CN103600086B - Powder used in metallurgy tantalum and/or niobium powder and preparation method thereof - Google Patents
Powder used in metallurgy tantalum and/or niobium powder and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder, the method comprising the steps of: (1) heat treatment sintering: by raw material tantalum and/or niobium powder heat treatment sintering, sintering finishes rear cooling and carry out passivation, obtains agglomerate; (2) hydrogenation powder process: powder process after the agglomerate hydrogenation that heat treatment is obtained, obtains tantalum and/or the niobium powder of hydrogenation; (3) oxygen falls in dehydrogenation: add reducing metal to carry out dehydrogenation and deoxidation heat treatment the tantalum of hydrogenation and/or niobium powder, obtain the tantalum of reducing metal oxide, residual reducing metal, dehydrogenation and deoxidation and/or the mixture of niobium powder; (4) pickling impurity removal: the mixture obtaining after oxygen is fallen in dehydrogenation and carry out pickling, oven dry, obtain being applicable to tantalum and/or the niobium powder of powder metallurgy. The method is applicable to reclaim and process the useless tantalum and/or the niobium powder that in the production process of capacitor high specific capacitance tantalum and/or niobium powder, produce, thereby prepare the tantalum and/or the niobium powder that are applicable to powder used in metallurgy, and the equipment investment needing is little, adaptable to raw material, technological process is short, and processing procedure safety coefficient is high.
Description
Technical field
The present invention relates to rare metal field of smelting, and be specifically related to tantalum powder and/or niobium powder and preparation thereofMethod.
Background technology
Tantalum and niobium are rare elements, and their performance is closely similar. Due to the oxidation of tantalum and niobiumFilm has very high dielectric constant, and therefore they are widely used in tantalum and/or niobium electrochemical capacitorDevice is made. In addition, because tantalum and/or niobium have high-melting-point and low-vapor pressure, therefore also applicationHeat generating components, boat and insulation material in Aero-Space, national defence, vacuum high temperature furnace.In addition, tantalum and/or niobium have excellent anti-corruption for liquid metal and the strong acid except hydrofluoric acidErosion ability, and there is good thermal conductivity and chemical stability, be also applied to chemical industry and smeltingAnti-corrosion material in the fields such as gold. In addition, because tantalum and/or niobium have good bio-compatibleProperty, therefore conventionally can be used in medical field as operation suture thread, custom-made prosthesis, intervertebralFusion device, joint prosthesis, bone fracture repair materials etc. Tantalum has strong anti-electronics stress and movesMove ability, therefore also can be used for the barrier layer between copper cash and silicon in manufacturing integration circuit.
In the time that tantalum and/or niobium are used for making electrolytic capacitor, conventionally use powder type tantalum and/ or niobium raw material prepare the anode block of porous, anode block also needs to insert tantalum and/or niobium while makingSilk thread as lead-in wire, also usually utilize tantalum and/or niobium sheet to be processed into capacitor case. ?In the application of other side, first tantalum and/or niobium powder to be pressed in most casesRod or bar, then carry out sintering, or even further electronic torch melting or electric arc melting, so thatReach densified, High Purity; And then be rolled, the processing such as drawing, form rod, plate,Sheet, pipe, silk, paper tinsel and other tantalum and/or niobium goods processing material.
Tantalum and/or niobium are as high temperature refractory, and it is smelted and conventionally adopts following technique: firstCompound is reduced into metal dust, and then purification, sintering, adjustment performance, thereby systemMake tantalum and/or the niobium powder of various satisfied different instructions for uses. If tantalum and/or niobium powder be forBe processed into rod, plate, sheet, pipe, silk, paper tinsel and other tantalum and/or niobium goods processing material,Be commonly called powder used in metallurgy tantalum and/or niobium powder. With tantalum and/or niobium powder phase for capacitorRatio, the feature of powder used in metallurgy tantalum and/or niobium powder is: (1) apparent density is large; (2)The impurity contents such as oxygen, nitrogen, hydrogen are low. A for example powder used in metallurgy tantalum powder, its apparent densityBe greater than 3.7g/cm3, oxygen content is lower than 1500ppm, and nitrogen content is lower than 100ppm, and hydrogen containsAmount is lower than 50ppm. If tantalum and/or niobium powder are for the production of electrolytic capacitor, we are referred to asFor tantalum and/or niobium powder for capacitor; Compared with powder used in metallurgy tantalum and/or niobium powder, capacitor is usedTantalum and/or niobium powder feature are: want except the impurity contents such as apparent density, oxygen, nitrogen, hydrogen are hadOutside asking, the more important thing is and require to have good electric property. Conventionally tantalum and/or niobium for capacitorThe specific volume of powder is higher, and specific area is larger, and apparent density is less, and oxygen, nitrogen, hydrogen etc. are assortedMatter content is higher. For example capacity is the tantalum powder for capacitor of 200,000 μ FV/g, and its pine fills closeDegree is 1.5-1.9g/cm3, oxygen content is 9,000-12,500ppm, and hydrogen content reaches350-500ppm, and because production process must be carried out nitrating processing, nitrogen content conventionally willReach 1,500-2,800ppm.
In process at production capacitor with tantalum and/or niobium powder, the each operation of production line exists certainWaste product or the substandard products of amount. Recycle these useless tantalums and/or niobium powder, the simplest method isSet it as the raw material of producing tantalum and/or niobium compound, be made into and produce that tantalum and/or niobium powder useCompound, as potassium floutaramite, is then reused for the raw material of going back original production tantalum and/or niobium powder.Produce but recycle by this method in the production process of capacitor tantalum and/or niobium powderWhen raw useless tantalum and/or niobium powder, there is following problem: 1) above-mentioned recovery method is first with acidDissolve useless tantalum and/or niobium powder, this process produces a large amount of hydrogen, thereby it is quick-fried that hydrogen very easily occursCombustion accident, therefore production risk is high; 2) tantalum resource recycling rate is lower; 3) workProcess flow is long, and production cost is higher, 4) the discharge three wastes are many, and environmental pollution is more serious.
If the useless tantalum and/or the niobium that in the production process by capacitor with tantalum and/or niobium powder, producePowder, for the preparation of powder used in metallurgy tantalum and/or niobium powder, can reduce production risk and greatly improveThe utilization rate of tantalum and/or niobium, thus save day by day poor tantalum and/or niobium resource and be lowered intoThis, the pressure of environmental pollution is relatively light. But the useless tantalum that this class reclaims and/or niobium powder are logicalNormal apparent density is little, and specific area is large, and oxygen, nitrogen, hydrogen content are higher. Such tantalumAnd/or niobium powder in the time being pressed into base bar, porosity can be too large, a large amount of volatilizations of impurity when sinteringCan cause disconnected bar; Or impurity inner before the closing of pores does not fully volatilize, thereby difficultTo reach the object of purification, be unfavorable for next step processing. Especially at high ratio for capacitorHold in tantalum and/or niobium powder production process, in order to obtain higher specific volume, need to increase tantalum and/Or niobium powder specific area; Therefore capacitor produces by high specific capacitance tantalum and/or niobium powder production processUseless tantalum and/or niobium powder cause the more outstanding of the problems referred to above performance. For example, when tantalum powder specific areaBe greater than 1.5m2After/g, reclaiming the useless tantalum powder obtaining may apparent density only have 0.9g/cm3，And oxygen content may exceed 6,000ppm, nitrogen content exceedes 300ppm, and hydrogen content also reaches1500ppm; Be greater than 3.5m and work as specific area2After/g, reclaiming the useless tantalum powder obtaining may pineDress density only has 0.6g/cm3, and oxygen content may exceed 14, and 000ppm, nitrogen content exceedes400ppm, hydrogen content reaches 2500ppm or even higher. And niobium powder is along with specific areaIncrease, apparent density down ratio is larger, and the impurity content increasing degrees such as oxygen, nitrogen, hydrogen moreHigh. So reclaim the useless tantalum and/or the niobium that produce in the production process of capacitor with tantalum and/or niobium powderPowder and and then while setting it as powder used in metallurgy tantalum and/or niobium powder, must further processProcess.
Chinese patent application CN200610146912.5 discloses a kind of raising tantalum and/or niobium powderApparent density, reduce tantalum and/or niobium powder specific area, and reduce simultaneously tantalum and/or niobium powder oxygen,The method of the impurity such as nitrogen, hydrogen. The method comprises the following steps: 1) raw material tantalum and/or niobiumPowder stock is pressed into base bar, 2) the base bar of vacuum-sintering compacting; 3) by sintered blank bar hydrogenChange powder process; 4) add reducing agent to carry out deoxidation, dehydrogenation heat the tantalum of hydrogenation and/or niobium powderProcess; With 5) tantalum after deoxidation, dehydrogenation heat treatment and/or niobium powder are carried out to pickling, waterWash and dry. The method is suitable for processing specific area and is less than 1.0m2/ g raw material tantalum and/or niobiumPowder. But work as raw material tantalum and/or niobium powder specific area and be greater than 1.0m2When/g, described powderApparent density will be very little (may be less than 1.0g/cm3) and the higher (possibility of oxygen contentHigher than 6,000ppm). When such tantalum and/or niobium powder are pressed into base bar, easily occur as followsProblem: thus tantalum and/or niobium powder and mould inner wall adhesion cause demoulding difficulty, the effect of therefore workingRate reduces and even cannot carry out the compacting of base bar; And the method press device complexity used,Therefore equipment investment is larger.
For specific area is greater than 1.0m2/ g raw material tantalum and/or niobium powder can adapt to Chinese patentThe open method of application CN200610146912.5 is processed, and in prior art, reclaims useless tantalumAnd/or the common processing method of niobium powder is first to carry out the heat treatment of high temperature high vacuum powder process; WillThe tantalum obtaining and/or niobium powder fall oxygen after participating in reducing agent; Then carry out pickling, oven dry,Screening, obtains specific area and is less than 1.0m2/ g, oxygen content is lower than the tantalum powder of 4,000ppm.But along with capacitor with tantalum and/or niobium powder specific volume more and more higher, have useless tantalum to be recycled and/Or niobium powder specific area is more and more higher and active also more and more higher, such as the useless tantalum reclaimingAnd/or niobium powder specific area is greater than 1.8m2When/g is above, after the heat treatment of high temperature high vacuumAgglomerate intensity is too high, causes the broken difficulty of agglomerate, and easily in the time of fragmentation, rub and catch fire,Cause fire. On the other hand, if reduce heat treatment temperature, agglomerate strength decreased,But tantalum powder activity is not effectively reduced; Therefore the passivation time after heat treatment is long especially,Production efficiency of equipment is significantly reduced, and in subsequent treatment, tantalum powder easily occur certainlyCombustion firing accident; Even if missing of ignition, tantalum powder after treatment still has very little apparent density.In addition,, in the time using low heat treatment temperature, tantalum powder specific area is still larger and aliveProperty is more intense, and tantalum powder contacts with air dielectric in processing, transport, storage, use procedureAnd with airborne oxygen, nitrogen, reaction of moisture, so oxygen, nitrogen, hydrogen etc. are assorted in tantalum powderMatter is still very high, can not reach the requirement of powder used in metallurgy tantalum and/or niobium powder.
In sum, reclaim and process in capacitor high specific capacitance tantalum and/or niobium powder production processThere is following shortcoming in the useless tantalum producing and/or the prior art of niobium powder: (1) equipment structure is multipleAssorted, equipment investment is larger; (2) inefficiency; (3) process route length, tantalum powderThe rate of recovery is low, causes processing cost higher; (4) along with tantalum and/or niobium powder for capacitorSpecific volume is more and more higher, and useless tantalum to be recycled and/or niobium powder specific area and activity are more and more higher,Prior art cannot effectively be processed it. High specific capacitance tantalum and/or niobium for partition capacitance deviceThe useless tantalum producing in the production process of powder and/or niobium powder, by existing PROCESS FOR TREATMENT, not only can not obtainTo qualified powder used in metallurgy tantalum and/or niobium powder, may, due to tantalum and/or the spontaneous combustion of niobium powder, occurDeflagration accident having.
Therefore there is the useless tantalum producing in high specific capacitance tantalum and/or niobium powder production process reclaiming in this area,And/or the needs of the efficient and safe method of niobium powder.
Summary of the invention
The object of the invention is to overcome the problems referred to above of the prior art, provide a kind of and pass through backReceive and process the useless tantalum that produces in the production process of capacitor with high specific capacitance tantalum and/or niobium powder with/Or niobium powder, thereby prepare the method for the tantalum and/or the niobium powder that are applicable to powder used in metallurgy. ThisBright object be also to provide a kind of powder used in metallurgy tantalum that can process high-quality tantalum material and/Or niobium powder.
A first aspect of the present invention provides one to utilize capacitor high specific capacitance tantalum and/or niobiumThe useless tantalum producing in the production process of powder and/or niobium powder are prepared powder used in metallurgy tantalum and/or niobium powderMethod, the method comprising the steps of:
(1) heat treatment sintering: by raw material tantalum and/or niobium powder heat treatment sintering, sintering finishes rear coldBut and carry out passivation, obtain agglomerate;
(2) hydrogenation powder process: powder process after the agglomerate hydrogenation that heat treatment is obtained, obtains hydrogenationTantalum and/or niobium powder;
(3) oxygen falls in dehydrogenation: by the tantalum of hydrogenation and/or niobium powder add reducing metal carry out dehydrogenation andDeoxidation heat treatment, obtains reducing metal oxide, residual reducing metal, dehydrogenation and de-The mixture of the tantalum of oxygen and/or niobium powder; With
(4) pickling impurity removal: the mixture obtaining after oxygen is fallen in dehydrogenation and carry out pickling, oven dry,To the tantalum and/or the niobium powder that are applicable to powder metallurgy.
According to the method described in first aspect present invention, wherein said raw material tantalum and/or niobium powder canTo be useless tantalum and/or the niobium powder reclaiming in capacitor tantalum and/or niobium powder production process, also canThat special high-specific surface area, the low bulk of producing of technique that adopt industry technology personnel to know to know is closeTantalum and/or the niobium powder of degree, elevated oxygen level; Preferably, in described raw material tantalum and/or niobium powder, go backCan contain and be selected from one in tungsten, molybdenum, titanium, hafnium, zirconium, carbon, silicon, vanadium, aluminium and tinPlant or multiple element.
According to the method described in first aspect present invention any one, wherein said raw material tantalum and/Or niobium powder has the 1.0m of being greater than2The specific area of/g and/or higher than the oxygen content of 4000ppm,Preferably there is the 1.8m of being greater than2The specific area of/g, more preferably has the 2.0m of being greater than2/ g, be greater than3.0m2/ g, be greater than 4.0m2/ g, be greater than 5.0m2/ g, be greater than 6.0m2/ g, be greater than 7.0m2/gOr be greater than 8.0m2The specific area of/g. Further preferred raw material tantalum and/or niobium powder have greatlyIn 1m2The specific area of/g, the while is higher than the oxygen content of 4,000ppm.
According to the method described in first aspect present invention any one, wherein described in step (1)Heat treatment sintering be in 3.0 × 10 at low vacuum-1At the temperature of Pa, 1500-2100 DEG C, enterOK; The time of preferred heat treatment sintering is 1-25 hour, and preferred sintering time is3-20 hour, 3-18 hour, 3-15 hour, 2-10 hour or 3-10 hour.
According to the method described in first aspect present invention any one, wherein described in step (1)Passivation be temperature be cooled to 50 DEG C or lower than the condition of 50 DEG C under carry out, preferably,Described passivation is in agglomerating plant, to pass into air to carry out passivation.
According to the method described in first aspect present invention any one, wherein step (2) hydrogenation systemThe step of powder comprises:
A) oxide layer is destroyed: by Bas Discharged in equipment, in container, pass into hydrogen as guarantorProtect after gas, then agglomerate is heated to 800-950 DEG C of high temperature, insulation 1-10 hour, makesAgglomerate surface oxidation damage layer;
B) inhale hydrogen: oxide layer starts cooling after destroying, and lowers the temperature while pass into hydrogen,Last till that temperature drops to normal temperature (25 DEG C), makes agglomerate fully inhale hydrogen;
C) fragmentation: adopt this area to know the disintegrating apparatus of knowing and carry out broken powder process, for example, adoptAirslide disintegrating mill, Milling and screening machine, jaw crusher powder process. Preferably, the powder obtaining after fragmentationWith 250 mesh standard sieve sieve powder, obtain passing through tantalum and/or the niobium powder of 250 mesh sieves completely.
According to the method described in first aspect present invention any one, wherein step (2) hydrogenation systemThe hydrogen purity of using in powder is higher than 99.95%, and preferably hydrogen purity is higher than 99.995%;
Preferably, described Hydrogen Vapor Pressure is 0.1-3Mpa, and preferred Hydrogen Vapor Pressure is0.5-1.0Mpa。
According to the method described in first aspect present invention any one, wherein, step is middle conduct a)The pressure of the hydrogen of protection gas is 0.1～3.0Mpa, is preferably 0.5-1.0Mpa;
Preferably, the Hydrogen Vapor Pressure of step in b) remains on 0.1～3.0Mpa; More preferably,Hydrogen Vapor Pressure remains on 0.5～1.0Mpa.
According to the method described in first aspect present invention any one, wherein, step b) in fullyThe hydrogen content that absorbs the agglomerate of hydrogen is 3,000-6, and 000ppm, is preferably3,000-5,000ppm(is 4000ppm, 4300ppm or 4800ppm for example).
According to the method described in first aspect present invention any one, wherein said reproducibility goldBelong to and be selected from magnesium, calcium, rare earth metal or their alloy or combination, be preferably magnesium; Preferably,The consumption of reducing metal is that the oxygen in tantalum and/or the niobium powder of hydrogenation is converted into reproducibility completelyDoubly (for example 1.6 times, 1.7 of the stoichiometric 1.2-5 of the required reducing metal of metal oxideDoubly, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.25 times).
According to the method described in first aspect present invention any one, the wherein institute in step (3)The dehydrogenation of stating and deoxidation heat treatment are for example, in inert gas (argon gas, helium) circulation protectionOr heat treated under the condition vacuumizing. Preferably, described heat treatment is first at indifferent gasThe lower heat treated of circulation protection of body, 800-950 DEG C (for example 800 DEG C, 830 DEG C, 850 DEG C,880 DEG C, 900 DEG C, 920 DEG C or 950 DEG C) lower 1-3 hour (for example 2 hours) of insulation that continue,Then vacuumize (preferably in 20-80 minute, progressively reduce pressure to atmospheric pressure lower than0.06MPa), lower than atmospheric pressure 0.06MPa, in other words-0.06MPa, orUnder the lower pressure of person, at same temperature, be incubated again 1-6 hour and (be preferably 2-6 hour, exampleAs 3 hours).
According to the method described in first aspect present invention any one, wherein step (4) pickling impurity removalThe acid of using is nitre aqueous acid, preferred concentration be 5-30 (wt) %(for example 15%,8%, 10%, 18%, 20%, 25% or 28%). Preferably, the consumption of acid is to mixThe solid-to-liquid ratio of thing and aqueous solution of nitric acid is for example 1 ﹕ 2 of 1 ﹕ 1～3(). Preferably, mixAfter mixing with aqueous solution of nitric acid, stirs 10-90 minute (for example 60 minutes, 20 minutes, 30 thingMinute, 50 minutes, 80 minutes).
In a preferred embodiment, the tantalum obtaining after pickling and/or niobium powder are all rightWith pure water washing, then dry and obtain tantalum and/or niobium powder; More preferably, the tantalum after oven dryAnd/or niobium powder crosses 200 mesh sieves, must be powder used in metallurgy tantalum and/or the niobium powder of 200 mesh sieves.
A second aspect of the present invention provides a kind of powder used in metallurgy tantalum and/or niobium powder, and it passes throughMethod described in first aspect present invention any one prepares.
Preferably, described powder used in metallurgy tantalum and/or niobium powder had the grain of 200 mesh sievesFootpath.
Preferably, described powder used in metallurgy tantalum and/or niobium powder has the 5.0m of being less than2/ g'sSpecific area, for example, be less than 0.4m2/ g, be less than 0.3m2/g。
Preferably, the oxygen content of described powder used in metallurgy tantalum and/or niobium powder is300-1500ppm, be preferably 800-1500ppm(for example 890ppm, 1060ppm,1430ppm, 760ppm or 1230ppm).
Preferably, the hydrogen content of described powder used in metallurgy tantalum and/or niobium powder is 180ppmBelow, be preferably 150ppm following (for example 90ppm is following, 100ppm is following or120ppm is following), more preferably below 80ppm, (for example 20ppm is following, 30ppmBelow, 50ppm is following, 40ppm following, 60ppm is following or 70ppm following).
Preferably, the apparent density of described powder used in metallurgy tantalum powder is 3.5-7g/cm3, excellentElect 3.9-6.5g/cm as3。
Preferably, the apparent density of described powder used in metallurgy niobium powder is 2-6g/cm3, excellentElect 2-5g/cm as3(for example 2.6g/cm3Or 3.1g/cm3）。
Detailed Description Of The Invention
In this manual, mentioned each percentage, PPM and ratio all refers to heavilyAmount percentage, unless otherwise expressly noted.
In the present invention, term " tantalum and/or niobium powder " refers to mainly formed by tantalum and/or niobium eachPlant powder; Include but not limited to tantalum metal powder, niobium metal powder, tantalum powder and niobium powder mixture,Or tantalum-niobium alloy powder.
Method of the present invention can use high-specific surface area, low-apparent-density, elevated oxygen level tantalum and/Or niobium powder is as raw material, produces powder used in metallurgy tantalum and/or niobium powder.
In the method for the invention, described raw material tantalum and/or niobium powder can be to use from capacitorUseless tantalum and/or niobium powder that tantalum and/or niobium powder production process reclaim can be also the height of specially producingThe tantalum of specific area, low-apparent-density, elevated oxygen level and/or niobium powder. But preferably, makeUse by the useless tantalum and/or the niobium powder that reclaim in capacitor tantalum and/or the each operation of niobium powder production line and doFor described raw material tantalum and/or niobium powder. In addition, also can by desired content add tungsten, molybdenum, titanium,One or more of the elements such as hafnium, zirconium, carbon, silicon, vanadium, aluminium, tin are as adulterant.
In method step of the present invention (1), divide dish to pack height into raw material tantalum and/or niobium powderTemperature high vacuum heat-treatment furnace sintering, for fear of infiltrate objectionable impurities in target powder, instituteStating point crucible material that dish shove charge is used is the material that is difficult for infiltrating objectionable impurities in target powderMaterial, generally selects tantalum crucible, molybdenum crucible or graphite crucible; Sintering vacuum require lower than3.0×10-1Pa, sintering temperature is 1500-2100 DEG C, and sintering time to be preferably 1-25 littleTime, preferably 2-10 hour. Sintering is lowered the temperature after finishing, when temperature backward lower than 50 DEG CIn sintering furnace heating clamber, slowly pass into air and carry out passivation, finally obtain agglomerate.
In method step of the present invention (1), described sintering is lower than 3.0 × 10-1Pa pressesUnder the high vacuum of power, at the temperature of 1500-2100 DEG C, carry out 1-25 hour, preferably 2-10Hour. Step (1) sintering condition be final metallurgical with tantalum and/or niobium powder improve apparent density,Reduce the key of oxygen content, in the temperature range of 1500-2100 DEG C, temperature is higher, timeBetween longer, the amplitude that raw material tantalum and/or niobium powder granule merge, grow up is larger, seed activityLower, final metallurgy is with tantalum and/or niobium powder apparent density is higher, oxygen content is lower. Sintering temperatureDegree exceedes 2100 DEG C, and sintering time exceedes 10 hours, final metallurgical with tantalum and/or niobium powder pineDress density, oxygen content will tend towards stability. If sintering temperature is too low, the time is too short, than tableThe useless tantalum that area is large and/or niobium powder activity decreased are not thorough, when its in further processing with connectThe tactile substance reaction such as oxygen, water, cause the powder used in metallurgy tantalum that finally obtains and/or niobium powder oxygen,Hydrogen content will be higher, and involuntary ignition even occurs. After finishing, sintering lowers the temperature and passivation,So-called passivation is exactly by controlling tantalum surface oxidation rate, forming the form compact and stable oxygen of one deckChange film, make tantalum enter no longer vigorous oxidation of atmosphere rear surface from vacuum state, to avoid certainlyCombustion, obtains agglomerate after step (1) processing finishes.
In method step of the present invention (2), by packaged the sintering obtaining in (1) stepEnter after hydrogenation vessel, first the air in container is discharged by the row of finding time, then to containerIn pass into 0.5-1.0Mpa purity higher than 99.95% hydrogen as protective gas after, thenAgglomerate is heated to 800-950 DEG C of high temperature, and insulation 1-10 hour, makes its surface oxide layerDestroy, the cooling that then has a power failure, not open close enter purity higher than 99.95% hydrogen, preferably hydrogenGas purity is higher than 99.995% hydrogen, and makes Hydrogen Vapor Pressure maintain 0.1～3.0Mpa, excellentSelecting Hydrogen Vapor Pressure is 0.5～1.0Mpa, to make agglomerate fully inhale hydrogen, its hydrogen is containedAmount reaches 3,000-6, and 000ppm obtains having tantalum and/or niobium and the alloy thereof of good hydrogen fragilityPiece. If hydrogen purity is too low or Hydrogen Vapor Pressure is too low, agglomerate is inhaled hydrogen deleterious, itsHydrogen brittleness is bad, will make crushing efficiency reduce, even cannot be broken, if Hydrogen Vapor Pressure mistakeHeight, is unfavorable for production safety risk control. Then adopt and know the disintegrating apparatus of knowing as air-flow powderBroken machine, Milling and screening machine, jaw crusher powder process, with 250 mesh standard sieve sieve powder, obtain completelyCan be by tantalum and/or the niobium powder of 250 mesh sieves.
In the step (3) of the inventive method, described reducing metal be selected from magnesium metal, calcium,Rare earth metal or their alloy or combination, preferable alloy magnesium, its principle can be described as:Metal tantalum after hydrogenation and/or niobium have at high temperature low hydrogen and divide under the condition of depressing and can discharge itThe characteristic of middle hydrogen, obtains tantalum by step (2) and/or niobium powder is heated to high temperature, uses simultaneouslyArgon gas etc. do not circulate with the inert gas that material and equipment material react, and maybe will reactContainer vacuum-pumping, makes wherein hydrogen release out, simultaneously due to selected reducing metal and oxygen affinityClose can force rate tantalum and/or niobium stronger, so reducing metal by capture tantalum and/or niobium inOxygen, generates the reducing metal oxide easily being dissolved by hydrochloric acid, nitric acid, sulfuric acid etc., realThe object of oxygen is fallen when existing step (2) obtains tantalum and/or the dehydrogenation of niobium powder. In addition, described inThe consumption of reducing metal is that the oxygen in tantalum and/or the niobium powder of hydrogenation is converted to reproducibility completelyThe stoichiometric 1.2-5 of the required reducing metal of metal oxide doubly. In addition, described dehydrogenation is fallenThe heat treated of oxygen preferably continues insulation 1-3 in the situation that argon gas circulates at 800-900 DEG C littleTime, then under lower than atmospheric pressure 0.06MPa or lower pressure at same temperature againInsulation 1-6 hour, fully dehydrogenation, obtains reducing metal oxide, residual reproducibility goldThe mixture of the tantalum of genus, dehydrogenation and deoxidation and/or niobium powder.
More specifically, in method step of the present invention (3), by what obtain in step (2)Tantalum and/or niobium powder mix by a certain percentage with magnesium metal; The consumption of described magnesium metal is hydrogenationOxygen in tantalum and/or niobium powder is converted to magnesian 1.2-5.0 doubly completely, if use magnesium metalTime, magnesium metal deficiency, in tantalum and/or niobium powder is insoluble in generation sour tantalic acid magnesium, causesMagnesium in whole tantalum and/or niobium powder, oxygen content are too high. By the tantalum and/or the niobium that obtain in step (2)The mixture that powder mixes with magnesium metal, is divided into equalization and is distributed into boat, reinstalls dehydrogenation and falls oxygenStove first carries out heat treated under inert gas is protected as the circulation of argon gas or helium, described inDehydrogenation is fallen oxygen and preferably at 800-950 DEG C, is continued insulation 1-3 hour, if excess Temperature, tantalum powderUndue sintering, part Mg will wrap up wherein, cause Mg content in final product to increase,If temperature is too low, deoxidation in tantalum and/or niobium powder, dehydrogenation poor effect, cause product oxygen,Hydrogen content is higher, and then oxygen reaction vessel is fallen in dehydrogenation and vacuumize, in 20-80 minute,The pressure that progressively reduces reaction vessel is to lower than under atmospheric pressure 0.06MPa or lower pressureAt same temperature, be incubated 1-6 hour, fully dehydrogenation, with the powder that ensures finally to obtain againMetallurgy is reduced to below 80ppm with tantalum and/or niobium powder hydrogen content, in evacuation process, if anti-Answer container inner pressure to decline too fast, superfluous magnesium metal volatilizees fierceness, by tantalum and/or niobium powderFrom take up the boat of material, take out of, cause loss of material. Then cooling passivation, obtainThe tantalum of magnesia, kish magnesium, deoxidation and dehydrogenation and/or the mixture of niobium powder.
In the final step (4) of the inventive method, the mixture that step (3) is obtainedCarry out pickling, to remove magnesium metal, magnesia in the tantalum of deoxidation and dehydrogenation and/or niobium powder;The mixture that step 4 is obtained with contain 5-30(wt) aqueous solution of the nitric acid of %,Concentration of nitric acid is too high, will make tantalum powder oxygen content increase, the solid-to-liquid ratio of tantalum powder and aqueous solution of nitric acidFor 1:1-3.0, stir 10-90min, dissolve magnesium metal, magnesia wherein, then mistakeFilter acid pickle, then divide dish vacuum drying, with 200 mesh standard sieve sieve powder, thereby obtainBe applicable to tantalum and/or the niobium powder of powder used in metallurgy.
Obtain powder used in metallurgy tantalum and/or niobium powder by said method provided by the invention, itsThere is the particle diameter of 200 mesh sieves, the oxygen content of 300-1500ppm. Especially, by above-mentionedThe apparent density of the powder used in metallurgy tantalum powder that method obtains is typically 3.5-7.0g/cm3; And byThe apparent density of the powder used in metallurgy niobium powder that said method obtains is typically 3.0-6.0g/cm3。
Tantalum of the present invention and/or niobium powder Fei Shi particle diameter are by standard " refractory metal and compound powderThe assay method Fei Shi method of granularity " (standard No. GB/T3249) prescriptive procedure mensuration, pineDress density is by standard " the mensuration Part I funnel method of metal dust apparent density " (markStandard GB/T1479) prescriptive procedure mensuration, size distribution is by standard " metal dust granularity groupThe mensuration dry screen point-score becoming " (standard No. GB/T1480) prescriptive procedure mensuration, sampledJourney specifies by standard " sampling method of powder used in metallurgy powder " (standard No. GB/T5314)Method samples, and oxygen, nitrogen, hydrogen content and specific surface area analysis method are as institute in table 1Show.
Table 1 chemical impurity analytical method
The beneficial effect of the invention
Preparation method of the present invention is applicable to reclaim and process capacitor high specific capacitance tantalum and/or niobium powderProduction process in the useless tantalum and/or the niobium powder that produce, thereby prepare the tantalum that is applicable to powder used in metallurgyAnd/or niobium powder. The equipment investment that the inventive method needs is little, adaptable to raw material, techniqueFlow process is short, and processing procedure safety coefficient is high.
Detailed description of the invention
Prepare the useless tantalum powder 1095kg that tantalum powder for capacitor production process reclaims, be numberedTa powder 1, its physical property, chemical impurity analysis result are in table 2. Preparation capacitor is usedThe useless niobium powder 379kg that niobium powder production process reclaims, is numbered raw material niobium powder 1, and it is physicalEnergy, chemical impurity analysis result are in table 3.
Embodiment 1
Get Ta powder 1 and amount to 200kg, divide 30 dishes to take up with tantalum crucible it, then putOn bin, send into heat-treatment furnace, start evacuation system, low vacuum is in 3.0 × 10-2PaRear power transmission heating, sintering temperature is 1500 DEG C, and sintering time is 3 hours. Sintering knotAfter bundle, lower the temperature, when detected temperatures slow in lower than 50 DEG C of backward sintering furnace material place chambersSlowly pass into air and carry out passivation, after coming out of the stove, obtain agglomerate. Pack agglomerate into hydrogenation vesselAfter, first the air in container is discharged by the row of finding time, then in container, pass intoThe hydrogen of the purity 99.995% of 0.5Mpa as protective gas after, then agglomerate is heated to800-950 DEG C of high temperature, is incubated 3 hours, then have a power failure cooling, not open close enter purity be99.995% hydrogen, and make Hydrogen Vapor Pressure maintain 0.5～1.0Mpa, obtain having goodThe hydrogenated tantal piece of hydrogen brittleness. Then adopt jaw crusher powder process, with 250 mesh standard sieve sievesPowder, obtains passing through the hydrogenated tantal powder of 250 mesh sieves completely; Analyze oxygen, hydrogen in hydrogenated tantal powderContent, analysis result: oxygen content is 23,000ppm, and hydrogen content is 4,300ppm, to thisIn hydrogenated tantal powder, evenly mix stoichiometric 1.6 times of required magnesium metal, by hydrogenated tantal grain weightAmount conversion, for 5.5% magnesium metal of hydrogenated tantal grain weight amount, is divided into equalization and is distributed into metal tantalumBoat, reinstalls dehydrogenation and falls oxygen stove, first under inert gas is protected as the circulation of argon gas, carries out830 DEG C of heat treated 2 hours, then fall oxygen reaction vessel to dehydrogenation and vacuumize, 29 points, vacuumZhong Hou, the pressure of reaction vessel is progressively reduced to lower than atmospheric pressure 0.08MPa, then existsAt 830 DEG C, find time to be incubated 3 hours, then cooling passivation, obtain magnesia, residue gold againBelong to magnesium deoxidation and the tantalum of dehydrogenation and/or the mixture of niobium powder. Finally, by above-mentioned mixture withContaining 15(wt) the nitre aqueous acid of % by the solid-to-liquid ratio of tantalum powder and aqueous solution of nitric acid is1:2.0 mixes, and stirs 60min, then filters with pure water, removes acid pickle, then divides dish trueEmpty oven dry, with 200 mesh standard sieve sieve powder, obtains final powder used in metallurgy tantalum powder. By this powderEnd metallurgy is numbered powder used in metallurgy tantalum powder 1 with tantalum powder, analyzes its physical property, chemical assortedMatter, analysis result is in table 2.
Embodiment 2
Get Ta powder 1 and amount to 200kg, divide 30 dishes to take up with graphite crucible it, heat placeReason sintering temperature is 1500 DEG C, and sintering time is 10 hours, the same embodiment of other conditions1. The powder used in metallurgy tantalum powder finally obtaining is numbered to powder used in metallurgy tantalum powder 2, analyzes itPhysical property, chemical impurity, analysis result is in table 2.
Embodiment 3
Get Ta powder 1 and amount to 200kg, divide 30 dishes to take up with graphite crucible it, heat treatmentSintering temperature is 2100 DEG C, and sintering time is 10 hours, and other conditions are pressed embodiment 1Condition heat-treat sintering, hydrogenation powder process, analyze oxygen, hydrogen content in hydrogenated tantal powder,Analysis result: oxygen content is 13,000ppm, hydrogen content is 5,600ppm, to this hydrogenated tantalIn powder, evenly mix stoichiometric 2.0 times of required magnesium metal, by the conversion of hydrogenated tantal grain weight amount,For 4.0% magnesium metal of hydrogenated tantal grain weight amount, other conditions are undertaken by the condition of embodiment 1Oxygen, pickling impurity removal fall in dehydrogenation. This powder used in metallurgy tantalum powder is numbered to powder used in metallurgy tantalum powder3, analyze its physical property, chemical impurity, analysis result is in table 2.
Table 2 tantalum mealiness energy
Can find out from analysis result, the useless tantalum powder that tantalum powder for capacitor production process reclaims,Average grain diameter, apparent density are too little, and specific area is too large, and oxygen, hydrogen content are high especially,Cannot use as metallurgical Ta powder at all. Such tantalum powder will, by prior art processing, be depositedCatching fire or the problem of press strip difficulty, but according to PROCESS FOR TREATMENT of the present invention, process is simple,Safety, and it is good to obtain powder used in metallurgy tantalum powder physical property: and average grain diameter, pine fill closeDegree increases substantially, and specific area, oxygen content, hydrogen content significantly reduce, and adopts higherTemperature sintering, nitrogen content also obviously improves.
Embodiment 4
Get raw material niobium powder 1 and amount to 100kg, used niobium crucible to divide 30 dishes to take up, by embodiment1 condition is heat-treated sintering, hydrogenation powder process, sample analysis, analysis result: oxygen containsAmount is 28,000ppm, and hydrogen content is 3,400ppm, in this hydrogenated niobium powder, evenly mixes instituteNeeding stoichiometric 1.2 times of magnesium metal, by the conversion of hydrogenated niobium grain weight amount, is hydrogenated niobium grain weight5.0% magnesium metal of amount, is divided into equalization and is distributed into metal niobium boat, then press embodiment's 1Condition carries out that oxygen falls in dehydrogenation, this powder used in metallurgy niobium powder is numbered powder used in metallurgy niobium by picklingPowder 1, analyzes its physical property, chemical impurity, and analysis result is as table 3.
Embodiment 5
Get raw material niobium powder 1 and amount to 100kg, the condition by it by embodiment 3 is heat-treatedSintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 16,000ppm, hydrogenContent is 3,800ppm, stoichiometric to evenly mixing required magnesium metal in this hydrogenated niobium powder2.1 times, by hydrogenated niobium grain weight amount conversion, is 5.0% magnesium metal of hydrogenated niobium grain weight amount,Be divided into equalization and be distributed into metal niobium boat, then by the condition of embodiment 3 carry out dehydrogenation fall oxygen,Pickling demagging. This powder used in metallurgy niobium powder is numbered to powder used in metallurgy niobium powder 2, analyzes itPhysical property, chemical impurity, analysis result is as table 3.
Table 3 niobium mealiness energy
Can find out from analysis result, the useless niobium powder that niobium powder for capacitor production process reclaims,Average grain diameter, apparent density are too little, and specific area is too large, and oxygen, hydrogen content are high especially,Cannot use as metallurgical Ta powder at all. Such tantalum powder will, by prior art processing, be depositedCatching fire or the problem of press strip difficulty, but according to PROCESS FOR TREATMENT of the present invention, process is simple,Safety, and it is good to obtain powder used in metallurgy tantalum powder physical property: and average grain diameter, pine fill closeDegree increases substantially, and specific area, oxygen content, hydrogen content significantly reduce, and adopts higherTemperature sintering, nitrogen content also obviously improves.
Embodiment 6
Get Ta powder 1 and amount to 120kg, raw material niobium powder 1 amounts to 80kg, mixes, willIts condition by embodiment 3 is heat-treated sintering, hydrogenation powder process, sample analysis, analyzesResult: oxygen content is 17,800ppm, hydrogen content is 4,000ppm, closes to this hydrogenated tantal niobiumIn bronze, evenly mix stoichiometric 1.9 times of required magnesium metal, by hydrogenated tantal niobium alloy powderWeight conversion, for 5.0% magnesium metal of hydrogenated tantal niobium alloy grain weight amount, is divided into impartial packingEnter metal niobium boat, then carry out dehydrogenation by the condition of embodiment 3 and fall oxygen, pickling demagging. WillThis powder used in metallurgy tantalite niobite power is numbered powder used in metallurgy tantalum-niobium alloy powder 1, analyzes its physicsPerformance, chemical impurity, analysis result is as table 4.
Embodiment 7
Get Ta powder 1 and amount to 195kg, from market purchasing purity higher than 99.9% ,-200Object tungsten powder 5.0kg, mixes both, and it is carried out to heat place by the condition of embodiment 3Reason sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 14,200ppm,Hydrogen content is 4,600ppm, in this hydrogenated tantal alloyed powder, evenly mixes required magnesium metal chemistry2.25 times of metering, convert by hydrogenated tantal alloyed powder weight, for hydrogenated tantal alloyed powder weight5.0% magnesium metal, is divided into equalization and is distributed into metal tantalum boat, then presses the condition of embodiment 3Carry out dehydrogenation and fall oxygen, pickling demagging. This powder used in metallurgy tantalum tungsten powder is numbered to powder metallurgyWith tantalum alloy powder 1, analyze its physical property, chemical impurity, analysis result is as table 4.
Embodiment 8
Get Ta powder 1 and amount to 180kg, from market purchasing purity higher than 99.5% ,-200Object hafnium powder 20.0kg, mixes both, and it is carried out to heat by the condition of embodiment 3Process sintering, hydrogenation powder process, sample analysis, analysis result: oxygen content is 18,500ppm,Hydrogen content is 4,500ppm, in this hydrogenated tantal alloyed powder, evenly mixes required magnesium metal chemistry1.8 times of metering, convert by hydrogenated tantal alloyed powder weight, for hydrogenated tantal alloyed powder weight5.0% magnesium metal, is divided into equalization and is distributed into metal tantalum boat, then presses the condition of embodiment 3Carry out dehydrogenation and fall oxygen, pickling demagging. This powder used in metallurgy tantalum hafnium powder is numbered to powder metallurgyWith tantalum alloy powder 2, analyze its physical property, chemical impurity, analysis result is as table 4
Embodiment 9
Get raw material niobium powder 1 and amount to 99.0kg, from market purchasing purity higher than 99.6% ,-200 ordersZirconium powder 1.0kg, mixed, the condition by it by embodiment 3 is heat-treated burningKnot, hydrogenation powder process, sample analysis, analysis result: oxygen content is 19,500ppm, and hydrogen containsAmount is 5,300ppm, in this hydrogenated niobium alloyed powder, evenly mixes required magnesium metal stoichiometry1.7 times, by hydrogenated niobium alloyed powder weight conversion, be 5.0% of hydrogenated niobium alloyed powder weightMagnesium metal, be divided into equalization and be distributed into metal niobium boat, then undertaken by the condition of embodiment 3Oxygen, pickling demagging fall in dehydrogenation. This powder used in metallurgy niobium zirconium powder is numbered to powder used in metallurgy niobiumAlloyed powder 1, analyzes its physical property, chemical impurity, and analysis result is as table 4
Table 4 niobium mealiness energy
Can find out from analysis result, the useless tantalum that capacitor reclaims by tantalum and/or niobium powder production process and/ or niobium powder, because average grain diameter, apparent density are too little, and specific area is too large, oxygen, hydrogen contentHigh especially, cannot use as metallurgical Ta powder at all, also cannot be by prior art processing place smoothlyReason, but according to PROCESS FOR TREATMENT of the present invention, can obtain well behaved powder used in metallurgy tantalum and/or niobiumAlloyed powder.
Claims (57)
1. a method of preparing powder used in metallurgy tantalum and/or niobium powder, the method comprising the steps of:
(1) heat treatment sintering: by raw material tantalum and/or niobium powder heat treatment sintering, sintering finishes rear coldBut and carry out passivation, obtain agglomerate;
(2) hydrogenation powder process: powder process after the agglomerate hydrogenation that heat treatment is obtained, obtains hydrogenationTantalum and/or niobium powder;
(3) oxygen falls in dehydrogenation: by the tantalum of hydrogenation and/or niobium powder add reducing metal carry out dehydrogenation andDeoxidation heat treatment, obtains reducing metal oxide, residual reducing metal, dehydrogenation and de-The mixture of the tantalum of oxygen and/or niobium powder; With
(4) pickling impurity removal: the mixture obtaining after oxygen is fallen in dehydrogenation and carry out pickling, oven dry,To the tantalum and/or the niobium powder that are applicable to powder metallurgy;
Described raw material tantalum and/or niobium powder have the 1.0m of being greater than2The specific area of/g and/or higher thanThe oxygen content of 4000ppm.
2. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 1,Described raw material tantalum and/or niobium powder are reclaim in capacitor tantalum and/or niobium powder production process uselessTantalum and/or niobium powder, or employing industry technology personnel know the special Gao Bibiao producing of the technique of knowingThe tantalum of area, low-apparent-density, elevated oxygen level and/or niobium powder.
3. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 2,In described raw material tantalum and/or niobium powder, contain be selected from tungsten, molybdenum, titanium, hafnium, zirconium, carbon, silicon,One or more elements in vanadium, aluminium and tin.
4. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 1,Wherein the heat treatment sintering described in step (1) is in 3.0 × 10 at low vacuum-1Pa、At the temperature of 1500-2100 DEG C, carry out.
5. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 4,The time of heat treatment sintering is 1-25 hour.
6. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 4,The time of heat treatment sintering is 3-20 hour.
7. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 4,The time of heat treatment sintering is 3-18 hour.
8. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 4,The time of heat treatment sintering is 3-15 hour.
9. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 4,The time of heat treatment sintering is 2-10 hour.
10. a kind of method of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 4,The time of heat treatment sintering is 3-10 hour.
11. one claimed in claim 1 are prepared powderThe metallurgical method with tantalum and/or niobium powder in end, wherein the passivation described in step (1) is in temperatureDegree is cooled to 50 DEG C or lower than carrying out under the condition of 50 DEG C.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 12. claims 11Method, described passivation is in agglomerating plant, to pass into air to carry out passivation.
13. a kind of methods of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 1,Wherein the step of step (2) hydrogenation powder process comprises:
A) oxide layer is destroyed: by Bas Discharged in equipment, in container, pass into hydrogen as guarantorProtect after gas, then agglomerate is heated to 800-950 DEG C of high temperature, insulation 1-10 hour, makesAgglomerate surface oxidation damage layer;
B) inhale hydrogen: oxide layer starts cooling after destroying, and lowers the temperature while pass into hydrogen,Last till that temperature drops to normal temperature, make agglomerate fully inhale hydrogen;
C) fragmentation: adopt this area to know the disintegrating apparatus of knowing and carry out broken powder process.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 14. claims 13Method, described normal temperature is 25 DEG C.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 15. claims 13Method, wherein c) broken employing airslide disintegrating mill, Milling and screening machine or jaw crusher break stepBroken powder process.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 16. claims 13Method, 250 mesh standard sieve sieve powder for the powder obtaining after fragmentation, obtain passing through 250 orders completelyTantalum and/or the niobium powder of sieve.
One described in 17. claim 1 to 16 any one prepare powder used in metallurgy tantalum and/Or the method for niobium powder, the hydrogen purity of wherein using in step (2) hydrogenation powder process higher than 99.95％。
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 18. claims 17Method, described hydrogen purity is higher than 99.995%.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 19. claims 17Method, described Hydrogen Vapor Pressure is 0.1-3Mpa.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 20. claims 19Method, described Hydrogen Vapor Pressure is 0.5-1.0Mpa.
One described in 21. claim 13-16 any one prepare powder used in metallurgy tantalum and/orThe method of niobium powder, wherein, step a) in as the pressure of hydrogen of protection gas be 0.1～3.0Mpa。
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 22. claims 21Method, wherein, step is 0.5-1.0Mpa as the pressure of hydrogen of protection gas in a).
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 23. claims 21Method, the Hydrogen Vapor Pressure of step in b) remains on 0.1～3.0Mpa.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 24. claims 23Method, the Hydrogen Vapor Pressure of step in b) remains on 0.5～1.0Mpa.
One described in 25. claim 13-16 any one prepare powder used in metallurgy tantalum and/orThe method of niobium powder, wherein, the hydrogen content that step fully absorbs the agglomerate of hydrogen in b) is3,000-6,000ppm。
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 26. claims 25Method, wherein, the hydrogen content that step fully absorbs the agglomerate of hydrogen in b) is 3,000-5,000ppm.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 27. claims 26Method, wherein, the hydrogen content that step fully absorbs the agglomerate of hydrogen in b) be 4000ppm,4300ppm or 4800ppm.
28. a kind of methods of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 1,Wherein said reducing metal is selected from magnesium, calcium, rare earth metal or their alloy or combination.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 29. claims 28Method, wherein said reducing metal is magnesium.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 30. claims 28Method, the oxygen in tantalum and/or niobium powder that wherein the consumption of reducing metal is hydrogenation is converted into completelyThe stoichiometric 1.2-5 of the required reducing metal of reducing metal oxide doubly.
31. a kind of methods of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 1,Wherein the described dehydrogenation in step (3) and deoxidation heat treatment are in inert gas circulation protectionOr heat treated under the condition vacuumizing.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 32. claims 31Method, described inert gas is argon gas or helium.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 33. claims 31Method, described heat treatment is heat treated under the first circulation at inert gas is protected,At 800-950 DEG C, continue insulation 1-3 hour, then vacuumize, lower than atmospheric pressure 0.06MPaOr at same temperature, be incubated again 1-6 hour under lower pressure.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 34. claims 33Method, described heat treatment is first heat treated under the circulation protection of inert gas, 800 DEG C,At 830 DEG C, 850 DEG C, 880 DEG C, 900 DEG C, 920 DEG C or 950 DEG C, continue insulation 1-3 hour,Then vacuumize, under lower than atmospheric pressure 0.06MPa or lower pressure in same temperatureUnder be incubated again 1-6 hour.
One described described in 35. claims 33 is prepared powder used in metallurgy tantalum and/or niobium powderMethod, described heat treatment is first heat treated under the circulation protection of inert gas,At 800-950 DEG C, continue insulation 2 hours, then vacuumize, lower than atmospheric pressure 0.06MPaOr at same temperature, be incubated again 1-6 hour under lower pressure.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 36. claims 33Method, described in vacuumize be in 20-80 minute, progressively reduce pressure to atmospheric pressure lower than0.06MPa。
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 37. claims 33Method, described heat treatment is heat treated under the first circulation at inert gas is protected,At 800-950 DEG C, continue insulation 1-3 hour, then vacuumize, lower than atmospheric pressure 0.06MPaOr at same temperature, be incubated again 2-6 hour under lower pressure.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 38. claims 37Method, described heat treatment is heat treated under the first circulation at inert gas is protected,At 800-950 DEG C, continue insulation 1-3 hour, then vacuumize, lower than atmospheric pressure 0.06MPaOr at same temperature, be incubated again 3 hours under lower pressure.
39. a kind of methods of preparing powder used in metallurgy tantalum and/or niobium powder claimed in claim 1,The acid that wherein step (4) pickling impurity removal is used is nitre aqueous acid.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 40. claims 39Method, the sour concentration that wherein step (4) pickling impurity removal is used is 5-30wt%.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 41. claims 40Method, the sour concentration that wherein step (4) pickling impurity removal is used be 15wt%, 8wt%,10wt%, 18wt%, 20wt%, 25wt% or 28wt%.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 42. claims 39Method, the consumption of described acid is that the solid-to-liquid ratio of mixture and aqueous solution of nitric acid is 1 ﹕ 1～3.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 43. claims 42Method, the consumption of described acid is that the solid-to-liquid ratio of mixture and aqueous solution of nitric acid is 1 ﹕ 2.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 44. claims 39Method, stirs 10-90 minute after mixture mixes with aqueous solution of nitric acid.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 45. claims 39Method, stirring 60 minutes, 20 minutes, 30 minutes after mixture mixes with aqueous solution of nitric acid,50 minutes, 80 minutes.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 46. claims 39Method, the tantalum obtaining after pickling and/or niobium powder are washed with pure water again.
A kind of side of preparing powder used in metallurgy tantalum and/or niobium powder described in 47. claims 39Method, the tantalum after oven dry and/or niobium powder are crossed 200 mesh sieves.
48. powder used in metallurgy tantalum and/or niobium powders, it is by any one in claim 1-47The described method of preparing powder used in metallurgy tantalum and/or niobium powder prepares.
Powder used in metallurgy tantalum and/or the niobium powder of 49. claims 48, described powder smeltingGold had the particle diameter of 200 mesh sieves with tantalum and/or niobium powder.
Powder used in metallurgy tantalum and/or the niobium powder of 50. claims 48, described powder smeltingGold is 300-1500ppm by the oxygen content of tantalum and/or niobium powder.
Powder used in metallurgy tantalum and/or the niobium powder of 51. claims 50, described powder smeltingGold is 800-1500ppm by the oxygen content of tantalum and/or niobium powder.
Powder used in metallurgy tantalum and/or the niobium powder of 52. claims 51, described powder smeltingGold with the oxygen content of tantalum and/or niobium powder be 890ppm, 1060ppm, 1430ppm,760ppm or 1230ppm.
Powder used in metallurgy tantalum and/or the niobium powder of 53. claims 48, described powder smeltingGold is 3.5-7g/cm by the apparent density of tantalum powder3。
Powder used in metallurgy tantalum and/or the niobium powder of 54. claims 53, described powder smeltingGold is 3.9-6.5g/cm by the apparent density of tantalum powder3。
Powder used in metallurgy tantalum and/or the niobium powder of 55. claims 54, described powder smeltingGold is 2-6g/cm by the apparent density of niobium powder3。
Powder used in metallurgy tantalum and/or the niobium powder of 56. claims 55, described powder smeltingGold is 2-5g/cm by the apparent density of niobium powder3。
Powder used in metallurgy tantalum and/or the niobium powder of 57. claims 56, described powder smeltingGold is 2.6g/cm by the apparent density of niobium powder3Or 3.1g/cm3。
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| CN111604498B (en) * | 2020-06-29 | 2022-04-08 | 宁夏东方钽业股份有限公司 | Preparation method of niobium-zirconium alloy powder |
| CN111850325A (en) * | 2020-07-27 | 2020-10-30 | 宁夏东方钽业股份有限公司 | Method for preparing tantalum two-point pentatungsten alloy ingot from tantalum and tantalum-tungsten reclaimed materials |
| CN113373312A (en) * | 2021-06-10 | 2021-09-10 | 广东先导稀材股份有限公司 | Method for separating and recovering tantalum, scandium and aluminum |
| CN113427008B (en) * | 2021-06-30 | 2022-02-08 | 宁夏东方钽业股份有限公司 | Tantalum-tungsten alloy powder and preparation method thereof |
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