Patent Application
20050022906
The present invention relates to a bainite-type untempered steel to be nitrided and a method of manufacturing the same. The present invention also relates to a nitrided product, for example, a rocker arm product manufactured from the steel.
Steels called nitrided steel, including soft nitrided steel, have conventionally an alloy composition containing a comparatively large amount of aluminum. After the steel is shaped into the configuration of a mechanical component part and hardened and tempered, nitriding treatment is carried out to obtain a product. The conventional nitrided steel has many problems as described below.
1) Tempering is generally considered indispensable for securing a mechanical strength of a component part, but is a factor of making a manufacturing cost high. Therefore it is preferable that the steel is not tempered.
2) To secure the hardness of a surface layer of not less than 750 HV, it is necessary to add not only a large amount of Cr but also a large amount of Al (not less than 1% each) to the steel. Consequently, the material becomes hard and workability such as drilling efficiency is impaired.
3) To improve the drilling efficiency or the like, addition of Pb is conventionally conducted, however, the presence of Pb is not preferable in stabilizing a gas nitriding property.
4) The steel containing a large amount of Al has problems, for example, in manufacturability peculiar thereto especially castability, and in the quality of a steel ingot especially surface imperfection.
A large number of proposals have been made as a result of researches conducted for many years to improve the machinability of various kinds of steel. The following free-machining steels have been known: (1) free-machining steel to which elements for improving its machinability such as S, Pb, Bi, Se, and Te are added, (2) free-machining steel to which Ca is added, and (3) free-machining steel to which Ca and S, etc. are compositely added. As for the free-machining steel to which Ca and S, etc. are compositely added, Japanese Patent Application Laid-Open No. 49-5815 is publicly known. In the free-machining steel disclosed therein, the composition of non-metal inclusion shown by the ternary system state diagram of CaO—Al2O3—SiO2 is present in the mullite region and 5 to 15 ppm of Ca and 0.04 to 0.1% of S are contained therein. However, the machinability of the said conventional free-machining steel to which Ca and S, etc. are added varies widely, thus it cannot be said that the machinability is sufficiently high.
As a recent example of the known invention regarding steel formachine structural use, Japanese Patent Application No. 10-287953 “Steel for machine structural use superior in mechanical property and drilling efficiency” is a typical known invention. The free-machining steel is characterized in including calcium-manganese sulfide inclusion containing 1% or less of calcium in a spindle-shape with amajor axis/minor axis ratio of 5, which encloses a calcium aluminate oxide inclusion containing 8 to 62% of CaO. This invention has realized excellent machinability, however, variations in the machinability were sometimes observed during the operation. It can be understood that this is because the calcium-manganese sulfide inclusion has a variety of presence forms.
Also, disclosed in Japanese Patent Application Laid-Open No. 2000-34538 is a Ca free-machining steel where machinability of the above free-machining steel to which Ca and S, etc. are compositely added is improved. The Ca free-machining steel described in the publication is a free-machining steel with excellent lathe-turning performance which contains the following elements: C: 0.1 to 0.8%, Si: 0.01 to 2.5%, Mn: 0.1 to 3.5%, P: 0.001 to 0.02%, S: 0.005 to 0.4%, Al: 0.001 to 0.1%, Ca: 0.0005 to 0.02%, O: 0.0005 to 0.01% and N: 0.001 to 0.04%, and the residue composed of Fe and unavoidable impurities, and also satisfies the formulas X/(X+Y+Z)≦0.3 and Y/(X+Y+Z)≧0.1, supposing that the ratio of the area of a sulfide containing not less than 40% of Ca to the entire examination and observation visual field is X, the ratio of the area of a sulfide containing 3 to 40% of Ca to the entire examination and observation visual field is Y, and the ratio of the area of a sulfide containing less than 0.3% of Ca to the entire examination and observation visual field is Z. Although the machinability of the Ca free-machining steel has less difference than the conventional one containing an oxide inclusion, the machinability thereof is insufficient.
In the description “free-machining steel” disclosed in Japanese Patent Application Laid-Open No. 2000-219936, the number of inclusions that should be present is clarified, thus the free-machining steel has less difference in its machinability. The steel of the invention is characterized in that it includes not less than five sulfides containing 0.1 to 1% of Ca per 3.3 mm2. Each sulfide has a diameter of not less than 5 μm, supposing that the sulfide is circular.
It has been found that steel having an alloy composition for machine structural use shows stable machinability when the occupation area of sulfide inclusion containing not less than 1.0 wt % of Ca which is present in contact with oxide inclusion containing 8 to 62 wt % of CaO is not less than 2.0×10−4 mm per visual field area of 3.5 mm2. The method of manufacturing the steel has been established and proposed (Japanese Patent Application Laid-Open No. 2001-174606).
It has been proved by later studies that the inclusion having the form in which the oxide inclusion forming the core is surrounded with the inclusion containing the sulfide as its main component, which the present applicant calls “sulfide form control type free-machining component”, is applicable to a wide range of steels. However, the said inclusion is not applicable to steel containing a large amount of Al. To control the form of the inclusion favorably, the content of Al should be 0.02% or less. However, as described above, nitrided steel in common use contains at least 1% of Al, thus it is impossible to generate the free-machining component of sulfide form control type and utilize it.
Generally, a steel rocker arm mounted in an internal combustion engine as a component part for machine structural use is formed into a desired final configuration by means of rough processing by plastic work such as forging and following cutting process. A lathe-turning process is a manufacturing process which is applied to almost all component parts. Since the ratio of the cost of lathe-turning process to the manufacturing cost of a component part for machine structural use is considerably high, there have been increasing demands for development of a free-machining steel superior in machinability to reduce the cost.
It is an object of the present invention to provide free-machining steel to-be-nitrided which allows the free-machining component of sulfide form control type providing preferable machinability to be utilized in nitriding steel, having machinability equivalent of or higher than Pb free-machining steel, and nitrided in an untempered state to manufacture mechanical component parts, while its mechanical property and nitriding property maintained. It is another object of the present invention to provide a method of manufacturing the same. It is still another object of the present invention to provide mechanical component parts such as rocker arm products using the said nitriding steel.
It is general toperformheat treatment such as nitriding treatment on a rocker arm to impart a strength thereto so that it withstands a dynamic load generated therein. Since the nitriding treatment is not sufficiently considered in the conventional free-machining steel mentioned above, it is difficult to secure surface hardness and nitrided layer depth after nitriding treatment and also softening-resistant property in performing nitriding treatment. Thus it is impossible to obtain a favorable nitriding property. The softening-resistant property means prevention of an inner hardness from being reduced by a treating temperature in nitriding operation.
In addition, with regard to the nitriding treatment, generally a desired strength is imparted to steel by tempering it before nitriding. However, a tempering process is a factor of making the manufacturing cost high. Thus, to meet the recent demand for lowering the manufacturing cost, there has been a growing demand for development of a method of allowing steel untempered after it is hot-forged and plastically processed to have a strength as high as the conventional tempered steel. But the no tempering is not sufficiently considered for the conventional free-machining steel. Therefore, the conventional arts have been incapable of imparting properties of good productivity and favorable strength to untempered free-machining steel.
Although the above-described known Pb free-machining steel is superior in machinability, Pb free-machining steel is poisonous. Thus to cope with environmental problems in recent years, the use thereof should be restrained to the utmost.
The present invention has been made in view of the above-described situation, and an object of the present invention is, by solving the above-described problems, to provide an untempered free-machining steel to be nitrided having machinability equivalent to that of the known Pb free-machining steel even though Pb is not contained, having superior nitriding properties such as nitrided layer depth, and also having a strength equal to that of the known tempered steel without being tempered. It is also an object of the present invention to provide mechanical component parts using the nitrided steel, for example, steel for a rocker arm and a rocker arm product manufactured from the said steel for a rocker arm.
To solve the above-described problems, the present inventors have made energetic investigation. As a result, they have succeeded in solving the above problems and developing a bainite-type untempered steel to be nitrided having machinability equivalent to that of the known Pb free-machining steel, superior in its nitriding properties such as nitrided layer depth, and having a strength equal to that of the known tempered steel without being tempered. They have also succeeded in developing mechanical component parts using the nitrided steel such as a rocker arm product.
The free-machining steel to be nitrided of the present invention (bainite-type untempered steel) achieving the above-described object contains the following elements including C: 0.05 to 0.8 wt %, Si: 0.01 to 2.5 wt %, Mn: 0.1 to 3.5 wt %, P: 0.001 to 0.2 wt %, S: 0.01 to 0.2 wt %, Cr: 1.0 to 3.5 wt %, V: 0.1 to 0.5 wt %, Al: 0.001 to 0.020 wt %, Ca: 0.0005 to 0.02 wt %, and O: 0.0005 to 0.01 wt % as its basic alloy composition and the residue composed of unavoidable impurities and Fe, wherein an occupation area of a sulfide inclusion present in contact with an oxide inclusion containing 8 to 62 wt % of CaO and containing not less than 1.0 wt % of Ca is not less than 2.0×10−4 mm2 per visual field area of 3.5 mm2, provided that each content of the Mn, the S, and the Cr satisfies the formula:
([Mn]−55×[S]/32+[Cr])>2.0
(where [ ] indicates wt % (wt/wt) of each element).
In the method of manufacturing the bainite-type untempered free-machining steel to be nitrided, an alloy having the above-described alloy composition is melted, wherein an operation satisfying the following conditions 1) through 3) is performed:
Further, the steel for the rocker arm according to the present invention is a steel in which a hard oxide in contact with a sulfide composed of MnS and CaS is dispersed in a matrix; the hard oxide contains Al2O3 and CaO, the ratio of the content of the CaO to the entire hard oxide is 8.0 to 62% (wt/wt); the ratio of the content of the Ca to the entire sulfide is 1.0 to 45% (wt/wt); and the occupation area of the sulfide in the steel is 2.0×10−4 to 1.0×10−1 mm2 per area of 3.5 mm2. The present inventors have found that the hard oxide which contains Al2O3 and CaO and is in contact with the sulfide composed of MnS and CaS in the steel of the present invention functions as the free-machining component of sulfide form control type, and improves the grindability of the matrix itself outstandingly without deteriorating the anisotropy. The present inventors have also found that the above-described sulfide generates a tool protective sulfide film on the surface of a machining tool during cutting operation, whereby the life of the tool is greatly improved and its machinability is preferably improved. The use of the steel for the rocker arm allows various rocker arms to be manufactured at a low cost and with high productivity.
“The hard oxide in contact with the sulfide” described above may be any hard oxide as long as at least one part of the hard oxide is contacting with at least one part of sulfide. For example, the case where the surface of the hard oxide contacts that of the sulfide and the case where a part of or entire surface of the hard oxide is coated with a sulfide or a sulfide film are included.
The present inventors have found out that steel for a rocker arm containing C: 0.1 to 0.5% (wt/wt), Si: 0.01 to 2.5% (wt/wt), Mn: 0.1 to 3.5% (wt/wt), P: 0.001 to 0.2% (wt/wt), S: 0.01 to 0.2% (wt/wt), Cr: 1.0 to 3.5% (wt/wt), V: 0.1 to 0.5% (wt/wt), Al: 0.001 to 0.02% (wt/wt), Ca: 0.0005 to 0.02% (wt/wt), and O: 0.0005 to 0.01% (wt/wt) as basic components and the residue composed of Fe and unavoidable impurities, wherein the content of the elements Cr and V satisfies a formula of ([Cr]+1.97×[V])≧2.15% (wt/wt) facilitates the bond between Ca and O and accelerates the generation of the free-machining component of sulfide form control type by decreasing aluminum, thereby improvement of the machinability can be facilitated. The present inventors have also found that, by adjusting the amount of Cr and V to satisfy the above formula, it is possible to improve the softening-resistant property during nitriding treatment and preferably improve the surface hardness and nitrided layer depth after the steel is nitrided, thereby a superior nitriding property is provided.
The present inventors have also found that by adjusting the addition amount of elements C, Mn, S, and Cr contained in the steel for a rocker arm having the above basic components in such a way that the carbon equivalent Ceq indicated by theformula:([C]+0.27×([Mn]−55×[S]/32)+0.31×[Cr]+0.3×[V]) is set within the range of 0.8 to 1.1% (wt/wt), it is possible to form the structure of ferrite+bainite easily and adjust the inner hardness easily to 20 to 35 HRC when the steel is hot-forged and then allowed to cool. Thereby the steel is allowed to have both excellent machinability and favorable fatigue strength after nitriding treatment is performed, and therefore it is possible to manufacture the rocker arm of fine quality with high productivity.
It is also possible to improve hardenability, make crystalline grains fine, and make the sulfide fine by optionally adding one or more element(s) selected from Mo: ≦2.0% (wt/wt), Cu: ≦2.0% (wt/wt), Ni: ≦4.0% (wt/wt), B: 0.0005 to 0.01%(wt/wt), Nb: ≦0.2%(wt/wt), Ti: ≦0.2%(wt/wt), Ta: ≦0.5%(wt/wt), Zr: ≦0.5% (wt/wt), and Mg: ≦0.02% (wt/wt) to the above steel for a rocker arm.
The present inventors have also found that it is possible to easily form the untempered structure of ferrite+bainite formed after the hot-forged and allowed to cool having a strength equivalent to that of tempered steel, by adjusting the content of elements Mn, S and Cr to satisfy the formula:([Mn]−55×[S]/32+[Cr])>2.0 wt % when Mo is not included among the above elements, and by adjusting the content of the elements Mn, S, Cr and Mo to satisfy a formula:([Mn]−55×[S]/32+[Cr]+[Mo])>2.0 wt % when Mo is included, whereby a tempering process can be omitted.
The present inventors have further found that the method of manufacturing steel for the rocker arm can be embodied by melting an alloy comprising alloy components specified as described above and the residue with a chemical composition composed of unavoidable impurities and Fe, provided that a content (wt %) ofeachofMn, S, Cr, and Mo satisfies the formula: ([Mn]−55×[S]/32+[Cr]+[Mo])>2.0 wt % and conducting the above operation in such a manner that the said alloy in a molten states satisfies the following conditions 1) through 3): 1) [HS/[HO]: 8 to 80, where [HS] and [HO] indicate the activity of S and O defined by the formula shown below.
[HS]=[S]×10logGs, and [HO]×10logFo
[HS] and [HO] indicate the activity of S and O defined by the formula shown below.
LogFs and logFo are defined by the following formula:
logFs=0.113[C]+0.065[Si]−0.025[Mn]+0.043[P]−0.028[S]−0.013[Cu]−0.011[Cr]+0.0027[Mo]−0.27[O]+0.024[N]+0.054 Al]
logFo=−0.44[C]−0.131[Si]−0.02[Mn]−0.147[P]+0.133[S]−0.0095[Cu]+0.006[Ni]−0.041[Cr]+0.0035[Mo]-1.00[O]−0.1834[N]−0.20[Al]+0.11[V]
The present inventors have made various other studies and completed the present invention.
Therefore the present invention relates to,
(1) A bainite-type untempered steel to be nitrided containing alloy compositions C: 0.05 to 0.8 wt %, Si: 0. 01 to 2.5 wt %, Mn:0.1 to 3.5 wt %, P: 0.001 to 0.2 wt %, S: 0.01 to 0.2 wt %, Cr: 1.0 to 3.5 wt %, V: 0.1 to 0.5 wt %, Al: 0.001 to 0.020 wt %, Ca: 0.0005 to 0.02 wt % and O: 0.0005 to 0.01 wt %, and the residue composed of unavoidable impurities and Fe, wherein an occupation area of a sulfide inclusion present in contact with an oxide inclusion containing 8 to 62 wt % of CaO and containing not less than 1.0 wt % of Ca is not less than 2.0×10−4 mm2 per visual field area of 3.5 mm2, provided that each content of the Mn, the S, and the Cr satisfy the following formula:
([Mn]−55×[S]/32+[Cr])>2.0
(where [ ] indicates wt % (wt/wt) of each element).
(2) A bainite-type untempered steel to be nitrided according to the above (1), further contains, in addition to the alloy components specified in the above (1), one or more element(s) selected from Mo: 2.0% or less, Cu: 2.0% or less, Ni: 4.0% or less, and B: 0.0005 to 0.01%, wherein the formula:
([Mn]−55×[S]/32+[Cr]+[Mo])>2.0
(where [ ] indicates wt % (wt/wt) of each element) is established when Mo is comprised.
(3) A bainite-type untempered steel to be nitrided according to the above (1) or (2) further containing one or two element(s) selected from Nb: 0.2% or less and Ti: 0.2% or less.
(4) A bainite-type untempered steel to be nitrided according to any one of the above (1) through (3), further containing one or more element(s) selected from Ta: 0.5% or less, Zr: 0.5% or less, and Mg: 0.02% or less.
(5) A bainite-type untempered steel to be nitrided according to any one of the above (1) through (4), further containing one or more element(s) selected from Pb: 0.4% or less, Bi: 0.4% or less, Se: 0.4% or less, and Te: 0.2% or less.
(6) A method of manufacturing untempered steel according to any one of the above (1) through (5), which comprises an alloy having alloy components specified in any one of the above (1) through (5) and the residue composed of unavoidable impurities and Fe, provided that each content of Mn, S, Cr, and Mo satisfies the formula: ([Mn]−55×[S]/32+[Cr]+[Mo])>2.0 (where [ ] indicates wt % (wt/wt) of each element), wherein an operation satisfying the following conditions 1) through 3) is performed:
(7) A nitrided product formed by shaping the bainite-type untempered steel according to any one of the above (1) through (5) into a configuration of a mechanical component part, followed by nitriding said shaped bainite-type untempered steel.
(8) A steel for a rocker arm, wherein a hard oxide in contact with a sulfide composed of MnS and CaS is dispersed in a matrix; the hard oxide contains Al2O3 and CaO; a ratio of the content of CaO to the hard oxide is 8.0 to 62% (wt/wt); a ratio of the content of Ca to the sulfide i 1.0 to 45% (wt/wt), and an occupation area of the sulfide in the steel is 2.0×10−4 to 1.0×10−1 mm2 per area of 3.5 mm2.
(9) A steel for a rocker arm according to the above (8) containing C: 0.1 to 0.5% (wt/wt), Si: 0.01 to 2.5% (wt/wt), Mn: 0.1 to 3.5% (wt/wt), P: 0.001 to 0.2% (wt/wt), S: 0.01 to 0.2% (wt/wt), Cr: 1.0 to 3.5% (wt/wt), V: 0.1 to 0.5% (wt/wt), Al: 0.001 to 0.02% (wt/wt), Ca: 0.0005 to 0.02% (wt/wt), and O: 0.0005 to 0.01% (wt/wt), and the residue composed of Fe and unavoidable impurities,
(10) A steel for a rocker arm according to the above (9) having an inner hardness of 20 to 35 HRC and having a structure of ferrite+bainite, wherein carbon equivalent Ceq indicated by ([C]+0.27×([Mn]−55×[S]/32)+0.31×[Cr]+0.3×[V]) (where [ ] indicates wt % of each element) is set in a range of 0.8 to 1.1% (wt/wt).
(11) A steel for a rocker arm according to the above (9) or (10), further containing one or more element(s) selected from Mo: ≦2.0% (wt/wt), Cu: ≦2.0% (wt/wt), Ni: ≦4.0% (wt/wt) and B: 0.0005 to 0.01% (wt/wt).
(12) A steel for a rocker arm according to any one of the above (9) through (11), wherein each content of elements Mn, S, and Cr satisfies the formula:
([Mn]−55×[S]/32+[Cr])>2.0 wt %
(where [ ] indicates wt % of each element);
(13) A steel for a rocker arm according to any one of the above (9) through (12), further containing one or two element(s) selected from Nb: ≦0.2% (wt/wt) and Ti: ≦0.2% (wt/wt).
(14) A steel for a rocker arm according to any one of the above (9) through (13), further containing one or more element(s) selected from Ta: ≦0.5% (wt/wt), Zr: ≦0.5% (wt/wt), and Mg: ≦0.02% (wt/wt).
(15) A method of manufacturing a steel for a rocker arm according to any one of the above (8) through (14), which comprises melting an alloy having alloy components specified in anyone of the above (8) through (14) and the residue composed of unavoidable impurities and Fe, provided that each content of Mn, S, Cr, and Mo satisfies the formula: ([Mn]−55×[S]/32+[Cr]+[Mo])>2.0 wt % (where [ ] indicates wt % (wt/wt) of each element, and conducting the above operation in such amanner that the said alloy inamolten states satisfies the following conditions 1) through 3):
(16) A rocker arm manufactured from the steel for a rocker arm according to any one of the above (8) through (14).
The reason for limiting the basic alloy composition of the to-be-nitrided bainite-type untempered steel of the present invention to the above weight percentages is as follows:
Carbon: 0.05% to 0.8%
Carbon is a necessary component for securing the strength of the steel. If the content of carbon is less than 0.05%, the steel has an insufficient strength. On the other hand, if the steel contains a large amount of carbon, the steel has low toughness and machinability. Therefore the upper limit of carbon is set to 0.8%.
Silicon: 0.01 to 2.5%
Silicon makes a component of the steel acting as a deoxidizing agent in an operation of melting an alloy and has a function of improving the hardenability. Thus, Si is necessary for untempered steel. This effect cannot be obtained if the content of Si is less than 0.01%. If a large amount of more than 2.5% of Si is added, ductility is lost and cracking tends to take place in plastic working.
Manganese: 0.1 to 3.5%
Manganese is an important element for generating a sulfide. If the content of manganese is 0.1%, the amount of the inclusion is insufficient. On the other hand, if the content of manganese exceeds 3.5%, the steel becomes hard and its machinability deteriorates.
Phosphorous: 0.001 to 0.2%
Phosphorous is positively contained at not less than 0.001% in the steel as a component for improving the machinability, particularly the property of a machined surface. However, phosphorous is disadvantageous for toughness. Thus phosphorous cannot be contained at 0.2% or more in the steel.
Sulfur: 0.01 to 0.2%
Because sulfur is a useful, or indispensable to be more accurate, component for improving the machinability of the steel, not less than 0.01% thereof is contained in the steel. If the content of the sulfur exceeds 0.2%, the steel loses its toughness and ductility, and the sulfur reacts with calcium to generate CaS. Since CaS has a high melting point, it presents obstacles to a casting process.
Chromium: 1.0 to 3.5%
To secure hardenability and hardness of a nitrided layer, not less than 1.0% of chromium is added to the steel. If a large amount of chromium is added, hot workability deteriorates and the steel cracks in a forging operation. Thus the upper limit of the addition amount of chromium is set at 3.5%.
Vanadium: 0.1 to 0.5%
To secure the softening-resistant property in nitriding treatment and allow a product to maintain the hardness of the surface layer thereof, at least 0.1% of V is added to the steel. When a large amount of V is added to the steel, the hardness of the steel increases and a yield strength ratio and a durability ratio decrease. Therefore the upper limit of the addition amount of V is set at 0.5%.
Aluminum: 0.001 to 0.020%
Aluminum is necessary for appropriately adjusting the composition of the oxide inclusion, thus not less than 0.001% of aluminum is added to the steel. The reason why the upper limit of aluminum is set at 0.2%, which is much lower that of the conventional nitrided steel, is that if the addition amount of aluminum exceeds 0.20%, an alumina cluster is generated and the machinability of the steel deteriorates.
Calcium: 0.0005 to 0.02%
Calcium is a very important component for the steel of the present invention. To contain Ca in a sulfide, it is essential to add not less than 0.0005% of Ca. On the other hand, if not less than 0.02% of Ca is added, said calcium sulfide having a high melting point is formed. Calcium sulfide presents obstacles to a casting process.
Oxygen: 0.0005 to 0.01%
Oxygen is an element necessary for forming an oxide. A large amount of CaS having a high melting point is formed in steel excessively deoxidized and presents obstacles to acastingprocess. Therefore the addition of at least 0.0005% and preferably more than 0.0015% of oxygen to the steel is necessary. On the other hand, if more than 0.01% of O is added, a large amount of a hard oxide is formed, which deteriorates the machinability of the steel and makes it difficult to form a desired calcium sulfide. Formula: ([Mn]−55×[S]/32+[Cr])>2.0
The condition shown by the above formula must be satisfied to form the structure of the to-be-nitrided untempered steel not of pearlite but of the structure containing bainite as its main component and a small amount of ferrite. The structure containing the bainite as its main component which is only hot-forged has a strength almost equal to that of hardened and tempered steel even, and allows nitrogen to have a higher diffusion speed than a structure containing the pearlite as its main component. Therefore the structure containing the bainite as its main component has an advantage of faster nitriding speed.
In addition to the above-described basic alloy composition, the to-be-nitrided untempered free-machining steel of the present invention is capable of additionally containing one or more element (s) belonging to the following group in a specified composition range in dependence on a demand for a product. Description is made on the action of each alloy component which can be arbitrarily added in its altered form and the reason the composition range thereof is limited.
Molybdenum: 2.0% or less
Because molybdenum enhances the hardenability of the steel, a proper amount thereof should be added to the steel. On the other hand, if a large amount of Mo is added, hot workability deteriorates and the steel cracks during a forging operation. Taking the manufacturing cost into account, the upper limit of the addition amount of Mo is set at 2.0%. In adding Mo to the steel, the condition formula for obtaining the above bainite structure changes as follows:
([Mn]−55×[S]/32+[Cr]+[Mo])>2.0
Copper: 2.0% or less
Copper makes the structure of the steel dense and increases its strength. The addition of a large amount of Cu is not preferable for both the hot workability and the machinability, thus upper limit of the addition of Cu is set at 2.0%.
Nickel: 4.0% or less
Similarly to Cr and Mo, Ni also enhances the hardenability, but is disadvantageous for the machinability of the steel. Taking this disadvantage and the manufacturing cost into account, the upper limit of the addition amount of Ni is set at 4.0%.
Boron: 0.0005 to 0.01%
The hardenability can be enhanced by the addition of a slight amount of B. To obtain this effect, it is necessary to add not less than 0.0005% of B to the steel. It is disadvantageous to add more than 0.01% of B to the steel because the hot workability deteriorates. One or two selected from Nb: 0.2% or less and Ti: 0.2% or less
Nb and Ti are useful for preventing crystalline grains from becoming coarse at a high temperature. The extent of the effect is maximized and does not change with an increase of the amount thereof. Thus it is advisable to add them at 0.2% or less.
Tantalum: 0.5% or less, zirconium: 0.5% or less, manganese: 0.02% or less
These elements have an action of making crystalline grains fine and improving the toughness of the steel. Thus it is preferable to add one or more of these elements to the steel. It is advisable to add the element(s) up to the upper limit of 0.5%, at which the extent of the effect is maximized and does not change even though more than 0.5% thereof is added.
Lead: 0.4% or less, bismuth: 0.4% or less, selenium: 0.4% or less, and tellurium: 0.2% or less
Each of these elements has an action of improving the machinability. Lead is present independently or attaches to the periphery of a sulfide, and lead itself improves the machinability. The upper limit of 0.4% is determined for the reason that, if not less than 0.4% of Pb is added it is not dissolved in the steel but is aggregated and deposited, making the steel defective. The same reason is applied to Bismuth. The upper limit of the addition amount of each of selenium and tellurium is set in consideration of bad influence on hot workability.
The inclusion present inside the to-be-nitrided untempered free-machining steel according to the present invention has a double structure, as described above. An analysis made by EPMA (JXA8800 manufactured by Nippon Denshi Kabushiki Kaisha) proved that the core of the inclusion is composed of an oxide of each Ca, Mg. Si, and Al, and Manganese sulfide containing CaS surrounds the core. The presence form of the inclusion is that the occupation area of the sulfide inclusion present in contact with the oxide inclusion containing 8 to 62 wt % of CaO and containing not less than 1.0 wt % of Ca is not less than 2.0×10−4 mm2 per visual field area of 3.5 mm2. Such a form of the inclusion is necessary to achieve a high machinability targeted in the present invention through a mechanism which will be described later. The condition for realizing such a form of the inclusion becomes the operation condition for the said manufacture. The significance of the condition is described below.
Data obtained from experiments relating to the condition 1) is as shown in
The present inventors think that the reason for the to-be-nitrided bainite-type untempered steel of the present invention showing excellent machinability is the below-mentioned favorable protection of the surface of a tool and the lubricating mechanism due to the free-machining component of sulfide form control type.
As described above, the core of the free-machining component of sulfide form control type is composed of a CaO.Al2O3-based composite oxide surrounded with a (Ca, Mn)S-based composite sulfide. Among the CaO—Al2O3-based composite oxides, the said oxide has a low melting point, while the said composite sulfide has a higher melting point than a simple sulfide MnS. In the free-machining component of sulfide form control type, the sulfide securely deposits with the sulfide surrounding the oxide when the oxide is composed of the CaO—Al2O3-based oxide having a low melting point. It is well known that inacutting operation, asulfide inclusion melts and coats, thus protecting the surface of a tool, however, in case only the sulfide is present, the formation and maintenance of a formed coating are unstable. The present inventors have found that when the CaO—Al2O3-based oxide having a low melting point is present together with the sulfide inclusion, the coating is formed stably, and the (Ca, Mn)S-based composite sulfide has higher lubricating property than a simple MnS.
The significance of the coating the (Ca, Mn)S-based composite sulfide forms on the surface of the tool is admitted most clearly in cutting made by a carbide tool. That is, significance of the coating is wear-suppressing effect of a carbide tool called “thermal diffusion wear”. Describing the thermal diffusion wear, when the tool contacts chip generated from a workpiece at a high temperature, a carbide represented by tungsten-carbide constructing the material of the tool is thermally decomposed. As a result, C is lost by diffusing into the metal of the chip and thus the tool becomes frail, which makes wear progress. Temperature rise of the tool is prevented by the coating having high lubricating property formed on the surface of the tool, thereby diffusion of C is suppressed.
In a different point of view, it can be said that the free-machining component of sulfide form control type CaO—Al2O3/(Ca, Mn)S of the free-machining steel according to the present invention has both advantages of MnS which is the inclusion of the conventional sulfur free-machining steel and anorthite CaO.Al2O3.2SiO2 which is the inclusion of the conventional calcium free-machining steel. The MnS on the surface of the tool shows lubricating property but the stability of the coating is not sufficient. Thus it is vulnerable to the thermal diffusion wear. The CaO.Al2O3.2SiO2 prevents the thermal diffusion wearby forming a stable coating, but has low lubricating property. On the other hand, the free-machining component of sulfide form control type according to the present invention effectively prevents the thermal diffusion wear by forming a stable coating and shows favorable lubricating property.
The generation of the free-machining component of sulfide form control type starts from preparation of the composite oxide having a low melting point as described above, so the amount of aluminum is important, and at least 0.001 wt % of the Al is necessary. The amount of Al should be 0.020 wt % or less, because, if the amount of Al is too much, the melting point of the composite oxide becomes high. To adjust the generation amount of CaS, [Ca]X [S] and [Ca]/[S] are adjusted to the above-described values.
As described later, the steel for a rocker arm of the present invention has machinability equivalent to that of the known Pb free-machining steel, nitriding property superior in a nitrided layer depth or the like, and a strength equal to that of the known tempered steel, although the steel is not tempered. To manufacture the steel for a rocker arm having the said properties, an alloy having alloy components specified as will be described later and the residue having a chemical composition composed of unavoidable impurities and Fe, wherein wt % of each of Mn, S, Cr and Mo of the alloy is required to satisfy the formula:
([Mn]−55×[S]/32+[Cr]+[Mo])>2.0% (wt/wt)
(where [ ] indicates wt % (wt/wt) of each element of the alloy) is melted.
In the above, the operation is carried out in the way that the alloy in molten states satisfies the following conditions 1) through 3):
Description is made below on the reason for controlling the form and the chemical composition of the hard oxide in contact with the sulfide which is the inclusion of the steel for a rocker arm of the present invention.
Hereinafter, the content (%) of each element is indicated by wt %.
With regard to the hard oxide in contact with the sulfide, the ratio of the content of CaO to the entire hard oxide (for example, CaO.Al2O3-based oxide) is 8.0 to 62%. The ratio of the content of Ca to the entire sulfide is 1.0 to 45%. The occupation area of the sulfide in the entire steel is 2.0×10−4 mm2 to 1×10−1 mm2 per 3.5 mm2, which can be confirmed by face analysis using an electron microscope EPMA (JXA8800 manufactured by Nippon Denshi Kabushiki Kaisha).
When the content of the Ca is not less than 1.0%, a tool protection coating of (Ca.Mn)S is formed sufficiently on the surface of a tool when a cutting operation is performed, thereby desired machinability can be obtained. In the steel composed of the above-described chemical composition, the sulfide contains MnS as its main component, and CaS is formed by substituting a part of Mn with Ca. It is necessary, however, to prevent the sulfide from having various properties in dependence on the extent of the substitution of Mn with Ca and prevent the formation of the tool protection coating from being difficult. To obtain desired machinability, it is preferable to adjust the content of the Ca to not more than 45%.
According to the present invention, when Mn and Ca are added in the amount within the range of above-described composition, it is possible to improve the life of the tool and obtain both superior machinability and castability. To improve the machinability, the occupation area of the sulfide in the steel is preferably not less than 2.0×10−4 mm2 per3.5 mm2 and more preferably not more than 1.0×10−1 mm2 per 3.5 mm2 to also obtain superior castability.
Also, when Ca, Al and O are contained within the range of above-described composition, it is possible to adjust the generation amount of CaO oxide to a specified range and prevent generation of a large amount of CaS having a high melting point which deteriorates castability. Thereby it is possible to form the free-machining component of sulfide form control type whose anisotropy does not deteriorate and which has excellent machinability. To obtain machinability to a higher extent, it is preferable to set the content of the CaO in the entire hard oxide to not less than 8.0%. To prevent deterioration of castability, it is preferable to set the content of the CaO in the entire hard oxide to not more than 62%.
The chemical composition of each of the elements contained in the steel for a rocker arm of the present invention is described below.
Carbon: 0.1 to 0.5%
Carbon is a necessary component for securing the strength of the steel. To allow the steel to securely obtain a higher strength, not less than 0.1% of carbon is necessary. To avoid decrease of the toughness and machinability of the steel, it is preferable to set the content of carbon to at 0.5% or less.
Silicon: 0.01 to 2.5%
Silicon is contained as a deoxidizing agent in a melting operation. In addition, Si has an action of improving the hardenability. To secure preferable hardenability, it is necessary to add not less than 0.01% of Si to the steel. To secure superior ductility and prevent the steel from cracking in plastic working, it is preferable to add not more than 2.5% of Si to the steel.
Manganese: 0.1 to 3.5%
Manganese is an element for forming the free-machining component of sulfide form control type. To form better free-machining component, it is preferable to add not less than 0.1% of Mn to the steel. To obtain superior machinability, it is preferable to add not more than 3.5% of Mn to the steel.
Phosphorous: 0.001 to 0.2%
Phosphorous is added to the steel to improve the machinability, and particularly the property of the machined surface of the steel. To improve the machinability and the property of the machined surface of the steel to a higher extent, it is preferable to add not less than 0.001% of P to the steel. To allow the steel to have a higher ductility, it is preferable to add not more than 0.2% of P to the steel.
Sulfur: 0.01 to 0.2%
Sulfur is an element for forming the free-machining component of sulfide form control type. To form better free-machining components, it is preferable to add not less than 0.01% of S to the steel. To obtain superior machinability, it is preferable to add not more than 0.2% of S to the steel.
Chromium: 1.0 to 3.5%
Chromium is an element effective for improving hardenability and securing surface hardness, depth, and softening-resistant property in nitriding treatment by an appropriate combination of the addition amount of Cr with that of V. To allow the steel to have the said better properties, it is preferable to add not less than 1.0% of Cr. To manufacture the steel at a low cost and prevent cracking of the steel in a hot working operation, it is more preferable that the addition amount of Cr is not more than 3.5%.
Vanadium: 0.1 to 0.5%
Vanadium is an element effective for securing surface hardness, depth, and softening-resistant property in nitriding treatment by an appropriate combination of the addition amount of Cr with that of V. The V combines with C and N to form a carbonitride and has the effect of making crystalline grains fine. To secure the softening-resistant property in the nitriding treatment, it is preferable to add not less than 0.1% of V to the steel. To reduce the manufacturing cost, it is preferable to add not more than 0.5% of V.
Aluminum: 0.001 to 0.02%
Aluminum is an element necessary for deoxidization. To obtain sufficient deoxidizing effect, addition of not less than 0.001% of Al is preferable. The addition of not more than 0.02% of Al is preferable to prevent generation of a hard alumina cluster which deteriorates the machinability of the steel, makes it difficult to form the free-machining component of sulfide form control type, and deteriorates the anisotropy of the steel.
Calcium: 0.0005 to 0.02%
Calcium is an element very important for the steel of the present invention. Ca is an element for forming the free-machining component of sulfide form control type. To obtain superior effect of Ca, it is preferable to add not less than 0.0005% of Ca to the steel. To prevent formation of an excessive amount of CaS having a high melting point due to the excessive addition of Ca, it is preferable to add not more than 0.02% of Ca to the steel.
Oxygen: 0.0005 to 0.01%
Oxygen is an element necessary for forming an oxide in the free-machining component of sulfide form control type. To form a preferable oxide, the addition of not less than 0.0005% of O is preferable. To form a more preferable oxide, the addition of not less than 0.0015% is preferable. To form a Ca sulfide in the free-machining component of sulfide form control type and also allow the steel to have favorable machinability, the addition of less than 0.01% of O is preferable.
In addition to the above-described components, one or not less than two elements selected from Mo, Cu, Ni, and B may be added to the steel for a rocker arm of the present invention. In addition to these elements, one or two elements selected from Nb and Ti and one or more element(s) selected from Ta, Zr and Mg may be added to the steel. These elements of alloy may be contained in the steel of the present invention in various combinations in dependence on purpose. The effect of these elements of alloy and the reason for controlling the content thereof will be described below.
Molybdenum: ≦2.0%
Similarly to Cr, molybdenum is an effective element for improving hardenability. It is preferable to add not more than 2.0% of Mo to allow the steel to be manufactured at a low cost, to be highly machinable, and improve hot workability.
Copper: ≦2.0%
Copper is an element effective for making the structure of the steel dense and increasing its strength. It is preferable to add not more than 2.0% of Co to allow the steel to be highly machinable and improve hot workability.
Nickel: ≦4.0%
Similarly to Cr, Niis an effective element for improving the hardenability of the steel. It is preferable to add not more than 4.0% of Ni to allow the steel to be manufactured at a low cost and to be highly machinable.
Boron: 0.0005 to 0.01%
The hardenability of the steel can be enhanced by the addition of a slight amount of B. To obtain better hardenability, it is preferable to add not less than 0.0005% of B to the steel. It is preferable to add not more than 0.01% of B to improve the hot workability and prevent crystalline grains from becoming coarse.
Niobium: ≦0.2%
Nb is an effective element for preventing crystalline grains from becoming coarse at high temperatures. It is preferable to add not more than 0.2% of Nb to manufacture the steel at a low cost and also obtain a higher effect.
Titanium: ≦0.2%
Ti combines with N in nitriding treatment to form TiN, thus allowing B to display hardenability-improving effect. It is preferable to add not more than 0.2% of Nb to form TiN favorably and improve the hot workability.
Tantalum: ≦0.5%
Ta is an element effective for making crystalline grains fine and improving the toughness of the steel. It is preferable to add not less than 0.5% of Ta to manufacture the steel at a low cost and also obtain higher effect.
Zirconium: ≦0.5%
Zr has properties similar to that of Ta, and is an effective element for making crystalline grains fine and improving the toughness of the steel. It is preferable to add not more than 0.5% of Zr to manufacture the steel at a low cost and also obtain higher effect.
Magnesium: ≦0.02%
Mg has properties similar to that of Ta and Zr, and is an effective element for making crystalline grains fine and improving the toughness of the steel. It is preferable to add not more than 0.02% of Mg to manufacture the steel at a low cost and also obtain higher effect.
As the control (1) of the chemical component, the content of Cr and V are adjusted to satisfy the formula of ([Cr]+1.97×[V])≧2.15% (wt/wt).
In performing nitriding treatment of the steel for a rocker arm of the present invention, the content of Cr and V are adjusted to satisfy the formula of ([Cr]+1.97×[V])≧2.15 wt %. Thereby the surface hardness of not less than 750 HV is obtained in a gas nitrocarburizing condition (for example, 580° C.×3 hr) and the nitrided layer depth and the softening-resistant property in the nitriding treatment can be preferably improved. That is, the steel is allowed to have a preferable nitriding property.
As the control (2) of the chemical component, the content of Mn, S, and Cr are adjusted to satisfy the formula of ([Mn]−55×[S]/32+[Cr])>2.0 wt % or the content of Mn, S, Cr, and Mo are adjusted to satisfy the formula of ([Mn]−55×[S]/32+[Cr]+[Mo])>2.0 wt %.
To further improve productivity in manufacturing a rocker arm product from the steel for a rocker arm of the present invention, it is preferable to form the structure of the untempered ferrite+bainite which is formed after the hot-forged steel is cooled and which has a strength almost equal to that of the tempered steel. By adjusting the content of the elements Mn, S, and Cr or the content of the elements Mn, S, Cr, and Mo to satisfy the above formula, the steel is allowed to have a favorable structure after hot forging is carried out.
To control the carbon equivalent Ceq indicated by ([C]+0.27×([Mn]−55×[S]/32)+0.31×[Cr]+0.3×[V]), the Ceq is adjusted within the range of 0.8 to 1.1 wt %.
Further, the present inventors have found that to allow the rocker arm product to have superior machinability and preferable fatigue strength after nitriding treatment is performed in manufacturing the rocker arm product by hot forging from the steel for a rocker arm of the present invention, it is preferable to set the inner hardness of the steel within the range of 20 to 35 HRC, supposing that a test is conducted in accordance with JIS;Z2245. The said inner hardness can be easily obtained by adjusting the content of C, Mn, S, Cr, and V in the steel for a rocker arm having above-mentioned basic components within the above range of Ceq.
In examples A1 to A17 and comparison examples a1 to a8, steels each having an alloy composition shown in tables 1 and 2 were melted in a 5-ton arc furnace to cast them into ingots. To form hard oxides covered with sulfide coatings in melting the steels, the content of elements S, Al, Ca, and O in each steel was adjusted to values shown in tables 1 and 2 using an FS shot, a CaSi shot, and an Al shot as a sulfur source, a calcium source, and an aluminum source respectively. Each ingot was hot-forged to a round rod having a diameter of 15 mm or 22 mm. In addition to the composition of each alloy, the value of each of [HS]/[HO], [Ca]×[S] and [Ca]/[S] is shown in tables 1 and 2.
Hot-forged steels were allowed to air-cooled and then gas-nitrided at 580° C. for three hours. The surface hardness (HV) of each nitrided steel, the depth of hardened layer (depth of layer having hardness not less than 450HV) thereof, the hardness (HRC) of the core thereof, and the ductility thereof were measured.
The relationship between the surface hardness of each nitrided steel after nitriding and the drilling efficiency ratio thereof was plotted.
The steel for a rocker arm of the present invention will be described below in conjunction with the following examples.
Steels each having a chemical composition shown in tables 5 and 6 were melted in a 5-ton arc furnace or a 150 kg high-frequency vacuum induction furnace. To form a hard oxide in contact with a sulfide, FeS grains, CaSi grains, and Al grains were used as a sulfur source, a calcium source, and an aluminum source respectively. The content of S, Al, Ca, and O in each steel was adjusted to values shown in tables 5 and 6. Each of obtained ingots was rolled or forged to a round rod having a diameter of 25 mm. The steels shown in table 6 were examined after nitriding treatment was conducted. With regard to the comparison steels, an SCr435HL steel (comparison steel; b1) shown in table 5 was adopted to examine the machinability of each steel, and an SAC430AL steel (comparison steel; b2) shown in table 6 was adopted and to examine the nitriding property of each steel.
Firstly, to evaluate the machinability of the steel of the present invention, the machinability of the steel of the present invention was compared with the cutting resistance and cutting torque of the known SCr435HL steel containing 0.2% of Pb serving as a free-machining component in the same cutting condition. The wear degree of a tool in a cutting operation was evaluated by comparing the observation of the wear state of the cutting face of the tool after the cutting operation finished. The smaller the value of the cutting resistance and the cutting torque are in relation to the SCr435HL steel, the better the machinability of the steel is. Also, the lower the wear degree of the tool is, the better the machinability of the steel is. Thus, synthetic evaluation of the machinability of the steel of the present invention shown in Table 5 is judged based on the above-described determining method.
To obtain data of the cutting resistance and the cutting torque shown in table 5, a commercially-available rotary cutting dynamometer (9123C manufactured by Kisler Inc.) was mounted on a spindle of NC milling machine (VF-Center manufactured by Enshu Seisakusho) which is a commonly used machine, and cutting processing was carried out with a φ16.5 drill provided on a chucking portion of the said rotary cutting dynamometer when a φ16.5 opening was formed and with a φ18 reamer provided on the chucking portion thereof to perform finish machining of a φ18 opening. A voltage output value obtained from the rotary cutting dynamometer was measured in each cutting operation. As the cutting conditions, in the drilling operation performed with φ16.5 drill, rotational frequency of the spindle: 2500 rpm, feeding amount: 150 m/min, and cutting amount: 0.080 mm per rotation were employed; and in the finish machining of the φ18 reamer opening, rotational frequency of the spindle: 2000 rpm, feeding amount: 400 m/min, and cutting amount: 0.200 mm per rotation were employed. Both operations were performed bywet process (non-aqueous cutting oil; Cutting Lubricant X-5 produced by General Sekiyu).
As an example, the graphs shown in
Table 5 and
Next, to evaluate the nitriding property of the steel of the present invention, under a gas nitrocarburizing condition (for example, 580° C.×3 hr[RX:NH3=200:700(CFH)]), comparison was made between the above-described SAC430AL steel which is the conventional nitrided steel and the steel of the present invention on the transition of the nitrided layer depth to determine the nitriding property, based on the sectional hardness and the nitrided layer depth in the neighborhood of the surface of each steel. When the sectional hardness in the neighborhood of the surface of the steel of the present invention was equivalent of or harder than that of the surface of the SAC430AL steel and also the nitrided layer depth of the former was equivalent of or larger than that of the latter in the same nitriding condition, it was determined that the former had favorable nitriding property. The synthetic evaluation of the nitriding property of the steel of the present invention shown in table 6 was made based on the above-described determination method.
A graph of
As apparent from table 6 and
The results of the observation and analysis made by the EPMA reveal that the form of said free-machining component of sulfide form control type is controlled in a spherical shape as shown in an SEM photograph of
As shown by the photograph of structure obtained by using a metal microscope shown in
Steels each having the chemical composition shown in table 7 were melted in a 5-ton arc furnace or a 150 kg high-frequency vacuum induction furnace, and each steel ingot obtained was hot-forged at 1200° C. to a round rod having a diameter of 20 mm, and thereafter allowed to cool. The hardness of the inside of the round rod having a diameter of 20 mm was examined, and the results shown in table 7 and
Table 7 and
As described above, since the softening-resistant property after nitriding treatment is secured in the steel of the present invention, it is possible to restrain nitriding-caused reduction of the internal hardness and impart good fatigue strength to the steel after nitriding treatment is performed. Thereby it is possible to produce rocker arm products superior in the strength property.
Steels each having the chemical composition shown in table 8 were melted in the 5-ton arc furnace or the 150 kg high-frequency vacuum induction furnace, and each steel ingot obtained was hot-forged at 1200° C. into a desired configuration, and thereafter allowed to cool. Then the steel ingots formed into a desired configuration were processed into the configuration of a JIS-14A specimen, and after that, gas nitrocarburizing treatment (580° C.×1.5 hr[RX:NH3=200:450(CFH)] was carried out to examine the tensile strength. Table 8 and
Table 8 and FIG. 11 indicate that the steel of the present
invention is allowed to have the structure of the ferrite+bainite in a condition where the steel is hot-forged and cooled. Thus it is possible to improve the tensile strength of the steel, thereby it is possible to manufacture the steel for a rocker arm excellent in the strength property.
The inclusion providing high machinability, specifically the free-machining component of sulfide form control type is present in the most suitable form in the to-be-nitrided bainite-type untempered steel of the present invention. Therefore it becomes possible to realize the superior machinability.
Until now, the form of inclusions imparting preferable machinability to the steel has been investigated to some extent in various free-machining steels. However, there has been no satisfactory means for forming such inclusions providing superior machinability with high reproducibility. The present invention has overcome the problem of the conventional art in this regard, and is capable of manufacturing the bainite-type untempered free-machining steel to-be-nitrided which constantly has excellent machinability by producing in such a way satisfying the above-described operating conditions.
The distinctive advantage of the to-be-nitrided bainite-type untempered steel of the present invention is that, without adding Pb which has been indispensable for improving the machinability of this type of nitrided steel in conventional methods, the steel is provided with machinability equal to or higher than that of the conventional steel containing Pb. It is well known that the use of Pb tend to cause problems in environment where steel is manufactured or processed, and using and discarding of Pb are not preferable, therefore nowadays efforts are made to the utmost to avoid the use of Pb.
The steel for the rocker arm of the present invention has machinability equivalent to that of the known Pb free-machining steel and is superior in nitriding property such as a nitrided layer depth. Further, a strength equivalent to that of the known tempered steel can be obtained even it is not tempered. Therefore it is possible to manufacture rocker arm products from various kinds of steel at a low cost and with high productivity.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2002-19412 | Jan 2002 | JP | national |
| 2002-19750 | Jan 2002 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP03/00694 | 1/24/2003 | WO |
