Patent Application
20170033539
The present disclosure relates to a spark plug.
Spark plugs have been used for internal combustion engines. These spark plugs have electrodes that form a gap. The electrodes used are, for example, electrodes having noble metal tips, in order to restrain consumption of the electrodes. One technique proposed to restrain an increase in the temperature of a center electrode is to join a noble metal tip to a shaft having a copper core embedded therein. With this technique, the increase in the temperature of the noble metal tip is restrained, and the consumption of the electrode can thereby be restrained.
However, long-term use may cause consumption of the noble metal tip. When the noble metal tip is consumed, discharge may not be generated appropriately. This problem is not specific to the center electrode but is common to the center electrode and a ground electrode.
The present disclosure discloses a technique for restraining consumption of an electrode.
The present disclosure discloses, for example, the following application examples.
In accordance with a first aspect of the present invention, there is provided a spark plug comprising a center electrode and a ground electrode that forms a gap with the center electrode,
wherein at least one of the center electrode and the ground electrode includes a shaft portion and an electrode tip joined to one surface of the shaft portion,
the shaft portion includes a first core formed of a material containing copper and a first outer layer that is formed of a material having higher corrosion resistance than the first core and covers at least part of the first core, and
the electrode tip includes a second outer layer that is formed of a material containing a noble metal and forms an outer surface of the electrode tip and a second core that is formed of a material having a higher thermal conductivity than the second outer layer and is at least partially covered with the second outer layer.
According to this configuration, heat can be released from the second outer layer through the second core to the shaft portion, so that an increase in the temperature of the second outer layer can be restrained. Therefore, consumption of the second outer layer can be restrained.
In accordance with a second aspect of the present invention, there is provided a spark plug according to Application Example 1, wherein the second outer layer is formed of a material containing as a main component at least one of six noble metals including platinum, iridium, rhodium, ruthenium, palladium, and gold or a material containing as a main component an alloy of copper and any one of the six noble metals.
According to this configuration, the consumption of the second outer layer can be restrained appropriately.
In accordance with a third aspect of the present invention, there is provided a spark plug according to Application Example 2, wherein the second outer layer contains an oxide having a melting point of 1,840° C. or higher.
According to this configuration, the consumption of the second outer layer can be restrained appropriately.
In accordance with a fourth aspect of the present invention, there is provided a spark plug according to any one of Application Examples 1 to 3, wherein the first core and the second core are joined directly to each other.
According to this configuration, the increase in the temperature of the second outer layer can be appropriately restrained through the first core and the second core, so that the consumption of the second outer layer can be restrained.
In accordance with a fifth aspect of the present invention, there is provided a spark plug according to Application Example 4, wherein the first core and the second core are formed of an identical material.
According to this configuration, the first core and the second core can be easily joined to each other.
In accordance with a sixth aspect of the present invention, there is provided a spark plug according to any one of Application Examples 1 to 5, wherein
the center electrode includes the shaft portion extending in an axial direction and the electrode tip joined to a forward end of the shaft portion,
the electrode tip has a substantially cylindrical shape, and
a thickness s is 0.03 mm or more and equal to or less than one-third of an outer diameter D, where the outer diameter D is an outer diameter of the electrode tip, and the thickness s is a radial thickness of a portion of the second outer layer that covers an outer circumferential surface of the second core.
According to this configuration, the consumption of the second outer layer can be restrained appropriately.
In accordance with a seventh aspect of the present invention, there is provided a spark plug according to Application Example 6, wherein an axial thickness t of a forward end portion of the second outer layer that covers a forward end portion of the second core is 0.1 mm or more and 0.4 mm or less.
According to this configuration, the consumption of the second outer layer can be restrained appropriately.
In accordance with an eighth aspect of the present invention, there is provided a spark plug according to Application Example 6 or 7, wherein
the shaft portion and the electrode tip are joined to each other by a joining method including laser welding, and
at least part of an axial range of a joint portion between the first core and the second core overlaps an axial range of a fused joint portion formed by fusing the first outer layer and the second outer layer.
According to this configuration, deterioration in the joint strength between the shaft portion and the electrode tip can be restrained.
The technique disclosed in the present description can be implemented in various forms. For example, the technique can be implemented in different forms such as a spark plug, an internal combustion engine including a spark plug, and a method of producing a spark plug.
The spark plug 100 includes an insulator 10 (hereinafter referred to also as a “ceramic insulator 10”), the center electrode 20, the ground electrode 30, the metallic terminal 40, a metallic shell 50, an electrically conductive first seal portion 60, a resistor 70, an electrically conductive second seal portion 80, a forward-end-side packing 8, talc 9, a first rear-end-side packing 6, and a second rear-end-side packing 7.
The insulator 10 is a substantially cylindrical member having a through hole 12 (hereinafter referred to also as an “axial hole 12”) extending along the center axis CL and penetrating the insulator 10. The insulator 10 is formed by firing alumina (other insulating materials may be used). The insulator 10 has a leg portion 13, a first outer-diameter decreasing portion 15, a forward-end-side trunk portion 17, a flange portion 19, a second outer-diameter decreasing portion 11, and a rear-end-side trunk portion 18, which are arranged in this order from the forward end side in the rearward direction D2. The outer diameter of the first outer-diameter decreasing portion 15 decreases gradually from the rear end side toward the forward end side. An inner-diameter decreasing portion 16 having an inner diameter decreasing gradually from the rear end side toward the forward end side is formed in the insulator 10 in the vicinity of the first outer-diameter decreasing portion 15 (in the forward-end-side trunk portion 17 in the example in
The rod-shaped center electrode 20 extending along the center axis CL is inserted into a forward end portion of the axial hole 12 of the insulator 10. The center electrode 20 has a shaft portion 200 and an electrode tip 300 joined to the forward end of the shaft portion 200. The shaft portion 200 has a leg portion 25, a flange portion 24, and a head portion 23, which are arranged in this order from the forward end side in the rearward direction D2. The electrode tip 300 is joined to the forward end of the leg portion 25. The electrode tip 300 and a forward end portion of the leg portion 25 protrude outward from the axial hole 12 on the forward end side of the insulator 10. The other part of the shaft portion 200 is disposed within the axial hole 12. A surface of the flange portion 24 that is located on the forward direction D1 side is supported by the inner-diameter decreasing portion 16 of the insulator 10. The shaft portion 200 includes an outer layer 21 (referred to also as a “first outer layer 21”) and a core 22 (referred to also as a “first core 22”). The rear end of the core 22 protrudes from the outer layer 21 and forms a rear end portion of the shaft portion 200. The other part of the core 22 is covered with the outer layer 21. The entire core 22 may be covered with the outer layer 21.
The outer layer 21 is formed of a material having higher corrosion resistance than the core 22, i.e., a material that is less likely to be consumed when exposed to combustion gas in a combustion chamber of an internal combustion engine. The material used for the outer layer 21 is, for example, nickel (Ni) or an alloy containing nickel as a main component (e.g., INCONEL (“INCONEL” is a registered trademark)). The main component is a component with the highest content (the same applies to the following). The content used is expressed in terms of percent by weight. The core 22 is formed of a material having a higher thermal conductivity than the outer layer 21, for example, a material containing copper (such as pure copper or an alloy containing copper).
The metallic terminal 40 is inserted into a rear end portion of the axial hole 12 of the insulator 10. The metallic terminal 40 is formed of an electrically conductive material (for example, a metal such as low-carbon steel). The metallic terminal 40 has a cap attachment portion 41, a flange portion 42, and a leg portion 43, which are arranged in this order from the rear end side in the forward direction D1. The cap attachment portion 41 protrudes outward from the axial hole 12 on the rear end side of the insulator 10. The leg portion 43 is inserted into the axial hole 12 of the insulator 10.
The resistor 70 having a circular columnar shape is disposed between the metallic terminal 40 and the center electrode 20 within the axial hole 12 of the insulator 10, in order to suppress electrical noise. The electrically conductive first seal portion 60 is disposed between the resistor 70 and the center electrode 20, and the electrically conductive second seal portion 80 is disposed between the resistor 70 and the metallic terminal 40. The center electrode 20 and the metallic terminal 40 are electrically connected to each other through the resistor 70 and the seal portions 60 and 80. The use of the seal portions 60 and 80 allows the contact resistance between the stacked members 20, 60, 70, 80, and 40 to be stabilized to thereby stabilize the electric resistance between the center electrode 20 and the metallic terminal 40. The resistor 70 is formed using glass particles (such as B2O3—SiO2-based glass) serving as a main component, ceramic particles (such as TiO2), and an electrically conductive material (such as Mg). The seal portions 60 and 80 are formed using, for example, the same glass particles as those for the resistor 70 and metal particles (such as Cu).
The metallic shell 50 is a substantially cylindrical member having a through hole 59 that extends along the center axis CL and penetrates the metallic shell 50. The metallic shell 50 is formed of low-carbon steel (other electrically conductive materials (e.g., metallic materials) may be used). The insulator 10 is inserted into the through hole 59 of the metallic shell 50. The metallic shell 50 is fixed to the outer circumference of the insulator 10. The forward end of the insulator 10 (a forward end portion of the leg portion 13 in the present embodiment) protrudes outward from the through hole 59 on the forward end side of the metallic shell 50. The rear end of the insulator 10 (a rear end portion of the rear-end-side trunk portion 18 in the present embodiment) protrudes outward from the through hole 59 on the rear end side of the metallic shell 50.
The metallic shell 50 has a trunk portion 55, a seat portion 54, a deformable portion 58, a tool engagement portion 51, and a crimp portion 53, which are arranged in this order from the forward end side toward the rear end side. The seat portion 54 is a flange-shaped portion. A threaded portion 52 to be screwed into an attachment hole of an internal combustion engine (e.g., a gasoline engine) is formed on the outer circumferential surface of the trunk portion 55. An annular gasket 5 formed by bending a metal plate is fitted between the seat portion 54 and the threaded portion 52.
The metallic shell 50 has an inner-diameter decreasing portion 56 disposed on the forward direction D1 side of the deformable portion 58. The inner diameter of the inner-diameter decreasing portion 56 decreases gradually from the rear end side toward the forward end side. The forward-end-side packing 8 is held between the inner-diameter decreasing portion 56 of the metallic shell 50 and the first outer-diameter decreasing portion 15 of the insulator 10. The forward-end-side packing 8 is an O-shaped ring formed of iron (other materials (e.g., metallic materials such as copper) may be used).
The tool engagement portion 51 has a shape (e.g., a hexagonal columnar shape) suitable for engagement with a spark plug wrench. The crimp portion 53 is disposed rearward of the tool engagement portion 51. The crimp portion 53 is disposed rearward of the second outer-diameter decreasing portion 11 of the insulator 10 and forms the rear end (namely, an end on the rearward direction D2 side) of the metallic shell 50. The crimp portion 53 is bent inward in the radial direction.
An annular space SP is formed between the inner circumferential surface of the metallic shell 50 and the outer circumferential surface of the insulator 10 on the rear end side of the metallic shell 50. In the present embodiment, the space SP is surrounded by the crimp portion 53 of the metallic shell 50, the tool engagement portion 51 of the metallic shell 50, the second outer-diameter decreasing portion 11 of the insulator 10, and the rear-end-side trunk portion 18 of the insulator 10. The first rear-end-side packing 6 is disposed within the space SP on its rear end side. The second rear-end-side packing 7 is disposed within the space SP on its forward end side. In the present embodiment, these rear-end-side packings 6 and 7 are iron-made C-shaped rings (other materials may be used). The gap between the two rear-end-side packings 6 and 7 within the space SP is filled with powder of talc 9.
When the spark plug 100 is produced, the crimp portion 53 is bent inward and crimped. The crimp portion 53 is thereby pressed toward the forward direction D1 side. In this manner, the deformable portion 58 is deformed, and the insulator 10 is pressed forward within the metallic shell 50 through the packings 6 and 7 and the talc 9. The forward-end-side packing 8 is pressed between the first outer-diameter decreasing portion 15 and the inner-diameter decreasing portion 56 to thereby establish a seal between the metallic shell 50 and the insulator 10. In this manner, leakage of gas in the combustion chamber of the internal combustion engine to the outside through the gap between the metallic shell 50 and the insulator 10 is suppressed. In addition, the metallic shell 50 is fixed to the insulator 10.
The ground electrode 30 is joined to the forward end of the metallic shell 50 (i.e., the end on the forward direction D1 side). In the present embodiment, the ground electrode 30 is a rod-shaped electrode. The ground electrode 30 extends from the metallic shell 50 in the forward direction D1, is bent toward the center axis CL, and forms a forward end portion 31. The forward end portion 31 and a forward end surface 315 of the center electrode 20 (a surface 315 on the forward direction D1 side) form a gap g therebetween. The ground electrode 30 is joined to the metallic shell 50 so as to be electrically continuous with the metallic shell 50 (by, for example, resistance welding). The ground electrode 30 includes a base member 35 that forms the surface of the ground electrode 30 and a core 36 embedded in the base member 35. The base member 35 is formed using, for example, INCONEL. The core 36 is formed using a material having a higher thermal conductivity than the base member 35 (e.g., pure copper).
First, the configuration of the electrode tip 300 before joining will be described. The electrode tip 300 has a substantially cylindrical shape with its center on the center axis CL. The electrode tip 300 has a second outer layer 310 that forms the outer surface of the electrode tip 300 and a core 320 (referred to also as a “second core 320”) partially covered with the second outer layer 310. The second outer layer 310 is formed of a material containing a noble metal (such as iridium (Ir) or platinum (Pt)) (hereinafter referred to also as a “noble metal layer 310”). The core 320 is formed of a material (e.g., copper (Cu)) having a higher thermal conductivity than the noble metal layer 310.
The core 320 has a substantially cylindrical shape with its center on the center axis CL. The noble metal layer 310 has a tubular portion 313 having a substantially circular tubular shape with its center on the center axis CL and a forward end portion 311 that is a substantially disk-shaped portion with its center on the center axis CL. The tubular portion 313 covers an outer circumferential surface 323 of the core 320. The forward end portion 311 is connected to the forward end of the tubular portion 313 and covers a forward end surface 321 of the core 320. The forward end surface 315 of the forward end portion 311 (i.e., the forward end surface of the electrode tip 300) forms the gap g after the spark plug 100 (
Any of various methods can be used to produce the electrode tip 300 configured as described above. For example, the following method can be used. The material of the noble metal layer 310 is molded into a cup shape having a recess, and the material of the core 320 is placed in the recess. Then the member, with the material of the core 320 placed in the recess, is stretched by rolling. Excess portions of the stretched member are cut, whereby the electrode tip 300 is formed.
Alternatively, the following method may be used. The material of the noble metal layer 310 is molded into a cylindrical shape, and the material of the core 320 is inserted into the cylindrical hole. The member, with the material of the core 320 inserted into the cylindrical hole, is stretched by rolling. Next, the stretched member is cut to obtain a cylindrical member having a prescribed length (this member corresponds to the tubular portion 313 and the core 320). Then a disk formed of the material of the noble metal layer 310 (the disk corresponds to the forward end portion 311) is joined to one end of the cylindrical member by laser welding, whereby the electrode tip 300 is formed.
Alternatively, the following method may be used. The material of the noble metal layer 310 is fired into a shape shown in
Next, the configuration of the forward end portion of the shaft portion 200 before joining will be described. In the forward end portion of the shaft portion 200, the entire core 22 is covered with the outer layer 21. The shaft portion 200 has a diameter decreasing portion 220 that has an outer diameter decreasing in the forward direction D1. A forward end surface 211 is formed on the forward direction D1 side of the diameter decreasing portion 220. The rear end surfaces 316 and 326 of the electrode tip 300 are joined to the forward end surface 211.
The shaft portion 200 and the electrode tip 300 joined to each other are shown in
The exterior shape of the shaft portion 200a before joining is substantially the same as the exterior shape of the shaft portion 200 in
The shaft portion 200a and the electrode tip 300 joined to each other are shown in
In the embodiment in
As described above, the joint portion 240 joins the core 22a of the shaft portion 200a to the core 320 of the electrode tip 300. The fused joint portion 230a is formed by fusion of the outer layer 21a of the shaft portion 200a and the noble metal layer 310 of the electrode tip 300. Next, attention is focused on positions in the axial direction. As shown in
When the first range Ra is spaced apart from the second range Rb, the joint portion 240 may be formed at a position apart from the fused joint portion 230a. In this case, a gap (not shown), which is an unjoined portion between the electrode tip 300 and the shaft portion 200a, may be formed between the joint portion 240 and the fused joint portion 230a within the center electrode 20a after the electrode tip 300 is joined to the shaft portion 200a. When such a gap is formed within the center electrode 20a, the joint strength of the center electrode 20a can be lower than that when no gap is formed. When the first range Ra is contained in the second range Rb as in the embodiment in
In the embodiment in
The exterior shape of the electrode tip 300z before joining is substantially the same as the exterior shape of the electrode tip 300 in
The shaft portion 200 and the electrode tip 300z joined to each other are shown in
In
The smaller the second thickness t, the closer the forward end surface 321 of the core 320 is to the discharge surface 315. Therefore, the smaller the second thickness t, the higher the second temperature T2 of the forward end surface 321 of the core 320. A second melting point Tm2 in the figure is the melting point of the core 320. To suppress fusion of the core 320, it is preferable that the second thickness t is large, and it is particularly preferable that the second thickness t is larger than a thickness tL at which the second temperature T2 becomes equal to the second melting point Tm2.
In a first evaluation test using a spark plug sample, the amount of increase in the distance of the gap g after repeated electric discharges was evaluated. The distance of the gap g (
In the first evaluation test, seven samples with different combinations of three differently configured center electrodes (the center electrodes 20, 20a, and 20z in
In the seven samples used for the evaluation test, components of the spark plugs other than the center electrodes were common to these samples and were the same as those shown in
Material of base member 35 of ground electrode 30: INCONEL 600
Material of core 36 of ground electrode 30: Copper
Material of outer layer 21, 21a of shaft portion 200, 200a: INCONEL 600
Material of core 22, 22a of shaft portion 200, 200a: Copper
Outer diameter D of electrode tip 300, 300z: 0.6 mm
Total length Lt of electrode tip 300, 300z: 0.8 mm
Material of noble metal layer 310 and electrode tip 300z: Platinum
First thickness s of tubular portion 313 (only center electrodes 20 and 20a): 0.2 mm
Thickness t of forward end portion 311 (only center electrodes 20 and 20a): 0.2 mm
Initial value of distance of gap g: 1.05 mm
The evaluation test was performed as follows. A spark plug sample was placed in air at 1 atmosphere, and electric discharge was repeated at 300 Hz for 100 hours. The electric discharge was generated by applying discharge voltage between the metallic terminal 40 and the metallic shell 50. The distance of the gap g was measured using pin gauges in steps of 0.01 mm before and after the repeated electric discharges. Then the difference between the measured distances was computed as the amount of increase. In Table 1, an A rating indicates that the amount of increase is 0.04 mm or less, and a B rating indicates that the amount of increase is more than 0.04 mm.
As shown in Table 1, the results of evaluation of the center electrodes 20 and 20a each having the core 320 (i.e., an A rating) are better than the results of evaluation of the center electrode 20z having no core 320 (i.e., a B rating). The reason for this is presumed to be that the core 320 of the electrode tip 300 allows heat generated by the electric discharges to be released from the electrode tip 300 to the shaft portion 200 or 200a to thereby restrain an increase in the temperature of the electrode tip 300. The results of evaluation of the center electrodes 20 and 20a each having the core 320 were good irrespective of the material of the core 320. The reason for this is presumed to be that the thermal conductivity of each of the three materials (copper, silver, and gold) of the core 320 is higher than the thermal conductivity of the noble metal layer 310 (platinum).
The amount of increase in the distance of the gap g tended to be smaller when the center electrode 20a in
In the case in which the center electrode 20a was used, the amount of increase in the distance of the gap g was smaller in the sample in which the material of the core 320 of the electrode tip 300 was copper which was the same as the material of the core 22a of the shaft portion 200a than in other samples. The reason for this is presumed to be that the use of the same material allows the two cores 320 and 22a to be appropriately joined and the increase in the temperature of the electrode tip 300 can thereby be restrained appropriately.
In a second evaluation test using a spark plug sample, the amount of increase in the distance of the gap g after operation of an internal combustion engine with the spark plug sample mounted thereto was evaluated. The following Table 2 shows the configuration of each sample, the amount of increase in the distance of the gap, and the results of evaluation.
In the second evaluation test, seven samples having the same configurations as those of the seven samples evaluated in the first evaluation test were evaluated. Table 2 above includes three separate tables corresponding to the three materials of the core 320 of the electrode tip 300. The data of the center electrode 20z in the reference example is common to these three tables.
The evaluation test was performed as follows. The internal combustion engine used was an inline four cylinder engine with a displacement of 2,000 cc. The engine was operated at a rotation speed of 5,600 rpm for 20 hours. The distance of the gap g was measured using pin gauges before and after the operation. Then the difference between the measured distances was computed as the amount of increase. In Table 2, an A rating indicates that the amount of increase is 0.3 mm or less, and a B rating indicates that the amount of increase is more than 0.3 mm.
As shown in Table 2, the results of evaluation of the center electrodes 20 and 20a each having the core 320 (i.e., an A rating) are better than the results of evaluation of the center electrode 20z having no core 320 (i.e., a B rating). The reason for this is presumed to be that the core 320 of the electrode tip 300 allows heat generated by combustion to be released from the electrode tip 300 to the shaft portion 200 or 200a to thereby restrain an increase in the temperature of the electrode tip 300. The results of evaluation of the center electrodes 20 and 20a each having the core 320 were good irrespective of the material of the core 320. The reason for this is presumed to be that the thermal conductivity of each of the three materials (copper, silver, and gold) of the core 320 is higher than the thermal conductivity of the noble metal layer 310 (platinum).
The amount of increase in the distance of the gap g tended to be smaller when the center electrode 20a in
In the case in which the center electrode 20a was used, the amount of increase in the distance of the gap g was smaller in the sample in which the material of the core 320 of the electrode tip 300 was copper which was the same as the material of the core 22 of the shaft portion 200a than in other samples. The reason for this is presumed to be that the use of the same material allows the two cores 320 and 22a to be appropriately joined and the increase in the temperature of the electrode tip 300 can thereby be restrained appropriately.
In a third evaluation test using a spark plug sample, the relation among the second thickness t, the amount of increase in the distance of the gap g after repeated electric discharges, and the concentration of platinum on the discharge surface 315 was evaluated. The following Table 3 shows the relation among the material of the core 320, the second thickness t, the amount of increase in the distance of the gap, the concentration of platinum (Pt) on the discharge surface 315, and the results of evaluation.
In the third evaluation test, the center electrode used was the center electrode 20 in
In each of the 15 samples, a noble metal tip (not shown) formed of platinum was provided in a portion of the ground electrode 30 (
Material of base member 35 of ground electrode 30: INCONEL 600
Material of core 36 of ground electrode 30: Copper
Material of outer layer 21 of shaft portion 200: INCONEL 600
Material of core 22 of shaft portion 200: Copper
Outer diameter D of electrode tip 300: 0.6 mm
Total length Lt of electrode tip 300: 0.8 mm
Material of noble metal layer 310: Platinum
First thickness s of tubular portion 313: 0.2 mm
Initial value of distance of gap g: 1.05 mm
The details of the evaluation test are the same as those in the first evaluation test. Specifically, a spark plug sample was placed in air at 1 atmosphere, and electric discharge was repeated at 300 Hz for 100 hours. The amount of increase in the distance of the gap g is the difference (unit: mm) in the distance of the gap g before and after the repeated electric discharges. The concentration of platinum is the platinum concentration (unit: at %) on the discharge surface 315 after the repeated electric discharges. The concentration of platinum was measured using a WDS (Wavelength Dispersive X-ray Spectrometer) of an EPMA (Electron Probe Micro Analyzer). Ordinarily, the concentration of platinum on the discharge surface 315 is 100 at %. However, if the core 320 is fused, a component of the fused core 320 (copper in this case) moves to the discharge surface 315, and this may cause a reduction in the concentration of platinum on the discharge surface 315. In Table 3, an A rating indicates that the amount of increase in the distance of the gap g is 0.04 mm or less and the concentration of platinum is 90 at % or more. A B rating indicates that the amount of increase in the distance of the gap g is more than 0.04 mm or the concentration of platinum is less than 90 at %.
As shown in Table 3, the larger the second thickness t, the larger the amount of increase in the distance of the gap g. The reason for this is presumed to be that, as described in
When the second thickness t was small, the concentration of platinum was low. The reason for this is presumed to be that, as described in
An A rating was obtained when the second thickness t was 0.1, 0.2, and 0.4 (mm). Any of these values can be used as the lower limit of a preferred range (a range from the lower limit to the upper limit) of the second thickness t. Any of the above values that is equal to or larger than the lower limit can be used as the upper limit. For example, the preferred range of the second thickness t can be 0.1 mm or more and 0.4 mm or less.
In a fourth evaluation test using a spark plug sample, the relation between the first thickness s and the amount of increase in the distance of the gap g after repeated electric discharges was evaluated. Table 4 below shows the relation among the material of the core 320, the first thickness s, the amount of increase in the distance of the gap g, and the results of evaluation.
In the fourth evaluation test, the center electrode used was the center electrode 20 in
In each of the 18 samples, a noble metal tip (not shown) formed of platinum was provided in a portion of the ground electrode 30 (
Material of base member 35 of ground electrode 30: INCONEL 600
Material of core 36 of ground electrode 30: Copper
Material of outer layer 21 of shaft portion 200: INCONEL 600
Material of core 22 of shaft portion 200: Copper
Outer diameter D of electrode tip 300: 0.6 mm
Total length Lt of electrode tip 300: 0.8 mm
Material of noble metal layer 310 and electrode tip 300z: Platinum
Thickness t of forward end portion 311: 0.2 mm
Initial value of distance of gap g: 1.05 mm
The details of the evaluation test are the same as those in the first evaluation test. Specifically, a spark plug sample was placed in air at 1 atmosphere, and electric discharge was repeated at 300 Hz for 100 hours. The amount of increase in the distance of the gap g is the difference (unit: mm) in the distance of the gap g before and after the repeated electric discharges. In Table 4, an A rating indicates that the amount increase in the distance of the gap g is 0.04 mm or less. A B rating indicates that the amount of increase in the distance of the gap g is more than 0.04 mm.
As shown in Table 4, the larger the first thickness s, the larger the amount of increase in the distance of the gap g. The reason for this is presumed to be that, as described in
An A rating was obtained when the first thickness s was 0.02, 0.03, 0.05, 0.1, and 0.2 (mm). Any of these values can be used as the lower limit of a preferred range (a range from the lower limit to the upper limit) of the first thickness s. Any of the above values that is equal to or larger than the lower limit can be used as the upper limit. For example, a value equal to or larger than 0.02 mm can be used as the first thickness s. A value equal to or less than 0.2 mm can be used as the first thickness s.
The temperature of the noble metal layer 310 is more likely to increase as the size of the core 320 relative to the size of the noble metal layer 310 decreases. For example, the temperature of the noble metal layer 310 is more likely to increase as the ratio of the first thickness s to the outer diameter D of the electrode tip 300 increases. Therefore, a preferred range of the first thickness s obtained in the fourth evaluation test can be defined using the ratio of the first thickness s to the outer diameter D. For example, in the fourth evaluation test, the outer diameter D is 0.6 mm. Therefore, an A rating was obtained when the ratio of the first thicknesses s to the outer diameter D was 1/30, 1/20, 1/12, ⅙, and ⅓. Any of these values can be used as the lower limit of the preferred range (a range from the lower limit to the upper limit) of the first thickness s. Any of the above values that is equal to or larger than the lower limit can be used as the upper limit. For example, a value equal to or larger than 1/30 of the outer diameter D can be used as the first thickness s. A value equal to or less than ⅓ of the outer diameter D can be used as the first thickness s.
In a fifth evaluation test using a spark plug sample, the relation among the outer diameter D, the first thickness s, and the amount of increase in the distance of the gap g after repeated electric discharges was evaluated. The following Table 5 shows the relation among the material of the core 320, the outer diameter D, the first thickness s, the amount of increase in the distance of the gap g, the threshold value of the amount of increase, and the results of evaluation.
In the fifth evaluation test, the center electrode used was the center electrode 20 in
In each of the 30 samples, a noble metal tip (not shown) formed of platinum was provided in a portion of the ground electrode 30 (
Material of base member 35 of ground electrode 30: INCONEL 600
Material of core 36 of ground electrode 30: Copper
Material of outer layer 21 of shaft portion 200: INCONEL 600
Material of core 22 of shaft portion 200: Copper
Total length Lt of electrode tip 300: 0.8 mm
Material of noble metal layer 310: Platinum
Thickness t of forward end portion 311: 0.2 mm
Initial value of distance of gap g: 1.05 mm
The details of the evaluation test are the same as those in the first evaluation test. Specifically, a spark plug sample was placed in air at 1 atmosphere, and electric discharge was repeated at 300 Hz. The repetition time of the electric discharge was 100 hours when the outer diameter D was 0.3, 0.6, and 0.9 mm, 200 hours when the outer diameter D was 1.8 mm, and 800 hours when the outer diameter D was 3.6 mm. The amount of increase in the distance of the gap g is the difference (unit: mm) in the distance of the gap g before and after the repeated electric discharges. An A rating indicates that the amount of increase in the distance of the gap g is equal to or less than the threshold value. A B rating indicates that the amount of increase in the distance of the gap g is larger than the threshold value.
As shown in Table 5, the larger the outer diameter D, the smaller the amount of increase in the distance of the gap g. The reason for this is presumed to be that, since the volume of the noble metal layer 310 increases as the outer diameter D increases, the increase in the temperature of the noble metal layer 310 is restrained.
In samples with the same outer diameter D, the larger the first thickness s, the larger the amount of increase in the distance of the gap g. The reason for this is presumed to be that, as described in
As shown in Table 5, in samples with outer diameters D equal to or larger than 0.6 mm, the results of evaluation were good when the first thickness s was one-third of the outer diameter D. Specifically, the amount of increase in the distance of the gap g was 0.04 mm or less. When the outer diameter D was 0.3 mm, the amount of increase in the distance of the gap g exceeded 0.04 mm. However, when the first thickness s was one-third of the outer diameter D, the amount of increases could be suppressed to 0.10 mm or less. As described above, the preferred range of the first thickness s discussed in the fourth evaluation test can be applied to various outer diameters D.
The results of evaluation were improved by reducing the first thickness s to one-third of the outer diameter D when the outer diameter D was 0.3, 0.6, 0.9, 1.8, and 3.6 (mm). Therefore, any of these values can be used as the lower limit of a preferred range (a range from the lower limit to the upper limit) of the outer diameter D. Any of the above values that is equal to or larger than the lower limit can be used as the upper limit. For example, a value equal to or larger than 0.3 mm can be used as the outer diameter D. A value equal to or less than 3.6 mm can be used as the outer diameter D.
In a sixth evaluation test, samples of the electrode tip 300 were used to evaluate the relation between the thickness s and the presence or absence of a crack caused by thermal cycles in each electrode tip 300. The following Table 6 shows the relation among the material of the core 320, the first thickness s, the presence or absence of a crack, and the results of evaluation.
Three materials (copper (Cu), silver (Ag), and gold (Au)) were evaluated as the material of the core 320 of the electrode tip 300. Table 6 above includes three separate tables corresponding to the three materials. Five values, 0.02, 0.03, 0.05, 0.1, and 0.2 (mm), were used as the first thickness s, and evaluation was performed for each of the materials using these values. As described above, in the sixth evaluation test, 15 samples were evaluated. The following components were common to the 15 samples.
Outer diameter D of electrode tip 300, 300z: 0.6 mm
Total length Lt of electrode tip 300, 300z: 0.8 mm
Material of noble metal layer 310: Platinum
Thickness t of forward end portion 311: 0.2 mm
In the sixth evaluation test, a plate of INCONEL 600 was welded to the rear end surfaces 316 and 326 of each sample of the electrode tip 300 (
As shown in Table 6, a crack occurred when the first thickness s was small. The reason for this is presumed to be that, when the first thickness s is small, the noble metal layer 310 cannot withstand the expansion of the core 320.
An A rating was obtained when the first thickness s was 0.03, 0.05, 0.1, and 0.2 (mm). Any of these values can be used as the lower limit of a preferred range (a range from the lower limit to the upper limit) of the first thickness s. Any of the above values that is equal to or larger than the lower limit can be used as the upper limit. For example, a value equal to or larger than 0.03 mm can be used as the first thickness s. A value equal to or less than 0.2 mm can be used as the first thickness s.
The preferred range of the first thickness s can be determined by combining the fourth evaluation test and the sixth evaluation test. For example, a value of 0.03 mm or more and 0.2 mm or less can be used as the first thickness s.
The ignition system 600 includes the spark plug 100, a discharge power source 641, a high-frequency power source 651, a mixing circuit 661, an impedance matching circuit 671, and a control unit 681. The discharge power source 641 applies a high voltage to the spark plug 100 to generate spark discharge in the gap g of the spark plug 100. The discharge power source 641 includes a battery 645, an ignition coil 642, and an igniter 647. The ignition coil 642 includes a core 646, a primary coil 643 wound around the core 646, and a secondary coil 644 wound around the core 646 and larger in the number of turns than the primary coil 643. One end of the primary coil 643 is connected to the battery 645, and the other end of the primary coil 643 is connected to the igniter 647. One end of the secondary coil 644 is connected to the end of the primary coil 643 that is connected to the battery 645, and the other end of the secondary coil 644 is connected to the metallic terminal 40 of the spark plug 100 through the mixing circuit 661.
The igniter 647 is a so-called switching element and is, for example, an electric circuit including a transistor. The igniter 647 controls, i.e., establishes or breaks, the electrical continuity between the primary coil 643 and a ground in response to a control signal from the control unit 681. When the igniter 647 establishes the electrical continuity, a current flows from the battery 645 to the primary coil 643, and a magnetic field is thereby formed around the core 646. Then, when the igniter 647 breaks the electrical continuity, the current flowing through the primary coil 643 is cut off, and the magnetic field changes. A voltage is thereby generated in the primary coil 643 due to self-induction, and a higher voltage (e.g., 5 kV to 30 kV) is generated in the secondary coil 644 due to mutual induction. This high voltage (i.e., electrical energy) is supplied from the secondary coil 644 to the gap g of the spark plug 100 through the mixing circuit 661, and spark discharge is thereby generated in the gap g.
The high-frequency power source 651 supplies relatively high-frequency electric power (e.g., 50 kHz to 100 MHz, AC power in the present embodiment) to the spark plug 100. The impedance matching circuit 671 is disposed between the high-frequency power source 651 and the mixing circuit 661. The impedance matching circuit 671 is configured such that the output impedance on the high-frequency power source 651 side matches the input impedance on the mixing circuit 661 side.
The mixing circuit 661 supplies both the output power from the discharge power source 641 and the output power from the high-frequency power source 651 to the spark plug 100 while a current is prevented from flowing from one of the discharge power source 641 and the high-frequency power source 651 to the other. The mixing circuit 661 includes a coil 662 connecting the discharge power source 641 to the spark plug 100 and a capacitor 663 connecting the impedance matching circuit 671 to the spark plug 100. The coil 662 allows the relatively low-frequency current from the discharge power source 641 to flow and prevents the relatively high-frequency current from the high-frequency power source 651 from flowing. The capacitor 663 allows the relatively high-frequency current from the high-frequency power source 651 to flow and prevents the relatively low-frequency current from the discharge power source 641 from flowing. The secondary coil 644 may be used instead of the coil 662, and the coil 662 may be omitted.
In the ignition system 600 in
In the seventh evaluation test using a spark plug sample, the consumption volume of the electrode tip 300 of the center electrode 20 (
In the seventh evaluation test, 5 samples different in the composition of the oxide added to the second outer layer 310 were evaluated. Configurational factors of the spark plugs other than the composition of the oxide were common to the five samples. Specifically, the configuration shown in
Material of base member 35 of ground electrode: INCONEL 600
Material of core 36 of ground electrode: Copper
Material of electrode tip of ground electrode: Platinum
Material of outer layer 21 of shaft portion 200: INCONEL 600
Material of core 22 of shaft portion 200: Copper
Material of second outer layer 310 of electrode tip 300: Iridium+oxide
Amount of oxide added to material of second outer layer 310: 7.2% by volume (vol %)
Material of second core 320 of electrode tip 300: Copper
Outer diameter D of electrode tip 300: 1.6 mm
Total length Lt of electrode tip 300: 3.0 mm
First thickness s of tubular portion 313: 0.2 mm
Second thickness t of forward end portion 311: 0.2 mm
Initial value of distance of gap g: 0.8 mm
The evaluation test was performed as follows. A spark plug sample was placed in nitrogen at 0.4 MPa, and electric discharge was repeated at 30 Hz for 10 hours using the ignition system 600 in
As shown in Table 7, the oxides in the five samples are Sm2O3, La2O3, Nd2O3, TiO2, and Fe2O3. The melting points of these oxides are 2,325, 2,315, 2,270, 1,840, and 1,566 (° C.), respectively. The higher the melting point of the oxide, the smaller the consumption volume. When the second outer layer 310 of the electrode tip 300 contained any of these oxides, the consumption of the second outer layer 310, i.e., the electrode tip 300, could be restrained. Preferably, the second outer layer 310 of the electrode tip 300 contains at least one of the five oxides shown in Table 7, as described above.
As shown by the melting point and consumption volume in Table 7, the higher the melting point of the oxide, the more the consumption is restrained. The reason for this is presumed to be as follows. The heat generated by electric discharge causes the temperature of the second outer layer 310 to increase. The increase in the temperature of the second outer layer 310 can cause the oxide to fuse. When the oxide fuses, the oxide flows and moves, and this can cause consumption of the noble metal, as in the case in which no oxide is added. When the melting point of the oxide is high, the oxide is less likely to fuse as compared to the case in which the melting point is low. Therefore, the higher the melting point of the oxide, the more the consumption of the second outer layer 310 (i.e., the electrode tip 300) can be restrained.
As shown in Table 7, when the oxide having a melting point of 1,566° C. (Fe2O3 in this case) was added, the consumption volume was 0.61 mm3. When the oxide having a melting point of 1,840° C. (TiO2 in this case) was added, the consumption volume was 0.35 mm3. By changing the oxide from one of these two oxides to the other having a higher melting point, the consumption volume could be reduced by 40% or more ((0.61−0.35)/0.61=0.426). When the melting point of the oxide was higher than 1,840° C., the consumption volume could be further reduced. As described above, when the second outer layer 310 of the electrode tip 300 contained an oxide having a melting point of 1,840° C. or higher, the consumption of the electrode tip 300 could be significantly restrained. Specifically, it is preferable that the second outer layer 310 contains at least one of Sm2O3, La2O3, Nd2O3, and TiO2.
As shown in Table 7, various oxides could restrain the consumption of the electrode tip 300. It is generally presumed that the consumption of the electrode tip 300 can be restrained even when an oxide other than the oxides evaluated in the seventh evaluation test is used. Particularly, as shown in Table 7, various metal oxides could restrain the consumption of the electrode tip 300. Therefore, it is presumed that not only the metal oxides evaluated in the seventh evaluation test but also other various metal oxides can restrain the consumption of the electrode tip 300. In any case, it is presumed that, when the melting point of the oxide is high, the consumption of the electrode tip 300 can be more restrained as compared to the case in which the melting point of the oxide is low.
An A rating indicating that the consumption volume was 0.35 mm3 or less was obtained when the melting point was 2,325, 2,315, 2,270, and 1,840 (° C.). Any of these four values can be used as the lower limit of a preferred range (a range from the lower limit to the upper limit) of the melting point of the oxide contained in the second outer layer 310 of the electrode tip 300. For example, the preferred range of the melting point of the oxide may be a range of 1,840° C. or higher. Any of the above four values that is equal to or higher than the lower limit can be used as the upper limit. For example, the preferred range of the melting point may be a range of 2,325° C. or lower. It is presumed that, even when the melting point is higher than the above values, the addition of the oxide can restrain the consumption of the electrode tip 300. For example, an oxide having a melting point of 3,000° C. or lower may be used as a practical oxide.
In the electrode tip 300 with the second outer layer 310 containing an oxide, it is preferable that the first thickness s (
(1) The material of the core 320 of the electrode tip 300 is not limited to copper, silver, and gold, and various materials having a higher thermal conductivity than the second outer layer 310 can be used. For example, pure nickel can be used. In any case, since the core 320 is formed of a material having a higher thermal conductivity than the second outer layer 310, the increase in temperature (i.e., consumption) of the second outer layer 310 can be restrained. Therefore, it is presumed that, when copper, silver, gold, or any material having a higher thermal conductivity than the second outer layer 310 is used as the material of the core 320, the above-described preferred range of the first thickness s can be applied.
It is presumed that the ease of heat transfer from the electrode tip 300 to the shaft portion 200 or 200a varies significantly according to the first thickness s and the ratio of the first thickness s to the outer diameter D. Therefore, it is presumed that the above-described preferred range of the first thickness s can be applied irrespective of configurational factors other than the first thickness s and the ratio of the first thickness s to the outer diameter D. For example, it is presumed that the above-described preferred range of the first thickness s can be applied even in the case where at least one of the outer diameter D, the total length Lt, the material of the second outer layer 310, the material of the core 320, and the second thickness t differs from that of the above-described samples of the electrode tip 300.
(2) It is presumed that the temperature of the core 320 of the electrode tip 300 when the core 320 receives heat from the second outer layer 310 varies significantly according to the distance between the forward end surface 321 of the core 320 and the discharge surface 315 of the second outer layer 310, i.e., the second thickness t. Therefore, it is presumed that the above-described preferred range of the second thickness t can be applied irrespective of configurational factors other than the second thickness t. For example, it is presumed that the above-described preferred range of the second thickness t can be applied even in the case where at least one of the outer diameter D, the total length Lt, the material of the second outer layer 310, the material of the core 320, and the first thickness s differs from that of the above-described samples of the electrode tip 300.
(3) As described above, the consumption of the electrode tip 300 is largely influenced by the first thickness s, the ratio of the first thickness s to the outer diameter D, and the second thickness t. Therefore, it is presumed that the above-described preferred range of the outer diameter D can be applied irrespective of configuration factors other than the first thickness s, the ratio of the first thickness s to the outer diameter D, and the second thickness t. For example, it is presumed that the above-described preferred range of the outer diameter D can be applied even in the case where at least one of the total length Lt, the material of the second outer layer 310, and the material of the core 320 differs from that of the above-described samples of the electrode tip 300. Particularly, it is presumed that, when the first thickness s, the ratio of the first thickness s to the outer diameter D, and the second thickness t are within the above-described preferred ranges, the above-described preferred range of the outer diameter D can be appropriately applied.
(4) The shape of the core 320 of the electrode tip 300 is not limited to a substantially cylindrical shape with its center on the center axis CL, and various shapes can be used. For example, in the above embodiments, the forward end surface 321 of the core 320 is a flat surface perpendicular to the center axis CL, but the forward end surface of the core 320 may be a curved surface. In any case, a surface portion of the core 320 that can be seen when the core 320 is observed in the rearward direction D2 from the forward direction D1 side of the core 320 can be used as the forward end surface of the core 320. The portion of the core 320 that forms the forward end surface can be used as a forward end portion. As the axial thickness t of the forward end portion of the second outer layer 310 that covers the forward end portion of the core 320, the minimum of the distance between the forward end surface of the core 320 and the outer surface of the forward end portion of the second outer layer 310 in the direction parallel to the center axis CL can be used.
As the radial thickness s of a portion of the second outer layer 310 that covers the outer circumferential surface of the core 320, the thickness of a circle with its center on the center axis of the substantially cylindrical electrode tip 300 (in the above embodiments, this center axis is the same as the center axis CL of the spark plug 100) can be used. As the outer circumferential surface of the core 320, a surface portion of the core 320 other than the above-described forward end surface and the rear end surface described later can be used. As the rear end surface of the core 320, a surface portion of the core 320 that can be seen when the core 320 is observed in the forward direction D1 from the rearward direction D2 side of the core 320 can be used. In the example in
(5) The material of the second outer layer 310 of the electrode tip 300 is not limited to platinum (Pt), and a material containing any of various noble metals can be used. Each of platinum (Pt), iridium (Ir), rhodium (Rh), ruthenium (Ru), palladium (Pd), and gold (Au) has high corrosion resistance. Therefore, when a material containing any one of these noble metals as a main component is used, the consumption of the second outer layer 310 can be appropriately restrained. Not only a material containing a specific element and another element but also a material containing only the specific element can be referred to as a material containing the specific element as a main component.
A material containing as a main component an alloy of a noble metal and copper may be used as the material of the second outer layer 310. For example, a material containing as a main component an alloy of copper and any one of the above-described six noble metals (Pt, Ir, Rh, Ru, Pd, and Au) may be used. It is presumed that, even when such a material is used, the consumption of the second outer layer 310 can be restrained appropriately. The second outer layer 310 formed of a material containing a noble metal as a main component or a material containing as a main component an alloy of a noble metal and copper may further contain an oxide having a melting point of 1,840° C. or higher. In this case, it is presumed that the consumption of the second outer layer 310 can be further restrained. However, the oxide may be omitted.
(6) The material of the outer layer 21, 21a of the shaft portion 200, 200a is not limited to a material containing Ni, and various materials having higher corrosion resistance than the core 22 can be used. For example, stainless steel may be used.
(7) The configuration of the spark plug is not limited to the configuration described in
An electrode tip having the same configuration as the electrode tip 300 may be provided in a portion of the ground electrode that forms the gap g.
Arrows LZb
The use of the ground electrode 30b described above allows heat to be released from the second outer layer 310 through the core 320 to the shaft portion 34. Therefore, an increase in the temperature of the second outer layer 310 can be restrained. The consumption of the second outer layer 310 can thereby be restrained. The fused joint portion 353 may be spaced apart from the core 320 of the electrode tip 300b. Even in this case, heat can be released from the second outer layer 310 through the core 320 to the shaft portion 34, so that the consumption of the second outer layer 310 can be restrained. For example, the fused joint portion 353 may join the second outer layer 310 to the base member 35 of the shaft portion 34. The electrode tip of the center electrode and the electrode tip of the ground electrode may have different configurational factors (e.g., material, dimensions, shape, etc.). When the ground electrode 30b is used, the electrode tip 300z in
As the configurational factors (e.g., material, dimensions, shape, etc.) of the ground electrode 30b, the same configurational factors as those described as the configurational factors of the center electrode 20 or 20a can be used. For example, it is preferable to use a material having higher corrosion resistance than the core 36 of the shaft portion 34 (e.g., nickel or an alloy containing nickel as a main component) as the material of the base member 35 (corresponding to the outer layer) that covers at least part of the core 36. It is preferable to use a material having a higher thermal conductivity than the base member 35, such as a material containing copper (e.g., pure copper or an alloy containing copper), as the material of the core 36 of the shaft portion 34.
Various materials containing noble metals can be used as the material of the second outer layer 310 of the electrode tip 300b. For example, it is preferable to use a material containing as a main component any one of platinum, iridium, rhodium, ruthenium, palladium, and gold. It is preferable to use a material having a higher thermal conductivity than the second outer layer 310 of the electrode tip 300b as the material of the core 320 of the electrode tip 300b. For example, it is preferable to use a material containing at least one of copper, silver, and pure nickel.
A material containing as a main component an alloy of a noble metal and copper may be used as the material of the second outer layer 310 of the electrode tip 300b. For example, a material containing as a main component an alloy of copper and any one of the above-described six noble metals (Pt, Ir, Rh, Ru, Pd, and Au) may be used. It is presumed that, even when such a material is used, the consumption of the second outer layer 310 can be restrained appropriately. The second outer layer 310 formed of a material containing a noble metal as a main component or a material containing as a main component an alloy of a noble metal and copper may further contain an oxide having a melting point of 1,840° C. or higher. In this case, it is presumed that the consumption of the second outer layer 310 of the electrode tip 300b can be further restrained. However, the oxide may be omitted.
The core 36 may be exposed at a surface of the shaft portion 34, i.e., its surface joined to the electrode tip 300b, and the core 320 of the electrode tip 300b may be joined directly to the core 36 of the shaft portion 34. With this configuration, an increase in the temperature of the second outer layer 310 can be appropriately restrained through the core 320 and the core 36. In addition, the core 36 of the shaft portion 34 and the core 320 of the electrode tip 300b may be formed of the same material. With this configuration, the core 36 and the core 320 can be joined easily to each other.
As preferred ranges of the parameters D, Lt, s, and t of the electrode tip 300b of the ground electrode 30b, the above-described preferred ranges of the parameters D, Lt, s, and t of the electrode tip 300 of the center electrode 20 or 20a can be used. It is presumed that the use of the above-described preferred ranges can restrain the consumption of the electrode tip 300b of the ground electrode 30b.
(8) As described above, the shaft portion having the first core and the first outer layer (referred to also as a “shaft portion with a core”) and the electrode tip having the second core and the second outer layer (referred to also as a “tip with a core”) can be applied to at least one of the center electrode and the ground electrode. A center electrode having the shaft portion with the core and the tip with the core (e.g., the center electrodes 20 and 20a in
Although the present invention has been described on the basis of the embodiments and modifications, the above-described embodiments of the present invention are provided for facilitating an understanding of the present invention and do not limit the present invention. The present invention may be modified and improved without departing from the scope and claims of the present invention and encompasses equivalents thereof.
The present disclosure can be preferably used for spark plugs used for internal combustion engines etc.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-264292 | Dec 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2014/083267 | 12/16/2014 | WO | 00 |
