CN103878364B - A kind of preparation method of the middle pressure tantalum powder for improving proof voltage energy - Google Patents
A kind of preparation method of the middle pressure tantalum powder for improving proof voltage energy Download PDFInfo
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- CN103878364B CN103878364B CN201410164506.6A CN201410164506A CN103878364B CN 103878364 B CN103878364 B CN 103878364B CN 201410164506 A CN201410164506 A CN 201410164506A CN 103878364 B CN103878364 B CN 103878364B
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Abstract
The present invention relates to the preparation method and the tantalum powder prepared by the method for a kind of middle pressure tantalum powder for improving proof voltage energy.The preparation method of the present invention drops oxygen after being heat-treated twice by introducing, and then carries out third time heat treatment, finally drops the scheme of oxygen again, control oxygen content, improve the granule-morphology of tantalum powder, improves the resistance to sparking energy of product, improve leakage current.Preparation method pressure tantalum powder suitable for specific volume is between 15000 μ FV/g～50000 μ FV/g.
Description
Technical field
The invention belongs to press tantalum powder to make field in capacitor level, and in particular to a kind of middle pressure for improving proof voltage energy
The preparation method of flaked tantalum powder, and the middle wafer-like tantalum powder prepared by the method.
Background technology
Metal tantalum is a kind of valve metal, and it can have the property of unilateal conduction in one layer of fine and close oxide-film of Surface Creation
Matter.Anode film stable chemical performance made by tantalum powder (stable particularly in acidic electrolyte bath), resistivity high (7.5 × 1010
Ω cm), dielectric constant big (27.6), leakage current it is little, also there is operating temperature range width (- 80～200 DEG C), reliability in addition
The advantages of high, antidetonation and long service life.Tantalum powder is the ideal material for making the high tantalum capacitor of small volume, reliability.Due to
Tantalum capacitor has the advantages that many, therefore is extensively made in the electronic equipments such as Aeronautics and Astronautics, communication, computer, mobile phone
With.
Existing more than the 70 years history of the large-scale production of tantalum powder, but the development of mass rapid degree only has 50 years or so.It is early
In 1904, people's just once reduction with carbon tantalum pentoxide, refining of reduzate Jing vacuum high-temperatures obtained first piece in the world
Has malleable tantalum ingot.The fused salt electrolysis process economical rationality that grew up later, equipment are simple, therefore, once obtain extensive
Using.But the tantalum powder being electrolysed with traditional handicraft, grain type is simple, particle is thick, specific volume is low, it is impossible to meet electronics industry to Gao Rong
The requirement of amount tantalum powder.The methods such as tantalum oxide carbon thermal reduction, tantalic chloride hydrogen reduction and aluminothermic reduction all could not also be used for industry
Production.And tantalum powder prepared by sodium reduction has the features such as purity is high, grain type is complicated, specific volume is high, it has also become prepare tantalum powder both at home and abroad
Main production.Mainly there is Cabot groups, the HCST groups of Germany and the China in the U.S. in tantalum powder manufacturer of the world at present
Dongfang Tantalum Industry Co., Ltd., Ningxia Hui autonomy Region.
On materials classification, the tantalum powder for being specifically used to make capacitor is referred to as Ta powder used in capacitor.Tantalum powder is made according to which
High pressure tantalum powder can be divided into again with voltage is different（It is more than operating voltage 25V）, low pressure high specific capacitance tantalum powder（Operating voltage 25V with
Under）.Tantalum powder application on the capacitor accounts for the 60%～70% of world's tantalum aggregate consumption.Especially in recent years, with calculating
Developing rapidly for machine and electronics industry, is always maintained at stablizing ascendant trend to the demand of tantalum, it is contemplated that 5 from now on～
In 10 years, the speed with annual more than 15% is continued development by global tantalum industry.
High pressure tantalum powder for military products refers mainly to the 63V series tantalum powders produced by electronic torch melting, hydrogenation, milling method,
Its operating voltage use range is extend between 50V-75V, space flight, aviation, military field important role.Also one
High pressure tantalum powder of the part operating voltage for 35V-50V, mainly including middle wafer-like tantalum powder and some other pressure higher tantalum powder.
In recent years, operating voltage for 16V-35V middle pressure tantalum powder be Future Development a focus.
This two parts high pressure tantalum powder has preferable electrical property, and reliability is higher, very steady always in fields such as national defence, military projects
It is fixed.This several years under the influence of Global finance, other grade tantalum powders all significantly atrophys, but army grade Ta powder used in capacitor is still
Growing trend is remain, becomes a large focal spot of our concerns.The development of army's grade Ta powder used in capacitor and the extension of NPD projects
Become an important directions of our next step, the lifting of its electrical property is particularly important.
In order to understand the preparation method of high pressure tantalum metal powder, we are analyzed to domestic and international patent.
Patent US4017302 discloses a kind of preparation method of high pressure tantalum metal powder.The idiographic flow of the method is tantalum
Ingot hydrogenates, grinds, be classified sieve, dehydrogenation the pre-heat treatment, crushed 80 mesh sieves, dough, it is broken, cross 35 mesh, 250 mesh and then-
250 mesh mutually mix again dough, test with -35/+25 mesh powder, obtain product.Tantalum powder prepared by the method is relatively specific for height and forces down appearance
Amount tantalum powder（63V）.
Patent US4141719 discloses a kind of preparation method of high pressure tantalum metal powder.The idiographic flow of the method is tantalum
Ingot hydrogenates, grinds, is classified, deaerates（1200℃）, mill sieve, cross 35 mesh, mixing.The tantalum powder apparent density that the method is obtained is big, oxygen
Content is low, and embryo bulk strength is high, the leakage current of sintered anode is low.Tantalum powder prepared by the method is relatively specific for high pressure low capacity tantalum powder
（63V）.
Patent US4555268 is related to the flaked tantalum powder that a kind of processing characteristics improves.The powder contains the sheet tantalum of 20-40%
Powder and 70% granular tantalum powder, mixing before 1250 DEG C～1550 DEG C be heat-treated 5～120 minutes.The secondary dough of mixing tantalum powder, changes
It has been apt to processing characteristics.Tantalum powder prepared by the method is relatively specific for medium operating voltage（20V～35V）.
Patent US4740238 is related to a kind of tantalum powder containing flake powder.Its concrete preparation process is：Tantalum powder degassing, film-making（Ball
Mill, wet-milling）, pickling, screening, p-doped, once heat treatment, mill sieve, p-doped, secondary heat treatment, mill sieve, Mg reduce.Party's legal system
Standby tantalum powder is relatively specific for medium operating voltage（20V～35V）.
Patent CN1004614A is related to a kind of method for preparing spherical tantalum powder and products thereof.The method is used and carries gas by tantalum
Powder sends into plasma reaction area, cools down in spraying into vacuum tank, makes spherical tantalum powder, pickling, 1000～1250 DEG C of heat treatments.The tantalum
Powder is pressure 300～450V.Tantalum powder mouldability extreme difference prepared by the method.
At present, the tantalum powder that medium operating voltage is used, which is produced, and mode is more diversified, but numerous preparation methods is all
There is weak point, above commenting.
As mentioned above, although the existing method for making tantalum powder describes the process of several high and medium voltage tantalum powders
Method, but these methods are to being only applicable to tantalum powder is pressed in sub-fraction.And in another, press tantalum powder technique as described above
But it is difficult to be obtained, or cause electrical property very poor.
The content of the invention
In order to solve the problem, inventor is through concentrating on studies, testing proposition solution below：Tantalum powder original powder is being entered
Oxygen drops in row after being heat-treated twice, carry out three heat treatment, finally drop oxygen again after drop oxygen.The program controls oxygen content, improves
The granule-morphology of tantalum powder, improves the resistance to sparking energy of product, improves leakage current.
For this purpose, a first aspect of the present invention provides a kind of preparation method of middle pressure tantalum powder, the method is comprised the following steps：It is right
Tantalum powder original powder carries out drop oxygen for the first time after being heat-treated twice, then carries out third time heat treatment, finally carries out second again
Drop oxygen.
In a preferred embodiment, the preparation method described in first aspect present invention, wherein second drop oxygen
Temperature than first time drop oxygen temperature it is high 0 DEG C～100 DEG C（Such as 20 DEG C, 50 DEG C or 80 DEG C）.
In a preferred embodiment, the preparation method described in any one of first aspect present invention, described tantalum powder
Former powder be sodium reduction tantalum powder, preferred impurity content be O≤2600ppm, C≤30ppm, N≤200ppm, Fe≤20ppm sodium also
Former tantalum powder.
In a preferred embodiment, the preparation method described in any one of first aspect present invention, also including film-making
The step of, described flaking step is carried out before the heat treatment, by tantalum powder original powder processing slabbing, obtains flaked tantalum powder original powder,
Preferred processing method is ball milling, and preferably with absolute ethyl alcohol as ball-milling medium, the weight ratio of preferred ball material is 3:1
～8:1（Such as 6:1）, preferred drum's speed of rotation is 80～200 revs/min, and preferred Ball-milling Time is 12～18 hours（For example
15 hours）.
In a preferred embodiment, the preparation method described in any one of first aspect present invention, described film-making
The step of also including conventional pickling in step.For example, conventional acid washing conditions are：First pass：Use 5-15%HNO3+0.3-0.7%
HF pickling 2-3 hours, steep 1-2 hours, pour out supernatant.Second time：It is identical with first pass.3rd time with 5-15%HNO3+0.3-
0.7%HF+1-2%H2O2Pickling 2-3 hours, steep 1-2 hours, finally pour out supernatant, plus enough water rinses twice discharging plus pure water
Suction filtration.When the electrical conductivity of diafiltration liquid is less than 30us/cm, suction filtration stops, and proceeds to baking oven and is dried.It is true at 120 DEG C -160 DEG C
Empty drying 12-15 hours, in drying course, vacuum is more than or equal to 4 × 104Pa, then sieve 80～100 mesh.
In a preferred embodiment, the preparation method described in any one of first aspect present invention, wherein, for the first time
Heat treatment（That is degassing or pre-sintered）Treatment conditions be：Vacuum is more than 6 × 10-3Pa, 800～1400 DEG C of heating 60～240
Minute（Can be divided into and heating twice or thrice, for example, be first to heat to 800～1050 DEG C, be incubated 60～120 minutes, then add again
Heat to 1250～1350 DEG C is incubated 60～120 minutes）,
Preferably, disintegrating machine is used after first time is heat-treated（Such as jaw crusher）Broken 50～80 mesh the magnetic of sieving
Choosing,
It is preferred that add water after magnetic separation carrying out pre- dough, tantalum powder weight 10-30% is added（Such as 18%）Water be well mixed,
Sieve 30～60 mesh（Twice of such as 50 mesh）, then dry, preferred drying condition be vacuum drying 10 at 100～120 DEG C～
15 hours, in preferred drying course, vacuum was more than or equal to 4 × 104Pa（Such as 2 × 104Pa MPa）.
In a preferred embodiment, the preparation method described in any one of first aspect present invention, wherein, second
The treatment conditions of heat treatment are：Vacuum is more than 6 × 10-3Pa, 800～1500 DEG C are heated 60～200 minutes（Can be divided into twice
Or three heating, 800～1050 DEG C are for example first to heat to, 60～120 minutes are incubated, 1350～1450 DEG C of guarantors are then heated to
Temperature 60～120 minutes),
It is preferred that crushing 60 mesh～100 mesh (such as 80 mesh) that sieve after being heat-treated at second.
In a preferred embodiment, the preparation method described in any one of first aspect present invention, wherein described
Drop oxygen is that oxygen drops in magnesium-reduced, is 9 × 10 preferably in vacuum4Pa～1.2 × 105In inert gas (such as argon gas) atmosphere of Pa
Heated.
Preferably, drop oxygen condition is for the first time：Mix 1.5～3%, 800～950 DEG C of heating 2～3 that magnesium amount is tantalum powder weight
The row's of vacuumizing magnesium 2～3 hours after hour,
It is preferred that carrying out pickling and drying after row's magnesium again, preferred acid washing conditions are 8～12%HNO3Pickling 1～2 hour
(such as 10%HNO3Pickling 1.5 hours), preferred drying condition be vacuum drying 8 under 100～140 DEG C (such as 120 DEG C)～
14 hours (such as 12 hours).
In a preferred embodiment, the preparation method described in any one of first aspect present invention, wherein third time
The treatment conditions of heat treatment：Vacuum is more than 6 × 10-3Pa, 800～1500 DEG C heat 60～200 minutes (can be divided into twice or
Three heating, for example, be first to heat to 800～1050 DEG C, is incubated 30～60 minutes, is then heated to 1350～1500 DEG C of insulations
60～120 minutes),
It is preferred that with broken 50～80 mesh (such as 60 that sieve of disintegrating machine (such as jaw crusher) after third time is heat-treated
Mesh) and magnetic separation.
In a preferred embodiment, the preparation method described in any one of first aspect present invention, wherein, second
Drop oxygen condition be：The row's of vacuumizing magnesium 2 after 1.5～3%, 920～960 DEG C of heating for mixing that magnesium amount is tantalum powder weight 2～3 hours～
3 hours,
It is preferred that carrying out pickling and drying after row's magnesium again, preferred acid washing conditions are 8～12%HNO3Pickling 1～2 hour
(such as 10%HNO3Pickling 1.5 hours), preferred drying condition be vacuum drying 8 under 100～140 DEG C (such as 120 DEG C)～
14 hours (such as 12 hours).
A second aspect of the present invention presses tantalum powder in providing one kind, is obtained by the preparation method of any one of first aspect present invention
Arrive.Preferably, the specific volume of described middle pressure tantalum powder is 15000 μ FV/g～50000 μ FV/g, or, described middle pressure tantalum powder
Specific volume is 13000 μ FV/g～30000 μ FV/g.
A third aspect of the present invention provides a kind of electrolytic capacitor, its middle pressure tantalum powder system by described in second aspect present invention
It is standby to obtain.Described electrolytic capacitor can be solid capacitor, or liquid tantalum capacitor.Described solid capacitance
The operating voltage of device is 10V-35V, and described liquid tantalum capacitor operating voltage is 25V-50V.
In a specific embodiment, the preparation method of the middle pressure tantalum powder described in first aspect present invention selects sodium also
Former tantalum powder is required as raw material, major parameter：O≤2600ppm、C≤30ppm、N≤200ppm、Fe≤20ppm.With anhydrous second
Alcohol is ball-milling medium, from the steel ball 30Kg of ф 2～ф 4mm, it is ensured that ball milling bucket, stirring slurry and steel ball are rustless, cleaning.Ball material weight
Amount is than controlling 3:1～8:1, load weighted tantalum powder is added in the ball milling bucket of ball mill carries out ball milling, drum's speed of rotation 80
～200 revs/min, Ball-milling Time 12～18 hours.Then suction filtration alcohol, routinely acid washing conditions pickling, sieves 80～100
Mesh.
Former powder after ball milling carries out first time heat treatment (i.e. once degassing or pre-sintered), treatment conditions first：Vacuum
More than 6 × 10-3Start power transmission to heat during Pa, 800～1050 DEG C/60 minutes～120 minutes, 1250～1350 DEG C/60 minutes～
120 minutes, sieved 50 mesh～80 mesh magnetic separation with jaw crushing crusher machine after being once heat-treated.Then adding water carries out pre- dough,
Treatment conditions：The pure water of tantalum powder weight 10-30% is added to be well mixed with shovel, sieve twice of 50 mesh.100～120 DEG C of drying
Lower vacuum drying 10～15 hours, in drying course, vacuum is more than 4 × 104Pa。
Then second heat treatment, treatment conditions are carried out again：Vacuum is more than 6 × 10-3Start power transmission to heat during Pa, 800
～1050 DEG C/60 minutes～120 minutes, 1350～1450 DEG C/60 minutes～120 minutes.Subsequently break up 60 mesh～100 of sieving
Mesh, carries out first time magnesium-reduced drop oxygen, drops oxygen condition：1.5～3%, 900～950 DEG C of insulations 2 for mixing that magnesium amount is tantalum powder weight～
The row's of vacuumizing magnesium 2～3 hours after 3 hours, then carry out pickling and drying, acid washing conditions 10%HNO again3Pickling 1.5 hours.
Drying condition is vacuum drying 12 hours at 120 DEG C.
Followed by carrying out third time heat treatment, third time heat treatment condition:Vacuum is more than 6 × 10-3Start power transmission during Pa
Heating, is heated to 800～1050 DEG C/30～60 minutes, 1350～1500 DEG C/60～120 minutes, uses jaw after three heat treatment
Crusher in crushing sieve 60 mesh, use magnetic separator magnetic separation, remove ferromagnetic material such as iron for bringing into etc. in shattering process.Finally enter again
Oxygen condition, drops in the secondary drop oxygen of row：1.5～3%, 920～960 DEG C of insulations for mixing that magnesium amount is tantalum powder weight were vacuumized after 2～3 hours
Row's magnesium 2～3 hours, then carries out pickling and drying, acid washing conditions 10%HNO again3Pickling 1.5 hours.Drying condition is 120
Vacuum drying 12 hours at DEG C, vacuum are more than 4 × 104Pa.Then product obtains the tantalum powder of our needs through allotment.Need
It is being higher than once to drop 0 DEG C～100 DEG C of oxygen temperature to be pointed out that secondary magnesium-reduced drop oxygen temperature should be controlled, better.
The preparation method of the present invention employs drop oxygen technique twice, a middle plus step Technology for Heating Processing.The advantage of the method
It is the oxygen inside tantalum powder is migrated to particle surface by first time drop oxygen, reduces the oxygen content of tantalum inside particles, subsequently
The three Technology for Heating Processing main purposes for carrying out be make tantalum powder in some tiny tantalum powder particles combined with bulky grain, and be attached to
Together, product leakage current is reduced, the breakdown chance of product is reduced, is reduced the loss of product, improve the electric leakage of product
Stream.The purpose of second drop oxygen is then the thickness for adjusting tantalum powder oxide-film again, and oxide-film capacity extraction rate if too thick is low,
Oxide-film if too thin if leakage current can be caused to increase.
The preparation method of the present invention improves the proof voltage energy of tantalum powder, the method increases the resistance to sparking energy of product,
Reduce the leakage current of tantalum powder so as to can work at higher voltages, and suitable for the tantalum powder compared with Fabrication of High Specific Capacitance.This
Bright preparation method is pressure tantalum powder 15000 μ FV/g～50000 μ FV/g suitable for specific volume, or is existed suitable for specific volume
The middle pressure tantalum powder of 13000 μ FV/g～30000 μ FV/g.The solid electrolytic capacitor made by middle wafer-like tantalum powder prepared by the present invention
The operating voltage of device is in 10V-35V, liquid tantalum capacitor operating voltage 25V-50V.
In the present invention, unless otherwise expressly noted, % refers to mass percent.
In the present invention, when the granularity of powder is represented with mesh number, the "+" or "-" number before mesh number represents " logical respectively
But " or " passing through " described mesh number screen cloth.For example, " -60 mesh " represents the screen cloth by 60 mesh, and "+200 mesh " is represented and led to not
Cross the screen cloth of 200 mesh.
In the present invention, the analytical equipment and model of involved parameters are as shown in the table：
| Analysis project | Analytical equipment title | Specifications and models |
| CV | LCR precision measuring instruments | HP-4284A |
| Leakage current | Leakage current tester | QE2621 |
| O、N | Oxygen-nitrogen analyzer | LECO CS-436 |
| Fe | Direct-reading spectrometer | GV-5 |
| C | Carbon and sulfur analytical instrument | LECO CS-406 |
| SBD | Apparent density tester | FL4-1 |
| FSSS | Average granulometry instrument | WLP-202 |
| P | Inductive coupling plasma emission spectrograph | PE8000ACP |
Description of the drawings
Fig. 1：1 Sample Scan electromicroscopic photograph of embodiment（×10K）
Fig. 2：2 Sample Scan electromicroscopic photograph of embodiment（×10K）
Fig. 3：3 Sample Scan electromicroscopic photograph of embodiment（×10K）
Fig. 4：4 Sample Scan electromicroscopic photograph of embodiment（×10K）
Fig. 5：1 Sample Scan electromicroscopic photograph of comparative example（×10K）
Specific embodiment
In order to further appreciate that the present invention, embodiment of the present invention is described with reference to embodiment and subordinate list, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention model
The restriction enclosed.
The raw material selected in example below and comparative example is with a batch of sodium reduction tantalum powder, to illustrate the present invention's
The technique effect and advantage of preparation method.
Embodiment 1：
From the tantalum powder after sodium reduction as raw material, major parameter：O:1800ppm、C：20ppm、N：150ppm、Fe：
15ppm.With absolute ethyl alcohol as ball-milling medium, from the steel ball 30Kg of ф 3mm.Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clear
It is clean.Ratio of grinding media to material is controlled 6:1, load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill carries out ball milling, drum's speed of rotation
80 revs/min, Ball-milling Time 15 hours.Then suction filtration alcohol, routinely acid washing conditions pickling.Acid washing conditions：First pass：With
10%HNO3+0.5%HF pickling 2 hours, steeps 2 hours, pours out supernatant, second time：Identical with first pass, the 3rd time with 12%
HNO3+0.7%HF+1%H2O2 pickling 2 hours, steeps 2 hours, finally pours out supernatant, plus enough water rinses twice discharging plus pure water
Suction filtration.When the electrical conductivity of diafiltration liquid is less than 30us/cm, suction filtration stops, and proceeds to baking oven and is dried.Vacuum drying at 120 DEG C
14 hours, in drying course, vacuum was more than 4 × 104Pa, then sieve 100 mesh.
Former powder after ball milling carries out first time heat treatment first（That is once degassing or pre-sintered）, treatment conditions：Vacuum
More than 6 × 10-3Start power transmission heating during Pa, be heated to 1050 DEG C and be incubated 120 minutes, be heated to 1350 DEG C and be incubated 60 minutes,
Sieved 80 mesh magnetic separation with jaw crushing crusher machine after being heat-treated for the first time, then adding water carries out pre- dough, treatment conditions：Add
The water of tantalum powder weight 18% is well mixed with shovel, and sieve twice of 50 mesh.At 120 DEG C of drying, vacuum drying 15 hours, dried
In journey, vacuum is 2 × 104Pa。
Then second heat treatment, treatment conditions are carried out again：Vacuum is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are incubated to 1050 DEG C, 1400 DEG C are then heated to and are incubated 60 minutes, subsequently breaking up 80 mesh that sieve carries out first time magnesium also
Oxygen condition, drops in former drop oxygen：Mix that magnesium amount is tantalum powder weight 3.0%, is evacuated to more than 2 × 104Pa, be then charged with argon gas to 9 ×
104Pa, after being warming up to 880 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying, pickling again
Condition 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Followed by carrying out third time heat treatment, third time heat treatment condition：Vacuum is more than 6 × 10-3Start power transmission during Pa
Heating, is heated to 1050 DEG C and is incubated 60 minutes, is heated to 1450 DEG C and is incubated 60 minutes, and third time uses jaw crushing after being heat-treated
Crusher machine sieve 80 mesh, use magnetic separator magnetic separation, remove ferromagnetic material such as iron for bringing into etc. in shattering process.It is last to carry out the again
Oxygen condition, drops in secondary drop oxygen：Mix that magnesium amount is tantalum powder weight 1.5%, is evacuated to more than 2 × 104Pa, is then charged with argon gas to 9
×104Pa, after being warming up to 900 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying again, acid
Wash condition 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C, obtains middle pressure tantalum powder.
Embodiment 2：
From the tantalum powder after sodium reduction as raw material, major parameter：O:1800ppm、C：20ppm、N：150ppm、Fe：
15ppm.With absolute ethyl alcohol as ball-milling medium, from the steel ball 30Kg of ф 3mm.Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clear
It is clean.Ratio of grinding media to material is controlled 6:1, load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill carries out ball milling, drum's speed of rotation
80 revs/min, Ball-milling Time 15 hours.Then suction filtration alcohol, routinely acid washing conditions pickling.Acid washing conditions：First pass：With
10%HNO3+ 0.5%HF pickling 2 hours, steeps 2 hours, pours out supernatant.Second time：It is identical with first pass.3rd time with 12%HNO3
+0.7%HF+2%H2O2Pickling 2 hours, steeps 2 hours, finally pours out supernatant, plus enough water rinses twice discharging plus pure water suction filtration.
When the electrical conductivity of diafiltration liquid is less than 30us/cm, suction filtration stops, and proceeds to baking oven and is dried.At 120 DEG C, vacuum drying 14 is little
When, in drying course, vacuum is more than 2 × 104Pa, then sieve 100 mesh.
Former powder after ball milling carries out first time heat treatment first（That is once degassing or pre-sintered）, treatment conditions：Vacuum
More than 6 × 10-3Start power transmission heating during Pa, be heated to 1050 DEG C and be incubated 120 minutes, be heated to 1350 DEG C and be incubated 60 minutes,
Sieved 80 mesh magnetic separation with jaw crushing crusher machine after being heat-treated for the first time, then adding water carries out pre- dough, treatment conditions：Add
The water of tantalum powder weight 18% is well mixed with shovel, and sieve twice of 50 mesh.Vacuum drying 15 hours, drying course at 120 DEG C of drying
Middle vacuum is 2 × 104Pa。
Then second heat treatment, treatment conditions are carried out again：Vacuum is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are incubated to 1050 DEG C, 1400 DEG C are heated to and are incubated 60 minutes, subsequently breaking up 80 mesh that sieve carries out magnesium-reduced drop oxygen, drop
Oxygen condition：Mix that magnesium amount is tantalum powder weight 3.0%, is evacuated to more than 2 × 104Pa, is then charged with argon gas to 9 × 104Pa, heats up
After 2.5 hours are incubated to 880 DEG C, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying, acid washing conditions 10%HNO again3
Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Followed by third time heat treatment is carried out, third time heat treatment condition is that vacuum is more than 6 × 10-3Start power transmission during Pa
Heating, is heated to 1050 DEG C and is incubated 60 minutes, is heated to 1450 DEG C and is incubated 60 minutes, and third time uses jaw crushing after being heat-treated
Crusher machine sieve 80 mesh, use magnetic separator magnetic separation, remove ferromagnetic material such as iron for bringing into etc. in shattering process.It is last to carry out the again
Oxygen condition, drops in secondary drop oxygen：Mix that magnesium amount is tantalum powder weight 1.5%, is evacuated to more than 2 × 104Pa, is then charged with argon gas to 9
×104Pa, after being warming up to 930 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying again, acid
Wash condition 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C, obtains middle pressure tantalum powder.
Embodiment 3：
From the tantalum powder after sodium reduction as raw material, major parameter：O:1800ppm、C：20ppm、N：150ppm、Fe：
15ppm.With absolute ethyl alcohol as ball-milling medium, from the steel ball 30Kg of ф 3mm.Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clear
It is clean.Ratio of grinding media to material is controlled 6:1, load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill carries out ball milling, drum's speed of rotation
80 revs/min, Ball-milling Time 15 hours.Then suction filtration alcohol, routinely acid washing conditions pickling, acid washing conditions：First pass：With
10%HNO3+ 0.5%HF pickling 2 hours, steeps 2 hours, pours out supernatant.Second time：It is identical with first pass.3rd time with 12%
HNO3+0.7%HF+2%H2O2Pickling 2 hours, steeps 2 hours, finally pours out supernatant, plus enough water rinses twice discharging plus pure water
Suction filtration.When the electrical conductivity of diafiltration liquid is less than 30us/cm, suction filtration stops, and proceeds to baking oven and is dried.Vacuum drying at 120 DEG C
14 hours, in drying course, vacuum was more than 2 × 104Pa, then sieve 100 mesh.
Former powder after ball milling carries out first time heat treatment first（That is once degassing or pre-sintered）, treatment conditions：Vacuum
More than 6 × 10-3Start power transmission heating during Pa, be heated to 1050 DEG C and be incubated 120 minutes, be heated to 1350 DEG C and be incubated 60 minutes,
Sieved 80 mesh magnetic separation with jaw crushing crusher machine after being heat-treated for the first time, then adding water carries out pre- dough, treatment conditions：Add
The water of tantalum powder weight 18% is well mixed with shovel, and sieve twice of 50 mesh.Vacuum drying 15 hours, drying course at 120 DEG C of drying
Middle vacuum is 2 × 104Pa。
Then second heat treatment, treatment conditions are carried out again：Vacuum is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are incubated to 1050 DEG C, 1400 DEG C are heated to and are incubated 60 minutes, subsequently breaking up 80 mesh that sieve carries out first time magnesium-reduced
Oxygen condition, drops in drop oxygen：Mix that magnesium amount is tantalum powder weight 3.0%, is evacuated to more than 2 × 104Pa, be then charged with argon gas to 9 ×
104Pa, after being warming up to 880 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying, pickling again
Condition 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Followed by third time heat treatment is carried out, third time heat treatment condition is that vacuum is more than 6 × 10-3Start power transmission during Pa
Heating, is heated to 1050 DEG C and is incubated 60 minutes, is heated to 1450 DEG C and is incubated 60 minutes, and third time uses jaw crushing after being heat-treated
Crusher machine sieve 80 mesh, use magnetic separator magnetic separation, remove ferromagnetic material such as iron for bringing into etc. in shattering process.It is last to carry out the again
Oxygen condition, drops in secondary drop oxygen：Mix that magnesium amount is tantalum powder weight 1.5%, is evacuated to more than 2 × 104Pa, is then charged with argon gas to 1
×105Pa, after being warming up to 960 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying again, acid
Wash condition 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C, obtains middle pressure tantalum powder.
Embodiment 4：
From the tantalum powder after sodium reduction as raw material, major parameter：O:1800ppm、C：20ppm、N：150ppm、Fe：
15ppm.With absolute ethyl alcohol as ball-milling medium, from the steel ball 30Kg of ф 3mm.Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clear
It is clean.Ratio of grinding media to material is controlled 6:1, load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill carries out ball milling, and ball mill turns
80 revs/min of speed, Ball-milling Time 15 hours.Then suction filtration alcohol, routinely acid washing conditions pickling, acid washing conditions：First pass：With
10%HNO3+ 0.5%HF pickling 2 hours, steeps 2 hours, pours out supernatant.Second time：It is identical with first pass.3rd time with 12%HNO3
+0.7%HF+2%H2O2Pickling 2 hours, steeps 2 hours, finally pours out supernatant, plus enough water rinses twice discharging plus pure water suction filtration.
When the electrical conductivity of diafiltration liquid is less than 30us/cm, suction filtration stops, and proceeds to baking oven and is dried.At 120 DEG C, vacuum drying 14 is little
When, in drying course, vacuum is more than 2 × 104Pa, then sieve 100 mesh.
Former powder after ball milling carries out first time heat treatment first（That is once degassing or pre-sintered）, treatment conditions：Vacuum
More than 6 × 10-3Start power transmission heating during Pa, be heated to 1050 DEG C and be incubated 120 minutes, be heated to 1350 DEG C of insulation 60min, the
Sieved 80 mesh magnetic separation with jaw crushing crusher machine after being once heat-treated, then adding water carries out pre- dough, treatment conditions：Add tantalum
The water of grain weight amount 18% is well mixed with shovel, and sieve twice of 50 mesh.Vacuum drying 15 hours at 120 DEG C of drying, in drying course
Vacuum is 2 × 104Pa。
Then second heat treatment, treatment conditions are carried out again：Vacuum is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are incubated to 1050 DEG C, 1400 DEG C are heated to and are incubated 60 minutes, subsequently breaking up 80 mesh that sieve carries out first time magnesium-reduced
Oxygen condition, drops in drop oxygen：Mix that magnesium amount is tantalum powder weight 3.0%, is evacuated to more than 2 × 104Pa, be then charged with argon gas to 1 ×
105Pa, after being warming up to 880 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying, pickling again
Condition 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Followed by third time heat treatment is carried out, third time heat treatment condition is that vacuum is more than 6 × 10-3Start power transmission during Pa
Heating, is heated to 1050 DEG C and is incubated 60 minutes, is heated to 1400 DEG C and is incubated 60 minutes, and third time uses jaw crushing after being heat-treated
Crusher machine sieve 80 mesh, use magnetic separator magnetic separation, remove ferromagnetic material such as iron for bringing into etc. in shattering process.It is last to carry out the again
Oxygen condition, drops in secondary drop oxygen：Mix that magnesium amount is tantalum powder weight 1.5%, is evacuated to more than 2 × 104Pa, is then charged with argon gas to 1
×105Pa, after being warming up to 960 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and drying again, acid
Wash condition 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C, obtains middle pressure tantalum powder.
Comparative example 1：
From the tantalum powder after sodium reduction as raw material, major parameter：O:1800ppm、C：20ppm、N：150ppm、Fe：
15ppm.With absolute ethyl alcohol as ball-milling medium, from the steel ball 30Kg of ф 3mm.Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clear
It is clean.Ratio of grinding media to material is controlled 6:1, load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill carries out ball milling, drum's speed of rotation
80 revs/min, Ball-milling Time 15 hours.Then suction filtration alcohol, routinely acid washing conditions pickling, acid washing conditions：First pass：With
10%HNO3+ 0.5%HF pickling 2 hours, steeps 2 hours, pours out supernatant.Second time：It is identical with first pass.3rd time with 12%HNO3
+0.7%HF+2%H2O2Pickling 2 hours, steeps 2 hours, finally pours out supernatant, plus enough water rinses twice discharging plus pure water suction filtration.
When the electrical conductivity of diafiltration liquid is less than 30us/cm, suction filtration stops, and proceeds to baking oven and is dried.At 120 DEG C, vacuum drying 14 is little
When, in drying course, vacuum is more than 2 × 104Pa, then sieve 100 mesh.
Former powder after ball milling carries out first time heat treatment first（That is once degassing or pre-sintered）, treatment conditions：Vacuum
More than 6 × 10-3Start power transmission heating during Pa, be heated to 1050 DEG C and be incubated 120 minutes, be heated to 1350 DEG C and be incubated 60 minutes,
Sieved 80 mesh magnetic separation with jaw crushing crusher machine after being heat-treated for the first time, then adding water carries out pre- dough, treatment conditions：Add
The water of tantalum powder weight 18% is well mixed with shovel, and sieve twice of 50 mesh.Vacuum drying 15 hours, drying course at 120 DEG C of drying
Middle vacuum is 2 × 104Pa, then carries out secondary heat treatment, treatment conditions again：Vacuum is more than 6 × 10-3Start power transmission during Pa
Heating, is heated to 1050 DEG C and is incubated 60 minutes, is heated to 1450 DEG C and is incubated 60 minutes, and subsequently breaking up 80 mesh that sieve carries out magnesium also
Oxygen condition, drops in former drop oxygen：Mix that magnesium amount is tantalum powder weight 3.0%, is evacuated to more than or equal to 2 × 104Pa, is then charged with argon
Gas is to 1 × 105Pa, after being warming up to 880 DEG C of insulations 2.5 hours, then the row's of vacuumizing magnesium 2.5 hours carry out pickling and baking again
It is dry, acid washing conditions 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 14 hours at 120 DEG C, obtains middle pressure tantalum powder.
Embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example 1 are analyzed, as a result such as Tables 1 and 2 institute
Show：
Table 1：The physical properties of tantalum powder
| Sample | Fsss（μm） | SBD(g/cc) | + 80 mesh (%) | - 325 mesh (%) |
| Embodiment 1 | 2.26 | 1.75 | 1.32 | 52.58 |
| Embodiment 2 | 2.49 | 1.88 | 1.08 | 48.40 |
| Embodiment 3 | 2.62 | 1.82 | 1.66 | 49.34 |
| Embodiment 4 | 2.51 | 1.78 | 1.56 | 50.24 |
| Comparative example 1 | 2.10 | 1.45 | 0.06 | 60.32 |
Table 2：Major impurity content in tantalum powder（Unit：ppm）
Middle pressure tantalum powder sample prepared by embodiment 1-4 and comparative example 1 is compressing, and the density of briquet is 5.5g/
cm3, fuse grain weight be 0.3g, mould：Ф 4.0mm, according to standard（GBT3137-2007 tantalum powder electrical performance test methods）Carry out
Detection.10-3The agglomerate that obtains for 30 minutes is sintered in the vacuum drying oven of Pa at 1600 DEG C 0.01%（Mass percent）Phosphoric acid
In solution, 140V energizes, and energizes 120 minutes time, temperature of energizing：90 DEG C, current density 35mA/g.Determine the electrical of each sample
Can be listed in Table 3 below.
Table 3：Electrical Property Correlation
In table 3, SHV (%) represents the cubical contraction of capacitor anode block, and VB (V) is breakdown potential during capacitor testing
The abbreviation of pressure（English full name：Breakdown voltage test or disruptive voltage test）, it is capacitor
Limiting voltage, more than this voltage, the medium in capacitor becomes conductor by breakdown.
The stereoscan photograph of the sample by shown in the Data Comparison and Fig. 1-5 of example 1 above-4 and comparative example 1 can
To find out, oxygen is dropped after being heat-treated twice by introducing, third time heat treatment is then carried out, is finally dropped the scheme of oxygen again,
Oxygen content is controlled, the granule-morphology of tantalum powder is improved, as the ultramicron shown in Fig. 5 is greatly reduced, tantalum powder particle is more
Plus it is uniform, porosity is improved, and substantially increases the resistance to sparking energy of product, improves leakage current.From 1 sample of comparative example
Product stereoscan photograph（Fig. 5）The presence of middle ultramicron is to embodiment 1 to 4（Fig. 1 to Fig. 4）The disappearance of middle ultramicron, then
The secondary advantage for embodying preparation method of the present invention.
The preparation method of the present invention meets requirement of the capacitor product to aspects such as tantalum powder proof voltage and leakage currents.This
The appropriate products of bright preparation method be 15000 μ FV/g～50000 μ FV/g capacitor level in wafer-like tantalum powder.
The specification and embodiment of the open present invention in this article is exemplary illustrated, it is obvious that for this area
For technical staff, the essential scope and spirit that the present invention also has other embodiments, the present invention is defined in the patent claims.
Claims (54)
1. a kind of preparation method of middle pressure tantalum powder, the method comprises the following steps：Tantalum powder original powder is heat-treated twice laggard
Oxygen drops in row for the first time, then carries out third time heat treatment, finally carries out second drop oxygen again.
2. preparation method according to claim 1, wherein the temperature of second drop oxygen is higher 0 DEG C than the temperature of first time drop oxygen
～100 DEG C.
3. preparation method according to claim 1, described tantalum powder original powder is sodium reduction tantalum powder.
4. preparation method according to claim 1, described tantalum powder original powder be impurity content be O≤2600ppm, C≤
The sodium reduction tantalum powder of 30ppm, N≤200ppm, Fe≤20ppm.
5. preparation method according to claim 1, also including the step of film-making, described flaking step is before the heat treatment
Carry out, by tantalum powder original powder processing slabbing, obtain flaked tantalum powder original powder.
6. preparation method according to claim 5, processing method is ball milling.
7. preparation method according to claim 6, ball milling is with absolute ethyl alcohol as ball-milling medium.
8. preparation method according to claim 6, during ball milling, the weight ratio of ball material is 3:1～8:1.
9. preparation method according to claim 6, during ball milling, the weight ratio of ball material is 6:1.
10. preparation method according to claim 6, drum's speed of rotation are 80～200 revs/min.
11. preparation methods according to claim 6, Ball-milling Time are 12～18 hours.
12. preparation methods according to claim 6, Ball-milling Time are 15 hours.
13. preparation methods according to claim 5, also including the step of conventional pickling in described flaking step.
14. preparation methods according to any one of claim 1 to 13, wherein, the treatment conditions of heat treatment are for the first time：Very
Reciprocal of duty cycle is more than 6 × 10-3Pa, 800～1400 DEG C are heated 60～240 minutes.
15. preparation methods according to claim 14, for the first time heat treatment are divided into and heating twice or thrice.
16. preparation methods according to claim 14, for the first time heat treatment are incubated 60 to be first to heat to 800～1050 DEG C
～120 minutes, then it is heated to 1250～1350 DEG C and is incubated 60～120 minutes.
17. preparation methods according to claim 14, are sieved 50～80 mesh with crusher in crushing after first time is heat-treated
And magnetic separation.
18. preparation methods according to claim 17, the disintegrating machine are jaw crusher.
19. preparation methods according to claim 14, adding water after magnetic separation carries out pre- dough, adds tantalum powder weight 10-
30% water is well mixed, and sieve 30～60 mesh, then dries.
20. preparation methods according to claim 19, drying condition are vacuum drying 10～15 hours at 100～120 DEG C.
21. preparation methods according to claim 20, in drying course, vacuum is more than or equal to 4 × 104Pa。
22. preparation methods according to any one of claim 1 to 13, wherein, the treatment conditions of second heat treatment are：Very
Reciprocal of duty cycle is more than 6 × 10-3Pa, 800～1500 DEG C are heated 60～200 minutes.
23. preparation methods according to claim 22, wherein, second heat treatment is divided into heats twice or thrice.
24. preparation methods according to claim 22, wherein, second heat treatment is protected to be first to heat to 800～1050 DEG C
Temperature 60～120 minutes, is then heated to 1350～1450 DEG C and is incubated 60～120 minutes.
25. preparation methods according to claim 22, crush 60 mesh～100 mesh that sieve after being heat-treated at second.
26. preparation methods according to claim 22, crush 80 mesh that sieve after being heat-treated at second.
27. preparation methods according to any one of claim 1 to 13, wherein described drop oxygen is magnesium-reduced drops oxygen.
28. preparation methods according to claim 27, dropping oxygen condition for the first time is：Mix magnesium amount be tantalum powder weight 1.5～
3%, the row's of vacuumizing magnesium 2～3 hours after 800～950 DEG C of heating 2～3 hours.
29. preparation methods according to claim 28, carry out pickling and drying after row's magnesium again.
30. preparation methods according to claim 29, acid washing conditions are 8～12%HNO3Pickling 1～2 hour.
31. preparation methods according to claim 29, acid washing conditions are 10%HNO3Pickling 1.5 hours.
32. preparation methods according to claim 29, drying condition are vacuum drying 8～14 hours at 100～140 DEG C.
33. preparation methods according to claim 29, drying condition are vacuum drying 8～14 hours at 120 DEG C.
34. preparation methods according to claim 29, drying condition are vacuum drying 12 hours at 120 DEG C.
35. preparation methods according to any one of claim 1 to 13, wherein the treatment conditions of third time heat treatment are vacuum
Degree is more than 6 × 10-3Pa, 800～1500 DEG C are heated 60～200 minutes.
36. preparation methods according to claim 35, third time heat treatment is divided into heats twice or thrice.
37. preparation methods according to claim 35, third time heat treatment are incubated 30 to be first to heat to 800～1050 DEG C
～60 minutes, then it is heated to 1350～1500 DEG C and is incubated 60～120 minutes.
38. preparation methods according to claim 35, are sieved 50～80 mesh with crusher in crushing after third time is heat-treated
And magnetic separation.
39. preparation methods according to claim 38, the disintegrating machine are jaw crusher.
40. preparation methods according to claim 38, are sieved 60 mesh magnetic with crusher in crushing after third time is heat-treated
Choosing.
41. preparation methods according to any one of claim 1-13, wherein, the condition of second drop oxygen is：Mixing magnesium amount is
The row's of vacuumizing magnesium 2～3 hours after the 1.5～3% of tantalum powder weight, 800～960 DEG C of heating 2～3 hours.
42. preparation methods according to claim 41, carry out pickling and drying after row's magnesium again.
43. preparation methods according to claim 42, acid washing conditions are 8～12%HNO3Pickling 1～2 hour.
44. preparation methods according to claim 42, acid washing conditions are 10%HNO3Pickling 1.5 hours.
45. are 100～140 DEG C of vacuum dryings 8～14 hours according to the preparation method of claim 42, drying condition.
46. preparation methods according to claim 42, drying condition are vacuum drying 8～14 hours at 120 DEG C.
47. preparation methods according to claim 42, drying condition are vacuum drying 12 hours at 120 DEG C.
Tantalum powder is pressed in 48. one kind, the preparation method by described in 7 any one of Claims 1-4 is prepared.
49. middle pressure tantalum powders according to claim 48, the specific volume of described middle pressure tantalum powder is 15000 μ FV/g～50000 μ
FV/g。
50. middle pressure tantalum powders according to claim 48, the specific volume of described middle pressure tantalum powder is 13000 μ FV/g～30000 μ
FV/g。
A kind of 51. electrolytic capacitors, its middle pressure tantalum powder by described in any one of claim 48 to 50 are prepared.
52. electrolytic capacitors according to claim 51, described electrolytic capacitor are solid capacitor or liquid tantalum electricity
Container.
53. electrolytic capacitors according to claim 52, the operating voltage of described solid capacitor is 10V-35V.
54. electrolytic capacitors according to claim 52, described liquid tantalum capacitor operating voltage are 25V-50V.
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