Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C5/00—Alloys based on noble metals
  • C22C5/04—Alloys based on a platinum group metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/12—Metallic powder containing non-metallic particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/14—Treatment of metallic powder
  • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/04—Making non-ferrous alloys by powder metallurgy
  • C22C1/05—Mixtures of metal powder with non-metallic powder
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/10—Alloys containing non-metals
  • C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
  • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
  • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
  • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
  • B22F2998/10—Processes characterised by the sequence of their steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

• the present invention relates to an oxide dispersion strengthened platinum material in which an oxide is dispersed in platinum or a platinum alloy.
• the present invention relates to an oxide dispersion strengthened platinum material that can maintain strength for a long time at high temperature and has good weldability.
• An oxide-dispersed platinum material in which a metal oxide such as zirconium oxide (zircoua) is finely dispersed in platinum or a platinum alloy is used in the environment because of its excellent high-temperature strength characteristics, particularly creep strength. It is used as a structural material for glass manufacturing equipment.
• a powder metallurgy method is generally used as a method for producing the oxide-dispersed platinum material.
• a powder metallurgy method is generally used.
• an alloy powder of platinum and zirconium is manufactured, and this is oxidized to convert the zirconium in the alloy powder into an internal acid to make an acidic zirconium.
• Dispersed platinum powder is sintered and processed to form a platinum material.
• the applicant of the present application has made various improvements with respect to the oxide-dispersed platinum material in order to improve the high-temperature strength.
• platinum or a matrix An oxide-dispersed platinum material that optimizes the crystal grain size and crystal aspect ratio of the platinum alloy is disclosed.
• This platinum material uses a mixed solution of a platinum suspension solution and a zirconium nitrate solution as a raw material, and performs a predetermined treatment to produce platinum powder loaded with zirconium hydroxide.
• the crystal grain size and the like of the matrix are adjusted.
• Patent Document 1 Japanese Patent Laid-Open No. 2002-12926
• the oxide-dispersed platinum material improves the high-temperature strength (creep strength) of the platinum material, and has a remarkable effect in that respect.
• the first improvement point of the oxide-dispersed platinum material is stability when used for a long time in a high temperature environment. In glass manufacturing equipment that uses platinum materials, the ambient temperature can sometimes be 1500 ° C or higher.
• voids cavities
• blisters blows
• the oxide-dispersed platinum material has good weldability, improvement is required. Glass melting tanks and the like are manufactured by welding, but the oxide-dispersed platinum material has a relatively high possibility of occurrence of welding defects such as blow holes in the joint after welding. If this welding defect is overlooked, it will lead to the breakage of the device, and even if it can be found in advance by inspection, the problem of yield remains.
• an object of the present invention is to provide an oxide-dispersed platinum material that can be used stably at high temperatures and has excellent weldability. Disclosure of the invention
• the present inventors examined the causes of the above-mentioned problems, and as a result, the behavior of oxygen in the material as a cause of blistering at high temperatures and blowholes during welding. Focused on.
• Oxygen is an element constituting dispersed particles and an essential constituent element for oxide-dispersed alloys.
• the amount of oxygen in the material exceeds the amount for constituting the dispersed particles, and in combination with the added metal, atomic or molecular oxygen is present in the material. ing. This is considered to be due to the fact that in the manufacturing method, a process in high-temperature air is essential, and excess oxygen may be introduced into the material.
• the atomic or molecular oxygen that does not bond to the additive metal is in a high temperature environment.
• the present invention relates to an oxide dispersion-strengthened platinum material in which dispersed particles composed of a metal oxide of an additive metal are dispersed in a matrix that also has platinum or platinum alloy strength, and oxygen bonded to the additive metal.
• This is an oxide dispersion strengthened platinum material characterized by having an oxygen concentration power of lOOppm or less.
• the dispersed particles are not formed!
• the oxygen concentration (hereinafter sometimes referred to as excess oxygen concentration) is set to lOOppm or less because oxygen exceeding lOOppm exists. In this case, the formation of gaseous oxygen becomes prominent at high temperatures or when the material is melted, and blisters and blowholes are easily generated. This oxygen concentration is better as it approaches 50 ppm or less, which is more preferable.
• the excessive oxygen concentration of the oxide-dispersed platinum material that has been commercially available in the past is 150 ppm or more.
• the oxygen concentration of the entire platinum material and the oxygen concentration theoretically obtained from the added calo metal concentration are multiplied by the oxidation rate of the added metal described later. It can be calculated by calculating the difference.
• the oxygen concentration of the platinum material as a whole is dissolved by heating and heating the platinum material to a temperature of about 3000 ° C in a carbon crucible. Quantitative analysis of the carbon dioxide generated at this time, oxygen concentration analysis such as GD-MS, etc. It can be measured by instrumental analysis.
• the excess oxygen concentration can also be calculated by subtracting the oxygen concentration combined with the added metal from the oxygen concentration of the entire platinum material.
• the oxygen concentration combined with the added metal is the amount of oxygen generated at each temperature while gradually raising the temperature of the platinum material to about 3000 ° C, when analyzing the oxygen concentration of the entire platinum material.
• the peak detected near the melting point of platinum is distinguished from the peak of oxygen derived from added metal oxides detected at 2500 ° C or higher, and the oxygen content of the latter oxygen peak is quantified. It can be calculated by
• the present invention it is most effective to regulate the oxygen concentration in the platinum material.
• it is also effective to define the state of the dispersed particles. is there.
• the strengthening mechanism of the particle-dispersed alloy is not based on the amount of dispersed particles (volume fraction), but is exhibited even if a minute amount is finely dispersed.
• the above patent document 1 the strength of the particle-dispersed platinum material increases with the aspect ratio of the crystal grains, but this aspect ratio depends on the average inter-particle distance of the dispersed particles. That is, in order to ensure weldability while fully exerting the strengthening mechanism in the particle dispersion type alloy, it is preferable to disperse fine dispersed particles uniformly and in a highly dispersed state.
• the platinum material according to the present invention preferably has an average particle diameter of dispersed particles of not more than 0 and an average interparticle distance of 0.01-2.7 / zm.
• the average particle size of the dispersed particles is set to 0.2 m or less in order to sufficiently strengthen the particles while considering the particle size of the dispersed particles that can be produced. It is also a necessary force.
• the setting of the range of the average particle spacing is to improve the aspect ratio of the crystal grains of the platinum matrix and to ensure the effect of improving the strength.
• the amount (concentration) of the dispersed particles is preferably 0.01 to 0.5% by weight.
• the amount of dispersed particles does not affect the weldability of the alloy, but there is a minimum amount to exert the effect of improving the strength by dispersing the particles. It also affects the workability of the alloy (drawing workability, extensibility, etc.).
• the reason why the dispersed particle concentration is set to 0.01 to 0.5% by weight in the present invention is that the minimum necessary concentration for exhibiting the effect of improving the strength by particle dispersion is 0.01% by weight. Moreover, in order not to deteriorate the workability, an amount exceeding 0.5% by weight is not preferable.
• the alloy when used for applications that do not require much drawability, such as when processing into a pushing base plate, it is preferable to set the dispersed particle concentration within the above range. If so, it may be 0.3% by weight or 0.4% by weight. On the other hand, when using alloys for applications that require drawability and ductility, such as when processing into large platinum equipment, the concentration of dispersed particles is set to 0.01 to 0. It is preferable to further reduce the upper limit of 14% by weight.
• the dispersed state and amount of the dispersed particles are in the above range, all of the added metals in the platinum material are not necessarily in an oxide state.
• a method for producing a particle-dispersed platinum material there is a method in which a platinum alloy powder is oxidized to oxidize an added metal to form dispersed particles. Even if all of the added metal is not an oxide, it is sufficient if the required amount of dispersed particles is finely dispersed. [0021] Therefore, the oxidation rate of the added metal is preferably 50 to 100%.
• the oxidation rate refers to the ratio of the number of atoms (mole number) of the added metal that has become an oxide to the number of atoms (mole number) of the added metal in the platinum material.
• the reason why the acid ratio is 50 to: L 00% is that when a reinforced platinum material is used at a high temperature, oxygen in the atmosphere diffuses in the platinum material and so-called internal oxidation proceeds. In this case, oxygen diffusion occurs preferentially at the crystal grain boundaries, and the added metal diffuses and precipitates at the crystal grain boundaries where oxygen preferentially diffuses. When a large amount of added metal precipitates at the grain boundaries, the material becomes brittle, and it is necessary to keep the lower limit of the acid ratio to 50%.
• the oxidation rate can be calculated by the following formula: (amount of added metal that forms an oxide) Z (amount of added metal) X 100.
• the amount of added metal that has formed an oxide is determined by dissolving the platinum material with aqua regia or hydrochloric acid-chlorine solution, filtering the residue, weighing it, and measuring the amount of added metal oxide. be able to.
• the additive metal is preferably calcium, yttrium, or samarium in addition to zirconium. These oxides exist stably in the platinum material, and can exhibit the effect of improving the strength by the particle dispersion effect.
• the matrix may be platinum alloy in addition to (pure) platinum.
• the platinum alloy is preferably a platinum rhodium alloy, a platinum gold alloy, a platinum rhodium gold alloy, or a platinum iridium alloy.
• the oxide-dispersed platinum material according to the present invention basically limits the oxygen concentration in the material, and a conventional manufacturing method can be applied as long as the oxygen concentration can be reduced. That is, in the method of forming and solidifying the platinum alloy powder after the internal oxidation treatment, the internal oxidation conditions are adjusted so that excessive oxygen does not enter the material.
• platinum powder carrying an additive metal hydroxide is molded and solidified, and this is heat-treated to form dispersed particles. Do not enter inside.
• the inventors of the present invention prefer that the oxide-dispersed platinum material according to the present invention can be formed at a relatively low temperature, and the specific method is a high method such as an attritor.
• the powder stirred by the high energy dispersion mill is subjected to high energy impact and repeats crushing, compression and adhesion.
• the powder is pulverized, a new surface is exposed, but it can be said that this new surface is active and easily oxidized. Therefore, by setting the atmosphere of stirring to water, the exposed new surface of the alloy is oxidized by water.
• the oxidation reaction in the high energy dispersion mill can proceed even at high temperatures. Therefore, since the alloy can be oxidized at room temperature, the problem of grain growth occurs 1 and the oxide can be in an ideal dispersion state.
• an alloy powder or alloy wire made of platinum and an additive metal is manufactured.
• an atomizing method gas atomization, water atomization
• the alloy powder produced here preferably has a particle size of 300 m or less. This is because if a particle having a larger particle size is used, a long time is required for the subsequent treatment by the high energy dispersion mill.
• alloy wire is used, the melted and forged alloy lump is manufactured by drawing or drawing. At this time, it may be cut appropriately for introduction into the apparatus.
• the alloy powder is introduced into a high energy ball mill together with water and stirred to oxidize the added metal in the alloy powder.
• a high energy ball mill is a device in which a steel ball or ceramic ball as a grinding medium is filled in a container, and a stirring blade is further arranged.
• a dynol mill and an ultra pisco mill are known.
• the constituent material of the high energy ball mill is a constituent material of the apparatus by high energy stirring. It is necessary to select materials in consideration of contamination by In the present invention, ceramic is preferred, and in particular, zircoure is preferred. This is because even if mixing of constituent materials is difficult to occur, it has the least effect on material properties.
• the diameter of the grinding medium is preferably 1 to: LOmm. If it is smaller than this, it is necessary to rotate the stirring blade at a high speed in order to compensate for the decrease in the pulverization force, and it becomes difficult to separate the powder from the pulverization medium after the oxidation treatment. If it is larger than this, the torque required for rotation will increase excessively, and the container will be more likely to damage the stirring blades.
• the filling amount of the grinding medium is preferably set with 50% of the container volume as a guideline, but harmful effects are unlikely to occur unless this value is excessively exceeded.
• the water to be introduced into the high energy ball mill together with the alloy is preferably highly pure, and particularly ultrapure water.
• the impurities adhere to the powder and are accompanied by the oxide dispersion type alloy that is produced. This is because it may cause gas generation and reduce its strength.
• the atmosphere in the container may be air, but an oxygen atmosphere is preferred. This is to prevent nitrogen in the air from being contained in the material.
• the added metal is oxidized by stirring in a high-energy ball mill, but if the final excess oxygen concentration is set to lOOppm or less, it is further added thereafter.
• An oxidation treatment in which the alloy powder is heated in an oxidizing atmosphere may be performed. This is because in the acid treatment using a high energy ball mill, if all of the added metal in the alloy powder is not oxidized (when the acid ratio is less than 100%), the heat treatment is performed later.
• the supplementary metal oxidation is performed to increase the amount of oxide.
• the conditions for this supplemental acid treatment are that the oxygen pressure is set to a high pressure of about 7 to 9 atmospheres, and the temperature is 700 Heating in the range of ⁇ 900 ° C preferable.
• oxygen shows a solid solution in platinum.
• the powder is heat-treated in a reduced pressure atmosphere at a temperature of 700 to 900 ° C. By doing so, it is possible to release excess oxygen.
• the above-described alloy powder that has been subjected to an acid bath treatment by a high energy ball mill can be formed into a Balta-like alloy by performing a forming and solidifying treatment.
• This molding and solidification treatment is preferably a method of sintering while applying pressure as in a hot press.
• the hot press conditions are preferably a temperature of 700 to 1300 ° C. and a press pressure of 1 OPa or more.
• the hot press atmosphere is preferably a vacuum atmosphere.
• the density of the alloy after the forming and solidifying treatment can be improved by forging.
• plastic molding such as rolling, extrusion, and drawing can be performed in order to form into a predetermined shape, and heat treatment may be performed for these plastic processing.
• the rolling rate of the material is important, and this enables the density of the acid-dispersed particles in the rolling direction and the plate thickness direction to be changed. That is, when the rolling process is performed, the distance between the oxide dispersed particles in the sheet thickness direction of the material is shortened while it is increased in the rolling direction.
• the rolling ratio is preferably 70% or more, and the higher the efficiency or the higher the efficiency, the higher the aspect ratio.
• FIG. 1 is a SEM image of platinum-zircoua alloy powder produced by the atomizing method in the first embodiment.
• FIG. 2 is an SEM image of alloy powder after the attritor treatment in the first embodiment.
• FIG. 3 is an SEM image of a wire after two hours of attritor processing in the third embodiment.
• FIG. 4 is an SEM image of a wire after 30 hours of attritor processing in the third embodiment.
• FIG. 5 is a photograph showing the state of a blow hole in a comparative example after welding.
• First embodiment IV platinum-0.05 wt% zirconium alloy was produced by vacuum melting, and the molten alloy was gas atomized in an argon atmosphere to produce platinum-zirconium alloy powder.
• the atomization conditions were a spray temperature of 2000 ° C and a gas pressure of 40 kPa.
• the particle size of the alloy powder at this time was 40 m.
• Figure 1 shows the SEM image of this alloy powder. As can be seen from Fig. 1, the alloy powder produced here is a nearly spherical powder.
• the alloy powder was taken out and filled in a die, and pre-sintered by heating at 1,200 ° C for 1 hour in an atmosphere of 1.5 X 10-2 Pa.
• the sintered alloy had dimensions of 40 mm X 40 mm X I 35 mm, a density of 7.42 gZcm3, and a density of 34.6%.
• the pre-sintered alloy was formed and solidified by hot pressing.
• the press temperature at this time was 1200 ° C., and the press pressure was 20 MPa.
• the atmosphere was a vacuum atmosphere of 1.5 X 10_2 Pa and the pressing time was 1 hour.
• an alloy compact having a size of 40.34 mm ⁇ 40.45 mm ⁇ 60.53 mm, a density of 16.23 gZcm 3 , and a density of 75.6% was obtained.
• the veg molded body for further improving the density was hot forged at a temperature of 1300 ° C.
• the alloy dimensions after forging were 65mm x 65mm x 18mm, and the density was about 100%.
• this alloy was cold rolled to a thickness of 4 mm, annealed by heat treatment (1250 ° C x 30 min), and further cold rolled to a thickness of 1. Omm, 0.8 mm, 0.3 mm.
• a plate of platinum-zirconium dispersed alloy was obtained.
• the excess oxygen concentration was quantified with an oxygen analyzer.
• the platinum material was dissolved in aqua regia, and the residue was filtered and weighed to determine the amount of zircoure (the amount of added metal oxide). From these measured values When calculating the excess oxygen concentration and the acid ratio of the platinum material of the embodiment, the excess oxygen concentration
• the oxygen concentration was 50%.
• the manufactured alloy was immersed in aqua regia (temperature 80 ° C.), dissolved in platinum and observed, and the particle size and dispersion state of the dispersed particles were confirmed.
• the particle size of the zirconium alloy of the platinum alloy of this embodiment was estimated to be 0.
• the average particle spacing was calculated as a regular tetrahedron model (dispersed particles placed at the apex of the regular tetrahedron), and was estimated to be 0.19 m.
• Second embodiment ⁇ Here, in the first embodiment, after the platinum alloy powder after the attritor treatment is further oxidized in an oxidation pot, the powder is molded and solidified under the same conditions as in the first embodiment. Platinum material.
• the acid treatment conditions were an oxygen pressure of 9 atm, a temperature of 800 ° C, and a heating time of 10 hours.
• the oxidation rate and excess oxygen concentration were calculated in the same manner as in the first embodiment.
• the excess oxygen concentration was 95 ppm
• the acid concentration was 100. %Met.
• the diameter of the dispersed particles and the state of dispersion were confirmed for the manufactured alloy. It was done.
• Third embodiment Here, the platinum alloy melt after vacuum melting in the first embodiment is formed into an ingot, which is drawn to obtain a 0.1 mm diameter wire, and then this wire is used. Cut to 3mm length. Then, this was subjected to attritor processing at 340 rpm for 30 hours.
• Figure 3 shows the state after 2 hours of the attritor treatment
• Figure 4 shows the state of the powder after 30 hours.
• the treated powder was heat treated under reduced pressure of 1.5 ⁇ 10 ” 2 Pa for 10 hours at 800 ° C.
• the powder was molded and solidified under the same conditions as in the first embodiment to obtain a platinum material.
• the oxidation rate and excess oxygen concentration of the platinum-zirconium dispersion alloy produced in this embodiment were calculated in the same manner as in the first embodiment. As a result, the excess oxygen concentration was 60 ppm and the oxidation rate was 100%.
• the particle size and dispersion state of the dispersed particles were confirmed for the manufactured alloy, it was estimated that the particle size of the zirconium particles was 0.02 m and the average particle spacing was 0.34. m was estimated.
• Comparative Example Here, a platinum material having a higher excess oxygen concentration than that of the first to third embodiments was produced.
• the platinum alloy powder after the attritor treatment is further removed in an oxidation pot. After the oxidation treatment, the powder was molded and solidified under the same conditions as in the first embodiment to obtain a platinum material.
• the oxidation treatment conditions were such that the oxygen pressure was 9 atm, the temperature was 800 ° C, and the heating time was 15 hours.
• the oxidation rate and excess oxygen concentration of the platinum-zirconium dispersion alloy produced in this comparative example were calculated in the same manner as in the first embodiment. As a result, the excess oxygen concentration was 115 ppm and the oxygen concentration rate was 100%.
• the platinum materials manufactured in each of the above embodiments and comparative examples were subjected to a creep rupture test. Further, the presence or absence of blowholes during welding and the occurrence of pre-stars when the materials were heated to a high temperature. The presence or absence was investigated.
• the creep rupture strength is 1400 using a 0.8mm thick plate. The time to break was measured at C and 20 MPa.
• the welding test was as follows: 1. The surface of the Omm thick plate was swept with an automatic welder, and the presence or absence of blowholes in the molten part was visually observed. In the heating test, a 0.3 mm thick plate was heated to 1700 ° C and held for 3 hours, and then the presence or absence of blistering on the surface was visually observed. The results of these studies are shown in the table below.
• the platinum material according to the present embodiment exhibited a good appearance without occurrence of blowholes and pre-stars after welding and after high-temperature heating.
• a slight amount of blowholes and blisters were observed.
• Figure 5 shows the state of blowholes during welding. Such blowholes and blisters are When used, the material grows into voids, resulting in a decrease in material strength.
• the oxide-dispersed platinum material according to the present invention is stable without causing a phenomenon that affects the material strength such as generation of blisters, even when used for a long period of time in a high temperature environment. Can be used. Also, the weldability is good, and a sound weld can be obtained without welding defects such as blow holes.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Powder Metallurgy (AREA)
• Manufacture Of Alloys Or Alloy Compounds (AREA)
• Contacts (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=36148290

Family Applications (1)

Country Status (8)

Cited By (4)

Families Citing this family (9)

Citations (3)

Family Cites Families (6)

• 2005
  • 2005-10-06 KR KR1020067016022A patent/KR20060122914A/ko not_active Application Discontinuation
  • 2005-10-06 TW TW094134944A patent/TWI299756B/zh active
  • 2005-10-06 RU RU2006127038/02A patent/RU2333974C2/ru active
  • 2005-10-06 EP EP05790584A patent/EP1712646A4/en not_active Withdrawn
  • 2005-10-06 US US10/583,827 patent/US20090047170A1/en not_active Abandoned
  • 2005-10-06 CN CNB2005800030326A patent/CN100507041C/zh active Active
  • 2005-10-06 WO PCT/JP2005/018519 patent/WO2006040995A1/ja active Application Filing
  • 2005-10-06 JP JP2006540903A patent/JPWO2006040995A1/ja active Pending

Patent Citations (3)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events