CN103975414B - Tungsten alloy part and the discharge lamp using this tungsten alloy part, transmitting tube and magnetron - Google Patents

Tungsten alloy part and the discharge lamp using this tungsten alloy part, transmitting tube and magnetron Download PDF

Info

Publication number
CN103975414B
CN103975414B CN201280060372.2A CN201280060372A CN103975414B CN 103975414 B CN103975414 B CN 103975414B CN 201280060372 A CN201280060372 A CN 201280060372A CN 103975414 B CN103975414 B CN 103975414B
Authority
CN
China
Prior art keywords
tungsten alloy
tungsten
zro
alloy part
discharge lamp
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201280060372.2A
Other languages
Chinese (zh)
Other versions
CN103975414A (en
Inventor
山本慎
山本慎一
中野佳代
堀江宏道
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Toshiba Materials Co Ltd
Original Assignee
Toshiba Corp
Toshiba Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toshiba Corp, Toshiba Materials Co Ltd filed Critical Toshiba Corp
Publication of CN103975414A publication Critical patent/CN103975414A/en
Application granted granted Critical
Publication of CN103975414B publication Critical patent/CN103975414B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J23/00—Details of transit-time tubes of the types covered by group H01J25/00
    • H01J23/02—Electrodes; Magnetic control means; Screens
    • H01J23/04—Cathodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J23/00—Details of transit-time tubes of the types covered by group H01J25/00
    • H01J23/02—Electrodes; Magnetic control means; Screens
    • H01J23/04—Cathodes
    • H01J23/05—Cathodes having a cylindrical emissive surface, e.g. cathodes for magnetrons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J25/00—Transit-time tubes, e.g. klystrons, travelling-wave tubes, magnetrons
    • H01J25/50—Magnetrons, i.e. tubes with a magnet system producing an H-field crossing the E-field
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/04—Electrodes; Screens; Shields
    • H01J61/06—Main electrodes
    • H01J61/073—Main electrodes for high-pressure discharge lamps
    • H01J61/0735—Main electrodes for high-pressure discharge lamps characterised by the material of the electrode

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Discharge Lamp (AREA)
  • Powder Metallurgy (AREA)
  • Solid Thermionic Cathode (AREA)

Abstract

The present invention provides one kind to comprise tungsten and be selected from Zr, ZrO2, ZrC and C at least two compositions tungsten alloy part.Tungsten alloy part contains with ZrO2Conversion is calculated as the Zr of 0.1～5wt%.

Description

Tungsten alloy part and the discharge lamp using this tungsten alloy part, transmitting tube and magnetic Keyholed back plate
Technical field
Embodiments of the present invention be related to tungsten alloy part and using the discharge lamp of this tungsten alloy part, transmitting tube and Magnetron.
Background technology
Tungsten alloy part is used in field miscellaneous because of the elevated temperature strength of tungsten.For example, as discharge lamp, send out Penetrate pipe, magnetron.In discharge lamp (HID lamp), tungsten alloy part is used as cathode electrode, electrode support rod, coil component Deng.In transmitting tube, tungsten alloy part is used as filament or mesh grid etc..In magnetron, tungsten alloy part is used as Coil component etc..These tungsten alloy parts are taken to be had the sintered body of regulation shape, wire rod, wire rod is formed as the line of coiled type The shape of coil component.
In the past, using as described in Japanese Patent Laid-Open 2002-226935 publication (patent documentation 1) containing thorium (or Thorium compound) tungsten alloy as these tungsten alloy parts.The tungsten alloy of patent documentation 1 is to make thorium particle and thorium compound particle Fine dispersion is carried out below 0.3 μm with mean diameter, makes the alloy that deformation resistance improves.Because the emitter-base bandgap grading of the tungsten alloy of thoriated Mechanical strength under characteristic and high temperature, so be used in aforesaid field.
But, because thorium or thorium compound are radioactive substances, it is contemplated that to the impact to environment, expecting not using thorium Tungsten alloy part.In Japanese Patent Laid-Open 2011-103240 publication (patent documentation 2), develop containing lanthanum boride (LaB6) tungsten alloy part as the tungsten alloy part not using thorium.
In addition, recorded in patent documentation 3 employing containing lanthana (La2O3) and HfO2Or ZrO2Tungsten alloy Short circuiting arc type high-pressure discharge lamp.The tungsten alloy recorded by patent documentation 3 can not obtain enough emission characteristicss.This is because The fusing point of lanthana is 2300 DEG C about, relatively low, is improving applied voltage or electric current density, when part reaches a high temperature, oxidation Lanthanum is evaporated long since, and emission characteristicss decline.
Prior art literature
Patent documentation
Patent documentation 1:Japanese Patent Laid-Open 2002-226935 publication
Patent documentation 2:Japanese Patent Laid-Open 2011-103240 publication
Patent documentation 3:No. 4741190 publication of Japanese Patent Laid
Content of the invention
For example, by the discharge lamp of one of tungsten alloy part purposes be roughly divided into low-pressure discharge lamp and high-pressure discharge lamp this two Kind.Low-pressure discharge lamp can enumerate general lighting, using in the special lighting of road or tunnel etc., paint solidification device, UV The discharge lamp of the various arc discharge types of the light cleaning device of solidification equipment, sterilizing unit, quasiconductor etc. etc..In addition, High-pressure discharge lamp can be enumerated：The outdoor lighting of the processing meanss of water supply and draining, general lighting, arena etc., UV solidification dress Put, the high voltage mercury lamp of the exposure device of quasiconductor or printed base plate etc., wafer inspector, projector etc., metal halide Lamp, ultrahigh pressure mercury lamp, xenon lamp, sodium vapor lamp etc..
Discharge lamp applies the voltage of more than 10V according to its purposes.Tungsten containing lanthanum boride described in patent documentation 2 is closed Gold with less than 100V applied voltage it becomes possible to obtain the life-span equal with the tungsten alloy of thoriated.But, increase to voltage More than 100V, emission characteristicss reduce, and its result is also to greatly shorten in the life-span.
With regard to transmitting tube and magnetron, similarly there is increasing it is impossible to obtain enough characteristics with applied voltage Problem.
It is an object of the invention to provide thorium as radioactive substance is not used, show the tungsten alloy part phase with thoriated With or the tungsten alloy part in its above characteristic and using the discharge lamp of this tungsten alloy part, transmitting tube and magnetron.
According to embodiment, one kind is provided to comprise tungsten and be selected from Zr, ZrO2, ZrC and C at least two compositions (hereinafter referred to as For Zr composition) tungsten alloy part.Tungsten alloy part contains with ZrO2Conversion is calculated as the described Zr composition of 0.1～5wt%.Tungsten closes Golden part preferably contains with ZrO2Conversion is calculated as the described Zr composition of 0.1～3wt%.The content of Zr and O is scaled ZrOx When, preferably x ＜ 2, more preferably 0 ＜ x ＜ 2.
Tungsten alloy part can also containing below 0.01wt% selected from K, Si and Al at least one element.Additionally, tungsten Alloy can the Ti containing below 2wt%, Hf, V, Nb, Ta, Mo, at least one in rare earth element.Particularly by Zr's When total content is denoted as 100 mass parts, can be containing the Hf below 15 mass parts.
ZrO2Primary particle less than 15 μm more fortunately of mean diameter, more preferably mean diameter below 5 μm, maximum diameter Below 15 μm.ZrO2Offspring less than 100 μm more fortunately of maximum diameter.
Described Zr composition is preferably as ZrO2Exist with metal Zr both forms.At least a portion of metal Zr is preferable It is to be solid-solubilized in tungsten.Metal Zr is preferably present in the surface of tungsten alloy part.Additionally, the total content of Zr is denoted as 100 mass During part, constitute ZrO2Zr content be preferably 30～98 mass parts.
The line footpath of tungsten alloy part is preferably 0.1～30mm, Vickers hardness Hv more fortunately more than 330, spy fortunately 330～ In the range of 700.
Electrode for discharge lamp part preferably has makes the leading section of taper and columned main part by its front end Part.When observing the crystalline structure of cross section (radial section) of main part, per unit area (such as 300 300 μm of μ m) On, there is the area occupation ratio more fortunately more than 90% of the tungsten crystallization of 1～80 μm of crystallization particle diameter.In the longitudinal section observing main part During crystalline structure, on per unit area (such as 300 300 μm of μ m), there is the face of the tungsten crystallization of 2～120 μm of crystallization particle diameter Long-pending rate more fortunately more than 90%.
The tungsten alloy part of embodiment is used for such as use for discharge lamp part, transmitting tube part or magnetron portion Part.
The discharge lamp of embodiment is the use of the discharge lamp of the tungsten alloy part of embodiment.The transmitting tube of embodiment It is the use of the transmitting tube of the tungsten alloy part of embodiment.The magnetron of embodiment is the use of the tungsten alloy of embodiment The magnetron of part.
When the tungsten alloy part of embodiment is applied to the electrode of discharge lamp, applying voltage on this electrode is more fortunately More than 100V.Constitute electrode for discharge lamp embodiment tungsten alloy part because do not contain radioactive substance thorium (or acid Change thorium), so baneful influence is not produced to environment.And the electrode for discharge lamp tool being made up of the tungsten alloy part of embodiment There is the electrode for discharge lamp constituting with by the tungsten alloy of thoriated identical or in its above characteristic.For this reason, employing embodiment Tungsten alloy part discharge lamp environmentally friendly.
Brief description
Fig. 1 is showing the figure of of the electrode for discharge lamp part of embodiment.
Fig. 2 is showing other figure of the electrode for discharge lamp part of embodiment.
Fig. 3 is showing the figure of of the discharge lamp of embodiment.
Fig. 4 is showing the figure of of the magnetron part of embodiment.
Fig. 5 is showing the figure of of the electrode for discharge lamp part of embodiment.
Fig. 6 is showing other figure of the electrode for discharge lamp part of embodiment.
Fig. 7 is showing the figure of of the cross section of the main part of electrode for discharge lamp part of embodiment.
Fig. 8 is showing the figure of of the longitudinal section of the main part of electrode for discharge lamp part of embodiment.
Fig. 9 is showing the figure of of the discharge lamp of embodiment.
Figure 10 is the figure of the relation of emission-applied voltage showing embodiment 1 and comparative example 1.
Specific embodiment
The tungsten alloy part of embodiment comprises tungsten and is selected from Zr, ZrO2, at least two compositions of ZrC and C, and contain With ZrO2Conversion is calculated as the Zr of 0.1～5wt%.Preferably contain with ZrO2Conversion is calculated as the Zr of 0.1～3wt%.
By containing with ZrO2(zirconium oxide) conversion is calculated as the Zr (zirconium) of 0.1～5wt%, it is possible to increase emission characteristicss and strong The characteristic of degree etc..That is, if Zr content is with ZrO2Conversion meter is less than 0.1wt%, then the effect added is inadequate, if it exceeds 3wt%, then characteristic reduction.Zr content is with ZrO2Conversion meter is preferably 0.5～2.5wt%.
In the tungsten alloy part of embodiment, containing selected from Zr, ZrO2, at least two compositions of ZrC and C.Specifically, ZrO is contained with any one in following compound modes2Composition：Zr and ZrO2Combination, ZrO2Combination with ZrC (zirconium carbide), ZrO2Combination with C (carbon), Zr and ZrO2Combination with ZrC, ZrO2Combination with ZrC and C, Zr and ZrO2Combination with C, Zr And ZrO2Combination with ZrC and C (carbon).If relatively respective fusing point, metal Zr is 1850 DEG C, ZrO2For 2720 DEG C, ZrC is 3420 DEG C, tungsten is 3400 DEG C (referring to Yan Bo bookstore (Yan Bodian)《Physicochemical topical reference book》).The fusing point of metal thorium be 1750 DEG C, Thorium oxide (ThO2) fusing point be 3220 ± 50 DEG C.Zirconium because having the fusing point higher than thorium, the tungsten alloy portion of embodiment Part, compared with the tungsten alloy part of thoriated, can make elevated temperature strength identical or more than it.
The content of Zr and O is scaled ZrOxWhen, preferably x ＜ 2.X ＜ 2 means contained ZrO in tungsten alloy2Composition It is not all with the ZrO of Chemical Measurement2Form exist, but a portion is formed as metal Zr and ZrC.The work(of metal Zr Function is 4.1, and the work function 3.4 than metal Th is larger, it is believed that emission characteristicss reduce, but in the purposes such as use for discharge lamp Do not become significant problem.In addition, metal zirconium is because form solid solution with tungsten, it is the effective unit improving intensity Element.The content of Zr and O is scaled ZrOxWhen, preferably 0 ＜ x ＜ 2.With regard to x ＜ 2, as previously mentioned.0 ＜ x is meant that tungsten Exist in alloy ZrC or C any one.ZrC or C has the deoxidation effect removing the impurity oxygen contained by tungsten alloy.Because The resistance value of tungsten part can be reduced by reducing impurity oxygen, so improving the characteristic as electrode.ZrOxIf x in above-mentioned model In enclosing, metal Zr, ZrO2, ZrC or C then can balance presence, the characteristic in emission characteristicss, intensity, resistance, life-span etc. improves.
Zr, ZrO in tungsten alloy part2, the content of ZrC, O can use icp analysis method and noble gases melting-infrared ray Absorption process measures.Can be measured the Zr amount of metal Zr and ZrO with icp analysis method2And ZrC Zr amount total obtained by Zr amount. By noble gases melting-infrared absorption, can measure ZrOxO (oxygen) amount and the oxygen amount of individualism or conduct Other oxides exist oxygen amount add up to obtained by oxygen amount.In embodiment, melted by icp analysis method and noble gases-red Outside line absorption process measures Zr amount, O amount, is converted into ZrOx.
The tungsten alloy part of embodiment can containing below 0.01wt% selected from K, Si and Al at least one element.K (potassium), Si (silicon), Al (aluminum) are so-called dopant materials, can improve recrystallization characteristic by adding these dopant materials. By improving recrystallization characteristic, it is easy for when carrying out recrystallization heat treatment obtaining uniform recrystallization tissue.For blending material The lower limit of the amount of material is not particularly limited, preferably more than 0.001wt%.If less than 0.001wt%, the effect meeting of interpolation Reduce；If it exceeds 0.01wt%, agglutinating property and processability can be deteriorated, production may decline.
In the tungsten alloy part of embodiment, when the content of Zr is denoted as 100 mass parts, preferably also contain 15 mass parts Following Hf.The content of Zr represents Zr, ZrO2Zr amount with the total of ZrC.The fusing point of Hf (hafnium) is 2207 DEG C, higher, so Even if being contained in tungsten alloy part, harmful effect is also few.Commercially available Zr powder is different according to grade, also can contain several percentage points Hf.Using the high-purity Zr powder eliminating impurity or high-purity ZrO2Powder, is effective on characteristic improves.But, raw material High purity becomes the principal element of cost increase.When Zr is denoted as 100 weight portion, if the content of Hf (hafnium) is in 15 mass parts Hereinafter, characteristic excessive descent will not be made.
For the tungsten alloy part of embodiment, the carbon amounts of surface element is denoted as C1 (wt%), by the carbon amounts note of central part When making C2 (wt%), preferably C1 ＜ C2.Surface element represents the part starting to 20 μm from the surface of tungsten alloy part.In Center portion refers to the core in the section of tungsten alloy part.This carbon amounts be the carbon of the carbide of ZrC etc. and individualism carbon this It is worth obtained by both are total, be analyzed by burning-infrared absorption.The carbon amounts of the carbon amounts C1 ＜ central part of surface element C2 represents that the carbon of surface element becomes CO by deoxidation2, and go to outside system.If the carbon amounts of surface element reduces, surface element Zr amount relatively increase.For this reason, when Zr being used as emitter materials, especially effectively.
The tungsten crystallization that the tungsten alloy part of embodiment is preferably 1～100 μm containing average crystallite particle diameter.Tungsten alloy part Preferably sintered body.If sintered body, the part of variety of shapes then can be made by using forming process.By implementing Sintered body is easily processed into wire rod (inclusion filament) and coil component etc. by forging process, calendering procedure, wire-drawing process etc..Sintering The tungsten crystallization of body is isotropism crystalline structure more than 90% for the crystallization that length-width ratio is less than 3.If by such sintered body Wire Drawing, then can form flat crystals tissue more than 90% for the crystallization more than 3 for the length-width ratio.The particle diameter of tungsten crystallization is as follows Described try to achieve：First, crystalline structure is shot by the enlarged photograph of metallurgical microscopes etc..For 1 existing in this section Individual tungsten crystallization, measures maximum Fu Leite diameter (Japanese：Maximum Off ェ レ footpath), as particle diameter.Tungsten to any 100 Crystallization carries out this mensure, is averaged value as average crystallite particle diameter.
If the meansigma methodss of the maximum Fu Leite diameter of tungsten crystallization little to less than 1 μm, more difficult make Zr, ZrO2, ZrC or C Dispersion component reach uniform dispersity.If this is because tungsten crystallization maximum Fu Leite diameter meansigma methodss little to not Sufficient 1m, then crystal boundary diminish, dispersion component is difficult to be dispersed on the crystal boundary between tungsten crystallization.On the other hand, if tungsten crystallization The meansigma methodss of maximum Fu Leite diameter big arrive more than 100 μm, then as the intensity decline of sintered body.Therefore, tungsten crystallizes Preferably 1～100 μm of the meansigma methodss of big Fu Leite diameter, more preferably 10～60 μm.
From the viewpoint of dispersed, Zr, ZrO2, ZrC or C the maximum Fu Leite diameter of dispersion component meansigma methodss Preferably it is less than the meansigma methodss of the maximum Fu Leite diameter of tungsten crystallization.Specifically, in the maximum Fu Leite diameter crystallizing tungsten Meansigma methodss be denoted as A (μm), when the meansigma methodss of the maximum Fu Leite diameter of dispersion component are denoted as B (μm), preferably B/A≤ 0.5.Zr、ZrO2, the dispersion component of ZrC or C be present in tungsten crystallization between crystal boundary, emitter materials or intercrystalline strengthening material can be played The function of material.By the mean diameter of dispersion component is reduced to less than the 1/2 of the average crystallite particle diameter of tungsten, dispersion component then holds Easily it is dispersed on the crystal boundary of tungsten crystallization, reduce the uneven of characteristic.
Aforesaid tungsten alloy part be relatively used on use for discharge lamp part, transmitting tube part, at least the 1 of magnetron part Kind.
As use for discharge lamp part, cathode electrode used by discharge lamp, electrode supporting rod, coil component can be enumerated.Fig. 1 and Fig. 2 shows of use for discharge lamp cathode electrode.The 1 of in figure is cathode electrode, and 2 is electrode body portion, and 3 is the front end of electrode Portion.Cathode electrode 1 is formed by the sintered body of tungsten alloy.The front end of electrode leading section 3 can be the truncated cone shown in Fig. 1, also may be used To be the cone shown in Fig. 2.As needed, leading section is ground processing.Electrode body portion 2 preferably diameter 2～ 35mm, long 10～600mm cylindric.
Fig. 3 shows of discharge lamp.In figure 1 is cathode electrode, and 4 is discharge lamp, and 5 is electrode support rod, and 6 is glass Pipe.In discharge lamp 4, to make to configure a pair of cathode electrode 1 in the way of electrode leading section is opposite.Cathode electrode 1 and electrode support Rod 5 joint.The inner face of glass tubing 6 is provided with luminescent coating (not shown).As needed the inside of glass tubing 6 enclose hydrargyrum, Halogen, argon (or neon) etc..In the case that the tungsten alloy part of embodiment is used as electrode supporting rod 5, can be entirely electric Pole supporting rod is the tungsten alloy that the tungsten alloy of embodiment or the part engaging with cathode electrode use embodiment, And the shape that remainder is engaged with other lead materials.
Species according to discharge lamp, it is possible to use coil component is arranged on electrode support rod and uses as electrode Discharge lamp.The tungsten alloy that embodiment can also be used is as this coil component.
The discharge lamp of embodiment is the use of the discharge lamp of the tungsten alloy part of embodiment.Species for discharge lamp It is not particularly limited, go for any one in low-pressure discharge lamp and high-pressure discharge lamp.Low-pressure discharge lamp can enumerate common photograph Bright, using in the special lighting of road or tunnel etc., paint solidification device, UV solidification equipment, sterilizing unit, quasiconductor etc. The various arc discharge types of light cleaning device etc. discharge lamp.In addition, high-pressure discharge lamp can be enumerated：Supply water and draining Processing meanss, general lighting, the outdoor lighting of arena etc., UV solidification equipment, the exposure of quasiconductor or printed base plate etc. The high voltage mercury lamp of electro-optical device, wafer inspector, projector etc., metal halide lamp, ultrahigh pressure mercury lamp, xenon lamp, sodium vapor lamp etc..
The tungsten alloy part of embodiment is also suitable as transmitting tube part.As transmitting tube part, enumerate Filament or mesh grid.Mesh grid can be by webbed for yarn woven mesh grid or in sintered body plate The upper mesh grid forming multiple holes.The transmitting tube of embodiment is because employ the tungsten alloy part of embodiment as transmitting Effective part, so emission characteristicss etc. are more satisfactory.
The tungsten alloy part of embodiment is also suitable as magnetron part.As magnetron part, can arrange Lift coil component.Fig. 4 shows the magnetron cathode structure body as of magnetron part.In figure 7 is coil portion Part, 8 is upper support member, and 9 is lower support part, and 10 is support rod, and 11 is magnetron cathode structure body.Upper support Part 8 and lower support part 9 are integrally formed by support rod 10.The surrounding of support rod 10 is configured with coil component 7, with top Supporting member 8 and lower support part 9 are integrally formed.Such magnetron part is suitable for microwave oven.More handy line footpath 0.1 The tungsten wire material of～1mm makes coil component.The diameter of coil component preferably 2～6mm.In the tungsten alloy portion using embodiment When part is as magnetron part, show excellent emission characteristicss and elevated temperature strength.For this reason, can improve that tungsten alloy portion is employed The reliability of the magnetron of part.
Then, the manufacture method of the tungsten alloy part of embodiment is illustrated.The tungsten alloy part of embodiment is only There is aforesaid construction, its manufacture method is not particularly limited, following method can be enumerated as efficient manufacture method.
First, prepare the tungsten powder as raw material.Preferably 1～10 μm of the mean diameter of tungsten powder.If mean diameter Less than 1 μm, then the easy coagulation of tungsten powder, it is difficult to make ZrO2Composition is dispersed.If mean diameter is more than 10 μm, as sintering The average crystallite particle diameter of body is then possible to more than 100 μm.The purity of tungsten powder is different according to purposes difference, more fortunately More than 99.0wt%, more preferably in the high-purity of more than 99.9wt%.
Then, prepare the ZrO as Zr composition2Powder, the ZrC powder as ZrC composition.Also Zr powder and carbon can be used The mixture of powder is to replace ZrC powder.Also ZrC powder can not be used alone, and be used in ZrC powder being mixed with Zr powder The powder of end or 1～2 kind of carbon dust.Wherein, preferably using ZrO2Powder or ZrC powder.ZrC powder is in sintering circuit In, a part of carbon is decomposed, and reacts with the impurity oxygen in tungsten powder, generates carbon dioxide, is discharged into beyond system, and tungsten is closed The homogenization of gold contributes, thus ideal.In the case of the mixed-powder using Zr powder and carbon dust, in order to by Zr Both powder and carbon dust uniformly mix, and increased the load of manufacturing process.Because metal Zr easily aoxidizes, preferably make Use ZrC powder.
As in the after-mentioned, ZrO2Less than 15 μm more fortunately of the mean diameter of the primary particle of powder, more preferably 0.5～5 μm. If mean diameter is less than 0.5 μm, ZrO2The coagulation of powder increases, and is difficult to make it dispersed.If mean diameter exceedes 15 μm, then it is difficult to make it dispersed on the crystal boundary of tungsten crystallization.Preferably 0.5～5 μm of the mean diameter of ZrC powder.If Less than 0.5 μm, the coagulation of ZrC powder increases mean diameter, is difficult to make it dispersed.If mean diameter is more than 5 μm, very Difficulty makes it dispersed on the crystal boundary of tungsten crystallization.From the viewpoint of dispersed, preferably ZrO2Powder or ZrC powder The mean diameter of mean diameter≤tungsten powder.
As it was previously stated, by ZrO2When the Zr amount of powder, ZrC powder and Zr powder is denoted as 100 mass parts, Hf content is preferable Below 15 mass parts, more preferably below 10 mass parts.Hf amount is more few better, but the high purity of raw material can become cost increase Principal element, so Hf measure more preferably 0.1～3 mass parts.
As needed, add the dopant material of at least one element selected from K, Si and Al, its addition is preferably Below 0.01wt%.
Then each material powder is uniformly mixed.Mixed processes are preferably carried out using the mixer of ball mill etc..Mixing work Sequence is preferably by more than 8 hours, more preferably more than 20 hours.As needed it is also possible to mix with organic bond, organic solvent Slurry is made in conjunction.Also granulating working procedure can be carried out as needed.
Then formed body is made with mould.As needed degreasing process is carried out to formed body.Then, it is sintered work Sequence.Sintering circuit is preferably carried out in the inert atmosphere of hydrogen, nitrogen etc. or vacuum.Sintering is more fortunately at 1400～3000 DEG C of temperature Carry out 1～20 hour.If less than 1400 DEG C or sintering time was less than 1 hour for sintering temperature, sinter insufficient, sintered body Intensity declines.If more than 3000 DEG C or sintering time was more than 20 hours for sintering temperature, tungsten crystallization may excessively grain life Long.By being sintered in hydrogen, inert atmosphere or vacuum, the carbon of sintered body surface element easily can be discharged into system Outward.Sintering can be carried out by resistance sintering, normal pressure-sintered, pressure sintering etc., and this is not particularly limited.
Then, enter to be about to the operation that sintered body is processed as part.As manufacturing procedure, forging process, flattener can be enumerated Sequence, wire-drawing process, cutting action, grinding step etc..When being processed as coil component, coiling operation (Japanese can be enumerated：コイリ Application グ engineering).When making the mesh grid as transmitting tube part, can enumerate and filament is processed webbed operation.
Then as needed the part processing is carried out correcting heat treatment.Correct heat treatment more fortunately inert atmosphere or Carry out in the range of 1300～2500 DEG C in vacuum.Can be relaxed produced in the operation be processed into part by rectification heat treatment Internal stress, to improve the intensity of part.
The tungsten alloy part of embodiment preferably contains with ZrO2Conversion is calculated as the Zr of 0.1～5wt%, and ZrO2Particle Primary particle mean diameter below 15 μm.
Tungsten alloy part preferably contains ZrO2With Zr both.For ZrO2(hafnium oxide), the atomic ratio of O/Zr is not limited to 2, Also can be in 1.6～2 scope.Zr content is with ZrO2(O/Zr atomic ratio=2) conversion is calculated as 0.1～5wt%.Zr is in discharge lamp With playing the composition of emitter materials function in electrod assembly.The content of Zr is with ZrO2When conversion meter is less than 0.1wt%, emission characteristicss Not.If it exceeds 5wt% is it is likely that lead to intensity decline etc..For this reason, Zr is with ZrO2Conversion meter preferably 0.3～ 3.0wt%, more preferably 0.5～2.5wt%.
ZrO2Existed with the form of particle, ZrO2Primary particle less than 15 μm more fortunately of mean diameter.ZrO2Particle is deposited It is on the crystal boundary between tungsten crystalline particle.If for this reason, ZrO2Particle is excessive, then the gap between tungsten crystalline particle can increase Greatly, become density and decline the reason decline with intensity.If ZrO2Particle is present on the crystal boundary between tungsten crystalline particle, not only Play the function of emissive material moreover it is possible to play the function of dispersion-strengthened material, so the intensity to raising electrod assembly is favourable 's.
ZrO2The mean diameter of the primary particle of particle more fortunately less than 5 μm and maximum diameter below 15 μm.In addition, ZrO2 The mean diameter of the primary particle of particle more fortunately less than more than 0.1 μm 3 μm and maximum diameter less than 10 μm more than 1 μm.If Using the little ZrO that mean diameter is less than 0.1 μm or maximum diameter is less than 1 μm2Particle, because consumption produced by transmitting can consume early To the greatest extent.In order to extend the life-span as electrode, preferably ZrO2The mean diameter of particle more than 0.1 μm or maximum diameter 1 μm with On.
ZrO in tungsten alloy part2The dispersity of particle is preferably：Long 200 μm of arbitrary line there are 2～ 30 ZrO2The scope of particle.If ZrO2The number of particle is on the straight line of 200 μm of every length less than 2 (0～1), part The ZrO in region2Particle tails off, and the inhomogeneities of transmitting increase.On the contrary, if ZrO2The number of particle is straight 200 μm of every length More to more than 30 (more than 31), the ZrO of subregion on line2Particle is excessive, it is possible to produce intensity decline etc. severe Impact.ZrO2The dispersity of particle is investigated by the arbitrary section of bust shot tungsten alloy.The multiplying power of enlarged photograph exists More than 1000 times.Long 200 μm of arbitrary line (line rugosity is 0.5mm) is drawn on enlarged photograph, calculates existing on this line ZrO2The number of particle.
ZrO2Offspring less than 100 μm more fortunately of maximum diameter.ZrO2Offspring refer to the coagulation of primary particle Body.If greatly to more than 100 μm, the intensity of tungsten alloy part then can decline offspring.For this reason, ZrO2The offspring of particle Maximum diameter below 100 μm, less than 50 μm more fortunately, be more preferably small enough to less than 20 μm.
In Zr composition, with regard to Zr (metal Zr), there is dispersity miscellaneous.
First dispersity is the state that metal Zr exists as particle.Metal Zr particle and ZrO2Particle similarly there are On the crystal boundary between tungsten crystalline particle.By being present on the crystal boundary between tungsten crystalline particle, metal Zr particle also can play Function as emissive material and dispersion-strengthened material.For this reason, the mean diameter of the primary particle of metal Zr more fortunately 15 μm with Under, more preferably below 10 μm, more preferably 0.1～3 μm further.The maximum diameter of the primary particle of metal Zr more fortunately 15 μm with Under, more preferably below 10 μm.When making tungsten alloy, can be in advance by ZrO2Particle and metal Zr mix particles, also can manufacture By ZrO in operation2Particle deoxidation, generates metal Zr particle.If using to ZrO2The method that particle carries out deoxidation, also can obtain Oxygen in tungsten is released into the effect outside system, thus ideal.If can deoxidation, the resistance of tungsten alloy can be reduced, So the electric conductivity as electrode can be improved.
Second dispersity is that metal Zr is present in ZrO2The state on the surface of particle.Identical with the first dispersity, During the sintered body of making tungsten alloy, oxygen is from ZrO2Particle surface deoxidation, is formed at the state that surface is formed with metal Zr envelope.I.e. Making is the ZrO with metal Zr envelope2Particle, displays that excellent emission characteristicss.Additionally, the ZrO with metal Zr envelope2's Less than 15 μm more fortunately of the mean diameter of primary particle, more preferably below 10 μm, more preferably 0.1～3 μm further.Additionally, band There is the ZrO of metal Zr envelope2Primary particle less than 15 μm more fortunately of maximum diameter, more preferably below 10 μm.
3rd dispersity is some or all states being solid-solubilized in tungsten of metal Zr.Metal Zr and tungsten form solid Solution.The intensity of tungsten alloy can be improved by forming solid solution.The presence or absence of solid solution can be judged by XRD analysis.First, survey Determine the content of Zr composition and oxygen.The content of Zr and oxygen is scaled ZrOx, confirm x ＜ 2.Then, carry out XRD analysis and confirm do not have The peak of detection metal Zr.So, although ZrOxX be less than 2, existed with not becoming the zirconic zirconium in Chemical Measurement, do not have The peak having detection metal Zr means that metal Zr is solid-solubilized in tungsten.
On the other hand, in ZrOxX be less than 2, exist and detect gold not become the zirconic zirconium in Chemical Measurement It is meant that being that metal Zr does not have solid solution but is present in the first dispersion on the crystal boundary between tungsten crystallization in the case of belonging to the peak of Zr State.Additionally, the second dispersity can (transmission electron be micro- by using EPMA (electron probe microanalyzer) or TEM Mirror) it is analyzed.
The dispersity of metal Zr can be the first dispersity, the second dispersity, any in the 3rd dispersity One or more kinds of combinations.
When the total content of Zr is denoted as 100 mass parts, become ZrO2The ratio of the Zr of particle preferably 30～98 mass parts. Zr can also be entirely ZrO2Particle.If ZrO2Particle just can obtain emission characteristicss.In addition, being disperseed by making metal Zr, Electric conductivity and the intensity of tungsten alloy can be improved.But, if Zr is entirely metal Zr, emission characteristicss and elevated temperature strength drop Low.The fusing point of metal Zr is 1850 DEG C, ZrO2Fusing point be 2720 DEG C, the fusing point of tungsten is 3400 DEG C.Because ZrO2Fusing point Higher than the fusing point of metal Zr, so containing ZrO2Tungsten alloy part elevated temperature strength improve.Because ZrO2Surface current density With ThO2Essentially identical, so it is same with the tungsten alloy part containing thorium oxide to circulate in the tungsten alloy part of embodiment Electric current.For this reason, when the tungsten alloy part by embodiment is using electrode in discharge lamp, because setting and containing thorium oxide The same electric current density of tungsten alloy electrode, so do not need the design of Variation control circuit etc..In terms of these viewpoints, Zr is being become When the total content dividing is denoted as 100 mass parts, constitute ZrO2Zr content preferably 30～98 mass parts, more preferably 60～95 matter Amount part.
ZrO in tungsten alloy2Proceed as described below analysis with the content of metal Zr.Tungsten alloy is measured by icp analysis method In total Zr amount.Then, the total oxygen demand in tungsten alloy is measured by noble gases melting-infrared absorption.In tungsten alloy it is It is believed that measured total oxygen demand substantially all becomes for ZrO during the binary system of tungsten and Zr2.For this reason, according to being surveyed The total Zr amount obtaining and total oxygen demand are it becomes possible to calculate ZrO2Amount.In the case of the method, O/Zr is set as 2, calculates ZrO2Amount.
With regard to ZrO2The size of particle, shoots the enlarged photograph of the arbitrary section of tungsten alloy sintered body, measures in this section Existing ZrO2The long-diagonal of particle, as ZrO2Primary particle particle diameter.ZrO to 502Particle is carried out This mensure, is averaged value as ZrO2Primary particle mean diameter.By ZrO2Primary particle particle diameter (the longest diagonal Line) in maximum as ZrO2Primary particle maximum diameter.
The tungsten alloy part of embodiment can containing below 2wt% selected from Ti, V, Nb, Ta, Mo and rare earth element extremely A kind of few element.Selected from Ti, V, Nb, Ta, Mo and rare earth element at least one element with metal simple-substance, oxide, carbide In any one form exist.Also can be containing the two or more element in these elements.Even if containing two or more units In the case of element, its total amount also below 2wt% more fortunately.These elements primarily serve the function of dispersion-strengthened material.ZrO2Grain Son, because playing the function of emissive material, will be consumed using during discharge lamp for a long time.On the other hand, Ti, V, Nb, The emission characteristicss of Ta, Mo and rare earth element are weak, so the consumption causing because of transmitting is few, can be maintained as dispersion-strengthened material for a long time Function.Lower limit for the content of these elements is not particularly limited, but preferably more than 0.01wt%.In these elements preferably For rare earth element.The atomic radius of rare earth element is in more than 0.16nm, larger, so being favourable on increasing surface current density 's.In other words, preferably be used containing atomic radius the metal simple-substance of the element in more than 0.16nm or its compound as dividing Scattered strengthening material.
Fig. 5 and Fig. 6 shows of the electrode for discharge lamp part of embodiment.In figure, 21 is electrode for discharge lamp Part, 22 is the electrode for discharge lamp part of the leading section with taper, and 23 is leading section, and 24 is main part.Discharge lamp electricity consumption Pole part 21 is cylindric, and its leading section 23 is processed as taper, forms electrode for discharge lamp part 22.Before being processed as taper Electrode for discharge lamp part 21 be usually cylindrical shape but it is also possible to be quadrangular shape.
Electrode for discharge lamp part preferably has makes the leading section of taper and columned main part by its front end Part.By forming taper, that is, form the shape fined away in leading section and just can improve the spy as electrode for discharge lamp part Property.As shown in fig. 6, the length ratio for leading section 23 and main part 24 is not particularly limited, can be carried out suitably according to purposes Set.
Line footpath φ of electrode for discharge lamp part preferably 0.1～30mm.If less than 0.1mm, can not have conduct The intensity of electrod assembly, when being assembled in discharge lamp it is possible to fracture, or when leading section is processed as taper, has It may happen that fractureing.If greatly to during more than 30mm, as in the after-mentioned, controlling the uniformity of tungsten crystalline structure to become difficult.
When observing the crystalline structure of cross section (radial section) of main part, per unit area (such as 300 μ m 300 μ M) on, there is the area occupation ratio more fortunately more than 90% of the tungsten crystallization of 1～80 μm of crystallization particle diameter.Fig. 7 shows the horizontal stroke of main part One of section.In figure, 24 is main part, and 25 is cross section.When measuring the crystalline structure of cross section, shoot the length of main part The enlarged photograph of the radial section in central authorities of degree.The list of 300 μm of such as 300 μ m cannot be shot line footpath is thin, in a visual field When plane amasss, can repeatedly shoot arbitrary cross section.In enlarged photograph, by the tungsten crystalline particle in the presence of this section Diagonal the longest is as maximum diameter.In this section, calculate the face of tungsten crystalline particle in the range of 1～80 μm for the maximum diameter Long-pending rate.
On the per unit area of the cross section of main part, there is the area occupation ratio of the tungsten crystallization of 1～80 μm of crystallization particle diameter More than 90%, represent the little tungsten crystallization that crystallization particle diameter is less than 1 μm and the big tungsten crystallization more than 80 μm less.If less than 1 μm of tungsten crystallization is excessive, then the crystal boundary between tungsten crystalline particle can become too small.ZrO in tungsten crystal grain boundary2The ratio of particle is such as Fruit increases, then in the ZrO because of transmitting2When particle consumes, become big defect, the intensity decreases of tungsten alloy.On the other hand, if Big tungsten crystalline particle more than 80 μm is many, then crystal boundary becomes too much, and the intensity of tungsten alloy declines.In the cross section of main part On per unit area, there is the area occupation ratio more fortunately more than 96% of the tungsten crystallization of 1～80 μm of crystallization particle diameter, more preferably 100%.
Less than 50 μm more fortunately of the mean diameter of the tungsten crystalline particle in cross section, more preferably below 20 μm.In cross section The mean aspect ratio of tungsten crystalline particle be preferably less than 3.Length-width ratio calculates as follows.Shoot unit area (such as 300 μ m 300 μ M) enlarged photograph, using the maximum diameter (Fu Leite diameter) of tungsten crystalline particle present in this section as major diameter L, will be from major diameter The vertically extending particle diameter in center of L as minor axis S, using major diameter L/ minor axis S as length-width ratio.This is carried out to 50 tungsten crystalline particles Measure, be averaged value as mean aspect ratio.In addition, by (major diameter L+ minor axis S)/2 as particle diameter, by 50 tungsten crystalline particles Meansigma methodss as mean diameter.
When observing the crystalline structure of longitudinal section of main part, on per unit area (such as 300 300 μm of μ m), have 2 The area occupation ratio more fortunately more than 90% of the tungsten crystallization of～120 μm of crystallization particle diameter.Fig. 8 shows of longitudinal section.In figure, 24 It is main part, 26 is longitudinal section.When measuring the crystalline structure of longitudinal section, shoot the vertical of the center of diameter by main part and cut The enlarged photograph in face.In addition, when can not shoot the unit area of 300 μm of such as 300 μ m in a visual field, can repeatedly shoot Arbitrary longitudinal section.In enlarged photograph, using the diagonal the longest in the tungsten crystalline particle in the presence of this section as Big footpath.In this section, calculate the area occupation ratio of tungsten crystalline particle in the range of 2～120 μm for the maximum diameter.
On the per unit area of the longitudinal section of main part, the area occupation ratio with the tungsten crystallization of 2～120 μm of crystallization particle diameter exists 90% is indicated above：The little tungsten crystallization less than 2 μm for the crystallization particle diameter and the big tungsten crystallization more than 120 μm are less.If less than 2 μm Tungsten crystallization excessive, then the crystal boundary between tungsten crystalline particle can become too small.ZrO in tungsten crystal grain boundary2If the ratio of particle Increase, then in the ZrO because of transmitting2When particle consumes, become big defect, the intensity decreases of tungsten alloy.On the other hand, if super The big tungsten crystalline particle crossing 120 μm is many, then crystal boundary becomes too much, and the intensity of tungsten alloy declines.The longitudinal section of main part every In unit area, there is the area occupation ratio more fortunately more than 96% of the tungsten crystallization of 2～120 μm of crystallization particle diameter, more preferably 100%.
Less than 70 μm more fortunately of the mean diameter of the tungsten crystalline particle in longitudinal section, more preferably below 40 μm.In longitudinal section Tungsten crystalline particle mean aspect ratio more fortunately more than 3.In addition, the assay method of mean diameter and mean aspect ratio with right Method described in cross section is identical.
As described above, by the size, the ZrO that control tungsten crystalline particle2The size of particle and ratio are it becomes possible to provide electric discharge Excellent and the tungsten alloy of intensity especially elevated temperature strength.Therefore, the characteristic of electrode for discharge lamp part also improves.
The relative density of tungsten alloy part more fortunately more than 95.0%, more preferably more than 98.0%.If relative density is not To 95.0%, then bubble increases, it is possible to produce intensity decline and partial discharge etc. baneful influence.Relative density can be according to base In actual density and the solid density of Archimedes method, by (actual density/solid density) × 100 (%)=relative density Formula is tried to achieve.Solid density is tried to achieve by calculating by the density of known composition and mass ratio.Here, the density of tungsten is 19.3g/ cm3, the density of zirconium is 6.51g/cm3, zirconic density is 6.52g/cm3.For example, in the ZrO by 1wt%2, 0.2wt% In the case of Zr, the tungsten alloy that remaining is constituted for tungsten, solid density is 6.52 × 0.01+6.51 × 0.002+19.3 × 0.988 =19.14662g/cm3.Additionally, when calculating theoretical density, the presence of impurity can not be considered.
Vickers hardness Hv of the tungsten alloy part of embodiment more fortunately more than 330, more preferably in the scope of Hv330～700 Interior.If, less than 330, tungsten alloy is excessively soft for Vickers hardness Hv, intensity decreases.On the other hand, if Hv is more than 700, Tungsten alloy really up to the mark it is difficult to by leading section process into a cone shape.If additionally, really up to the mark, in the feelings of the electrod assembly of main body minister Under condition, flexibility is not had to be possible to easily snap off.If Vickers hardness Hv is more than 330, can make bend at 3 points of tungsten alloy Intensity is up to more than 400MPa.
In the case that the tungsten alloy part by embodiment is used as electrode for discharge lamp, surface roughness Ra 5 μ more fortunately Below m.Less than 5 μm more fortunately of the surface roughness Ra of particularly electrode leading section, more preferably below 3 μm.If concave-convex surface Greatly, then emission characteristicss decline.
Above-mentioned tungsten alloy part can be applicable to various discharge lamps, such as low-pressure discharge lamp or high-pressure discharge lamp Deng to this, there is no particular limitation.Even if for this reason, applying the high voltage of more than 100V, also enabling the long-life.The line of main part Footpath can be the scope of 0.1～30mm, from the thin size for more than 0.1mm below 3mm for the line footpath, more than 3mm and below 10mm's Medium size, is all suitable for more than 10mm and in the thick line footpath of below 30mm.The length in electrode body portion preferably 10～ 600mm.
Fig. 9 shows of discharge lamp.In figure 22 is electrod assembly (carrying out taper processing to leading section), and 27 is to put Electric light, 28 is electrode support rod, and 29 is glass tubing.In discharge lamp 27, to make to configure a pair of electricity in the way of electrode leading section is opposite Pole part 22.Electrod assembly 22 is engaged with electrode support rod 28.The inner face of glass tubing 29 is provided with luminescent coating (not shown). Enclose hydrargyrum, halogen, argon (or neon) etc. in the inside of glass tubing 29 as needed.
The discharge lamp of embodiment is the use of the discharge lamp of the tungsten alloy part of embodiment.Species for discharge lamp It is not particularly limited, go for any one in low-pressure discharge lamp and high-pressure discharge lamp.Low-pressure discharge lamp can enumerate common photograph Bright, using in the special lighting of road or tunnel etc., paint solidification device, UV solidification equipment, sterilizing unit, quasiconductor etc. The various arc discharge types of light cleaning device etc. discharge lamp.High-pressure discharge lamp can be enumerated：The place supplying water with draining The exposure dress of the outdoor lighting of reason device, general lighting, arena etc., UV solidification equipment, quasiconductor or printed base plate etc. Put, the high voltage mercury lamp of wafer inspector, projector etc., metal halide lamp, ultrahigh pressure mercury lamp, xenon lamp, sodium vapor lamp etc..Additionally, Because improve the intensity of tungsten alloy, also apply be applicable to the neck with mobile (vibration) as automobile discharge lamp Domain.
Then, manufacture method is illustrated.As long as the tungsten alloy of embodiment has aforesaid construction, to its manufacturer Method is just not particularly limited, and can enumerate following method as the efficient manufacture method obtaining product.
First, modulate the tungsten alloy powder containing Zr composition.Prepare ZrO2Powder is using as Zr composition.ZrO2The one of powder Less than 15 μm more fortunately of the mean diameter of secondary particle, more preferably below 5 μm.Preferably using sieve in advance by maximum diameter more than 15 μm Particle remove.When maximum diameter to be made is below 10 μm, screen out big ZrO using what there is target mesh size2Particle.? The ZrO of small particle to be removed2During particle, also removed using the sieve with target mesh size.Before being sieved, preferably Using ball mill etc. to ZrO2Particle carries out pulverizing process.By carrying out pulverizing process, agglutination body can be destroyed, so easily entering Row is based on the size controlling sieving.
Next, hybrid metal tungsten powder.Preferably 0.5～10 μm of the mean diameter of tungsten powder.Tungsten powder , in more than 98.0wt%, in below 1wt%, impurity metal components are in below 1wt% for oxygen content for preferably purity.With ZrO2Particle Equally, preferably by advancing with the operation that ball mill etc. carries out pulverizing, sieving, small particles and big particle are removed in advance.
In order that Zr content is with ZrO2Conversion is calculated as 0.1～5wt%, adds tungsten powder.By ZrO2Particle and tungsten The mixed-powder of powder puts into stainless steel, so that stainless steel is rotated and is uniformly mixed.Now, by using drum Container can make it successfully mix as stainless steel so as to along the circumferential direction rotate.By this operation, can prepare containing ZrO2The tungsten powder of particle.In addition, it is contemplated that carry out deoxidation in sintering circuit described later, micro carbon dust can also be added End.
Then, contain ZrO using gained2The tungsten powder of particle is preparing formed body.When forming formed body, according to need Binding agent to be used.In the case of the formed body forming cylindrical shape, preferably its diameter is formed as 0.1～40mm.Additionally, As be described hereinafter in the case that the sintered body of tabular cuts out formed body, the size of formed body is arbitrary.Additionally, the length of formed body Degree (thickness) is arbitrary.
Then, presintering formed body.Presintering is preferably carried out at 1250～1500 DEG C.By this operation, can obtain To pre-sintered body.Then, resistance sintering pre-sintered body.Resistance sintering preferably reaches 2100～2500 DEG C of temperature with sintered body Condition carry out.If temperature, less than 2100 DEG C, is unable to reach sufficient densification, intensity decreases.If it exceeds 2500 DEG C, Then ZrO2The grain overgrowth of particle and tungsten particle is it is impossible to obtain target crystalline structure.
As additive method, the sintering method of 1～20 hour at 1400～3000 DEG C of temperature can be used formed body.As Less than 1400 DEG C or sintering time was less than 1 hour for fruit sintering temperature, then sinter insufficient, and the intensity of sintered body declines.If burnt More than 3000 DEG C or sintering time was more than 20 hours for junction temperature, then tungsten crystallization may excessively grain growth.
As sintering atmosphere, can enumerate in the inert atmosphere of nitrogen or argon etc., in the reducing atmosphere of hydrogen etc., in vacuum.As Fruit is these atmosphere, the ZrO in sintering circuit2The carbon of particle can decarburization.In decarburization, the impurity oxygen in tungsten powder is removed together Go, it is possible to the oxygen content in tungsten alloy is reduced to below 1wt%, be further reduced to below 0.5wt%.If tungsten closes Oxygen content in gold reduces, then electric conductivity improves.
By this sintering circuit, the tungsten sintered body containing Zr can be obtained.If pre-sintered body is cylindrical shape, sintered body Cylindric sintered body (ingot casting) can be become.In the case of tabular sintered body, just can by the operation cutting out given size Obtain cylindric sintered body (ingot casting).
Then cylindric sintered body (ingot casting) is carried out forging processing, calendering processing, Wire Drawing etc. to adjust line footpath.This When working modulus more fortunately 30～90% scope.This working modulus refers to be denoted as the sectional area of the cylindric sintered body before processing A, when the sectional area of the cylindric sintered body after processing is denoted as B, according to working modulus=[(A-B)/A] × 100% value calculating. Line footpath is adjusted preferably by multiple processing.By repeatedly being processed, can be by the hole of the cylindric sintered body before processing Destroy, obtain the high electrod assembly of density.
For example, entered using the situation of the cylindric sintered body that the cylindric sintered body of diameter 25mm is processed into diameter 20mm Row explanation.The sectional area A of the circle of diameter 25mm is 460.6mm2, the sectional area B of the circle of diameter 20mm is 314mm2, so processing Rate is [(460.6-314)/460.6] × 100=32%.Now, preferably by multiple Wire Drawing etc., diameter 25mm is added Work is diameter 20mm.
If working modulus is low, and to less than 30%, crystalline structure cannot fully extend in the direction of the machine, tungsten crystallization and ZrO2The size of particle difficult to reach target.If additionally, working modulus little to less than 30%, before processing can not being sufficiently destroyed Hole within cylindric sintered body is it is possible to remaining as former state.If remaining internal void, the resistance to of cathode assembly can be become The reason property etc. declines long.On the other hand, if working modulus is greatly to more than 90%, because overprocessing is possible to break and finished product Rate declines.For this reason, working modulus preferably 30～90%, more preferably 35～70%.In addition, (Japanese after the completion of sintering：Upper Ga It is also possible to be not necessarily processed with aforesaid working modulus in the case that the relative density of tungsten alloy り) is more than 95%.
The line footpath of sintered body is machined to after 0.1～30mm, by cutting into the length of needs, makes electrod assembly.Root According to needs, leading section is processed into a cone shape.Additionally, be ground as needed processing, heat treatment (recrystallization heat treatment etc.), Shape is processed.
Recrystallization heat treatment is preferably entered with 1300～2500 DEG C of scope in reducing atmosphere, inert atmosphere or vacuum OK.The rectification heat relaxing produced internal stress in the operation be processed into electrod assembly can be obtained by recrystallization heat treatment The effect processing, improves the intensity of part.
By aforesaid manufacture method, it is capable of the electrode for discharge lamp part of high efficiency manufacture embodiment.
Embodiment
(embodiment 1)
As material powder, in the tungsten powder (purity 99.99wt%) of 2 μm of mean diameter, add 2 μm of mean diameter ZrO2Powder (purity 99.0%) is to reach 1.5wt%.In addition, in ZrO2In powder, when Zr amount is denoted as 100 mass parts, Impurity Hf measures as 1.0 mass parts.
Material powder is mixed 10 hours with ball mill, mixed material powder has been obtained.Then, mixed material powder is thrown Enter in mould, make formed body.The stove sintering of 1800 DEG C × 10 hours is carried out in hydrogen to the formed body of gained.By this work Sequence, obtains the sintered body of vertical 16mm × horizontal 16mm × long 420mm.
Processed by forging, make the rod that section is square shape or toroidal, then cut out diameter 2.4mm × length The cylindrical sample of 150mm.Centreless grinding processing is implemented for sample, makes surface roughness Ra below 5 μm.Then, exist 1600 DEG C of rectification heat treatment is implemented in hydrogen.
Thereby, as the tungsten alloy part of embodiment 1, make emission characteristicss measuring electrode, carry out emission current survey Fixed.
(comparative example 1)
Make by the ThO containing 2wt%2Tungsten alloy constitute same size use for discharge lamp cathode assembly.
Its ZrO of tungsten alloy component survey for embodiment 12The carbon amounts of content, surface element and central part, tungsten crystallization Mean diameter.ZrO2Content analysis be by icp analysis, noble gases melting-infrared absorption analyze Zr amount, Oxygen amount, is scaled ZrOx.Additionally, the carbon amounts of surface element and central part is to cut measurement sample from the scope on 10 μm of surface And cut measurement sample from cylindrical cross-section, it is measured respectively by burning-infrared absorption.Tungsten crystalline particle Average crystallite particle diameter is the meansigma methodss of the crystallization particle diameter of 100 tungsten crystalline particles measuring in arbitrary section structure.Its knot Fruit is shown in table 1.
[table 1]
Then, the emission characteristicss of the use for discharge lamp cathode assembly of embodiment 1 and comparative example 1 have been investigated.The survey of emission characteristicss Surely it is to make applied voltage (V) change into 100V, 200V, 300V, 400V, measure emission (mA/mm2).To negative electrode The current capacity that part applies is 18 ± 0.5A/W, application time is determined under conditions of 20ms.The results are shown in Figure 10.
According to Figure 10, compared with comparative example 1, emission characteristicss are excellent for embodiment 1.It follows that the electric discharge of embodiment 1 Lamp cathode assembly is not used the thorium oxide as radioactive substance, also shows that excellent emission characteristicss.In addition, it is cloudy when measuring Pole part has reached 2100～2200 DEG C.It can thus be appreciated that the elevated temperature strength of the cathode assembly of embodiment 1 and life-span etc. are also excellent.
(embodiment 2～6)
Then, it is prepared for changing ZrO as shown in table 22Addition, the addition of ZrC, the K as dopant material The raw material mixed powder end of addition.Die forming is carried out to each raw material mixed powder end, in hydrogen with 1500～1900 DEG C sintering 7～ 16 hours, obtain sintered body.In addition, in embodiment 2～3, making sintered body size similarly to Example 1, carry out cutting action. In embodiment 4～5, it is adjusted to feature dimension, directly obtain the sintered body of diameter 2.4mm × long 150mm.In embodiment 6, add The ZrC powder (purity 99.0%) of 2 μm of the mean diameter of 0.5wt%.In addition, in ZrO2In powder, Zr amount is denoted as 100 matter During amount part, impurity Hf measures as 1.0 mass parts.Additionally, the ZrO using embodiment 62In the case of powder and ZrC powder, Zr is measured When being denoted as 100 mass parts, impurity Hf measures as 1.0 mass parts.
Centreless grinding processing is implemented for each sample, makes surface roughness Ra below 5 μm.Then leading section is processed into Inclination angle is 45 ° of cone shape.Then, implement 1400～1700 DEG C of rectification heat treatment in hydrogen.Thereby, make and implement The use for discharge lamp cathode assembly of example 2～5, has carried out mensure similarly to Example 1.The results are shown in table 3.
[table 2]
ZrO2 addition K addition ZrC addition
Embodiment 2 0.5 No No
Embodiment 3 1.0 No No
Embodiment 4 2.3 0.005 No
Embodiment 5 1.2 No No
Embodiment 6 1.0 No 0.5
[table 3]
Then, have rated emission characteristicss under conditions of similarly to Example 1.The results are shown in table 4.
[table 4]
According to table 4, any one of use for discharge lamp cathode assembly of the present embodiment all shows excellent characteristic. In addition, cathode assembly has reached 2100～2200 DEG C when measuring.It can thus be appreciated that the elevated temperature strength of the cathode assembly of embodiment 2～6 Also excellent with life-span etc..Zr and ZrO is contained in embodiment 12Both.Additionally, containing Zr, ZrO in embodiment 62With ZrC this three Kind.
(embodiment 11～20, comparative example 11)
As material powder, the tungsten powder (more than purity 99.0wt%) shown in table 5, ZrO are prepared2Powder.Each powder End is all fully disassembled with ball mill, carries out as needed sieving operation so that respective maximum diameter reaches the value shown in table 5.
[table 5]
Then, with the ratio mixing tungsten powder shown in table 6 and ZrO2Powder, is mixed again by ball mill.Then carry out Shape, be prepared for formed body.Then sintering circuit has been carried out with the condition shown in table 6.Obtain vertical 16mm × horizontal 16mm × length The sintered body of 420mm.
[table 6]
Then, cut out cylindric sintered body (ingot casting) from the tungsten alloy sintered body of gained, forging processing, calendering are added Work, Wire Drawing appropriately combined adjusting line footpath.Working modulus is as shown in table 7.Additionally, after adjustment line footpath, cutting out the length of regulation Degree, leading section is processed into a cone shape.Then, carry out surface grinding, be ground to surface roughness Ra below 5 μm.Then, exist 1600 DEG C of recrystallization heat treatment is implemented in nitrogen atmosphere.Thereby, complete electrode for discharge lamp part.
[table 7]
Then, shoot the cross section of main part of each electrode for discharge lamp part and the enlarged photograph of longitudinal section, determine ZrO2The mean diameter of composition, maximum diameter, the ratio of tungsten crystalline particle, mean diameter, length-width ratio.With regard to enlarged photograph, difference Cut out the circumferential section at center and the longitudinal section by main part, arbitrary unit area 300 μ m is adjusted for 300 μm Look into.The results are shown in table 8.
[table 8]
Then, for each electrode for discharge lamp part, determine the ZrO in Zr composition2Ratio.Additionally, calculate oxygen containing Amount, relative density (%), Vickers hardness (Hv), 3 points of bending strengths.
With regard to the ZrO in Zr composition2Ratio, by icp analysis method measure tungsten alloy in Zr amount, by burning-red Outside line absorption process measures the carbon amounts in tungsten alloy.It is believed that the carbon in tungsten alloy becomes ZrO2.Therefore, by the total Zr amount being detected It is denoted as 100 weight portions, conversion is changed into ZrO2Zr amount, obtain its mass ratio.Additionally, the oxygen content in tungsten alloy passes through indifferent gas Body burning-infrared absorption is analyzed.Additionally, relative density passes through the reality that will obtain according to Archimedes method analysis Survey density to calculate divided by solid density.In addition, solid density is tried to achieve by aforesaid calculating.Additionally, Vickers hardness (Hv) root Try to achieve according to JIS-Z-2244.Additionally, 3 points of bending strengths are tried to achieve according to JIS-R-1601.The results are shown in table 9.
[table 9]
The density of the electrode for discharge lamp part of the present embodiment is high, and Vickers hardness (Hv) also shows that excellent value.This is Because ZrO2A part there occurs deoxidation.Additionally, not forming ZrO2Zr composition be in any one state following：Define gold Belong to Zr particle；ZrO2The part on the surface of particle defines metal Zr；Define the solid solution of tungsten and hafnium.
(embodiment 21～25)
Then, as tungsten powder and ZrO2Powder, using powder similarly to Example 12, prepares to be changed to group shown in table 10 The composition becoming is as second composition.Sintering condition is set in nitrogen atmosphere, carries out stove sintering with 2000 DEG C, obtains ingot casting.To casting Ingot is processed with working modulus 50%, obtains the electrod assembly of line footpath 10mm.Additionally, implementing 1600 DEG C of weight in nitrogen atmosphere Crystallization heat treatment.Same mensure has been carried out to each embodiment.The results are shown in table 10～12.
[table 10]
[table 11]
[table 12]
Can be found according to table 10～12, by using addition element, dispersion-strengthened function is strengthened, the grain of tungsten crystallization becomes Length is inhibited, so intensity improves.
(embodiment 11A～25A, comparative example 11-1A～11-2A and comparative example 12)
The transmitting having investigated the electrode for discharge lamp part of embodiment 11～25, comparative example 11-1 and comparative example 11-2 is special Property.The mensure of emission characteristicss is to make applied voltage (V) change into 100V, 200V, 300V, 400V, measures emission (mA/mm2).The current capacity that electrode for discharge lamp part is applied be 18 ± 0.5A/W, application time be 20ms condition Under be determined.
Additionally, as comparative example 12, having made by the ThO containing 2wt%2Tungsten alloy constitute line footpath 8mm electric discharge Lamp electrod assembly.The results are shown in table 13.
[table 13]
Although the electrode for discharge lamp part of each embodiment, not using thorium oxide, still shows and the ratio using thorium oxide Identical compared with example 2 or in its above emission characteristics.Additionally, electrod assembly has reached 2100～2200 DEG C when measuring.So, each reality The elevated temperature strength applying the electrode for discharge lamp part of example is also excellent.
(embodiment 26～28)
Then, for embodiment 11, embodiment 13, embodiment 18 electrode for discharge lamp part, except by recrystallization heat Treatment conditions are changed to 1800 DEG C in addition, are manufactured with identical manufacture method, and manufactured electrode for discharge lamp part is made For embodiment 26 (the recrystallization heat treatment condition of embodiment 11 is changed to 1800 DEG C), the embodiment 27 (knot again by embodiment 13 Brilliant heat treatment condition is changed to 1800 DEG C), embodiment 28 (the recrystallization heat treatment condition of embodiment 18 is changed to 1800 DEG C) and accurate Standby.Carry out same mensure.The results are shown in table 14,15.
[table 14]
[table 15]
The density of the electrode for discharge lamp part of the present embodiment is high, and Vickers hardness (Hv) and 3 points of bending strengths also show that Excellent value.This is because ZrO2A part there occurs deoxidation.Additionally, to not forming ZrO2Zr composition analyzed, Result is to be respectively formed the solid solution of tungsten and zirconium.That is, as Zr composition, there is Zr and ZrO2Both.If therefore it is known that making Recrystallization heat treatment temperature reaches more than 1700 DEG C, then so that metal Zr is solid-solution in tungsten.Additionally, being surveyed by same method Emission characteristicss are determined.
[table 16]
As indicated above, it is known that being all solid-solution in tungsten by making metal Zr, emission characteristicss can be improved.It is believed that its reason It is：By solid solution, metal Zr is easily present in the surface of tungsten alloy.
Additionally, as noted previously, as emission characteristicss are excellent, so it is not limited to electrode for discharge lamp part it is also possible to make It is used in the field requiring magnetron part (coil component), the transmitting tube part (mesh grid) of emission characteristicss etc..

Claims (18)

1. a kind of tungsten alloy part, it is the tungsten alloy for use for discharge lamp part, transmitting tube part or magnetron part , it is characterised in that comprising tungsten and Zr composition, this Zr composition is by ZrO for part2, and selected from Zr, ZrC and C at least one composition structure Become, and containing with ZrO2Conversion is calculated as the described Zr composition of 0.1～5wt%；
By the content of Zr and O with ZrOxDuring conversion, 0 ＜ x ＜ 2.
2. tungsten alloy part as claimed in claim 1 is it is characterised in that contain with ZrO2Conversion is calculated as the Zr of 0.1～3wt% Composition.
3. tungsten alloy part as claimed in claim 1 or 2 is it is characterised in that also contained selected from K, Si with below 0.01wt% At least one element with Al.
4. tungsten alloy part as claimed in claim 1 or 2 is it is characterised in that when the content of Zr is denoted as 100 mass parts, contain There is the Hf of below 15 mass parts.
5. tungsten alloy part as claimed in claim 1 or 2 is it is characterised in that described ZrO2The mean diameter of primary particle exist Less than 15 μm.
6. tungsten alloy part as claimed in claim 5 is it is characterised in that described ZrO2Primary particle mean diameter at 5 μm Hereinafter, maximum diameter is below 15 μm.
7. tungsten alloy part as claimed in claim 5 is it is characterised in that described ZrO2Offspring maximum diameter at 100 μm Below.
8. tungsten alloy part as claimed in claim 1 or 2 is it is characterised in that at least a portion of metal Zr is solid-solubilized in tungsten.
9. tungsten alloy part as claimed in claim 1 or 2 is it is characterised in that metal Zr is present in described tungsten alloy part Surface.
10. tungsten alloy part as claimed in claim 1 or 2 is it is characterised in that when being denoted as 100 mass parts by the content of Zr, structure Become ZrO2Zr content be 30～98 mass parts.
11. tungsten alloy parts as claimed in claim 1 or 2 are it is characterised in that Vickers hardness Hv of described tungsten alloy part exists More than 330.
12. tungsten alloy parts as claimed in claim 1 or 2 it is characterised in that described tungsten alloy part line footpath be 0.1～ 30mm.
13. tungsten alloy parts as claimed in claim 1 or 2 are it is characterised in that described tungsten alloy part contains average crystallite grain Footpath is 1～100 μm of tungsten crystallization.
14. tungsten alloy parts as claimed in claim 13 are it is characterised in that the per unit of the cross section of described tungsten alloy part On area, the area occupation ratio of tungsten crystallization with 1～80 μm of crystallization particle diameter is more than 90%.
15. tungsten alloy parts as claimed in claim 13 are it is characterised in that the per unit of the longitudinal section of described tungsten alloy part On area, the area occupation ratio of tungsten crystallization with 2～120 μm of crystallization particle diameter is more than 90%.
A kind of 16. discharge lamps are it is characterised in that usage right requires 1 or 2 tungsten alloy part.
A kind of 17. transmitting tubes are it is characterised in that usage right requires 1 or 2 tungsten alloy part.
A kind of 18. magnetrons are it is characterised in that usage right requires 1 or 2 tungsten alloy part.
CN201280060372.2A 2012-07-03 2012-12-21 Tungsten alloy part and the discharge lamp using this tungsten alloy part, transmitting tube and magnetron Active CN103975414B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2012150019 2012-07-03
JP2012-150019 2012-07-03
JP2012154977 2012-07-10
JP2012-154977 2012-07-10
PCT/JP2012/083284 WO2014006779A1 (en) 2012-07-03 2012-12-21 Tungsten alloy part, and discharge lamp, transmitting tube and magnetron using same

Publications (2)

Publication Number Publication Date
CN103975414A CN103975414A (en) 2014-08-06
CN103975414B true CN103975414B (en) 2017-03-08

Family

ID=49881558

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280060372.2A Active CN103975414B (en) 2012-07-03 2012-12-21 Tungsten alloy part and the discharge lamp using this tungsten alloy part, transmitting tube and magnetron

Country Status (4)

Country Link
EP (1) EP2871666B1 (en)
JP (1) JP5911576B2 (en)
CN (1) CN103975414B (en)
WO (1) WO2014006779A1 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104611618A (en) * 2015-01-03 2015-05-13 北京工业大学 High temperature-resistant tungsten alloy material
JP2016181358A (en) * 2015-03-23 2016-10-13 東芝ライテック株式会社 Discharge lamp
CN104789844A (en) * 2015-04-23 2015-07-22 江苏峰峰钨钼制品股份有限公司 Tungsten crucible and preparation method thereof
CN105441766B (en) * 2016-01-05 2018-01-09 河南科技大学 High-specific gravity tungsten alloy and preparation method thereof
CN106480347A (en) * 2016-12-05 2017-03-08 郑州丽福爱生物技术有限公司 A kind of high-strength aluminum alloy material and preparation method thereof
CN107217995A (en) * 2017-05-05 2017-09-29 胜利油田胜鑫防腐有限责任公司 A kind of tungsten-plated alloy anti-corrosion tubing and casing
AT16409U1 (en) 2017-05-23 2019-08-15 Plansee Se Cathode material
CN108149103B (en) * 2017-12-29 2019-11-05 中国科学院合肥物质科学研究院 A kind of potassium zirconium carbide codope tungsten alloy and preparation method thereof
CN109378266A (en) * 2018-09-21 2019-02-22 厦门虹鹭钨钼工业有限公司 A kind of environment-friendly type cathode material and preparation method thereof
JP6972383B2 (en) * 2018-11-19 2021-11-24 株式会社東芝 Cathode parts for discharge lamps and discharge lamps
JP7098812B2 (en) * 2019-02-18 2022-07-11 株式会社東芝 Manufacturing method of cathode parts for discharge lamps, discharge lamps, and cathode parts for discharge lamps
JP7043680B2 (en) * 2019-03-22 2022-03-29 株式会社東芝 Cathode parts for discharge lamps and discharge lamps
CN110284843B (en) * 2019-07-01 2021-06-22 山西中能企服环保科技有限公司 Anti-corrosion anti-sticking high-temperature-resistant oil casing connector and preparation method thereof
CN114402415B (en) * 2019-10-09 2024-06-18 优志旺电机株式会社 Short arc discharge lamp

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1112285A (en) * 1993-10-07 1995-11-22 菲利浦电子有限公司 High-pressure metal halide discharge lamp
CN1288968A (en) * 1999-09-17 2001-03-28 哈尔滨工业大学 Preparation of zirconium carbide particle-reinforced composite tungsten material
WO2005073418A1 (en) * 2004-01-30 2005-08-11 Nippon Tungsten Co., Ltd. Tungsten based sintered compact and method for production thereof
CN1724469A (en) * 2001-07-03 2006-01-25 本田技研工业株式会社 Method for manufacturing multi-element ceramic powder and sintered compact
JP2007113104A (en) * 2005-10-24 2007-05-10 Toshiba Corp Tungsten electrode material
CN101167156A (en) * 2005-04-27 2008-04-23 皇家飞利浦电子股份有限公司 Discharge lamp with electrode made of tungsten alloy comprising 3 wt% of rhenium
JP2008196041A (en) * 2007-02-16 2008-08-28 Tungaloy Corp Cemented carbide

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5339738B1 (en) * 1970-12-29 1978-10-23
US4090875A (en) * 1973-10-01 1978-05-23 The United States Of America As Represented By The Department Of Energy Ductile tungsten-nickel-alloy and method for manufacturing same
JPH0499146A (en) * 1990-08-02 1992-03-31 Toshiba Corp Powder sintered material and its manufacture
JPH11283516A (en) * 1998-03-31 1999-10-15 Toshiba Corp Electron-emitting member for magnetron, cathode structural body for the magnetron, and the magnetron
JP2002042643A (en) * 2000-07-28 2002-02-08 Toshiba Corp Method for blackening anode inner surface of electron tube
US6559582B2 (en) * 2000-08-31 2003-05-06 New Japan Radio Co., Ltd. Cathode and process for producing the same
JP5086503B2 (en) 2001-02-02 2012-11-28 株式会社東芝 Method for manufacturing thorium tungsten wire
JP4263888B2 (en) * 2002-08-30 2009-05-13 株式会社東芝 Tungsten rod for tube and tube using the same
JP4231380B2 (en) * 2003-10-16 2009-02-25 株式会社アライドマテリアル Light bulb and current conductor used therefor
JP4815839B2 (en) * 2005-03-31 2011-11-16 ウシオ電機株式会社 High load high intensity discharge lamp
US8324918B2 (en) * 2007-09-27 2012-12-04 Kabushiki Kaisha Toshiba Probe needle material, probe needle and probe card each using the same, and inspection process
JP4486163B1 (en) * 2008-12-08 2010-06-23 株式会社アライドマテリアル Tungsten electrode material and method for producing tungsten electrode material
US9502201B2 (en) * 2008-12-08 2016-11-22 A.L.M.T. Corp. Tungsten electrode material and thermionic emission current measuring device
JP5239828B2 (en) * 2008-12-22 2013-07-17 ウシオ電機株式会社 Discharge lamp
JP2011103240A (en) 2009-11-11 2011-05-26 Toshiba Materials Co Ltd Tungsten electrode and discharge lamp using the same
EP2857534B1 (en) * 2012-05-29 2020-10-28 Kabushiki Kaisha Toshiba Tungsten alloy part, and discharge lamp, transmitting tube and magnetron using same, and use of the tungsten alloy part

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1112285A (en) * 1993-10-07 1995-11-22 菲利浦电子有限公司 High-pressure metal halide discharge lamp
CN1288968A (en) * 1999-09-17 2001-03-28 哈尔滨工业大学 Preparation of zirconium carbide particle-reinforced composite tungsten material
CN1724469A (en) * 2001-07-03 2006-01-25 本田技研工业株式会社 Method for manufacturing multi-element ceramic powder and sintered compact
WO2005073418A1 (en) * 2004-01-30 2005-08-11 Nippon Tungsten Co., Ltd. Tungsten based sintered compact and method for production thereof
CN101167156A (en) * 2005-04-27 2008-04-23 皇家飞利浦电子股份有限公司 Discharge lamp with electrode made of tungsten alloy comprising 3 wt% of rhenium
JP2007113104A (en) * 2005-10-24 2007-05-10 Toshiba Corp Tungsten electrode material
JP2008196041A (en) * 2007-02-16 2008-08-28 Tungaloy Corp Cemented carbide

Also Published As

Publication number Publication date
WO2014006779A1 (en) 2014-01-09
JP5911576B2 (en) 2016-04-27
CN103975414A (en) 2014-08-06
EP2871666A1 (en) 2015-05-13
EP2871666A4 (en) 2016-09-14
JPWO2014006779A1 (en) 2016-06-02
EP2871666B1 (en) 2022-09-07

Similar Documents

Publication Publication Date Title
CN103975414B (en) Tungsten alloy part and the discharge lamp using this tungsten alloy part, transmitting tube and magnetron
CN103987864B (en) Tungsten alloy and the tungsten alloy part using this tungsten alloy, discharge lamp, transmitting tube and magnetron
CN103998635B (en) Tungsten alloy, and tungsten alloy part, discharge lamp, transmitting tube and magnetron using tungsten alloy
US10998157B2 (en) Tungsten alloy part, and discharge lamp, transmitting tube, and magnetron using the same
JP5800922B2 (en) Cathode parts for discharge lamps
JPWO2020105644A1 (en) Cathode parts for discharge lamps and discharge lamps
JP5881740B2 (en) Tungsten alloy and tungsten alloy parts, discharge lamp, transmitter tube and magnetron using the same
JPWO2020196192A1 (en) Cathode parts for discharge lamps and discharge lamps
JP2013229179A (en) Discharge lamp electrode support rod and discharge lamp using the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant