CN101187313A - Exhaust guide assembly for variable giometry shape turbocharger with improved high-temperature endurance - Google Patents
Exhaust guide assembly for variable giometry shape turbocharger with improved high-temperature endurance Download PDFInfo
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- CN101187313A CN101187313A CNA2007101407119A CN200710140711A CN101187313A CN 101187313 A CN101187313 A CN 101187313A CN A2007101407119 A CNA2007101407119 A CN A2007101407119A CN 200710140711 A CN200710140711 A CN 200710140711A CN 101187313 A CN101187313 A CN 101187313A
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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Abstract
A novel exhaust gas guide assembly with an improved high-temperature wear resistance, oxidation resistance, high-temperature strength or the like for a VGS turbocharger is provided. According to the invention, the exhaust gas guide assembly (A) for a VGS turbocharger including adjustable blades (1), a turbine frame (2) and an adjusting mechanism (3) is characterized in that a novel heat resisting member constitute the exhaust gas guide assembly (A) to remarkably enhance high-temperature durability or the like of the exhaust gas guide assembly (A).
Description
The application is in the first to file (applying date: on May 10th, 2002; Application number: 028139240; Dividing an application denomination of invention: the exhaust gas guide assembly of the VGS type turbosupercharger that heat resistance is improved, the raw-material manufacture method that can be applicable to the manufacture method of heat-resistant part wherein and can be applicable to variable sweep wing wherein).
Technical field
The present invention relates to the turbosupercharger used in the motor car engine etc., particularly be assembled in wherein exhaust gas guide assembly and the variable sweep wing of one component parts.
Background technique
The pressurized machine that uses as making motor car engine realize high output, high performance a kind of device, turbosupercharger is known, this is that a kind of exhaust energy of motor that utilizes drives turbine, output by this turbine makes the compressor rotation, thereby makes motor be in the device of the pressurized state when being higher than natural aspiration.But, this turbosupercharger is when low engine speed is rotated, because extraction flow reduces and the not smooth sensation of work can occur before the rotation of exhaust driven gas turbine high efficiency, and needs a period of time to supercharging at one stroke afterwards, phenomenons such as so-called turbo-lag take place unavoidably.In addition, in the originally lower diesel engine of engine speed, exist the shortcoming that is difficult to obtain the turbosupercharging effect.
For this reason, even developed the variable geometry turbocharger that also can work expeditiously from slow-speed of revolution section.This is a kind of less air displacement to be carried out throttling with variable sweep wing (sheet), to improve the speed of exhaust, increase the acting amount of exhaust driven gas turbine, even thereby also can reach the turbosupercharger of high output during low speed rotation, particularly becoming the diesel engine that needs the problem that solves for the amount of the NOx in the discharging waste gas in recent years, is to make motor just can reach high efficiency a kind of effective turbosupercharger from the low speed rotation time-out.
Exhaust gas guide assembly in this variable geometry turbocharger uses under the high-temp waste gas atmosphere, what it made use always is to have stable on heating raw material, heat-resistant materials such as JIS standard, SUS, SUH, SCH, NCF superalloy for example, but owing to be under very harsh condition, to use, thereby its life-span durability has certain limit, and people wish further to improve its durability.
During variable sweep wing in making variable geometry turbocharger, be at first to form the raw material metal (the former material of shaping) that alar part and axial region are integrally formed with variable sweep wing appearance, again processing such as the former material of this shaping suitably cuts are finish-machined to desirable shape and size, and methods such as common precision casting and metal injection moulding, it is very difficult wanting the former material of the shaping of variable sweep wing is finish-machined to intimate net shape (near-net shape), present situation does not reach the stage of producing variable sweep wing in reality with the high level of all-the-time stable in enormous quantities as yet, from realizing mass production, also need to overcome the above problems.
In addition; in recent years; diesel engine particularly; consider to have proposed very strict restriction from environmental protection for exhaust gas discharged to atmosphere; as the originally lower diesel engine of engine speed; in order to reduce NOx and particulate matter (PM) etc., also urgent hope can reach high efficiency variable geometry turbocharger from slow-speed of revolution section motor and can realize mass production.
The understanding that the present invention is based on above-mentioned background proposes, for the long-term exhaust gas guide assembly that uses under the thermal cycle that is attended by high temperature more than 700 ℃, the waste gas atmosphere, raising with regard to performances such as the high temperature wear of its component parts, oxidative stability, high temperature hardness is attempted, in addition, also just by solving the problem that methods such as above-mentioned precision casting and metal injection moulding exist and utilizing these methods, the exploitation of novel manufacturing method that can obtain being close to the shaped material for adjustable blade applicable thereto of net shape in reality is attempted.
Summary of the invention
In addition, the exhaust gas guide assembly of the variable geometry turbocharger that technological scheme 1 described heat resistance is improved is that the flow with waste gas that motor is discharged is suitably regulated so that the variable sweep wing of exhaust driven gas turbine rotation, this variable sweep wing is supported in the turbine frame on the peripheral part of exhaust driven gas turbine free to rotately, and can makes this variable sweep wing suitably rotate changeable mechanism so that the flow of waste gas is regulated;
Less extraction flow is carried out throttling with variable sweep wing, improves the speed of exhaust,, it is characterized in that even also can reach the exhaust gas guide assembly in the turbosupercharger of variable geometry turbocharger of high output during low speed rotation,
Constitute the heat-resistant part of described exhaust gas guide assembly, use be superalloy.
In addition, the exhaust gas guide assembly of the variable geometry turbocharger that technological scheme 2 described heat resistances are improved, it is characterized in that, constitute the technological scheme 1 described heat-resistant part of described exhaust gas guide assembly, be formed with the overlay film of chromium carbide, titanium carbide, tungsten carbide, vanadium carbide, niobium carbide or molybdenum carbide on its surface.
Here, the chromium carbide as the overlay film composition has Cr
23C
6, Cr
7C
3, Cr
3C
2Deng, particularly from the angle of film forming, high temperature wear with Cr
7C
3For good; As titanium carbide, TiC, Ti are arranged
2C etc. are good with TiC from the angle of film forming, high temperature wear particularly; As tungsten carbide, WC, W are arranged
2C etc. are good with WC from the angle of film forming, high temperature wear particularly; As the molybdenum carbide, MoC, Mo are arranged
2C etc. are good with MoC from the angle of film forming, high temperature wear particularly.In addition, as vanadium carbide, niobium carbide, be advisable with VC, NbC respectively.
In addition, described superalloy is specifically can list Incoloy 800H, Incoloy 825, inconel 713C, IN-100, MAR-M246, Hasteloy S etc. at 700～1050 ℃ of heat resisting alloy that use down.
Description of drawings
Fig. 1 is the stereogram (a) of variable geometry turbocharger involved in the present invention, and the exploded perspective view of exhaust gas guide assembly (b),
Fig. 2 is plan view and the left side view as the variable sweep wing of a component parts of exhaust gas guide assembly,
Fig. 3 is the temperature and the viscosity relationship curve of Ni base heat-resistant material and Fe base heat-resistant material.
Embodiment
Below the present invention will be described.The present invention at first describes the exhaust gas guide assembly that is made of so heat-resisting raw material for the high temperature durability of the exhaust gas guide assembly A that improves variable geometry turbocharger and various heat-resisting raw material researchs are developed.Heat-resisting raw material are divided into following 8 classes, that is, form of implementation 1, form of implementation 2, form of implementation 3, form of implementation 4, form of implementation 5, form of implementation 6, form of implementation 7, form of implementation 8.
[1] exhaust gas guide assembly
Exhaust gas guide assembly A is used for when low engine speed is rotated waste gas G suitably being carried out throttling to regulate extraction flow especially, an one example as shown in Figure 1, have, be arranged on periphery, the substantive a plurality of variable sweep wings 1 of setting extraction flow of exhaust driven gas turbine T, variable sweep wing 1 is supported the turbine frame 2 that makes it free to rotate, and make variable sweep wing 1 rotate the changeable mechanism 3 of set angle for the flow of the waste gas G that suitably adjusts.Below, each component part is described.
At first variable sweep wing 1 is described.An one example is circular arc along the periphery of exhaust driven gas turbine T and is equipped with a plurality of (having an appointment about 10 to 15 on the exhaust gas guide assembly A) as shown in Figure 1, and its each variable sweep wing rotates substantially identical degree at every turn extraction flow is carried out suitable adjusting.In addition, each variable sweep wing 1 has alar part 11 and axial region 12.Alar part 11 forms mainly corresponding to the width dimensions of exhaust driven gas turbine T has certain width, and its section on width direction is the wing shape approximately, so that waste gas G can enter exhaust driven gas turbine T effectively.Here, for ease of illustrating, the width dimensions of alar part 11 is established made fin height h.Axial region 12 forms that to be integral ground mutually continuous with alar part 11, is the part that is equivalent to make the rotatingshaft that alar part 11 rotates.
In addition, at the two connected portion of alar part 11 and axial region 12, the flange 14 that tapered portion 13 that narrows down to alar part 11 from axial region 12 that being formed with is connected with each other forms continuously and diameter are a bit larger tham axial region 12.The end face of axial region 12 1 sides of the bottom surface of flange 14 and alar part 11 is formed on same substantially, by means of this plane, can guarantee that variable sweep wing 1 rotates sleekly under the state that is installed on the turbine frame 2.And, at the front end of axial region 12, be formed with reference level 15 as the installment state benchmark of variable sweep wing 1.To be aftermentioneds be fixed on position on the changeable mechanism 3 by modes such as riveted joints to this reference level 15, and an one example is axial region 12 relatively to be excised and the plane that forms is certain skewed morphogenetic substantially with respect to alar part 11 as shown in Figure 1 and Figure 2.
Below turbine frame 2 is described.This constitutes as a kind of frame parts that a plurality of variable sweep wings 1 are kept making it free to rotate, and an one example is clipped in the middle variable sweep wing 1 with frame assembly 21 and holding member 22 as shown in Figure 1.And, the axial region 12 that frame assembly 21 has a variable sweep wing 1 can insert wherein flange part 23 and as described later changeable mechanism 3 can be embedded in hub portion 24 on its periphery.According to this configuration, equally spaced form the patchhole 25 identical at the peripheral position of flange part 23 with the quantity of variable sweep wing 1.
In addition, holding member 22 is the discoid formation of central position opening as shown in Figure 1.And, size between 22 two parts of said frame assembly 21 and holding member keeps necessarily (width dimensions that is about the wing of variable sweep wing 1) substantially, all the time can rotate sleekly so that be clipped in the alar part 11 of the variable sweep wing 1 in the middle of them, as an example, utilize four rivet pin 26 at the periphery position that is located at patchhole 25 that two sizes between the parts are kept.In order to insert above-mentioned rivet pin 26, will be opened in hole on frame assembly 21 and the holding member 22 here, as pin-and-hole 27.
In this form of implementation, two flange portions of flange part 23B that the flange part 23 of frame assembly 21 is a bit larger tham holding member 22 by the identical substantially flange part 23A of diameter and holding member 22, with diameter constitute, they form parts, but making the occasion that parts can make processing become very complicated, also can form two flange parts that diameter is different respectively, connect to one by processing such as riveted joint or hard soldering afterwards.
Below changeable mechanism 3 is described.It is arranged on the periphery of the hub portion 24 of turbine frame 2, be to order about the mechanism that variable sweep wing 1 rotates in order to regulate extraction flow, an one example has substantially make rotatable parts 31 that variable sweep wing 1 rotates and the transferring elements 32 that this rotation is passed to variable sweep wing 1 in assembly as shown in Figure 1.Rotatable parts 31 are the porose discoid approximately formation of central position as shown in the figure, and the transferring elements 32 identical with variable sweep wing 1 quantity uniformly-spaced is set at its peripheral position.This transferring elements 32 has and is installed on the rotatable parts 31 and the driving key element 32A that can rotate freely and be installed in fixing state and be subjected to key element 32B on the reference level 15 of variable sweep wing 1, in above-mentioned driving key element 32A and the transmission that is subjected to realization rotation under the key element 32B state connected to one another.Specifically, the quadrilateral sheet is driven key element 32A to be fixed on pin and to make it on the rotatable parts 31 and can rotate freely, simultaneously, the key element 32B that is subjected to that will approximately be that the U font forms in order to embed this driving key element 32A is fixed on the reference level 15 of front end of variable sweep wing 1, at last rotatable parts 31 are installed in the hub portion 24, make the quadrilateral sheet drive key element 32A embedding U font and be subjected among the key element 32B, the two engages with each other.
Under the initial conditions that a plurality of variable sweep wings 1 have been installed, upwards arrange regular in order to make them in week, the two will install with certain substantially angle each variable sweep wing 1 with being subjected to key element 32B, in this form of implementation, mainly brings into play this effect by the reference level 15 of variable sweep wing 1.In addition, if rotatable parts 31 just embed in the hub portion 24 simply, then when rotatable parts 31 break away from turbine frame 2 a little, the fastening state of transferring elements 32 just can be removed, for preventing the generation of this situation, be provided with ring 33 of rotatable parts 31 being clamped from the opposite side of turbine frame 2 etc., rotatable parts 31 are pushed to turbine frame 2 one sides.
According to this formation, when low engine speed is rotated, the rotatable parts 31 of changeable mechanism 3 are suitably rotated, this rotation is delivered on the axial region 12 via transferring elements 32, variable sweep wing 1 is rotated as illustrated in fig. 1, waste gas G is suitably carried out throttling to regulate extraction flow.
Exhaust gas guide assembly A constitutes to have above-mentioned basic structure, below to constituting the heat-resisting raw material of this assembly, describes by each form of implementation.
[form of implementation 1]
Form of implementation 1 is that the nonmetallic substance that is present in the heating resisting metal parts reduces, a kind of form of size microminiaturization in order to make.As manufacture method, for the heating resisting metal parts, there are the calcium of interpolation, heating pressure treatment, pure oxygen to bessemerize methods such as processing, specifically make with following operation.
(I) reduce sonims in the heating resisting metal parts
Add calcium during by refining, self-evident for sulfide-based (category-A), be exactly generation for oxide-based (category-B, C class) sonims, also can eliminatings such as sulphur, silicon, aluminium be made it less generation by the compound of calcium.In addition, bessemerize processing, get rid of oxide slag to reduce category-B, C class sonims by pure oxygen.
(II) microminiaturization of sonims size in the heating resisting metal parts
The end that goes out that is attached to coiled material by oven is gone into the Steckel mill at end two places or the powerful continous way hot rolling mill of pressure work greatly, and sonims remaining after the refining is stretched (category-A) and fragmentation (category-B, C class).In addition, bessemerize by pure oxygen a large amount of oxides is evenly formed to seek the sonims small-sized.
(III) manufacturing of exhaust gas guide assembly
To cast through the raw material of above-mentioned processing, forging, pressure processing, smartly dash, punching, riveted joint, surface modification etc. handle to make exhaust gas guide assembly A.
(IV) durability
Compare with non-processing material, high temperature/thermal fatigue, creep properties, toughness, stress concentration factor, high temperature oxidation resistance reach below 1/5 and significantly improve, and the high temperature durability of exhaust gas guide assembly reaches more than 5 times.
[form of implementation 2]
The heat-resistant part of form of implementation 2 (alloy) is with the usual method manufacturing.Three kinds of concrete forms of implementation are as shown in table 1.
In addition, described to the reasons are as follows of limiting of each composition of this alloy.
C is to be in order to reduce sensibilization below 0.05%.
Mn is to be to lag behind for the generation that makes the σ phase more than 1%.
Ni is to be in order to increase the free energy of formation of σ phase more than 15%.
Cr is to be in order to increase the free energy of formation of σ phase below 30%.
Ti is to be in order to generate γ ' phase more than 0.1%.
Al is to be in order to generate γ ' phase more than 0.1%.
Ce or La are to be in order to suppress the generation of σ phase more than 0.05%.
(I) manufacturing of exhaust gas guide assembly
Carry out the control of above-mentioned set composition with the converter refining operation, pass through continuous casting, hot rolling and cold rolling common operation afterwards, produce raw material, use this material to carry out the processing and the manufacturing of exhaust gas guide assembly.
(II) inhibition of tissue embrittlement
Organize embrittlement to suppress data shown in the following table 1.
Table 1
(III) film covering method
(a) as the method for the surface of the alloy in this form of implementation being carried out overlay film, be advisable to adopt TD salt bath method, specifically carry out with following operation.
Be non-equilibrium in advance and hypersaturated state is carried out after case-carbonizing handles, the parts that are preheated to 500 ℃ be immersed in 1000 ℃ of salt baths up and down that are made of borax, chloride, chromium oxide just can generate the chromium carbide overlay film.
(b) inhibition of tissue embrittlement
Organize embrittlement to suppress data shown in the following table 2.
Table 2
(IV) stress is given processing
(a) content of Chu Liing
Before separating out heat treatment, in allowed limits parts are implemented certain processing as far as possible equably, according to circumstances and then apply hydrostatic pressures such as hydraulic pressure, import plastic strain giving under the stress.
(b) inhibition of tissue embrittlement
Organize embrittlement to suppress data shown in the following table 3.
Table 3
[form of implementation 3]
The alloy of form of implementation 3 is with the usual method manufacturing.Three kinds of concrete forms of implementation are as shown in table 4.
In addition, described to the reasons are as follows of limiting of each composition of this alloy.
W is to be for can be effectively and at high temperature produce the tempering secondary hardening post-curing more than 0.3%.
V is to be for can be effectively and at high temperature produce the tempering secondary hardening post-curing more than 1.0%.
Mo is to be for can be effectively and at high temperature produce the tempering secondary hardening post-curing more than 1.0%.
Hf is to be for can be effectively and at high temperature produce the tempering secondary hardening post-curing more than 0.5%.
(I) manufacturing of exhaust gas guide assembly
With converter refining one-tenth is grouped into and controls, in the hope of after forming further accurately, make slab, middle-size and small-size square billet, large-scale square billet etc., afterwards, produce the stainless steel raw material through hot rolling, cold rolling through continuous casting through external refining.Use that this material is processed, heat treatment makes exhaust gas guide assembly.
(II) durability
Following table 4 illustrates the data that durability improves.
Table 4
(III) film covering method
(a) as the method for the surface of the martensitic stainless steel of this form of implementation being carried out overlay film, become embrane method to be advisable to adopt the chromium carbide that is undertaken by the salt bath method, specifically carry out with following operation.
Owing to contain sufficient solid solution carbon, so after cleaning, be preheating to 500 ℃, be immersed in back taking-up in the salt bath of 1000 ℃ of degree that constitute by borax chloride chromated oxide, it is clean to neutralize.At this moment, for preventing secondary hardening post-curing state variation, preferably low temperature is handled in short-term as far as possible.
(b) high temperature durability
Following table 5 illustrates the data that high temperature durability improves.
Table 5
| Test product | High temperature durability |
| No overlay film | △ (high temperature oxidation, sintering take place) |
| Overlay film is arranged | Zero (above-mentioned phenomenon is difficult to take place) |
[form of implementation 4]
The heat-resistant part of form of implementation 4 (alloy) is with the usual method manufacturing.Two kinds of concrete forms of implementation are as shown in table 6.
In addition, described to the reasons are as follows of limiting of each composition of this alloy.
C is 0.2～0.5%, with the chromium carbide that obtains to have sufficient high temperature durability be prerequisite, the abundant proper range of film forming.
Mn is 5～10%, remains on for the solid solution capacity that makes carbon in 0.2～0.5% the proper range.
Ni is 10～20%, remains on for the solid solution capacity that makes carbon in 0.2～0.5% the proper range.
Cr is 15～25%, remains on for the solid solution capacity that makes carbon in 0.2～0.5% the proper range.
N is 0.05～0.2%, remains on for the solid solution capacity that makes carbon in 0.2～0.5% the proper range.
Among La, Ce, the Sm one or both are 0.01～0.1%, remain on for the solid solution capacity that makes carbon in 0.2～0.5% the proper range, help the chromium carbide film forming.
(I) manufacturing of exhaust gas guide assembly
With converter refining one-tenth is grouped into and controls, in the hope of after forming further accurately, make slab, middle-size and small-size square billet, large-scale square billet etc., afterwards, produce heat-resistant material through hot rolling, cold rolling through continuous casting through external refining.Use that this material is processed, heat treatment makes exhaust gas guide assembly.
(II) hot strength
Following table 6 illustrates the data that hot strength improves.
Table 6
(III) film covering method
(a) as the method for the surface of the alloy of this form of implementation being carried out overlay film, be advisable to adopt the salt bath method, specifically carry out with following operation.
After component parts cleaned, be preheating to 500 ℃, impregnated in 1000 ℃ of salt baths up and down that contain chloride and chromium oxide in the borax then after, it is clean to neutralize.
(b) durability
Following table 7 illustrates the data that durability improves.
Table 7
[form of implementation 5]
Form of implementation 5 is to add carbon and produced in JIS standard SUS310S, specifically carries out with following operation.Concrete form of implementation is shown in the table 8 of back.
With converter refining one-tenth is grouped into and controls, in the hope of after forming further accurately, make slab with continuous casting machine through external refining.Afterwards, slab in evenly heating more than 1 hour more than 1200 ℃, is carried out hot rolling gently depressing with Steckel mill etc. at first, rolling lower limit temperature is controlled at carries out hot rolling more than 950 ℃, carry out chilling with a large amount of cooling waters at last.The coils of hot rolled of such acquisition is carried out cold rolling, generate carbide for avoiding iron matrix, annealing is carried out about 1100 ℃ with continuous device, thereby makes the finished product raw material.
Why making carbon content rate is 0.15～0.35%, is it is limited in such scope, that is, make carbon pass through the processing of this form of implementation and solid solution, does not carry out carburizing and can form the chromium carbide overlay film.
(I) manufacturing of exhaust gas guide assembly parts
By converter refining one-tenth is grouped into and controls, the slab that continuous casting is formed carries out the high temperature heating more than 1250 ℃, afterwards, through rolling/forge the chilling operation to manufacture heat-resistant part.
(II) high strength
Following table 8 illustrates the high temperature hardness data.
Table 8
| Test product | Carbon content rate | High temperature hardness HV (800 ℃) * HV: Vickers hardness | Wearing and tearing (sintering) | Friction factor in the time of 850 ℃ |
| The steel of mode of execution 5 | 0.32 | 510 | Do not have | 0.4 |
| SUS310S | 0.05 | 290 | Take place | 1.8 |
(III) film covering method
(a) overlay film that this form of implementation alloy surface is carried out is to utilize the carbon of the major part disassociation solid solution in this heat-resistant material to carry out, and specifically carries out with following operation.
After these parts are cleaned, carry out preheating with 500 ℃, be immersed in then in the salt bath that contains chromium oxide/titanium/tungsten etc., carry out neutralisation treatment afterwards.
(b) high wear resistance
The data relevant shown in the top table 8 with high temperature hardness and high temperature abrasion resistance.
[form of implementation 6]
(I) manufacturing of exhaust gas guide assembly
By vacuum melting the various superalloy with set composition are carried out composition and adjust melting, casting is an ingot casting with superalloy (inconel 713C), its intermediate alloy of using as sand casting process or precision casting is made the parts of assembly.On the other hand, rolling/forging is ingot casting or the middle-size and small-size square billet of the large-scale square billet of slab that according to circumstances is made into continuous forging with superalloy (Incoloy 800H), afterwards, makes the superalloy raw material through rolling/forging.Afterwards, process (and heat treatment) and manufacture component parts.
(II) hot strength
Following table 9 illustrates the hot strength data.
Table 9
| Test product | Hot strength (tensile strength, MPa:800 ℃) |
| Incoloy 800H | 500 |
| Inconel 713C | 600 |
| Hasteloy S | 550 |
(III) film covering method
(a) surface coating that this form of implementation superalloy is carried out with chromium carbide, titanium carbide, tungsten carbide, vanadium carbide, niobium carbide or molybdenum carbide carries out carrying out after Carburization Treatment, the nitriding processing in advance, specifically carries out with following operation.
After ion carburizing, glowdischarge carburizing or the ion nitriding, the superalloy raw material are preheating to 500 ℃, be immersed in the salt bath that contains chromium, titanium, tungsten, vanadium, niobium or molybdenum after, carry out neutralisation treatment.
(b) inhibition of high temperature slip wearability reduction
Below table 10 data that the reduction of wearability is inhibited are shown.
Table 10
| Test product | Overlay film | The inhibition (900 ℃ time friction factor) of wearing and tearing deterioration |
| Incoloy 800H | Do not have | 1.5 |
| Incoloy 800H | Cr-C | 0.5 |
| Incoloy 800H | Ti-C | 0.4 |
| Incoloy 800H | W-C | 0.4 |
| Incoloy 800H | Mo-C | 0.5 |
| Incoloy 800H | V-C | 0.5 |
| Incoloy 800H | Nb-C | 0.5 |
[form of implementation 7]
The former material of shaping of the heat-resistant part of form of implementation 7 (alloy) is basically with microcast process or metal injection moulding manufactured (table 11 of material back, 12).
By converter refining one-tenth is grouped into and controls, in the hope of after forming further accurately, make slab with continuous casting machine through external refining.Afterwards, slab in evenly heating more than 1 hour more than 1200 ℃, is carried out hot rolling gently depressing Ezra Ke Ershi milling train etc. at first, rolling lower limit temperature is controlled at carries out hot rolling more than 950 ℃, carry out chilling with a large amount of cooling waters at last.The coils of hot rolled of such acquisition is carried out cold rolling, generate carbide for avoiding iron matrix, annealing is carried out about 1100 ℃ with continuous device, thereby makes the finished product raw material.
In addition, described to the reasons are as follows of limiting of each composition of this alloy cast steel.
C is 0.2～0.5%, in order to seek the improvement of liquation flowability, hot strength, the overlay film property handled.
Cr is 15～30%, in order to improve heat resistance.
Ni is 15～30%, in order to seek the particularly improvement of hot strength, resistance to high temperature oxidation, thermal fatigue, thermal expansion (variation of size).
Pb is 0.01～0.1%, for the shape that makes precision casting, MIM very becomes easily near the machine cut of part and in order to improve the agglutinating property of MIM.
Se is 0.01～0.1%, for the shape that makes precision casting, MIM very becomes easily near the machine cut of part and in order to improve the agglutinating property of MIM.
Te is 0.01～0.1%, for the shape that makes precision casting, MIM very becomes easily near the machine cut of part and in order to improve the agglutinating property of MIM.
O is 0.02～0.1%, has good liquation flowability during for precision casting.
S is 0.005～0.05%, has good liquation flowability during for precision casting.
(I) manufacturing of exhaust gas guide assembly
(a) microcast process
1. make
Taking into account the mentioned component composition with the investment casting casting process of representing microcast process makes.This method, be after forming the overlay film of refractory material around the wax-pattern identical with the article shape that will cast, only make wax-pattern fusing and make thereby integral body heats,, taked measure for improving the very approaching degree of shape specifically with following operation manufacturing.
Using Fe-Ni-Cr with electric furnace is that intermediate alloy carries out the composition adjustment, by the viscosity of high melt with the reduction liquation, in the mold that this refractory material is made does not produce the scope of thermal stress be full of cracks, do not carry out the casting of chilling formula, promptly improve dimensional accuracy so that tolerance of size is minimum.Secondly, after the cooling, take mold apart,, make the very approaching goods of shape through acidproof cleaning with cut-outs such as runners.Afterwards, make the part of assembly through the light cut operation.In this form of implementation, rubbed into the neodoxy that in the operations such as cutting, grinding of back operation, does not apply load as far as possible.
2. the data relevant with manufacturing
Following table 11 illustrates the correlation data with prior art.
Table 11 casting method
(b) metal injection moulding method
1. make
Atomized spray speed by increasing air/water, improve rate of cooling and control its shape of nozzle size to form small raw material powder, under reducing atmosphere, oxide on surface is removed, carry out sintering with the temperature that is lower than fusing point (low about 20 ℃) slightly and make it independent alveolation, make the very approaching goods of shape through injection moulding.Afterwards, make the part of assembly through the light cut operation.
2. the data relevant with goods
Following table 12 illustrates the correlation data with current material.
Table 12 metal ejection forming method
(III) durability
In order on the cutting piece of above investment casting casting or MIM, to form the carbide overlay film, carry out salt bath and handle (carrying out Carburization Treatment as required), thereby make the parts of assembly.
Following table 13 illustrates the data that durability improves.
High temperature friction coefficient when table 13 has or not overlay film to handle
[form of implementation 8]
(I) high alloy austenite heat-resistant stainless steel
(a) only carry out the example that ion carburizing, glowdischarge carburizing and TD salt bath are handled
Under the rare gas atmosphere of 2～3 holders, form glow discharge, make the hydrocarbon plasma effect that is produced carry out carburizing in the object being treated surface with the hydrocarbon gas that comprises methane or propane.Secondly, object being treated is immersed in the oxide and muriatic high temperature TD salt bath of mixed C r, V, Ti, W etc. in the borax, makes the carbide film forming by high-temperature chemical reaction as auxiliary agent.
(b) example of use SUS310S or SUH310
Basic identical with said method, but owing to exist C＜0.1% of SUS310S the difference of the C ≈ 0.2% of SUH310, so the ion carburizing, glowdischarge carburizing condition is answered corresponding change.Result after the TD salt bath is handled significantly improves based on the high temperature durability of high-temperature wearable resistance to high temperature oxidation.In addition, can realize grain refinement by interpolation Ti, Ni, B, Hf etc., so raisings such as high temperature hardness, fatigue strength, creep propertiess.Adopt the processing method of above-mentioned (a) again.
(c) example of use SCH21
Basic identical with said method, but because C ≈ 0.3% and more, thus the shortening ion carburizing, glowdischarge carburizing time get final product.The effect that the TD salt bath is handled is identical with SUS310S and SUH310 with grain refining effect.Adopt the processing method of above-mentioned (a) again.
(d) example of use rolling stock
Heat in advance, light pressure of austenite stage and after material phase transformation is ferrite, disposablely carry out rolling under the big pressure, making the crystallization nucleus generate quantity increases considerably again, in cooling procedure, avoid in a disguised form being ferrite (common hot rolling from austenite, can after pressing down, undergo phase transition and produce ferrite crystallization again from austenite crystal), can obtain fine-grain.Therefore heat resistance such as hot strength improves.Adopt the processing method of above-mentioned (a) again.
(II) example of use iron-based superalloy
Iron-based superalloy such as SUH660 and Incoloy 800H, not only the Ni amount is many, and has added Ti, Al etc., therefore, when carrying out ion carburizing, glowdischarge carburizing, also should be noted that the cleaning and the activation on surface.Other is with (a) basic identical.
(III) example of use nickel based super alloy
(a) only carry out the example that ion carburizing, glowdischarge carburizing and TD salt bath are handled
Ni base superalloys such as inconel 718 and inconel 713C because matrix is Ni, therefore will make the degree of vacuum minimum when carrying out ion carburizing, glowdischarge carburizing, glow discharge weight also will improve.Carry out salt bath when handling too, consider the diffusion velocity of solid solution carbon in the Ni matrix and add the balanced chloride of salt bath (the salt bath harmony that makes reducing agent and oxide with respect to the boric acid medium to the high concentration side shifting).
(b) example that γ ' is separated out mutually
At Ni
3Ti and Ni
3γ ' precipitation type Ni base superalloys (comprising SUH660) such as Al are necessary to make γ ' fine as far as possible, even dispersion mutually when being used for this high-temperature use.For this reason, before separating out processing, carry out the importing of strain, and/or separate out heat treatment and adopt polygonization to handle (secondary heat treatment) operation, with this as countermeasure.
The heat-resisting raw material that constitute exhaust gas guide assembly A are as above made or are formed, below, describe with regard to the manufacture method of the former material of shaping of aforementioned form of implementation 7 appearance that also how much relate to, that have variable sweep wing 1.
The former material of the shaping of variable sweep wing 1 is to make alar part before 11 and axial region 12 the two all-in-one-piece raw material metal, by it suitably being carried out rollforming processing and abrasive machining etc., forms the variable sweep wing 1 as object.In addition, as the raw material of the former material that is shaped, can adopt SUS310S etc. to have stable on heating raw material metal.Here, with microcast process or the metal injection moulding method former material that obtains being shaped, below, with microcast process as [form of implementation 9], the metal injection moulding method is described with regard to its manufacture method as [form of implementation 10].
[form of implementation 9]
In general the microcast process of form of implementation 9 is that foundry goods (former material is shaped) can reach high-precision method,, has adopted the investment casting casting process as an example here.The investment casting casting process is a kind of like this method, promptly, the general at first formation wax-pattern identical with the article shape that will cast, after forming refractory material overlay film layer around this wax-pattern, integral body heats, and only makes wax-pattern fusing and makes mold (overlay film layer), adopts this method, can access the mold of faithful to target product, make foundry goods be able to highi degree of accuracy and reproduce.
And, except above-mentioned investment casting casting process, also having Shaw process and CADIC method etc. as microcast process, these methods also can adopt.Additional disclosure, Shaw process, be a kind of aqueous alkyl silicate binder and the two the mixing postforming grade of powder shape refractory material to be wet mold, the mold that should wet is sharply dry, the microcrack that the crackle following drying and produce can't be seen with eyes produces, to prevent the method for mold generation integrity contraction deformation.
This microcast process, the shape of formed mold and target product (being variable sweep wing 1 here) is identical substantially with size, can highi degree of accuracy reproduces the foundry goods (former material is shaped) of very faithful to target product.Even but also there is following shortcoming in such microcast process, promptly, if do not take measures, it is difficult the former material that is shaped will being finish-machined to and being close to net shape, expect variable sweep wing 1 with target shape and precision, the dimensional accuracy of the former material of casting out of shaping is still inadequate, and has discreteness.In addition, the former material that is shaped is implemented after also existing to add the shortcoming that form sharp overlap man-hour easily behind the rollforming etc.For this reason, as this form of implementation, when casting, following technical measures have suitably been taked.
At first, be to improve the molten metal flow of casting in mold, having adopted with heating resisting metal is virgin's material of main mother metal, and makes the amount of the C (carbon), the Si (silicon) that contain in this virgin's material, O (oxygen) suitable.Specifically, draw GARMENT WASH to wash the process of waste material without the treasurer, directly reduce and the raw material (virgin's material) made and adopt from iron sand and iron ore etc., and component ratios such as C, Si, O are adjusted into 0.05～0.5%, 0.5～1.5%, 0.01～0.1% (respectively being weight %) respectively, with the shape and the dimensional accuracy of the raising molten metal flow and the former material that is shaped, and improve rollforming.Additional disclosure, when the component ratio of above-mentioned each element was adjusted, the limit monitored limit adjustment to variable quantity in electric furnace.
In addition, when casting, to mold and be shaped former material the two one or both of carry out chilling and attenuate to shorten to the time till the form removal, to make the be shaped solidified structure of former material.Specifically, for example water cools off to mold spraying before and after casting, and the needed time till the form removal, an one example has shortened to (common air cooling needs 1～4 hour) below 1 hour.At this moment, the cooling before the casting is just carried out mold, and then the two carries out the cooling after the casting to mold and the former material of shaping.Certainly, when carrying out chilling, should in not producing the scope of thermal stress be full of cracks, mold not carry out.If two periods that there is no need before and after casting cool off, which then carry out all can in period, and further improve the occasion of cooling effect in hope, except cooling off, can also spray with cooling water to the former material of the shaping of from mold, taking out again in former and later two periods of casting.
By taking abovementioned technology (chilling), an example as the solidified structure of the former material that is shaped, 50～100 μ m (crystal grain that solidifies that is about 100～500 μ m during common air cooling) have been refine to, rollforming after carrying out etc. adds man-hour, because strain evenly thereby be not easy to produce sharp overlap, makes rollforming processing etc. become more easy.
Have again, for the molten metal of in mould, casting, add among Pb (lead), Se (selenium), the Te (tellurium) one or more, and can not bring dysgenic scope to contain more O (oxygen), S (sulphur) in the existence of sonims.Specifically, can make Pb is 0.01～0.1%, and Se is 0.01～0.1%, and Te is 0.01～0.1% (respectively being weight %), is 0.02～0.1% and make O, and S is 0.005～0.5% (respectively being weight %).Here why adding Pb, Se, Te etc., be in order to improve the rollforming and the machinability (mainly showing machinability) of the former material that is shaped, and why add O, S etc., is in order to improve the liquation flowability.Additional disclosure about the liquation flowability, confirms that through the applicant the viscous flow of Stokes flow has improved 20～40% at least.
In addition, when casting, molten metal is to be warmed to more than the fusing point, in mould, cast under the state when viscosity is lower than melting temperature, with basic heat-resistant material of Ni (nickel) and the basic heat-resistant material of Fe (iron) is example, and the relation between temperature (representing with the situation of heating for fusing point) and the viscosity is shown in Fig. 3.The flowability of liquation shown in the figure (reference value), the flowability of the molten mass of being cast is suitable with viscosity.As known in the figure, the viscosity of molten metal, near fusing point to the dependence on temperature height, the high more then viscosity of raw-material temperature is low more, but also as can be known, heat again with respect to fusing point about 30 ℃ near, the temperature dependency of viscosity weakens, even the viscosity of heating can correspondingly not reduce yet.Therefore, as this form of implementation, consider the effect that viscosity reduces and the cost of heating, an one example is that raw material are cast to be warmed under the state that is higher than the about 30 ℃ of degree of fusing point.
[form of implementation 10]
The metal injection moulding method of form of implementation 10 injection moulding with existing known general synthetic resin (plastics) in fact is identical, for example mixing tackiness agent (mainly is to make it the additive that combines with metal powder in metal powders such as iron, titanium (material), an one example is the mixture of polyethylene resin, wax, phthalic acid ester), tax with plasticity.Afterwards, will be endowed plastic material and inject in the mould, be solidified as suitable shape, and will carry out sintering behind the binder removal, thereby obtain the former material of shaping of intended shape.
Like this, metal injection moulding also can similarly obtain the drip molding (former material is shaped) of faithful to target product (being variable sweep wing 1 here) substantially with microcast process, but then, the voids of the former material of shaping of formed thereby wants high with comparing as material admittedly, particularly heat-resisting high alloy material exists shortcomings such as the big inadequately and hot bending fatigue strength difference of volume density.Voids described here is cavity (aggregate of a plurality of point defects, they lump together even can cause the formation of microcrack) a kind of in the crystal of raw material metal etc., if its ratio is too high, then can bring harmful effect to raw material metal.According to the above,, when carrying out metal injection moulding, following technical measures have suitably been taked as this form of implementation.
At first, for independent bubbles (the spherical gap between metallic) can be produced little and equably, carry out long sintering of time, specifically, be the occasion of 1500 ℃ SUS310S for example, at the sintering that carries out about about 2 hours long periods under 1300 ℃ using fusing point.
Though carry out such sintering,, improve volume density can reduce the former material voids that is shaped, but to the former material of the shaping of injection moulding, also further implement HIP and handle (abbreviation of Hot IsostaticPressing, hydrostatic pressure hot-pressing processing), with further raising volume density.Specifically, the former material that will be shaped for example is heated to about 1300 ℃, simultaneously to be shaped former material each to the pressure that applies about 100MPa (1000 air pressure) degree equably.
Handle by above-mentioned sintering and HIP, the independent bubbles that is about 100 μ m degree before the sintering becomes about 10 μ m degree behind sintering, and it is about 5% that volume density improves, and this is confirmed by the inventor.And because the raising of this volume density, the intensity of the former material that not only is shaped improves, and the dimensional accuracy raising, can obtain the former material of shaping of more intimate net shape.
In addition, when metal powder is carried out sintering, for precipitation hardening type heat-resistant materials such as for example SUH660, by heating rapidly, make γ ' (being called loud, high-pitched sound agate original layers (prime), the intermetallic compounds of expression Ni3 (Al, Ti)) generate, suppress its growth, make it refinement.This is in order to suppress the overaging phenomenon under the hot environment, and the induction heating method that produces heating current by electromagnetic induction is preferably adopted in the heating rapidly of this moment.
In addition, as this form of implementation, the metal powder that injection moulding is used is spherical and fine, and the technical measure of implementing to make the high temperature rotating bending fatigue strength of the former material of shaping of formed thereby to be improved in the lump.Here, in order to make metal powder be spherical and fine, for example be that molten metal is sprayed from nozzle, make high speed fluids such as air or water act on the molten metal of this ejection, the impact force of utilizing high-velocity fluid makes it cooling after metal is divided into many drops, solidify and obtain metallic dust, and what adopt here is so-called air atomizing method or water atomization.In addition, when adopting this atomization, the jet velocity of its shape of nozzle and caliber size, the air that acts on molten metal or the water or other fluid of appropriate change ejection molten metal, rate of cooling etc. just can access the metallic dust of desired size.Cause, tiny when 200 μ m degree are carried out sintering at the metal powder of SUS310S, it is about 20% that high temperature rotating bending fatigue strength improves, and this point is confirmed by the inventor.
Have again, when carrying out metal injection moulding, reduce, specifically, make gases such as hydrogen with reducing atmosphere, ammonia, carbon monoxide cross, contact with it to reduce from the surface flow of metallic to the surface of the raw material metal before the sintering.Like this, the oxide on metallic surface is removed, and not only agglutinating property improves, and can increase the effect of hydrostatic pressure hot-pressing processing, goes far towards the reduction of voids.
According to the present invention, can be when reducing cost, the heat resistance such as hot strength, oxidative stability, high temperature wear resistant of exhaust gas guide assembly A is improved.Specifically, the minimizing of the amount by making sonims and the microminiaturization (with reference to form of implementation 1) of size or, by adding rare earth elements (with reference to form of implementation 2) etc., high temperature durability is improved.In addition, can also in the Martensitic Stain Less Steel that for example price such as SUS410, SUS440 is comparatively cheap, add W (tungsten), V (vanadium), Mo (molybdenum), Hf (with reference to forms of implementation 3) such as (hafniums).For the raw material such as rolled stock of high alloy austenite heat-resistance stainless steel or iron-based superalloy, can carry out rolling under the big pressure so that grain refinement in the ferrite stage, make hot strength be improved (with reference to form of implementation 8).And for for example raw material such as iron-based superalloy such as Incoloy 800H, inconel 713C or nickel based super alloy, can form overlay films such as chromium carbide, titanium carbide, tungsten carbide, vanadium carbide, niobium carbide or molybdenum carbide on its surface, the wearing and tearing (with reference to form of implementation 6) when sliding to improve the hot strength persistency and to alleviate high temperature.
In addition, according to the present invention, the performance that can suppress exhaust gas guide assembly A reduces along with using under high-temperature atmosphere.Specifically, for the heat-resisting raw material of precipitation hardening types such as SUH660, can implement stress in advance and give processing, make in the process that under high-temperature atmosphere (for example 700～800 ℃) use, γ ' the phase of being separated out (loud, high-pitched sound agate original layers) do not grow and small evenly, thereby the effect that avoids obsolescence (with reference to form of implementation 2).In addition, reduce used raw-material carbon content, and make grain refinement, can prevent near for example incidental sensitization phenomenon operating temperature is about 600～800 ℃.Have again, when reducing the content of raw-material Cr (chromium), increase Si (silicon) and Mn (manganese), for example can prevent near the generation of incidental σ embrittlement phenomenon 850 ℃ of operating temperatures.
In addition, according to the present invention, make the solid solution limit of carbon under the used raw-material high temperature increase (with reference to form of implementation 4), after perhaps raw material being melted refining, make the carbide disassociation reach high carbonization (with reference to form of implementation 5) by modes such as high temperature slab heating, then do not carry out Carburization Treatment and also can form the carbide overlay film.
In addition, can also accomplish, in Cr, Ni-Cr heat-resistant material, add Se (selenium), Te (tellurium), O (oxygen), S (sulphur) etc., liquation when making precision casting is mobile to be improved, independent bubbles refinement when perhaps making metal injection moulding, thus all very high former materials of shaping (with reference to form of implementation 7,9,10) such as dimensional accuracy and intensity obtained.
The possibility of utilizing on the industry
As mentioned above, the present invention is adapted at wishing consisting of the occasion that high temperature abrasion resistance, non-oxidizability, the high temperature hardness of parts of the exhaust gas guide assembly of variable geometry turbocharger be improved and uses. In addition, the present invention is adapted at wishing that will make the occasion that is close to net shape as the former material of shaping (appearance) of the adjustable wing of a component parts of exhaust gas guide assembly uses.
Claims (2)
1. the exhaust gas guide assembly of the variable geometry turbocharger that is improved of a heat resistance,
Be that the flow with waste gas (G) that motor is discharged is suitably regulated so that the variable sweep wing (1) of exhaust driven gas turbine (T) rotation, this variable sweep wing (1) is supported in the turbine frame (2) on the peripheral part of exhaust driven gas turbine (T) free to rotately, and can makes this variable sweep wing (1) suitably rotate changeable mechanism (3) so that the flow of waste gas (G) is regulated;
Less extraction flow is carried out throttling with variable sweep wing (1), improves the speed of exhaust,, it is characterized in that even also can reach the exhaust gas guide assembly (A) in the turbosupercharger of variable geometry turbocharger of high output during low speed rotation,
What constitute that the heat-resistant part of described exhaust gas guide assembly (A) uses is superalloy.
2. the exhaust gas guide assembly of the variable geometry turbocharger that heat resistance as claimed in claim 1 is improved, it is characterized in that, constitute the described heat-resistant part of described exhaust gas guide assembly (A), be formed with the overlay film of chromium carbide, titanium carbide, tungsten carbide, vanadium carbide, niobium carbide or molybdenum carbide on its surface.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP139945/01 | 2001-05-10 | ||
| JP139708/01 | 2001-05-10 | ||
| JP139675/01 | 2001-05-10 | ||
| JP140116/01 | 2001-05-10 | ||
| JP139904/01 | 2001-05-10 | ||
| JP2001139675A JP2002332850A (en) | 2001-05-10 | 2001-05-10 | Exhaust guide assembly for vgs turbocharger with improved high-temperature endurance composed of member with reduced non-metallic inclusion |
| JP140452/01 | 2001-05-10 | ||
| JP139866/01 | 2001-05-10 | ||
| JP140030/01 | 2001-05-10 | ||
| JP235676/01 | 2001-08-03 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028139240A Division CN100340749C (en) | 2001-05-10 | 2002-05-10 | Exhaust guide assembly for VGS type turbo charger improved in heat resistance and method of producing heat-resisting members applicable thereto, and method of producing raw material for variable vanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101187313A true CN101187313A (en) | 2008-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101407138A Pending CN101187314A (en) | 2001-05-10 | 2002-05-10 | Exhaust guide assembly for variable giometry shape turbocharger with improved high-temperature endurance |
| CNA2007101407161A Pending CN101187315A (en) | 2001-05-10 | 2002-05-10 | Exhaust gas guide assembly, heat resisting component and method for manufacturing shaped material for adjustable blade applicable thereto |
| CNA2007101407119A Pending CN101187313A (en) | 2001-05-10 | 2002-05-10 | Exhaust guide assembly for variable giometry shape turbocharger with improved high-temperature endurance |
| CN2007101407176A Expired - Lifetime CN101187316B (en) | 2001-05-10 | 2002-05-10 | Exhaust guide assembly for variable giometry shape turbocharger with improved high-temperature endurance |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101407138A Pending CN101187314A (en) | 2001-05-10 | 2002-05-10 | Exhaust guide assembly for variable giometry shape turbocharger with improved high-temperature endurance |
| CNA2007101407161A Pending CN101187315A (en) | 2001-05-10 | 2002-05-10 | Exhaust gas guide assembly, heat resisting component and method for manufacturing shaped material for adjustable blade applicable thereto |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101407176A Expired - Lifetime CN101187316B (en) | 2001-05-10 | 2002-05-10 | Exhaust guide assembly for variable giometry shape turbocharger with improved high-temperature endurance |
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| JP (1) | JP2002332850A (en) |
| CN (4) | CN101187314A (en) |
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| US9534280B2 (en) * | 2011-05-19 | 2017-01-03 | Borgwarner Inc. | Austenitic iron-based alloy, turbocharger and component made thereof |
| DE112016005491T5 (en) * | 2015-12-01 | 2018-08-09 | Ihi Corporation | MOUNTING STRUCTURE AND TURBOLADER |
| EP3321390B1 (en) * | 2016-07-29 | 2024-02-14 | Mitsubishi Steel MFG. CO., LTD. | Heat-resistant casting |
| DE102018211091A1 (en) * | 2018-07-05 | 2020-01-09 | Volkswagen Aktiengesellschaft | Method for operating an internal combustion engine and internal combustion engine |
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2001
- 2001-05-10 JP JP2001139675A patent/JP2002332850A/en active Pending
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2002
- 2002-05-10 CN CNA2007101407138A patent/CN101187314A/en active Pending
- 2002-05-10 CN CNA2007101407161A patent/CN101187315A/en active Pending
- 2002-05-10 CN CNA2007101407119A patent/CN101187313A/en active Pending
- 2002-05-10 CN CN2007101407176A patent/CN101187316B/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN101187316B (en) | 2012-09-05 |
| CN101187314A (en) | 2008-05-28 |
| CN101187316A (en) | 2008-05-28 |
| JP2002332850A (en) | 2002-11-22 |
| CN101187315A (en) | 2008-05-28 |
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