CN103429782B - Tantalum passivation of metal surfaces method and device - Google Patents
Tantalum passivation of metal surfaces method and device Download PDFInfo
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- CN103429782B CN103429782B CN201180069256.2A CN201180069256A CN103429782B CN 103429782 B CN103429782 B CN 103429782B CN 201180069256 A CN201180069256 A CN 201180069256A CN 103429782 B CN103429782 B CN 103429782B
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 303
- 238000002161 passivation Methods 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 57
- 229910052715 tantalum Inorganic materials 0.000 title abstract description 76
- 229910052751 metal Inorganic materials 0.000 title abstract description 26
- 239000002184 metal Substances 0.000 title abstract description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 261
- 239000001301 oxygen Substances 0.000 claims abstract description 178
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 177
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 174
- 239000007789 gas Substances 0.000 claims abstract description 169
- 229910052786 argon Inorganic materials 0.000 claims abstract description 131
- 238000010438 heat treatment Methods 0.000 claims abstract description 122
- 238000001816 cooling Methods 0.000 claims abstract description 63
- 238000005057 refrigeration Methods 0.000 claims abstract description 50
- 238000009413 insulation Methods 0.000 claims description 11
- 210000000038 chest Anatomy 0.000 claims description 5
- 150000001485 argon Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 230000008569 process Effects 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 229910052756 noble gas Inorganic materials 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 239000000498 cooling water Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005121 nitriding Methods 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BROYGXJPKIABKM-UHFFFAOYSA-N [Ta].[Au] Chemical compound [Ta].[Au] BROYGXJPKIABKM-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 230000004087 circulation Effects 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 210000003437 trachea Anatomy 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000519996 Teucrium chamaedrys Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000001146 hypoxic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
Abstract
A kind of method of tantalum passivation of metal surfaces, including by tantalum metal cools to 32 DEG C or following and/or be 0 DEG C by temperature or following oxygen-containing gas makes tantalum passivation of metal surfaces.Additionally provide a kind of tantalum metal surface passivation device for implementing described method, including heat-treatment furnace, argon forced cooling and/or oxygen-containing gas refrigeration system.
Description
Technical field
The present invention relates to tantalum Metal Production field, and particularly to being used for producing electrolysis condenser tantalum powder or porous tantalum gold
The method and device belonged to.
Background technology
The maximum purposes of tantalum metal is to manufacture tantalum electrolytic capacitor.The manufacture process of tantalum electrolytic capacitor is typically tantalum powder
Compacting forms briquet, briquet sinters in vacuum drying oven interconnective porous body between particle, then by above-mentioned porous sintered into
Block carries out anodic oxidation in suitable electrolyte, makes porous body particle surface form the dielectric oxidation interconnected uniformly
Film, i.e. forms anode, then is coated to cathode material on oxide-film surface, then encapsulate and formed capacitor anode and negative electrode.Evaluate
The parameter of tantalum electrolytic capacitor mainly has capacitance, DC(DC leakage current) and equivalent series resistance (ESR).The development of capacitor
Trend is to have high-capacitance, low leakage current and low equivalent series resistance (tg δ low for anode).As tantalum electricity
The impurity content of the Ta powder used in capacitor of the primary raw material of electrolysis condenser, particularly oxygen content are very big on the impact of leakage current, low
Leakage current requirement tantalum powder has low oxygen content.
As the tantalum powder of electrolysis condenser, generally will carry out heat treatment, on the one hand tantalum powder be purified, the opposing party
Face is the granule making fine tantalum particle coacervation become porous, improves the physical characteristic of tantalum powder, such as the mobility of tantalum powder, thus improves use
The performance of its electrolysis condenser manufactured, such as capacity, leakage current and the equivalent series resistance (ESR) of capacitor.The U.S. in early days
Patent US3473915 discloses the heat treatment technics of tantalum powder, by the tantalum powder of 2～30 μm under inactive atmosphere at 1200 DEG C～
1500 DEG C carry out heat-coagulation process, form the multiple-contact porous particle of adhesion, obtain condensing tantalum powder.Tantalum powder produces in recent decades
The heat treatment of tantalum powder, in the process of exploitation high specific surface area tantalum powder and midget capacitor, is carried out by person and capacitor manufacturer
Substantial amounts of research work.About tantalum powder being carried out the prior art of dough (cohesion) heat treatment referring also to following patent literature:
JP Laid-Open 2-34701, US5954856, WO99/61184, CN1197707A, CN1238251A, CN1899730A.
Tantalum powder deoxidation heat treatment is typically to be mixed into appropriate reducing agent alkaline-earth metal or rare earth metal or its hydrogenation in tantalum powder
Thing, carries out heat treatment at 700 DEG C～1100 DEG C in vacuum or inert atmosphere, makes tantalum powder be condensed and remove oxygen.About tantalum
The prior art of the deoxidation heat treatment of powder can be found in following patent literature US4483819, US4537641, CN1052070A etc..
Owing to tantalum metal is a kind of metal the biggest with oxygen affinity, tantalum closes with oxidation and forms tantalum pentoxide, is heat release
Reaction, if there is one layer of dense oxidation film on the surface of tantalum powder, is possible to prevent the continuation of tantalum to aoxidize.This covered by dense oxidation film
Tantalum particle one works as the temperature being heated to more than about 300 DEG C, and tantalum-oxide film ftractures and is destroyed, and part oxygen dissolves in tantalio body, portion
Divide oxygen loss, enrichment.So, oxidation is started with oxygen-containing medium when the tantalum powder after heating contacts after cooled again from surface,
Absorb new oxygen, make oxygen content increase, if the speed of oxygen can not effectively be controlled to absorb, tantalum powder spontaneous combustion will be caused, because of this person
Develop the passivating technique of tantalum powder controllable oxidization.Described tantalum powder passivation is again with oxygen-containing after the oxide-film of tantalum powder is destroyed
During medium contact, control the feed speed of oxygen artificially, thus under controlled case, control oxidation rate and the temperature of tantalum powder, make
Tantalum powder surface forms passive oxidation film, it is to avoid fierce oxidation.(specific surface area is more than 0.1m so the tantalum powder that specific surface area is higher2/
G) to be passivated after heat treatment processing.
Tantalum passivation of metal surfaces described in this specification includes tantalum powder surface passivation and is suppressed the porous body formed by tantalum powder
Surface passivation.
Development along with the miniaturization of electronic devices and components, it is desirable to use the finer tantalum with more bigger serface
Powder, for the tantalum powder of high-specific surface area, the heat produced when passivation due to the tantalum powder in unit volume scope is more, passivation
Time tantalum powder temperature rise get Geng Gao, in the passivating process after tantalum powder heat treatment, be frequently found temperature and fly up a lot, this returns
Because starting fierce oxidation in tantalum powder, thus inflation passivation must be stopped at once.Stop a period of time, continue slow after temperature reduces
Trickle charge gas is passivated.Coming out of the stove after being passivated discovery, there is white oxide tantalum speckle on tantalum powder surface, does not has the oxygen of the tantalum powder of white oxide tantalum
Content is the highest.Control bad during passivation, there is also tantalum powder and catch fire, bring about great losses.So, the passivation of tantalum powder becomes out
Send out difficult point and the key technology of high specific surface area tantalum powder.
The porous compact that the tantalum powder of high-specific surface area is formed, though as manufactured the tantalum briquet of electrolytic capacitor anode after sintering
So surface area decreases, but porous sintered piece of surface can aoxidize equally, and produces high temperature, makes porous tantalum agglomerate contain
The oxygen of too high amount, so that tantalum wire embrittlement, even causes the fierce oxidation of porous tantalum agglomerate, sinters with such porous tantalum
The tantalum anode of block manufacture has high leakage current.So porous sintered piece of the formation of high specific surface area tantalum powder should be entered after sintering
Row Passivation Treatment.
Including patent documentation US6927967B2, US6432161B1, US6238456B1, CN1919508A,
CN101404213A, US6992881B2, US7485256B2 and CN1899728A disclose the blunt of tantalum powder in interior prior art
Change, but these prior aries are that the oxygen-containing gas under room temperature is passed into equipped with through Overheating Treatment and be cooled to room temperature or more
Tantalum powder is made to be passivated in the vacuum drying oven of high-temperature；Such process passivation time length and often cause tantalum powder fierceness to aoxidize.Public
The Chinese patent that the number of opening is CN101348891A discloses a kind of tantalum powder controlled passivation magnesium processing deoxidization method, wherein uses pure oxygen
It is passivated processing；The method there is problems of being not suitable for high specific surface area tantalum powder is carried out heat treatment post-passivation；And it is blunt
The change time is long, and productivity ratio is low.
The problems referred to above existed due to prior art, therefore this area has still desired to a kind of in tantalum passivation of metal surfaces process
In it can be avoided that occur fierceness oxidation thus obtain hypoxic tantalum powder and the method and device of porous tantalum agglomerate.
Summary of the invention
In view of problems of the prior art, an object of the present invention is to provide it can be avoided that during passivating process
There is the tantalum passivation of metal surfaces method of fierceness oxidation；Another object of the present invention is to provide and is adapted for carrying out described tantalum metal surface
The device of passivating method.
The present invention achieves above-mentioned purpose by the passivating method and device providing a kind of tantalum metal surface；Described side
In method, reduce temperature after tantalum metal powder is carried out heat treatment, and use the oxygen-containing gas of lower temperature to be passivated.
Specifically, the technical scheme is that
(1) passivating method of a kind of tantalum metal surface, it is characterised in that comprise the steps:
A, offer tantalum metal, this tantalum metal heat-treated；
B, utilize cooled noble gas that the temperature of tantalum metal is reduced to 32 DEG C or less, be preferably reduced to 30 DEG C with
Under, and more preferably it is reduced to 10 DEG C～30 DEG C；
C, it is passed through oxygen-containing gas and makes tantalum passivation of metal surfaces；
D, optionally repeat the above steps c one or many.
(2) passivating method of a kind of tantalum metal surface, it is characterised in that comprise the steps:
A, offer tantalum metal, this tantalum metal heat-treated；
B, the temperature of tantalum metal is reduced to room temperature；
C, it is passed through temperature and is 0 DEG C or less and oxygen-containing gas preferably 0 DEG C to-40 DEG C makes tantalum passivation of metal surfaces；With
D, optionally repeat the above steps c one or many.
(3) a kind of tantalum passivation of metal surfaces method, it is characterised in that include step:
A, offer tantalum metal, this tantalum metal heat-treated,
B, utilize cooled noble gas that tantalum metal temperature is reduced to 32 DEG C or less, be preferably reduced to 30 DEG C with
Under, and more preferably it is reduced to 10 DEG C～30 DEG C；
C, it is passed through 0 DEG C or less and oxygen-containing gas preferably 0 DEG C to-40 DEG C makes tantalum passivation of metal surfaces；With
D, optionally repeat the above steps c one or many.
(4) according to the tantalum passivation of metal surfaces method of technical scheme (1) or (2) or (3), it is characterised in that described is oxygen-containing
Gas is the mixed gas of air, the gas mixture of noble gas and oxygen or noble gas and air.
(5) according to the tantalum passivation of metal surfaces method of technical scheme (1) or (2) or (3), it is characterised in that described is oxygen-containing
Gas is the mixed gas of argon and air composition.
(6) according to the tantalum passivation of metal surfaces method of technical scheme (1) or (2) or (3), it is characterised in that described is oxygen-containing
In gas, the concentration of oxygen is 21Vol% or following, preferably 5～20Vol%.
(7) according to the tantalum passivation of metal surfaces method of technical scheme (1) or (3), it is characterised in that described noble gas is
Argon.
(8) a kind of tantalum metal surface passivation device, it mainly includes heat-treatment furnace and argon forced cooling, Qi Zhongsuo
State heat-treatment furnace to include: burner hearth, form the band water-cooling jacket of described burner hearth furnace shell, passivation oxygen-containing gas enter described stove
The entrance of thorax, argon enter the Ar inlet of described burner hearth, are positioned at the argon gas export on heat-treatment furnace top, are arranged on described burner hearth
Internal heater and for accommodating the heat treatment crucible of pending tantalum metal；Described argon forced cooling includes system
Cold, heat-exchanging chamber, Ar inlet to be cooled, cooled argon gas export and circulating pump；
Wherein said Ar inlet to be cooled is connected with the argon gas export on heat-treatment furnace burner hearth top, when Passivation Treatment,
The higher argon of heat treatment in-furnace temperature from described argon gas export out, by periphery have the connection pipeline of cooling water cooling from
Heat-exchanging chamber side enters heat-exchanging chamber, and in described heat-exchanging chamber, the argon of entrance is freezed, then another from heat-exchanging chamber
The argon gas export of side out enters circulating pump, and the argon freezed is extruded by circulating pump, and via connecting pipeline from heat treatment
The described argon freezed is delivered into heat-treatment furnace by the Ar inlet of stove bottom, thus for the tantalum gold of Passivation Treatment will be treated
Belong to and be reduced to 32 DEG C or following temperature to be passivated by oxygen-containing gas.
(9) a kind of tantalum metal surface passivation device, it mainly includes heat-treatment furnace and oxygen-containing gas refrigeration system, Qi Zhongsuo
State heat-treatment furnace to include: burner hearth, form the band water-cooling jacket of described burner hearth furnace shell, passivation oxygen-containing gas enter described stove
The entrance of thorax, evacuate pipeline, be arranged on the heater inside described burner hearth and for accommodating the heat treatment of pending tantalum metal
Crucible；Described oxygen-containing gas refrigeration system specifically includes that refrigeration machine, heat-exchanging chamber, oxygen-containing with what heat-exchanging chamber one end was connected
Gas access, Ar inlet and the oxygen-containing gas outlet being connected with the heat-exchanging chamber other end；
Wherein during being passivated processing, oxygen-containing gas and argon enter heat-exchanging chamber from its corresponding entrance respectively and mix
Close, medium pipeline generation heat exchange in mixed gas and described heat-exchanging chamber and be refrigerated to the temperature of less than 0 DEG C, freezed
Oxygen-containing gas export out from the oxygen-containing gas of the opposite side of heat-exchanging chamber, through insulation connect pipeline from heat-treatment furnace top
Enter heat-treatment furnace, thus be passivated processing for treating the tantalum metal of passivation.
(10) passivating device of a kind of tantalum metal surface, it mainly includes heat-treatment furnace, argon forced cooling and contains
Carrier of oxygen refrigeration system, wherein said heat-treatment furnace includes: burner hearth, form the furnace shell of band water-cooling jacket of described burner hearth, passivation
Oxygen-containing gas enter the entrance of described burner hearth, argon enters the entrance of described burner hearth, be positioned at the argon on heat-treatment furnace top
Export, be located at the heater inside described burner hearth and for accommodating the heat treatment crucible of pending tantalum metal；
Described argon forced cooling includes that refrigeration machine, heat-exchanging chamber, Ar inlet to be cooled, cooled argon go out
Mouth and circulating pump；Wherein said Ar inlet to be cooled is connected with the argon gas export on heat-treatment furnace top, when Passivation Treatment, and heat
Process the higher argon of in-furnace temperature from described argon gas export out, have the connection pipeline of cooling water from heat exchange by periphery
Side, room enters heat-exchanging chamber, and in described heat-exchanging chamber, the argon of entrance is freezed, then from heat-exchanging chamber opposite side
Argon gas export out enters circulating pump, and the argon freezed is extruded by circulating pump, and via connecting pipeline from heat-treatment furnace bottom
Ar inlet the described argon freezed is delivered into heat-treatment furnace, thus for treating that the tantalum metal of Passivation Treatment reduces
Temperature below 32 DEG C；And
Described oxygen-containing gas refrigeration system specifically includes that refrigeration machine, heat-exchanging chamber, with containing that heat-exchanging chamber one end is connected
Carrier of oxygen entrance, Ar inlet and the oxygen-containing gas outlet being connected with the heat-exchanging chamber other end；Wherein it is being passivated the process phase
Between, oxygen-containing gas and argon enter heat-exchanging chamber mixing from its corresponding entrance respectively, in mixed gas and described heat-exchanging chamber
Medium pipeline generation heat exchange and be refrigerated to the temperature of less than 0 DEG C, the oxygen-containing gas freezed is from another of heat-exchanging chamber
Side outlet out, connects pipeline through insulation and enters heat-treatment furnace from heat-treatment furnace top, thus for treating the tantalum gold of passivation
Belong to and be passivated processing.
(11) according to technical scheme (8) or the tantalum metal surface passivation device of (10), it is characterised in that by described argon
Gas forced cooling device makes tantalum metal cools to 10 DEG C～30 DEG C of temperature to be passivated by oxygen-containing gas.
(12) according to technical scheme (9) or the tantalum metal surface passivation device of (10), it is characterised in that described mixed gas
The passivation oxygen-containing gas freezed thus provide temperature to be-40 DEG C～0 DEG C.
It is safe and reliable according to the advantage of the tantalum passivation of metal surfaces method of the present invention and productivity ratio is high, the tantalum powder obtained
Oxygen, hydrogen content low, from described tantalum powder prepare anode and the good electrical property of tantalum electrolytic capacitor.
Should be appreciated that above general describe and the retouching in detail of following detailed description of the accompanying drawings and preferred embodiment
It is all exemplary for stating, and its objective is further to explain the present invention for required protection, is not limitation of the present invention.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a kind of tantalum metal surface passivation device of prior art.
Fig. 2 shows a reality of the tantalum metal surface passivation device with noble gas forced cooling device of the present invention
Execute example.
Fig. 3 shows an enforcement of the tantalum metal surface passivation device with oxygen-containing gas refrigeration system of the present invention
Example.
Fig. 4 shows the tantalum metal watch with noble gas forced cooling device and oxygen-containing gas refrigeration system of the present invention
One embodiment of face passivating device.
Fig. 5 is the schematic diagram of the tantalum powder surface passivation device of another kind of prior art.
Fig. 6 shows another of the tantalum metal surface passivation device with noble gas forced cooling device of the present invention
Embodiment.
Fig. 7 shows another enforcement of the tantalum metal surface passivation device with oxygen-containing gas refrigeration system of the present invention
Example.
Fig. 8 shows that the present invention's forces cooling blunt with the tantalum metal surface of oxygen-containing gas refrigeration system with noble gas
Another embodiment of gasifying device.
Detailed description of the invention
The present invention will be further described with preferred embodiment below in conjunction with the accompanying drawings.
In this manual, unless otherwise expressly noted, unit ppm refers to " PPM " represented with mass ratio.
The invention provides a kind of tantalum passivation of metal surfaces method；In the method for the invention, described to carry out at heat
The tantalum metal managed and make it be passivated can be the tantalum powder without heat treatment of electronation, for example with sodium reduction potassium floutaramite
The tantalum powder of preparation, the former powder that tantalum ingot obtains through over hydrogenation grinding flour, it is also possible to be the tantalum powder through Overheating Treatment, it is also possible to be tantalum
Porous sintered piece of the tantalum that powder compacting is formed, is not limited to this.Before the heat treatment, preferably former powder is carried out pelletize, particularly preferred ball
Change pelletize to process.When any beneficially control tantalum powder of ratio required by can adding in tantalum powder granulation process is at high temperature sintering
Shrinkage factor and reduce surface area losses chemical substance as resistance burn agent, such as phosphorous, nitrogen, boron, the material of oxygen.The inventive method
In, can use known technology that tantalum metal carries out heat treatment, such as China Patent No. is CN1410209A, CN1238251A
Various methods with disclosed in CN1899730A, are incorporated herein by reference above-mentioned entirety.
In the method for the invention, noble gas forced cooling device can be used the tantalum metal cools after heat treatment
Temperature below 32 DEG C.Described noble gas can be argon, helium, xenon or their mixture.But for cost
Consider, argon is preferably used and carries out forcing cooling.
According to the inventive method, the particle shape for the tantalum powder of heat treatment to be carried out does not limits, and can be granular, lamellar
, polygonal or their combination in any.For the specific surface area the most particularly requirement of tantalum powder, can be 0.1m2/g
～10m2/ g, preferably 0.2m2/ g～5m2/g。
Tantalum powder deoxidation heat treatment in reducing atmosphere can be according to technology well known to those skilled in the art, generally,
Tantalum powder is mixed on a small quantity bigger than the affinity of tantalum Yu oxygen with the affinity of oxygen reducing agent, as alkaline-earth metal, rare earth metal and
Its hydride, is most commonly used that the metal magnesium powder being mixed into tantalum grain weight amount 0.5%～4% in tantalum powder.
Fig. 1 be prior art heat treatment after the schematic diagram of tantalum metal surface passivation device 100, tantalum after described heat treatment
Metal surface passivation device includes: burner hearth 110, form described burner hearth 110 with from 111-1 water inlet and from 111-2 water outlet
Pressure vacuum ga(u)ge 112, the oxygen-containing gas of passivation that the furnace shell 111 of water-cooling jacket and described burner hearth 110 communicate enter described stove
The entrance 120 of thorax 110, Ar inlet 140, evacuate pipeline 141, the heat protection screen 130 being arranged in burner hearth, be arranged on described guarantor
Temperature is shielded the heater 150 inside 130, the measurement thermocouple 160 of temperature, heat treatment crucible 180, is loaded in described crucible 180
Pending tantalum powder 170.
Fig. 2 is the schematic diagram of the tantalum metal surface passivation device with argon forced cooling of the present invention, this tantalum gold
The passivating device of metal surface includes: burner hearth 210, form described burner hearth 210 with from 211-1 water inlet and from 211-2 water outlet
The pressure vacuum ga(u)ge 212 that the furnace shell 211 of water-cooling jacket and described burner hearth 210 communicate, the oxygen-containing gas entrance 220 being passivated, argon
Gas entrance 240, evacuate pipeline 241, the heat protection screen 230 being arranged in burner hearth 210, be arranged on inside described heat protection screen 230
Heater 250, the measurement thermocouple 260 of temperature, heat treatment crucible 280, the pending tantalum powder loaded in described crucible 280
270, described tantalum metal surface passivation device also includes argon forced cooling 200A, described argon forced cooling
Parts that 200A mainly includes and effect are as follows: the argon gas export 207 on heat-treatment furnace top, and the higher argon of in-furnace temperature is from institute
The argon gas export 207 stated out, has the connection pipeline 208 of cooling water, from the Ar inlet 202 of heat-exchanging chamber side by periphery
Enter heat-exchanging chamber 201, in described heat-exchanging chamber 201, have the medium pipeline 204 freezed by refrigeration machine 200,200, refrigeration machine
The medium of refrigeration flows through heat-exchanging chamber 201, and in described heat-exchanging chamber 201, the argon of entrance is freezed, then from heat exchange
The opposite side argon gas export 205 of room out, enters circulating pump 209 through piping 206, and circulating pump 209 is by the described argon freezed
Air pressure goes out, and by connecting pipeline, delivers into heat-treatment furnace from heat-treatment furnace lower entrances 240.(wherein pipeline 208 periphery
Cooling water enters from the 208-1 near refrigeration heat-exchanging chamber one end, goes out from the 208-2 near heat-treatment furnace one end.It is passivated at tantalum powder
Before, carry out forcing cooling by described argon forced cooling, make tantalum powder temperature be reduced to 30 DEG C or less, preferably drop to 10
DEG C～30 DEG C, it is possible to efficiently control tantalum powder oxidation, it is to avoid tantalum powder fierceness aoxidize.Forcing, in cooling procedure, to pass through with argon
Supplement argon to blood circulation or aerofluxus makes system maintain pressure between 0.09MPa～0.11MPa.
Fig. 3 is the tantalum passivation of metal surfaces dress of the oxygen-containing gas refrigeration system with tantalum passivation of metal surfaces of the present invention
Putting, described tantalum metal surface passivation device includes: burner hearth 310, form described burner hearth 310 with from 311-1 water inlet and from
Pressure vacuum ga(u)ge 312 that the furnace shell 311 of the water-cooling jacket of 311-1 water outlet and described burner hearth 310 communicate, blunt in upper furnace
Change oxygen-containing gas entrance 320, Ar inlet 340, evacuate pipeline 341, the heat protection screen 330 being arranged in burner hearth, be arranged on institute
The heater 350 inside heat protection screen 330 stated, measure the thermocouple 360 of temperature, heat treatment crucible 380, load described crucible
Pending tantalum powder 370 in 380, described tantalum metal surface passivation device also includes passivation oxygen-containing gas refrigeration system
390A, described oxygen-containing gas refrigeration system 390A specifically includes that refrigeration machine 390, heat-exchanging chamber 391, the medium of refrigeration machine refrigeration
Flow through heat-exchanging chamber 391；Oxygen-containing gas and argon enter described heat-exchanging chamber from air inlet 392 and argon inlet mouth 393 respectively
391 inner mixing, the refrigerant pipe 394 that mixed oxygen-containing gas is connected with described refrigeration machine 390 carries out heat exchange, is freezed
Oxygen-containing gas from the outlet 395 of described heat-exchanging chamber 391 other end out, by connecting described outlet 395 and heat-treatment furnace
The utilidor 396 of the described entrance 320 on top enters burner hearth 310；It is provided with the pressure communicated with described heat-exchanging chamber 391
Power meter 398, exports 395 sides at described oxygen-containing gas and is provided with thermometer 397；And be arranged at bottom described heat exchanger 391
Flowing water mouth 399.Whenever completing the passivation of a collection of tantalum metal, with hot blast, parts each in heat exchanger are dried up, the water of thawing from
Described flowing water mouth 399 flows out.Oxygen-containing gas is through refrigeration, and temperature reaches less than 0 DEG C, preferably reaches less than-10 DEG C, more preferably up to
To-10 DEG C～-40 DEG C.
Fig. 4 is that the tantalum passivation of metal surfaces with argon forced cooling and oxygen-containing gas refrigeration system of the present invention fills
Put schematic diagram, including: burner hearth 410, form described burner hearth 410 with from 411-1 water inlet and from the water-cooling jacket of 411-2 water outlet
Furnace shell 411 and described burner hearth 410 communicate pressure vacuum ga(u)ge 412, passivation oxygen-containing gas entrance 420, Ar inlet
440, evacuate pipeline 441, the heat protection screen 430 being arranged in burner hearth, be arranged on the heater 450 inside described heat protection screen 430,
Measuring the thermocouple 460 of temperature, heat treatment crucible 480, the pending tantalum powder 470 loaded in described crucible 480, its feature exists
Argon forced cooling 400A and oxygen-containing gas refrigeration system 490A is also included in tantalum metal surface passivation device, wherein said
Argon forced cooling 400A mainly include that parts and effect are as follows: the argon gas export 407 on heat-treatment furnace top, warm in stove
Spend higher argon from described argon gas export 407 out, had from 408-1 water inlet from the cooling water of 408-2 water outlet by periphery
Connection pipeline 408, from the side of heat-exchanging chamber 401 enter heat-exchanging chamber 401, have in described heat-exchanging chamber 401 and freezed
The medium pipeline 404 of mechanism cold, in described heat-exchanging chamber in 401, after the argon of entrance is freezed, from heat-exchanging chamber 401
Opposite side argon gas export 405 out, enter circulating pump 409 through piping 406, circulating pump 409 is by the described argon freezed
Extrude, by connecting pipeline, deliver into heat-treatment furnace 410 from heat-treatment furnace lower entrances 440, described oxygenous system
Parts and effect that cooling system 490A mainly includes are as follows: refrigerant is freezed by refrigeration machine 490；The medium freezed is by being situated between
Matter pipeline 494 flows through heat-exchanging chamber 491, is provided with the piezometer 498 communicated with described heat-exchanging chamber 491；At heat-exchanging chamber
In 491, oxygen-containing gas and argon enter heat-exchanging chamber 491 from its corresponding entrance 492 and 493 respectively and mix；Mix is oxygen-containing
Gas occurs heat exchange to be freezed with the medium pipeline 494 in described heat-exchanging chamber 491, and the oxygen-containing gas freezed is handed over from heat
Change the opposite side outlet 495 of room 491 out, through there being the connection pipeline 496 of insulation to enter heat from heat-treatment furnace upper entrance 420
Process in stove 410.It is provided with thermometer 497 on oxygen-containing gas outlet side, is used for measuring the temperature of oxygen-containing gas；At heat-exchanging chamber
The bottom of 491 is provided with flowing water mouth 499.Whenever completing the passivation of a collection of tantalum powder, with hot blast, parts each in heat exchanger are dried up, melt
The water changed flows out from flowing water mouth 499.
Fig. 5 is tantalum passivation of metal surfaces after a kind of external heat (not shown) tantalum powder deoxidation heat treatment of the prior art
Device schematic diagram, specifically includes that deoxidation heat treatment reaction vessel 510, upper cover 511, the argon that is arranged on described upper cover 511 enter
In trachea 540, evacuation discharge duct 541, nitrogen inlet duct 542, passivation oxygen-containing gas air inlet pipe 520, measurement reaction vessel
The pressure vacuum ga(u)ge 512 of pressure, the tantalum crucible 580 being placed in described reaction vessel 510, be loaded in described crucible 580
The tantalum powder 570 being mixed into magnesium powder, measure upper in reaction vessel, to neutralize the temperature of lower position thermocouple 561,562 respectively
With 563, it is placed in the heat shield assembly 530 on described crucible 580 top.
Fig. 6 is at the external heat (not shown) tantalum powder deoxidation heat with noble gas forced cooling device of the present invention
Tantalum metal surface passivation device schematic diagram after reason, specifically includes that deoxidation heat treatment reaction vessel 610, upper cover 611, is arranged on institute
State the argon inlet pipe 640 stretching into reaction vessel 610 lower position on upper cover 611, evacuate discharge duct 641, nitrogen air inlet
Pipe 642, passivation oxygen-containing gas air inlet pipe 620, measure the pressure vacuum ga(u)ge 612 of pressure in reaction vessel, be placed on described instead
Answer the tantalum crucible 680 in container 610, the tantalum powder 670 being mixed into magnesium powder that is loaded in described crucible 680, respectively measure anti-
Go up in answering container, neutralize the thermocouple 661,662 and 663 of the temperature of lower position, be placed in the heat screen on described crucible 680 top
Assembly 630, it is characterised in that also include that argon forced cooling 600A, described argon forced cooling 600A mainly wrap
Including: the argon gas export 607 on reaction vessel 610 top, the higher argon of in-furnace temperature is from described argon gas export 607 out, logical
Cross periphery to have from 608-1 water inlet from the connection pipeline 608 of the cooling water of 608-2 water outlet, enter heat from the side of heat-exchanging chamber 601
, there is the medium pipeline 604 freezed by refrigeration machine switch room 601, in described heat-exchanging chamber in described heat-exchanging chamber 601
In 601, after the argon of entrance is freezed, from the opposite side argon gas export 605 of heat-exchanging chamber 601 out, enter through piping 606
Circulating pump 609, the described argon freezed is extruded by circulating pump 609, by connecting pipeline, defeated from reactor lower part entrance 640
It is fed in heat treatment reaction vessel 610.
Force cooling by argon, before tantalum powder is passivated, makes tantalum powder temperature be reduced to 30 DEG C or less, preferably drop to 10 DEG C
～20 DEG C.
After Fig. 7 is the external heat (not shown) tantalum powder deoxidation heat treatment with oxygen-containing gas refrigeration system of the present invention
Tantalum metal surface passivation device schematic diagram, specifically includes that on deoxidation heat treatment reaction vessel 710, upper cover 711, described upper cover 711
There is argon inlet pipe 740, evacuate discharge duct 741, nitrogen inlet duct 742, passivation oxygen-containing gas air inlet pipe 720, measurement stove
The pressure vacuum ga(u)ge 712 of interior pressure, the tantalum crucible 780 being placed in described reaction vessel 710, be loaded into described crucible 780
In the tantalum powder 770 being mixed into magnesium powder, measure reaction vessel and measure upper in reaction vessel, to neutralize lower position temperature respectively
Thermocouple 761,762 and 763, it is placed in the heat shield assembly 730 on described crucible 780 top, it is characterised in that also include that passivation is used
Oxygen-containing gas refrigeration system 790A, described oxygen-containing gas refrigeration system 790A specifically includes that refrigeration machine 790 is by refrigerant system
Cold；The medium freezed flows through heat-exchanging chamber 791 by medium pipeline 794, is provided with communicating with described heat-exchanging chamber 791
Piezometer 798；In heat-exchanging chamber 791, oxygen-containing gas and argon enter heat exchange from its corresponding entrance 792 and 793 respectively
Room 791 mixes；The oxygen-containing gas of mixing occurs heat exchange to be freezed with the medium pipeline 794 in described heat-exchanging chamber 791, quilt
The oxygen-containing gas of refrigeration from the opposite side outlet 795 of heat-exchanging chamber 791 out, passes through and has the connection pipeline 796 of insulation from reaction
Upper vessel portion entrance 720 enters in reaction vessel 710.It is provided with thermometer 797 on oxygen-containing gas outlet side, oxygenous for measuring
The temperature of body；It is provided with flowing water mouth 799 in the bottom of heat-exchanging chamber 791.
Whenever completing the passivation of a collection of tantalum powder, with hot blast, parts each in heat exchanger being dried up, the water of thawing is from described stream
The mouth of a river 799 is flowed out.
Fig. 8 is at the tantalum powder deoxidation heat with noble gas forced cooling device and oxygen-containing gas refrigeration system of the present invention
Reason post-passivation device schematic diagram, including: stretch into reaction on deoxidation heat treatment reaction vessel 810, upper cover 811, described upper cover 811
The argon inlet pipe 840 of container 810 lower position, evacuation discharge duct 841, nitrogen inlet duct 842, passivation oxygen-containing gas enter
Trachea 820, measure the pressure vacuum ga(u)ge 812 of furnace pressure, the tantalum crucible 880 that is placed in described reaction vessel 810, filled
Upper, the temperature of neutralization lower position in entering the tantalum powder 870 being mixed into magnesium powder in described crucible 880, respectively measurement reaction vessel
Thermocouple 861,862 and 863, be placed in the heat shield assembly 830 on described crucible 880 top, it is characterised in that also include argon
Forced cooling device 800A and oxygen-containing gas refrigeration system 890A, the portion that described argon forced cooling 800A mainly includes
Part and effect: reaction vessel 810 top is provided with argon gas export 807, and the argon that in reaction vessel, temperature is higher is from described argon
Outlet 807 out, is had from 808-1 water inlet from the connection pipeline 808 of the cooling water of 808-2 water outlet by periphery, from heat-exchanging chamber
The side of 801 enters heat-exchanging chamber 801, has the medium pipeline 804 freezed by refrigeration machine, in institute described heat-exchanging chamber 801
In the heat-exchanging chamber stated 801 li, after the argon of entrance is freezed, from the opposite side argon gas export 805 of heat-exchanging chamber 801 out,
Entering circulating pump 809 through piping 806, the described argon freezed is extruded by circulating pump 809, by connecting pipeline, from reaction
Device lower entrances 840 delivers in heat treatment reaction vessel 810.Described oxygen-containing gas refrigeration system 890A mainly includes
Parts and effect are as follows: refrigerant is freezed by refrigeration machine 890；The medium freezed flows through heat exchange by medium pipeline 894
Room 891, is provided with the piezometer 898 communicated with described heat-exchanging chamber 891；In heat-exchanging chamber 891, oxygen-containing gas and argon are respectively
Enter heat-exchanging chamber 891 from its corresponding entrance 892 and 893 to mix；In the oxygen-containing gas of mixing and described heat-exchanging chamber 891
Medium pipeline 894 occurs heat exchange to be freezed, and the oxygen-containing gas freezed exports 895 from the opposite side of heat-exchanging chamber 891 and goes out
Come, through there being the connection pipeline 896 of insulation to enter reaction vessel 810 from reaction vessel upper entrance 820.Go out at oxygen-containing gas
Mouth is other is provided with thermometer 897, is used for measuring the temperature of oxygen-containing gas；It is provided with flowing water mouth 899 in the bottom of heat-exchanging chamber 891.
Whenever completing the passivation of a collection of tantalum powder, with hot blast, parts each in heat exchanger being dried up, the water of thawing is from flowing water mouth
899 flow out.
The present invention loads not particularly requirement in heat-treatment furnace to tantalum powder, but from uniformity, nitriding and the passivation of heating
Uniformly adequacy considers, preferably tantalum powder thickness is 60mm or following, and the more preferably thickness of tantalum powder is 40～50mm;For both safety
There is again higher productivity ratio, the most lightly tantalum powder poured in tantalum crucible and strike off.The present invention generally uses the degree of depth shallower
Circular or square crucible, the multiple length x width x depth as used are the tantalum earthenware of about 350mm × 210mm × 75mm respectively
Crucible.
Temperature and the temperature retention time of the heat treatment of tantalum powder according to different types of tantalum powder and require to determine, typically very
Reciprocal of duty cycle pressure is less than 1.33 × 10-1In the vacuum of handkerchief, 900 DEG C～1400 DEG C are incubated 30～90 minutes.
Tantalum powder after heat treatment optionally can be passed through nitrogen in temperature-fall period and carry out nitriding.
Tantalum powder is after being incubated at 900 DEG C～1400 DEG C, at vacuum descent of temperature, and can be by the stove of band cooling water jecket
Shell cools down, and cools to certain temperature under vacuo, as to about 500 DEG C or lower, is cooled to about 80 DEG C or more with room temperature argon
Low, then it is circulated pressure cooling with less than the argon of room temperature, make tantalum powder temperature be cooled to 30 DEG C or less, preferably by tantalum powder temperature
Degree is reduced to 20 DEG C and less, is passed through oxygen-containing gas is again passivated processing as being reduced to 10 DEG C～20 DEG C.
Described oxygen-containing gas is mainly the mixed gas of argon and oxygen composition, from the point of view of economy, the most main
If the mixed gas that air forms with argon.According to the present invention, in oxygen-containing gas, the concentration of oxygen is 21Vol% or following, oxygen
Concentration is the lowest, more easily and efficiently controls the oxidation of tantalum；Relatively low due to the specific heat of gas again, consider from effect, in oxygen-containing gas
Oxygen concentration is the lowest more good, but combines production efficiency and economic consideration, when starting to be passivated, and the preferably content of oxygen in oxygen-containing gas
It is 5～15Vol%.
The tantalum powder that specific surface area is low, is once passivated the most permissible.The tantalum powder preferred cycle high for specific surface area is blunt
Change more than secondary.Use the gas passivation of oxygen content low concentration for the first time, be then stepped up the oxygen concentration of oxygen-containing gas, oxygen
Concentration is up to the concentration of oxygen, about 21Vol% in air.
According to the inventive method, by oxygen-containing gas and diluent gas, such as argon respectively from respective air inlet according to gas
Its volume ratio of calculation of pressure enter heat-exchanging chamber mixing and with heat exchanger generation heat exchange, exit measure discharge oxygen-containing
The temperature of gas.The temperature of oxygen-containing gas of the present invention refers to measure the temperature discharging gas in exit.
During the passivation of tantalum powder, first heat-treatment furnace is evacuated to about 200Pa, continuously oxygen-containing gas can be sent into heat treatment
Stove, it is also possible to discontinuously oxygen-containing gas is sent into heat-treatment furnace, makes heat treatment furnace pressure be finally reached about 0.1MPa.
Heat treatment described in this specification refers to be placed in vacuum or inert atmosphere or reducing atmosphere at 300 DEG C tantalum powder
At a temperature of above, the process of heating, also includes the sintering of porous tantalum briquet, as manufactured the sintering of tantalum electrolytic capacitor anode, and can
To use and device as tantalum powder heat treatment phase, as used the device shown in Fig. 2～Fig. 4.
Tantalum powder oxygen content disclosed in this specification is to use TC-436 oxygen, nitrogen combined measuring instrument to measure；The hydrogen of tantalum powder contains
Amount is to use RH-404 hydrogen content analyzer to measure.The wet type electrical performance data of tantalum powder disclosed in this specification is to pass through
Following manner measures: it is 4.5g/cm that tantalum powder is pressed into density3, diameter 3.0mm, height is embedded with 0.3mm tantalum for 4.72mm
The cylindrical billet blocks of silk, each briquet about 150mg in tantalum powder；Above-mentioned briquet forms agglomerate in 10 minutes at 1320 DEG C of sintering；Will
Above-mentioned agglomerate is placed in the phosphoric acid of 0.1 mass % of 80 DEG C, with the electric current density up voltage of 60mA/g to 30V constant voltage 120 points
Bell one-tenth tantalum particle surface is coated with the anode of dielectric oxide film layer；Anode leakage is measured in the phosphoric acid of 0.1 mass % of 25 DEG C
Electric current, measures specific capacitance (specific volume) and loss in 20 mass % sulfuric acid solutions.
In order to further illustrate the present invention, below in conjunction with embodiment and accompanying drawing, the preferred embodiment of the invention is retouched
State, it is to be understood that, these describe simply as to further illustrate the features and advantages of the present invention rather than to the scope of the invention
Limit.
Embodiment
Embodiment 1
It is 1.82m by specific surface area2/ g, apparent density is 0.51g/cm3, O content is the sodium reduction fluorotantalic acid of 6200ppm
Former powder prepared by potassium, mixes the phosphorus pressing tantalum grain weight gauge 120ppm, carries out nodularization pelletize, and obtaining apparent density is 1.02g/cm3
Spheroidal particle.Above-mentioned nodularization pelletize tantalum powder is poured in tantalum crucible, crucible is loaded tantalum powder heat treatment passivation as shown in Figure 4
In device, it is 1.33 × 10 at pressure-1The vacuum of below Pa is heated to 1200 DEG C and is incubated 30 minutes, then stop heating, fall
Temperature, to 200 DEG C, is passed through argon and cools to 80 DEG C, start argon pressure cooling system 400A, the argon that heat treatment in-furnace temperature is higher
Gas from outlet 407 out, through there being the pipeline 408 of cooling water cooling, from air inlet 402 enter into heat-exchanging chamber 401 with system
There is heat exchange in the refrigerant pipe 404 that cold is connected；Argon is freezed by heat exchange, and the argon freezed is from outlet
405 out, makes argon pass through pipeline 406 with circulating pump 409 and sends into heat-treatment furnace from the gas access 440 of heat-treatment furnace, constitutes
The circulation of argon.The argon of circulation makes the crucible in heat-treatment furnace and the cooling of tantalum powder, cools down about 2 hours, makes in-furnace temperature reduce
To 25 DEG C, making tantalum powder be passivated, passivating process is that furnace gas is evacuated from pump-line 441, vacuum to about 200 handkerchiefs,
Start oxygen-containing gas refrigeration system 490A, make air and argon enter 491 heat exchanges according to following condition from 492 and 493 respectively
Also there is heat exchange with 494 in room mixing, then from outlet 495 out by utilidor 496, enters burner hearth from 420 entrances
410: the oxygen-containing gas that oxygen concentration is about 5Vol% for the first time (each leads into 1 volumes of air and the argon of 3 volumes by piezometer
Gas enters into described heat-exchanging chamber 491 with air inlet 493 from air inlet 492) the system that is connected with refrigeration machine of oxygen-containing gas
Cold medium tube 494 occurs heat exchange to be freezed, and temperature reaches the oxygen-containing gas of-10 DEG C～-20 DEG C and exports 495 from oxygen-containing gas
Out, sending into heat-treatment furnace by insulating tube 496 from the gas access 420 on heat-treatment furnace top, point 83 hours stages are from 200
Handkerchief brings up to 0.1MPa:(200Pa～0.005MPa)/30 minutes, (0.005MPa～0.01MPa)/30 minute, (0.01MPa～
0.02MPa)/20 minutes, (0.02MPa～0.03MPa)/20 minute, (0.03MPa～0.045MPa)/20 minute,
(0.045MPa～0.06MPa)/20 minute, (0.06MPa～0.08MPa)/20 minute, (0.08MPa～0.1MPa)/20 point
Clock, 3 hours altogether；Oxygen concentration is about-10 DEG C～-20 DEG C of oxygen-containing gas (1 volumes of air and 1 volumes of 10Vol% by second time
Argon mixing) within 3 hours, bring up to 0.1MPa from 200Pa according to first time inflation procedure；Third time-10 DEG C～-20 DEG C of skies
Gas, brings up to 0.1MPa by pressure from 200Pa in 3 hours according to the most identical program；-10 DEG C～-20 DEG C skies of 4th use
Edema caused by disorder of QI 4 stage brings up to 0.1MPa:(200Pa～0.01MPa from 200 handkerchiefs in totally 2 hours)/30 minutes, (0.01MPa～
0.03MPa)/30 minutes, (0.03MPa～0.06MPa)/30 minute, (0.06MPa～0.10MPa)/30 minute.4 passivation are altogether
Count 11 hours, whole during, start in-furnace temperature and slowly rise to 28 DEG C, temperature is gradually steady subsequently, temperature at 25 DEG C～
Changing between 28 DEG C, temperature was very long later drops to 25 DEG C.After coming out of the stove, tantalum powder is taken out, there is no fierce oxidative phenomena.Above-mentioned heat
Tantalum powder after process sieves through 80 mesh sieve, obtains S-1h tantalum powder, analyzes the oxygen content of tantalum powder, hydrogen content, and result is listed in table 1
In.Calculating the magnesium powder mixing 2wt% by tantalum powder, form mixed-powder, the tantalum powder that above-mentioned mixed-powder is loaded as shown in Figure 6 takes off
In oxygen reaction vessel, within 3 hours, carrying out deoxidation treatment 850 DEG C of insulations, stop heating, cooling down, 280 DEG C of nitridings, then
Force cooling with argon, drop at a temperature of 15 DEG C at tantalum powder, according to passivation program as above-mentioned heat treatment phase, be passed through 31 DEG C
Oxygen-containing gas, divides and is passivated with the oxygen-containing gas of oxygen concentration about 5Vol%, 10Vol%, 21Vol% and 21Vol% respectively for 4 times,
3 times passivation time is respectively 3 hours, and last passivation time is 2 hours, 11 hours altogether.After tantalum powder after passivation is come out of the stove
Carrying out pickling, wash, dry, obtain S-1d tantalum powder, analyze the oxygen of tantalum powder, hydrogen content, the results are shown in Table 1.With above-mentioned tantalum powder
Carrying out electrical property detection, the results are shown in Table 2.
Embodiment 2
The Ta powder used by embodiment 1, loads the present invention as shown in Figure 2 with argon forced cooling tantalum
In powder heat-treatment furnace, the condition identical according to embodiment 1 carries out heat treatment, after tantalum powder temperature drops to about 200 DEG C, is passed through argon
Gas, starts argon pressure cooling system 200A, the higher argon of heat treatment in-furnace temperature from stove upper outlet 207 out, warp
Cross water cooled pipeline 208, enter into the refrigerant pipe 204 being connected with refrigeration machine 200 heat-exchanging chamber 201 from air inlet 202
Heat exchanges；Argon is freezed by heat exchange, and the argon freezed out by pipeline 206, uses circulating pump from outlet 205
209 make argon send into heat-treatment furnace 210 from the gas access 240 of heat-treatment furnace, make argon produce and circulate；The argon of circulation
Make the crucible in heat-treatment furnace and the cooling of tantalum powder, cool down about 4 hours, after cooling, force cooling that furnace temperature is reduced to 10 with argon
DEG C, making tantalum powder be passivated, heat-treatment furnace is evacuated to about 200 handkerchiefs, oxygen concentration is about the oxygen-containing of 32 DEG C of 5Vol% by first time
Gas divides 4 hours 8 stages to bring up to 0.1MPa:(200Pa～0.005MPa from 200 handkerchiefs)/30 minutes, (0.005MPa～
0.01MPa)/30 minutes, (0.01MPa～0.02MPa)/30 minute, (0.02MPa～0.03MPa)/30 minute, (0.03MPa
～0.045MPa)/30 minutes, (0.045MPa～0.06MPa)/30 minute, (0.06MPa～0.08MPa)/30 minute,
(0.08MPa～0.1MPa)/30 minute.Oxygen concentration is about 32 DEG C of oxygen-containing gas of 10Vol% according to inflation for the first time by second time
Program 4 hours brings up to 0.1MPa. 32 DEG C of air of third time from 200Pa, according to first time the most identical program 4 hours by pressure
0.1MPa is brought up to from 200Pa；32 DEG C of air of 4th use divided for 4 stages within totally 2 hours, brought up to from 200 handkerchiefs by oxygen-containing gas
0.1MPa:(200Pa～0.01MPa)/30 minutes, (0.01MPa～0.03MPa)/30 minute, (0.03MPa～0.06MPa)/
30 minutes, (0.06MPa～0.10MPa)/30 minute.4 times passivation amount to 14 hours, whole during, start in-furnace temperature delay
Slowly rising to 33 DEG C, temperature is gradually steady subsequently, and temperature changes between 28 DEG C～32 DEG C.After coming out of the stove, tantalum powder is taken out, do not have
Fierce oxidative phenomena.Tantalum powder after above-mentioned heat treatment sieves through 80 mesh sieve, obtains S-2h tantalum powder, and the oxygen analyzing tantalum powder contains
Amount, hydrogen content, the results are shown in Table 1.S-2h tantalum powder is pressed tantalum powder and calculates the magnesium powder mixing 2wt%, form mixed-powder, upper
State in the tantalum powder deoxygenation container that mixed-powder loads as shown in Figure 7, within 3 hours, carry out deoxidation treatment 850 DEG C of insulations, stop
Heating, cooling down, it is being cooled to 280 DEG C of nitridings, is then making the temperature of tantalum powder in reaction vessel drop to 31 DEG C, point be passed through for 4 times-
10 DEG C～the oxygen-containing gas of-40 DEG C, according to passivation program as above-mentioned heat treatment phase, respectively with oxygen concentration be 5Vol%,
The oxygen-containing gas of 10Vol%, 21Vol% and 21Vol% is passivated, and 3 times passivation time is respectively 3 hours, when being passivated for the last time
Between be 2 hours, 11 hours altogether.Tantalum powder after passivation carries out pickling, washes, dries after coming out of the stove, obtain S-2d tantalum powder, analyzes tantalum
The oxygen of powder, hydrogen content, the results are shown in Table 1.Carrying out electrical property detection with above-mentioned tantalum powder, the results are shown in Table 2.
Embodiment 3
Use annealing device as shown in Figure 3, carry out heat treatment by the tantalum powder identical with embodiment 1 and condition, at heat
Furnace shell water-cooled cooling after reason, and logical argon cooling 12 hours to 30 DEG C, make tantalum powder be passivated.Passivating process is argon in stove
Be evacuated to about 200 handkerchiefs, start oxygen-containing gas refrigeration system 390A, make air and argon respectively according to following condition from 392 and 393
Enter 391 heat-exchanging chamber mixing and with 394, heat exchange occur, then from outlet 395 out by utilidor 396, entering from 320
Mouthful enter burner hearth 310: for the first time the oxygen-containing gas of oxygen concentration about 5Vol% is cooled to-20 DEG C～-40 DEG C, points of 8 stages from
200 handkerchiefs bring up to 0.1MPa:(200Pa～0.005MPa)/30 minutes, (0.005MPa～0.01MPa)/30 minute,
(0.01MPa～0.02MPa)/30 minute, (0.02MPa～0.03MPa)/30 minute, (0.03MPa～0.045MPa)/30 point
Clock, (0.045MPa～0.06MPa)/30 minute, (0.06MPa～0.08MPa)/30 minute, (0.08MPa～0.1MPa)/30
Minute amount to 4 hours.Oxygen concentration is about-20 DEG C of 10Vol%～-40 DEG C of oxygen-containing gas according to inflation journey for the first time by second time
Sequence 4 hours brought up to 0.1MPa. third time-20 DEG C～-40 DEG C of air from 200 handkerchiefs, according to the most identical program 4 hours
Pressure is brought up to 0.1MPa from 200Pa；-20 DEG C～-40 DEG C air of 4th use divided for 4 stages carried by oxygen-containing gas from 200 handkerchiefs
High to 0.1MPa:(200Pa～0.01MPa)/30 minutes, (0.01MPa～0.03MPa)/30 minute, (0.03MPa～
0.06MPa)/30 minutes, (0.06MPa～0.10MPa)/30 minute.Whole process amounts to 14 hours, starts in-furnace temperature slow
Rising to 35 DEG C, temperature is gradually steady subsequently, and temperature changes between 32 DEG C～35 DEG C.After coming out of the stove, tantalum powder is taken out, do not swash
Strong oxidative phenomena.Tantalum powder after above-mentioned heat treatment sieves through 80 mesh sieve, obtains heat treatment tantalum powder S-3h and analyzes the oxygen of tantalum powder
Content, hydrogen content, the results are shown in Table 1.S-3h tantalum powder is pressed tantalum powder and calculates the magnesium powder mixing 2wt%, form mixed-powder,
Above-mentioned mixed-powder loads in tantalum powder deoxygenation container as shown in Figure 8, within 3 hours, carries out deoxidation treatment 850 DEG C of insulations, stops
Only heating, cooling down, 280 DEG C of nitridings, be then turned on argon pressure cooling system and make the temperature of tantalum powder in reaction vessel drop
To 15 DEG C, divide the oxygen-containing gas being passed through-10 DEG C～-40 DEG C for 4 times, according to passivation program as above-mentioned heat treatment phase, use oxygen respectively
The oxygen-containing gas of concentration about 5Vol%, 10Vol%, 21Vol% and 21Vol% is passivated, and 3 times passivation time is 3 hours,
A rear passivation time is 2 hours, 11 hours altogether.Tantalum powder after passivation carries out pickling, washes, dries after coming out of the stove, obtain S-
3d tantalum powder, analyzes the oxygen of tantalum powder, hydrogen content, and the results are shown in Table 1.Carrying out electrical property detection with above-mentioned tantalum powder, result is listed in table 2
In.
Comparative example 1
With the tantalum powder identical with embodiment 1, carry out heat treatment at that same temperature, after stopping heating, drop in vacuum
Temperature is to 200 DEG C, and logical argon cools down, and cools down 12 hours, and temperature drops to 32 DEG C, proceeds by passivation, and passivating process is stove
Interior argon is evacuated to about 200Pa, and 31 DEG C of air are filled with heat-treatment furnace by point 8 stages for the first time, make furnace pressure from 200Pa to
0.1MPa:(200Pa～0.005MPa)/120 minutes, (0.005MPa～0.01MPa)/60 minute, (0.01MPa～
0.02MPa)/60 minutes, (0.02MPa～0.03MPa)/60 minute, (0.03MPa～0.045MPa)/30 minute,
(0.045MPa～0.06MPa)/30 minute, (0.06MPa～0.08MPa)/30 minute, (0.08MPa～0.1MPa)/30 minute
Amount to 7 hours.Wherein in gas replenishment process, temperature flies up 6 times, and maximum temperature rises to 60 DEG C on finding that temperature is suddenly
Rising, stop inflation immediately, equitemperature is reduced to about 32 DEG C and inflates in stove.31 DEG C of air are filled with by 8 stages of second time point
Heat-treatment furnace, makes furnace pressure bring up to 0.1MPa:(200Pa～0.005MPa from 200 handkerchiefs)/60 minutes, (0.005MPa～
0.01MPa)/60 minutes, (0.01MPa～0.02MPa)/60 minute, (0.02MPa～0.03MPa)/60 minute, (0.03MPa
～0.045MPa)/30 minutes, (0.045MPa～0.06MPa)/30 minute, (0.06MPa～0.08MPa)/30 minute,
(0.08MPa～0.1MPa)/30 minute amount to 6 hours.1 temperature is wherein occurred to sharp rise to 50 DEG C.Third time and second
31 DEG C of air are passivated inflating by secondary same procedure, 6 hours altogether.31 DEG C of air of 4th use divided for 4 stages high from 200 iwans
To 0.1MPa:(200Pa～0.01MPa)/30 minutes, (0.01MPa～0.03MPa)/30 minute, (0.03MPa～
0.06MPa)/30 minutes, (0.06MPa～0.10MPa)/30 minute, 2 hours altogether.Amount to passivation 21 hours 4 times.After passivation
Being taken out by tantalum powder, heating is serious.Tantalum powder after above-mentioned heat treatment sieves through 80 mesh sieve, obtains E-1h tantalum powder, analyzes tantalum powder
Oxygen content, hydrogen content, the results are shown in Table 1.Calculate the magnesium powder mixing 2wt% by tantalum powder, form mixed-powder, above-mentioned mixed
Close in the tantalum powder deoxygenation container that powder loads as shown in Figure 5, within 3 hours, carry out deoxidation treatment 850 DEG C of insulations, stop adding
Heat, cooling down, 280 DEG C of nitridings, then according to passivating method as above-mentioned heat treatment phase, after temperature drops to 31 DEG C, divide 4
Secondary it be passed through 31 DEG C of air and be passivated, be 3 times each point of 8 stages, each 5 hours, be for the 4th time point 4 stages, be passivated 2 hours,
Amounting to passivation 17 hours, the tantalum powder after passivation carries out pickling, washes, dries after coming out of the stove, and obtains E-1d tantalum powder, analyzes the oxygen of tantalum powder
Content, hydrogen content, the results are shown in Table 1.Carrying out electrical property detection with above-mentioned tantalum powder, the results are shown in Table 2.
The oxygen content of table 1 tantalum powder and hydrogen content
| Tantalum powder sequence number | O | H |
| S-1h | 10600 | 70 |
| S-1d | 3800 | 140 |
| S-2h | 11300 | 78 |
| S-2d | 4100 | 140 |
| S-3h | 11600 | 60 |
| S-3d | 4000 | 130 |
| E-1h | 16500 | 180 |
| E-1d | 5800 | 200 |
The electrical property measurement result of table 2 tantalum powder
Find out from the result of table 1, table 2, prepare tantalum powder according to the inventive method, with short production cycle, the tantalum powder oxygen that obtains, hydrogen
Content is low, and the leakage current of tantalum powder is low.
Embodiment 4
Being pressed into density with the tantalum powder S-1d after embodiment 1 deoxidation heat treatment is 4.5g/cm3, diameter 3.0mm, height is
4.72mm is embedded with the cylindrical billet blocks of 0.3mm tantalum wire, each briquet about 150mg in tantalum powder；Above-mentioned briquet is as shown in Fig. 4
In device, within 10 minutes, form tantalum agglomerate at 1320 DEG C of sintering, then stop heating, cool to 200 DEG C, be passed through argon, start
Argon pressure cooling system 400A, cools down about 3 hours, makes in-furnace temperature be reduced to 20 DEG C, make tantalum agglomerate be passivated, passivation
Process is that argon in stove is evacuated, vacuum to about 200 handkerchiefs, for the first time oxygen concentration is about 10Vol%, and temperature reaches-10 DEG C
～the oxygen-containing gas of-40 DEG C, divide bring up to 0.1MPa:(200Pa～0.01MPa from 200 handkerchiefs 53 hours stages)/40 minutes,
(0.01MPa～0.03MPa)/40 minute, (0.03MPa～0.05MPa)/40 minute, (0.05MPa～0.07MPa)/30 point
Clock, (0.07MPa～0.1MPa)/30 minute.Second time with-10 DEG C～-40 DEG C of air divide 4 stages totally 2 hours from 200 iwans height
To 0.1MPa:(200Pa～0.01MPa)/30 minutes, (0.01MPa～0.03MPa)/30 minute, (0.03MPa～
0.06MPa)/30 minutes, (0.06MPa～0.10MPa)/30 minute.2 times passivation amount to 5 hours, whole during, start stove
Interior temperature slowly rises to 32 DEG C, and temperature is gradually steady subsequently, and temperature changes between 29 DEG C～31 DEG C, under temperature is very long later
Drop to 29 DEG C.After coming out of the stove, tantalum agglomerate is taken out, obtain S-4 tantalum agglomerate, analyze the oxygen content of tantalum agglomerate, hydrogen content, knot
Fruit is shown in Table 3.Above-mentioned agglomerate is placed in the phosphoric acid of 0.1 mass % of 80 DEG C, with the electric current density up voltage of 60mA/g
Within 120 minutes, form tantalum anode S-4a to 30V constant voltage, the phosphoric acid of 0.1 mass % of 25 DEG C measures anode leakage stream, in 20 matter
Measuring specific capacitance (specific volume) and loss in amount % sulfuric acid solution, the results are shown in Table 4.
Comparative example 2
It is pressed into identical tantalum briquet with the tantalum powder that embodiment 4 is identical, sinters at identical conditions, cool to 200 DEG C,
It is passed through argon to cool down about 6 hours, makes in-furnace temperature be reduced to 33 DEG C, make tantalum agglomerate be passivated.Passivating process is in stove
Argon evacuates, vacuum to about 200 handkerchiefs, and for the first time by the air that temperature is 32 DEG C, point 6 4.5 hours stages are high from 200 iwans
To 0.1MPa:(200Pa～0.005MPa)/60 minutes, (0.005MPa～0.01MPa)/30 minute, (0.01MPa～
0.02MPa)/30 minutes, (0.02MPa～0.03MPa)/30 minute, (0.03MPa～0.05MPa)/30 minute, (0.05MPa
～0.06MPa)/30 minutes, (0.06MPa～0.08MPa)/30 minute, (0.08MPa～0.1MPa)/30 minute.Second time is used
32 DEG C of air divided for 4 stages within totally 2 hours, from 200 handkerchiefs, oxygen-containing gas was brought up to 0.1MPa:(200Pa～0.01MPa)/30 minutes,
(0.01MPa～0.03MPa)/30 minute, (0.03MPa～0.06MPa)/30 minute, (0.06MPa～0.10MPa)/30 point
Clock.2 times passivation amount to 6.5 hours, whole during, start in-furnace temperature slowly rise to 41 DEG C, by tantalum agglomerate after coming out of the stove
Taking out, obtain E-2s tantalum agglomerate, analyze the oxygen of tantalum agglomerate, hydrogen content, the results are shown in Table 3.By above-mentioned agglomerate according to
The condition that embodiment 3 is identical forms anode E-2a, and above-mentioned anode is carried out electrical property detection, and the results are shown in Table 4 for it.
The oxygen content of table 3 tantalum agglomerate and hydrogen content
| Tantalum agglomerate sequence number | O | H |
| S-4 | 5200 | 30 |
| E-2 | 6500 | 70 |
The electrical property measurement result of table 4 tantalum agglomerate
By described above, the inventive method carries out tantalum powder heat treatment, safe and reliable, and production efficiency is high, and tantalum will not occur
Powder catches fire, and the tantalum powder oxygen, the hydrogen content that obtain are low, and the anode leakage stream prepared with tantalum powder of the present invention is low, good electrical property.
In the above description, although illustrate mainly for tantalum powder, but such as those skilled in the art it is conceivable that
, the present invention can also be suitable for and be applicable to other active metal powder, such as niobium powder etc..
Claims (4)
1. a tantalum metal surface passivation device, it includes that heat-treatment furnace, described heat-treatment furnace include: burner hearth, form described stove
The furnace shell of the band water-cooling jacket of thorax, the oxygen-containing gas of passivation enter described burner hearth entrance, evacuate pipeline, be arranged on described
Heater inside burner hearth and for accommodating the heat treatment crucible of pending tantalum metal；It is characterized in that described passivating device also
Including oxygen-containing gas refrigeration system, described oxygen-containing gas refrigeration system specifically includes that
-oxygen-containing gas entrance, it is for receiving for tantalum metal is passivated the oxygen-containing gas processed；
-heat-exchanging chamber, is freezed described oxygen-containing gas by heat exchange method in this heat-exchanging chamber；With
-oxygen-containing gas exports, and the oxygen-containing gas freezed thus leaves from heat-exchanging chamber and passes through insulation and connects pipeline from Re Chu
Reason stove top enters heat-treatment furnace.
2. a tantalum metal surface passivation device, it includes that heat-treatment furnace, described heat-treatment furnace include: burner hearth, form described stove
The furnace shell of the band water-cooling jacket of thorax, the oxygen-containing gas of passivation enter the entrance of described burner hearth, argon enters entering of described burner hearth
Mouthful, be positioned at the argon gas export on heat-treatment furnace top, be located at the heater inside described burner hearth and for accommodating pending tantalum metal
Heat treatment crucible；It is characterized in that described passivating device also includes argon forced cooling and oxygen-containing gas refrigeration system,
Wherein said argon forced cooling includes:
-Ar inlet to be cooled, this Ar inlet to be cooled is connected with the argon gas export on heat-treatment furnace top；
-heat-exchanging chamber, has the medium pipeline freezed by refrigeration machine in described heat-exchanging chamber, refrigeration machine flows through the medium of refrigeration
Heat-exchanging chamber, in described switch room, the argon of entrance is freezed；
-cooling argon gas export, argon cooled in heat-exchanging chamber is discharged via this argon gas export；
-circulating pump, this circulating pump is received cooled argon by cooling down argon gas export, and via connecting pipeline from heat-treatment furnace
The argon of described cooling is delivered into heat-treatment furnace by the Ar inlet of bottom；
And wherein said oxygen-containing gas refrigeration system specifically includes that
-oxygen-containing gas entrance, it is for receiving for tantalum metal is passivated the oxygen-containing gas processed；
-heat-exchanging chamber, is freezed described oxygen-containing gas by heat exchange method in this heat-exchanging chamber；
-oxygen-containing gas exports, and the oxygen-containing gas freezed thus is opened from heat-exchanging chamber and passed through insulation and connects pipeline from Re Chu
Reason stove top enters heat-treatment furnace.
Tantalum metal surface passivation device the most according to claim 2, it is characterised in that made by described argon forced cooling
Tantalum metal cools to 10 DEG C～30 DEG C.
4. according to the tantalum metal surface passivation device of skill claim 1 or 2, it is characterised in that by described oxygen-containing gas refrigeration be
System makes described oxygen-containing gas freeze, thus the passivation oxygen-containing gas providing temperature to be-40 DEG C～0 DEG C.
Applications Claiming Priority (1)
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|---|---|---|---|
| PCT/CN2011/000488 WO2012126143A1 (en) | 2011-03-23 | 2011-03-23 | Method for passivating tantalum metal surface and apparatus thereof |
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| US (1) | US20140076462A1 (en) |
| JP (1) | JP5774766B2 (en) |
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| US11534830B2 (en) * | 2017-12-28 | 2022-12-27 | Ningxia Orient Tantalum Industry Co., Ltd | Tantalum powder and preparation method therefor |
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| IL228504A0 (en) | 2013-12-31 |
| CN103429782A (en) | 2013-12-04 |
| CZ2013807A3 (en) | 2014-02-05 |
| CZ306250B6 (en) | 2016-10-26 |
| US20140076462A1 (en) | 2014-03-20 |
| JP2014516382A (en) | 2014-07-10 |
| JP5774766B2 (en) | 2015-09-09 |
| IL228504B (en) | 2018-04-30 |
| WO2012126143A1 (en) | 2012-09-27 |
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