured using a radiation thermometer, to adjust the surface temperature, swager rotation speed, bar material advance speed, lubrication so that the temperature was 300 to 400° C., and the application of oil per hour. The strain rate was calculated from the swager conditions described above.
Samples for X-ray diffraction for determining the crystallite size and orientation were obtained by cutting each processed base material having the rod shape in a plane perpendicular to the axial direction and embedding it in a phenolic resin. For the resin-filled sample, wet polishing was performed through SiC waterproof abrasive paper #400, #800, #1200, and #2400 in order from the rough side so that the surface was exactly perpendicular to the axial direction of each base material. Then, each sample was buffed with a silicon dioxide suspension (OP-S) to give a mirror finish.
The crystallite size was measured using a BRUKER X-ray diffractometer (D8 ADVANCE) with cobalt Kα rays at a cobalt tube output of 35 kV and a current of 40 mA, with the conditions: X-ray scanning range 2θ: 35.0° to 48.0°, the divergence slit diameter: 0.3 mm, and the collimator diameter: 0.3 mm. The measurement data were analyzed using analysis software DIFFRAC. EVA (manufactured by BRUKER).
Orientation was measured using an X-ray diffractometer (D8 ADVANCE) manufactured by BRUKER under the same conditions as described above.
The in-plane direction angle Φ of the sample was measured in 72 steps in 5-degree increments around 360 degrees, and the range of the tilt angle Y was measured with a starting point of 15 degrees and an end point of 45 degrees. The resulting data were analyzed using analysis software DIFFRAC. TEXTURE MRDB V4.1 (manufactured by BRUKER), to create a pole figure of the (1 0-1 0) plane. The pole figure is shown in
The maximum value of the relative intensities where the average intensity of the entire pole figure was defined as 1 was defined as the maximum specific intensity. Furthermore, in
For the resulting processed base materials each having a rod shape, the crystallite size and the orientation of the (1 0-1 0) plane of pure titanium in the axial direction were obtained under the conditions described above.
Mechanical properties such as tensile strength, Vickers hardness, and reduction of area were measured for the resulting processed base materials each having a rod shape.
The tensile test was carried out with an Amsler universal testing machine.
Hardness was measured with a micro Vickers hardness tester under a load of 2.94 N.
Further, the reduction of area (RA) was obtained by converting the diameter of the sample after breakage in the tensile test into an area according to Equation 4, wherein D0 means the diameter of the material before tensile testing and D1 means the diameter of the neck of the material after tensile testing.
Specifically,
Further,
More,
Therefore,
Further, the results of
Specifically, the vertical axis of
Further,
Table 1 shows the head formability of the screw formed using the processed base materials each having a rod shape.
Furthermore, it should be noted that the screw could be formed from the processed base material having the rod shape by upsetting (heading) like normal screw forming.
Table 1 shows that using ii) CP-T4 as the raw material, the processed base material having the rod shape obtained with a true strain of 2.65 (processing ratio: 93%) or more could be obtained at a temperature of 200° C., which is lower than that of 400° C. or higher heading processing was usually performed in the vicinity of true strain: 0 (processing ratio: 0%).
0(0%)
0(0%)
Conventionally, a medical screw made of pure titanium Grade 4, which have a high oxygen content among pure titanium, has high strength but poor plastic workability. Thus, it was difficult to heading process the medical screw at a temperature of 200° C. or less. Therefore, the head of the screw was formed by hot working (400° C. or higher) or cutting. Machining in these temperature ranges required solid lubrication, which significantly reduced productivity. In order to reduce costs and to improve productivity, there has been a demand for the same material that has plastic workability (especially reduction of area) that allows heading at 250° C. or lower.
However, as can be seen from Table 1, according to the present invention, head processing by heading is possible even at 250° C. or less.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-095318 | Jun 2021 | JP | national |
The present application is a national stage entry of International Application No. PCT/JP2022/015918 filed Mar. 30, 2022, which claims the benefit of Japanese Patent Application No. 2021-095318 filed Jun. 7, 2021, the disclosures of which are incorporated by reference in their entireties.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/015918 | 3/30/2022 | WO |
