CN101007350B - Method for manufacturing high density semi-products or elements - Google Patents

Method for manufacturing high density semi-products or elements Download PDF

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Publication number
CN101007350B
CN101007350B CN2006101675743A CN200610167574A CN101007350B CN 101007350 B CN101007350 B CN 101007350B CN 2006101675743 A CN2006101675743 A CN 2006101675743A CN 200610167574 A CN200610167574 A CN 200610167574A CN 101007350 B CN101007350 B CN 101007350B
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sintered body
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finished product
density
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CN101007350A (en
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W·施皮尔曼
G·莱希特弗里德
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Plansee SE
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Plansee SE
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02Manufacture of electrodes or electrode systems
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12Both compacting and sintering
    • B22F3/14Both compacting and sintering simultaneously
    • B22F3/15Hot isostatic pressing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/045Alloys based on refractory metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02Manufacture of electrodes or electrode systems
    • H01J9/04Manufacture of electrodes or electrode systems of thermionic cathodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24After-treatment of workpieces or articles
    • B22F2003/248Thermal after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00Gas-discharge or vapour-discharge lamps
    • H01J61/02Details
    • H01J61/04Electrodes; Screens; Shields
    • H01J61/06Main electrodes
    • H01J61/073Main electrodes for high-pressure discharge lamps
    • H01J61/0735Main electrodes for high-pressure discharge lamps characterised by the material of the electrode

Abstract

The invention relates to a method for producing semifinished products or elements made from material of molybdenum, molybdenum alloy, wolfram or wolfram alloy having average relative density >98.5%, relative core density >98.3%, the method includes sintering relative density D of material as 90%<D<98.5%, and ratio of closed pores relative to total porosity is >0.8, and processing hot-isostatic-bonding and pressing under temperature is 0.40 to 0.65x solidus temperature and pressure is 50 to 300 MPa. The elements produced by the method such as used as electrode having many improved service lifecharacteristic.

Description

Make the method for highdensity semi-finished product or element
Technical field
The present invention relates to a kind of by molybdenum, molybdenum alloy, tungsten or the average relative density of tungsten alloy material manufacturing>98.5%, relative core density>98.3% the semi-finished product or method of element.
Background technology
Refractory metal molybdenum, tungsten and their alloy are processed through powder metallurgy usually.Concentrate is as initial product, and to form intermediate product, reduction generates metal dust then through chemical process.In this case, reducing agent is a hydrogen.The reduction before, among or afterwards, alloying element possibly be blended in wherein.
Typical molybdenum alloy is TZM (Ti-Zr-C-alloy molybdenum), Mo-La 2O 3, Mo-Y 2O 3And Mo-Si-B.On the tungsten side, that should be mentioned in that is AKS-W (K-Doped Tungsten), W-ThO 2, W-La 2O 3, W-Ce 2O 3, W-Y 2O 3And AKS-W-ThO 2Especially, AKS-W and AKS-W-ThO 2Be used for lighting engineering, here in particular for filament and electrode.The potassium additives of the minute bubbles form of finding among the AKS-W makes grain growth stable, microstructure that can stable for extended periods of time thus even under very high processing temperature.This endurance life characteristic for the electrode that is used for heavily loaded lamp has the importance of essence, and heavily loaded lamp is metal halide and short-arc lamp for example, and its surface temperature reaches 2600 ℃.
Powder is neutralized tightly through mold pressing or isostatic cool pressing.Large-sized semi-finished product are preferably processed through isostatic cool pressing system.With regard to steel wire bar and little rolled sheet bar, mold pressing and isostatic cool pressing system all can be used.If molybdenum powder has the typical Fisher particle diameter of 2 to 5 μ m, tungsten powder has the typical Fisher particle diameter of 1.5 to 4.5 μ m, and the branch bulk density that then obtains is 0.11 to 0.17 (molybdenum) and 0.13 to 0.22 (tungsten).If used pressing pressure is 200 to 500MPa, resulting minute green compact density of molybdenum and tungsten is 0.6 to 0.68.
Next operation is the sintering green compact.Wherein, sintering process is carried out with a kind of like this method as far as possible, makes sintered body have low porosity, and has the fine grain microstructure.Molybdenum and tungsten is sintering in hydrogen usually, and its dew point is less than 0 ℃.Common sintering temperature is 18000 ℃ to 22000 ℃ with regard to molybdenum, is 21000 ℃ to 27000 ℃ with regard to tungsten.Common sintering time is 1 to 24 hour.Because sintering process is definite by the crystal boundary diffusion, therefore with regard to small particle diameter, can be at lower sintering temperature.Yet particle diameter is also confirmed half-finished aperture of sintering.For example, if the Fisher particle diameter of used molybdenum powder is reduced to 2.6 μ m from 10 μ m, the aperture can reduce 3 times so.
Yet a shortcoming of fine grain powder is that particularly the ratio of oxygen is higher in adsorbed gas.This is because in sintering process, oxygen and sintering gaseous hydrogen solid/liquid/gas reactions form water vapour.Because the low permeability to gas of green compact, and it further reduces in sintering process, so water vapour can not be removed to suitable degree, particularly from the center of sintered body.When the Fisher particle diameter of used fine grain powder<4.5 μ m, especially like this.
The inner high water vapour content of sintered body triggers CVT (chemical gaseous phase conveying) reaction.Through mass transferring in gas phase, the destruction that CVT reaction causes specific area, and therefore cause being used for the reduction of the driving force of sintering is particularly in the inside of sintered body.With regard to molybdenum and tungsten alloy, this process is strengthened, and the additives in the sintering process discharges a kind of oxygen carrier, and making water vapour form increases AKS-W, Mo-La 2O 3Or W-La 2O 3Situation also be like this.Therefore gas-phase reaction has limited the particularly size of these alloys of sintered body.When using large-sized sintered body or very thin crystal grain powder, the center of accessible sintered density, particularly sintered body is than using little sintered body or low during than corase meal.
After the sintering process, molybdenum, tungsten and their alloy stand mechanical heat treatment usually.Reach minimizing/elimination and the required machinery and the setting of microstructure characteristic of required form, porosity through mechanical heat treatment.Along with the increase of ratio of briquetting, density is increased to solid density and particle diameter reduces.Therefore, the minimizing of particle diameter is looked selected forming temperature and intermediate annealing temperature consumingly and is decided.
Mention that when using the fine grain powder, or alloy is when containing the material of in sintering process release oxygen or water vapour, the size of sintered body is restricted.If process the product with large-size by this sintered body, perhaps possible ratio of briquetting is not enough to the center of storage porosity, particularly sintered body.
AKS tungsten as the lamp electrode material also is like this.Short-arc lamp particularly, used anode diameter is at most 55mm.What determine the kind electrode life characteristics is their dimensional stability.The distortion of electrode originates from thermal stress.These thermal stress can for example cause generating the protruding place of electrode smooth region.Then, arc light focuses in these protruding places, causes hot-spot.This can cause electrode to melt in this zone.
And hot-spot causes the evaporation of electrode material to increase.The electrode material of evaporation is deposited on the bulb, has therefore reduced luminous flux hastily.
Research shows that creep is the reason that forms protruding place.If this material comprises the hole, because this hole is as vacancy source and cave, so these creeps increase.In addition, heat radiation has been reduced in this hole, the enhancing that it can cause local temperature to rise.
And the fine grain electrode material has long service life.This is attributable to the following fact: with regard to the coarse grain material, infringement is to concentrate on the minority grain boundary, and consequently, because the concentration of arc light, self-reinfocing effect has taken place in the there.
Summary of the invention
Therefore, the purpose of this invention is to provide high density semi-finished product or element, particularly its center also is highdensity, and has the fine grain microstructure.
According to the method for the invention, can make semi-finished product or element by molybdenum, tungsten and their alloy, the average relative density of said semi-finished product or element is greater than 98.5%, and core density is greater than 98.3% relatively.Average relative density is interpreted as the averag density with respect to the weight of unit volume.For a person skilled in the art, core density is interpreted as the density of the center of semi-finished product or element.Because core volume is not specific with respect to cumulative volume, core volume is as giving a definition with regard to the confirming of core density:
Transverse to deformation direction near 10% of total surface area center * towards the degree of deformation direction.
At deformation state, these semi-finished product or element transverse to the preferred number of die of its deformation direction greater than 100 crystal grain/mm 2
It is commercial molybdenum and the tungsten powder of 0.5 to 10 μ m that the inventive method is used the Fisher particle diameter.
Alloying element can be before reduction process, among or be added in the powder afterwards.This powder for example arrives under the pressing pressure of 500MPa through mold pressing or isostatic cool pressing 100 through common pressing process compacting.
At 0.55 powder after the said compacting of the sintering temperature of 0.92 * solidus temperature to form sintered body.Among the present invention, this sintering temperature is chosen such that so that said sintered body has 90% to 98.5% the sintered density of setting solid density.Preferably, closed pore is with respect to ratio>0.8 of total porosity.If relative density surpasses 98.5%, make number of die>100 particles/mm 2Element or half-finished purpose can not realize.
If rate of closed hole with respect to ratio>0.8 of total porosity, then can be guaranteed will obtain required characteristic in next step hot-isostatic pressing.If this value is lower than 0.8, then after sintering process, need the forming process of
Figure GSB00000575166700031
Figure GSB00000575166700032
.
Figure GSB00000575166700033
defines as follows:
((cross-sectional surface after initial cross sectional surface area-forming process is long-pending)/initial cross sectional surface area) * 100.
This can guarantee to close external holes.
The high temperature insostatic pressing (HIP) of said sintered body carries out under situation about not using jar, and carries out under the pressure of the temperature of 0.65 * solidus temperature and 50 to 300MPa 0.40.Be lower than 0.4 * solidus temperature if this temperature is arranged on, can not realize that then element or semi-finished product have the purpose of average relative density>98.5% and relative core density>98.3%.Normal or exaggerated grain growth if being arranged on, this temperature be higher than 0.65 * solidus temperature, owing to will exist undesirable grain coarsening phenomenon.Be lower than 50MPa if this pressure is arranged on, can not realize the density purpose equally.When pressure was higher than 300MPa, the inventive method no longer was economically viable.
The high temperature insostatic pressing (HIP) goods said sintered body of hot-isostatic pressing (promptly through) stand to be shaped in next step.Wherein ratio of briquetting
Figure GSB00000575166700041
is 15 to 90%.If this ratio of briquetting is lower than 15%, the purpose of core density>98.3% can not realize so relatively.If this ratio of briquetting is higher than 90%, according to the present invention, because dense product can also be processed without hot-isostatic pressing, this method is not again economically viable.
The inventive method be used to make be used for discharge tube, diameter range is that 15 to 55mm electrode is successful especially.If diameter is lower than 15mm, kind electrode can be processed by the production method of routine economically.Higher limit 55mm is got by the watts limit of this fluorescent tube.
The raw material of electrode preferably stands to be shaped by radially casting or rolling.Test shows, the electrode long 20% that the average life span of the electrode of processing through the inventive method is processed than conventional production method.
Below through an embodiment the present invention is detailed.
The specific embodiment
Use Fisher particle diameter is that the AKS-W powder of 4.1 μ m is made the AKS-W electrode.Under the pressing pressure of 200MPa, neutralize tight powder, to form green compact through isostatic cool pressing.Under 2250 ℃ temperature, in hydrogen, carry out sintering.The relative density D of the sintered bar of in this way processing measures with buoyancy method, is 92.0%.The ratio of the porosity of remaining silent that records with mercury porosimetry is>95%.Next step, sintered body under 1750 ℃ temperature, under the pressure of 195MPa, hot-isostatic pressing 3 hours.Relative averag density after the hot-isostatic pressing operation is 97.9%.Subsequently, this sintered bar is radially forming on the casting machine.Ratio of briquetting
Figure GSB00000575166700042
is 67%.After the forming process, the average relative density of this sintered bar is 99.66%, and core density is 99.63% relatively.Measure the unshaped state and at 1800 ℃ of particle diameters after the annealing 4 hours down.At the unshaped state, the center of this sintered bar and the particle diameter of marginal zone are about 10,000 crystal grain/mm 2In annealed condition, form very compact grained microstructure, the average crystal grain number of the center of sintered bar is 800 crystal grain/mm 2, the marginal zone is 850 crystal grain/mm 2
Made sintered bar has following chemical analysis results: potassium 15 μ g/g, silicon 6 μ g/g, carbon<5 μ g/g, oxygen 7 μ g/g.
The anode of short-arc lamp that is used for the 2.5kW of movie theatre projection with material manufacturing prepared in accordance with the present invention.Be 2060 hours the average life of confirming.Use a material as contrast, this material does not stand hot-isostatic pressing operation compacting subsequently after sintering process, yet other aspects but experience identical production technology.Be 1710 hours the average life that this material might obtain.

Claims (9)

1. method of making semi-finished product or element by molybdenum, molybdenum alloy, tungsten or tungsten alloy material; Said semi-finished product or element have with respect to the averag density of the weight of unit volume>98.5%; Said semi-finished product or element have core density>98.3% with respect to the weight of unit volume in the center; It is characterized in that this method comprises following steps at least:
● preparation Fisher particle diameter is the powder of 0.5 to 10 μ m;
● this powder of pressure pressed 100 to 500MPa;
● is the sintered body of D at 0.55 powder after the said compacting of the sintering temperature of 0.92 * solidus temperature to form relative density, wherein 90%<D<98.5%;
● 0.40 under the temperature of 0.65 * solidus temperature with 50 under the pressure of 300MPa, carry out the said sintered body of hot-isostatic pressing under the situation about not using jar;
Figure FSB00000575166600011
forms processing to the said sintered body through hot-isostatic pressing with ratio of briquetting, and wherein
Figure FSB00000575166600012
ratio of briquetting
Figure FSB00000575166600013
definition is as follows: ((cross-sectional surface after initial cross sectional surface area-forming process is long-pending)/initial cross sectional surface area) * 100.
2. the method for claim 1 is characterized in that, said element or the semi-finished product average crystal grain number>100 crystal grain/mm under deformation state 2
3. according to claim 1 or claim 2 method; It is characterized in that; Before hot-isostatic pressing; This sintered body stands extra shaping,
Figure FSB00000575166600014
4. according to claim 1 or claim 2 method is characterized in that the rate of closed hole of said sintered body is with respect to ratio>0.8 of total porosity.
5. according to claim 1 or claim 2 method it is characterized in that said element or semi-finished product are made up of potassium-Doped Tungsten, and potassium content is 5 to 70 μ g/g.
6. according to claim 1 or claim 2 method is characterized in that, carries out through radially casting or rolling handling through the shaping of the said sintered body of hot-isostatic pressing, processes rod thus.
7. method as claimed in claim 6 is characterized in that, this excellent diameter is 15 to 55mm.
8. method as claimed in claim 7 is characterized in that this rod is used to make the lamp electrode.
9. method as claimed in claim 8 is characterized in that, this lamp electrode is used for short-arc lamp.
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DE102006061375B4 (en) 2006-12-22 2019-01-03 Osram Gmbh Mercury high-pressure discharge lamp with an anode containing tungsten and potassium, which has a grain count greater than 200 grains per mm 2 and a density greater than 19.05 g / cm 3
US20090011266A1 (en) * 2007-07-02 2009-01-08 Georgia Tech Research Corporation Intermetallic Composite Formation and Fabrication from Nitride-Metal Reactions
RU2461910C2 (en) * 2007-09-21 2012-09-20 Осрам Аг Gas-discharge direct current lamp
KR101246754B1 (en) 2007-09-21 2013-03-26 오스람 게엠베하 Direct-current discharge lamp
DE102008014096A1 (en) * 2008-03-05 2009-09-10 Osram Gesellschaft mit beschränkter Haftung Tungsten electrode for high-pressure discharge lamps and high-pressure discharge lamp with a tungsten electrode
US9992917B2 (en) 2014-03-10 2018-06-05 Vulcan GMS 3-D printing method for producing tungsten-based shielding parts
CN105478772B (en) * 2014-09-15 2018-12-04 安泰科技股份有限公司 A kind of manufacturing method of molybdenum planar targets

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DE502006000455D1 (en) 2008-04-24
AT9340U1 (en) 2007-08-15
ATE389040T1 (en) 2008-03-15
CN101007350A (en) 2007-08-01
US20070148031A1 (en) 2007-06-28
JP5265867B2 (en) 2013-08-14
JP2007169789A (en) 2007-07-05
EP1801247B1 (en) 2008-03-12

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