CN103894601B - A kind of preparation method for the high pressure tantalum powder for improving proof voltage energy - Google Patents
A kind of preparation method for the high pressure tantalum powder for improving proof voltage energy Download PDFInfo
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Abstract
The present invention relates to it is a kind of improve proof voltage can high pressure tantalum powder preparation method and the tantalum powder that is prepared by this method.This method includes the following steps：Tantalum powder original powder is carried out to carry out drop oxygen after being heat-treated twice, then carries out third time heat treatment.The tantalum powder prepared by the preparation method of the present invention, coating mass are improved, and leakage current characteristic is improved, dough performance is good, mobility improves, and the improvement of coating mass substantially increases the voltage-resistent characteristic of tantalum powder so that it can using under higher operating voltage.
Description
Technical field
The invention belongs to capacitor level high pressure tantalum powder production fields, and in particular to a kind of high pressure for improving proof voltage energy
The preparation method of powder and the tantalum powder prepared by this method.
Background technology
Metal tantalum is a kind of valve metal, it can have the property of unilateal conduction in one layer of fine and close oxidation film of Surface Creation
Matter.Anode film stable chemical performance made of tantalum powder (particularly stablizing in acidic electrolyte bath), resistivity height (7.5 × 1010
Ω cm), dielectric constant big (27.6), leakage current it is small, in addition also there is operating temperature range wide (- 80~200 DEG C), reliability
High, the advantages that antidetonation and service life are long, be to make the ideal material of tantalum capacitor small, reliability is high.Due to tantalum electricity
Container has the advantages of many, therefore is used widely in the electronic equipments such as Aeronautics and Astronautics, communication, computer, mobile phone.
The large-scale production of tantalum powder has the history of more than 70 years, but the development of mass rapid degree only has 50 years or so.It is early
In 1904, just once reduction with carbon tantalum pentoxide, reduzate refined people through vacuum high-temperature, 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 with traditional handicraft be electrolysed tantalum powder grain shape it is simple, particle is coarse, specific volume is low, it is impossible to meet electronics industry to height
The requirement of capacity tantalum powder.The methods of tantalum oxide carbon thermal reduction, tantalic chloride hydrogen reduction and aluminothermic reduction, all could not also be used for work
Industry produces.And tantalum powder prepared by sodium reduction has the characteristics that purity is high, grain shape is complicated, specific volume is high, it has also become prepare tantalum both at home and abroad
The main production of powder.At present world's tantalum powder manufacturer mainly have the U.S. Cabot groups, Germany HCST groups and in
The Dongfang Tantalum Industry Co., Ltd., Ningxia Hui autonomy Region of state.
On material classification, the tantalum powder for being specifically used to make capacitor is referred to as Ta powder used in capacitor.Tantalum powder makes according to it
With voltage it is different can be divided into again high pressure tantalum powder (more than operating voltage 35V), mesolow high specific capacitance tantalum powder (operating voltage 25V with
Under).The application of tantalum powder on the capacitor accounts for about the 60%~70% of world's tantalum aggregate consumption.Especially in recent years, with calculating
The rapid development of machine and electronics industry is always maintained at stablizing ascendant trend to the demand of tantalum powder, it is contemplated that in 5 from now on
In~10 years, global tantalum industry will continue to develop with annual more than 15% speed.
The 63V series produced by electron-beam smelting, hydrogenation, milling method is wherein primarily referred to as the high pressure tantalum powder of military products
Tantalum powder, between operating voltage use scope extends to 50V-75V, space flight, aviation, military field important role.
Some operating voltage is the high pressure tantalum powder of 35V-50V, mainly higher including middle wafer-like tantalum powder and some other pressure resistance
Tantalum powder.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's grade capacitor level tantalum
Powder still remains growing trend, becomes a large focal spot of our concerns.The development of army's grade Ta powder used in capacitor and NPD projects
An important directions for extending into our next step, the promotion of electrical property is particularly important.
In order to understand the preparation method of high pressure tantalum metal powder, we analyze domestic and international patent.
Patent US4017302 discloses a kind of preparation method of high pressure tantalum metal powder.This method idiographic flow is tantalum ingot
Hydrogenate, grind, be classified sieving, dehydrogenation the pre-heat treatment, crushed 80 mesh sieves, dough, it is broken, cross 35 mesh, 250 mesh, then -250
Mesh mutually mixes dough, test, product again with -35/+25 mesh powder.Tantalum powder prepared by this method is relatively specific for high pressure low capacity tantalum powder
(63V)。
Patent US4141719 discloses a kind of preparation method of high pressure tantalum metal powder.This method is by the hydrogenation of tantalum ingot, mill
Broken, classification, mill sieve, crosses 35 mesh, mixing at dehydrogenation (1200 DEG C), and tantalum powder apparent density prepared by this method is big, and oxygen content is low, embryo
Bulk strength is high, the leakage current of sintered anode is low, 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 performance improves.The powder contains the sheet tantalum of 20-40%
Powder and 70% granular tantalum powder are heat-treated 5~120 minutes before mixing at 1250 DEG C~1550 DEG C.The secondary dough of tantalum powder is mixed, is changed
It has been apt to processing performance.Tantalum powder prepared by this method is relatively specific for medium operating voltage (20V~35V).
Patent US4740238 is related to a kind of tantalum powder containing flake powder.Specific preparation process：Tantalum powder degassing, film-making (ball milling,
Wet-milling), pickling, screening, p-doped, primary heat treatment, mill sieve, p-doped, secondary heat treatment, mill sieve, Mg restore.Prepared by this method
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.This method, which is used, carries gas by tantalum
Powder is sent into plasma reaction area, sprays into vacuum tank and cools down, and spherical tantalum powder, pickling, 1000~1250 DEG C of heat treatments are made.The tantalum
300~450V of powder pressure resistance.Tantalum powder mouldability prepared by this method is very poor.
At present, the preparation method of high pressure tantalum powder is more diversified, but numerous preparation methods has shortcoming,
It comments in front.
As mentioned above, although the existing method for making metal powder describes the processing side of several high pressure tantalum powders
Method, but these methods are to being only applicable to sub-fraction high pressure tantalum powder.And the technique of another high pressure tantalum powder as described above
It is difficult tantalum powder poor performance obtained or obtained.
Invention content
To solve the above-mentioned problems, inventor proposes solution below by concentrating on studies, testing：In tantalum powder original powder
Oxygen is dropped after secondary heat treatment, is then heat-treated three times.The advantage of the program be by drop oxygen make oxygen inside tantalum powder to
Particle surface migrates, and reduces the oxygen content of tantalum inside particles, the main purpose of heat treatment process three times then carried out is to make oxygen
Change film to thicken and repair defective oxidation film, reduce the breakdown chance of product, reduce the leakage current of product.
For this purpose, the first aspect of the present invention provides a kind of preparation method of high pressure tantalum powder, this method includes the following steps：It is right
Tantalum powder original powder carries out carrying out drop oxygen after being heat-treated twice, then carries out third time heat treatment.
The preparation method according to a first aspect of the present invention, wherein the temperature of third time heat treatment is heat-treated than second
Temperature it is 0 DEG C~150 DEG C low, preferably 20~100 DEG C low (such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C or 80 DEG C).
The preparation method according to a first aspect of the present invention, wherein the tantalum powder original powder is sodium reduction tantalum powder or tantalum ingot
The fine grained tantalum powder of hydrogenation,
It is preferred that in the sodium reduction tantalum powder impurity content for O≤1500ppm, C≤20ppm, N≤60ppm, Fe≤
20ppm,
It is preferred that in the fine grained tantalum powder of described tantalum ingot hydrogenation impurity content be O≤1000ppm, C≤15ppm, N≤
40ppm、Fe≤10ppm。
According to aforementioned first aspect present invention any one of them preparation method, the step of further including film-making, the system
Piece step carries out before the heat treatment, and tantalum powder original powder is processed slabbing, obtains flaked tantalum powder original powder.
Preferred processing method is ball milling, and preferably using absolute ethyl alcohol as ball-milling medium, the weight ratio of preferred ball material is 3:1
~8:1 (such as 6:1), preferably drum's speed of rotation be 80~200 revs/min, preferred Ball-milling Time for 12~18 hours (such as
15 hours).
According to aforementioned first aspect present invention any one of them preparation method, routine is further included in the flaking step
The step of pickling.Acid washing conditions：First pass：Use 5-15%HNO3+ 0.3-0.7%HF pickling 2-3 hours is steeped 1-2 hours, is poured out
Supernatant.Second time：It is identical with first pass.Third time uses 5-15%HNO3+ 0.3-0.7%HF+1-2%H2O2Pickling 2-3 is small
When, it steeps 1-2 hours, finally pours out supernatant, enough water is added to rinse twice of discharging plus pure water suction filtration.When the conductivity of diafiltration liquid is small
When 30us/cm, filter and stop, being transferred to baking oven and dried.Vacuum drying 12-15 hours at 120 DEG C -160 DEG C, drying course
Middle vacuum degree is greater than or equal to 4 × 104Pa, be then sieved 80-100 mesh.
According to aforementioned first aspect present invention any one of them preparation method, wherein, the processing item being heat-treated for the first time
Part is：Vacuum degree is more than 6 × 10-3Pa, 500~1500 DEG C of heat treatments (can be heated, such as first be added for 60~360 minutes in three times
Heat keeps the temperature 60~120 minutes to 500~800 DEG C, is heated to 800~1000 DEG C and keeps the temperature 60~120 minutes, then reheats
60~120 minutes are kept the temperature to 1050~1300 DEG C；It can also heat in two times, such as be first to heat to 500~800 DEG C, heat preservation 60
~120 minutes, it is heated to 900~1300 DEG C and keeps the temperature 60~120 minutes),
Preferably, with crusher (such as jaw crusher) 50~80 mesh of broken sieving and magnetic after being heat-treated in first time
Choosing,
It is preferred that water is added to carry out pre- dough after magnetic separation, the water for adding in tantalum powder weight 10-30% (such as 20%) is uniformly mixed,
Be sieved 30~60 mesh (such as 50 mesh twice), then dry, preferred drying condition be vacuum drying 10 at 100~120 DEG C~
15 hours, vacuum degree was greater than or equal to 4 × 10 preferably in drying course4Pa (such as 2 × 104Pa)。
According to aforementioned first aspect present invention any one of them preparation method, wherein, the processing item of second of heat treatment
Part is：Vacuum degree is more than 6 × 10-3Pa, 800~1500 DEG C of heat treatments (can be heated, such as first be added for 60~200 minutes in two times
Heat keeps the temperature 60~120 minutes to 800~1000 DEG C, is heated to 1100~1500 DEG C and keeps the temperature 60~120 minutes；Three can also be divided
Secondary heating, such as be first to heat to 800~1000 DEG C and keep the temperature 60~120 minutes, it is heated to 1100~1350 DEG C of heat preservations 30~60
Minute, then it is heated to 1400~1500 DEG C and keeps the temperature 60~120 minutes),
It is preferred that the mesh (such as 80 mesh) of 60 mesh of sieving~100 is crushed after being heat-treated second.
According to aforementioned first aspect present invention any one of them preparation method, wherein the drop oxygen is dropped for magnesium-reduced
Oxygen, preferably in inert gas, (such as argon gas, pressure can be 9 × 104Pa~1.2 × 105Pa drop oxygen) is carried out in atmosphere.
Preferably, drop oxygen condition is：Mix 0.5~3% (such as 1.5%, 1%) that magnesium amount is tantalum powder weight, 900~1000
The row's of vacuumizing magnesium 2~3 hours after DEG C (such as 960 DEG C or 980 DEG C) heat 2~3 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 100~140 DEG C (such as 120 DEG C) under vacuum drying 8~
14 hours (such as 12 hours).
According to aforementioned first aspect present invention any one of them preparation method, wherein the treatment conditions of third time heat treatment
For：Vacuum degree is more than 6 × 10-3Pa, 800~1500 DEG C of heat treatments (can be heated, such as first be heated for 60~200 minutes in two times
60~120 minutes are kept the temperature to 800~1000 DEG C, 1100~1500 DEG C is heated to and keeps the temperature 60~120 minutes；It can also be in three times
Heating, such as be first to heat to 800~1000 DEG C and keep the temperature 60~120 minutes, it is heated to 1100~1350 DEG C and keeps the temperature 30~60 points
Then clock is heated to 1400~1500 DEG C and keeps the temperature 60~120 minutes),
It is preferred that with 50~80 mesh of the broken sieving of crusher (such as jaw crusher) (such as 60 after third time is heat-treated
Mesh) and magnetic separation.
The second aspect of the present invention provides a kind of high pressure tantalum powder, is prepared by aforementioned first aspect present invention any one of them
Method obtains.The specific volume of the high pressure tantalum powder is the μ FV/g of 2500 μ FV/g~15000, preferably specific volume for 3000 μ FV/g~
10000μFV/g。
The third aspect of the present invention provides a kind of electrolytic capacitor, by aforementioned second aspect of the present invention any one of them
High pressure tantalum powder is prepared.The electrolytic capacitor is solid capacitor or liquid tantalum capacitor.The solid capacitor
Operating voltage for 30~63V, the operating voltage of the liquid tantalum capacitor is 50~150V.
The preparation method of the present invention is suitable for high pressure tantalum powder of the specific volume for the μ FV/g of 2500 μ FV/g~15000, preferably specific volume
High pressure tantalum powder (such as 4000 μ FV/g~5500 μ FV/g) for the μ FV/g of 3000 μ FV/g~10000.It is prepared by the present invention resistance to
The operating voltage for the solid electrolytic capacitor that high pressure tantalum powder makes is in 30~63V, 50~150V of liquid tantalum capacitor operating voltage.
The preparation method of the present invention is very different with the prior art, and preparation method of the invention is using hot three times
Treatment process, particularly last time are using heat treatment rather than drop oxygen.The tantalum powder prepared by the preparation method of the present invention,
Coating mass is improved, and leakage current characteristic is improved, and dough performance is good, and mobility improves.The improvement of coating mass
The voltage-resistent characteristic of tantalum powder is substantially increased so that it can using under higher operating voltage.
In the present invention, unless explicitly stated otherwise, % refers to mass percent.
In the present invention, when the granularity that powder is represented with mesh number, "+" or "-" number before mesh number represent " logical respectively
But " or the sieve of " passing through " described mesh number.For example, " -60 mesh " represents the sieve by 60 mesh, and "+200 mesh " represents to lead to not
Cross the sieve of 200 mesh.
The analytical equipment of involved parameters and model are as shown in the table in the present invention：
| 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 |
| K | Atomic absorption instrument | FS240 |
Specific embodiment mode
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 only for the feature and advantage that further illustrate the present invention rather than to the claims in the present invention model
The limitation enclosed.
The raw material selected in example 1 below -4 and comparative example 5 be with a batch of sodium reduction tantalum powder, embodiment 6-9 and
The raw material selected in comparative example 10 is the fine grained tantalum powder hydrogenated with a batch of tantalum ingot, to illustrate the preparation method of the present invention
Technique effect and advantage.
Embodiment 1：
Using the tantalum powder after sodium reduction as raw material, raw material selection：O≤1500ppm、C≤20ppm、N≤60ppm、Fe≤
20ppm, Fei Shi average grain diameter (FSSS)：1.5-5.0μm.Using absolute ethyl alcohol as ball-milling medium, the steel ball 30Kg of ф 4mm is selected.
Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill and is carried out
Ball milling, 200 revs/min of drum's speed of rotation, Ball-milling Time 5 hours.Then alcohol, routinely acid washing conditions pickling, pickling are filtered
Condition：First pass：Use 10%HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time：With first pass phase
Together.Third time uses 15%HNO3+ 0.7%HF+1.5%H2O2Pickling 2 hours steeps 2 hours, finally pours out supernatant, add enough water
Twice of discharging of rinsing plus pure water filter.When the conductivity of diafiltration liquid is less than 30us/cm, filters and stop, being transferred to baking oven and dried
It is dry.Vacuum drying 12 hours at 120 DEG C, vacuum degree is greater than or equal to 4 × 10 in drying course4Pa, be then sieved 100 mesh.
Original powder after ball milling carries out first time heat treatment, and treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 800 DEG C and keeps the temperature 60 minutes, is heated to 1000 DEG C and keeps the temperature 120 minutes, is again heated to 1300 DEG C and keeps the temperature 60 points
Clock with jaw crushing crusher machine 80 mesh of sieving and magnetic separation after being heat-treated for the first time, removes the ferromagnetism object brought into shattering process
Matter such as iron etc..
Then it carries out being heat-treated for second, treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are kept the temperature to 1000 DEG C, 1350 DEG C is heated to and keeps the temperature 30 minutes, 1500 DEG C is again heated to and keeps the temperature 60 minutes, second
After heat treatment with jaw crushing crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove the ferromagnetic material brought into shattering process
Such as iron.Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Magnesium amount is tantalum powder weight 1.5% is mixed, stove argon filling after evacuation
Protection, stove pressure 9 × 104Pa, then heat to 960 DEG C heat preservation 3 hours after, the row's of vacuumizing magnesium 3 hours at 960 DEG C.Then
Pickling and drying, acid washing conditions 10%HNO are carried out again3Pickling 1.5 hours.Drying condition is that vacuum drying 12 is small at 120 DEG C
When.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1480 DEG C and keeps the temperature 60 minutes, jaw crushing is used after being heat-treated three times
Crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..Obtain reuniting compared with
Tantalum powder product good, oxidation film is good.
Embodiment 2：
Using the tantalum powder after sodium reduction as raw material, raw material selection：O≤1500ppm、C≤20ppm、N≤60ppm、Fe≤
20ppm, Fei Shi average grain diameter (FSSS)：1.5-5.0μm.Using absolute ethyl alcohol as ball-milling medium, the steel ball 30Kg of ф 4mm is selected.
Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill and is carried out
Ball milling, 200 revs/min of drum's speed of rotation, Ball-milling Time 5 hours.Then alcohol, routinely acid washing conditions pickling, pickling are filtered
Condition：First pass：Use 10%HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time：With first pass phase
Together.Third time uses 15%HNO3+ 0.7%HF+1.5%H2O2Pickling 2 hours steeps 2 hours, finally pours out supernatant, add enough water
Twice of discharging of rinsing plus pure water filter.When the conductivity of diafiltration liquid is less than 30us/cm, filters and stop, being transferred to baking oven and dried
It is dry.Vacuum drying 12 hours at 120 DEG C, vacuum degree is greater than or equal to 4 × 10 in drying course4Pa, be then sieved 100 mesh.
Original powder after ball milling carries out first time heat treatment, and the condition of heat treatment is for the first time：Vacuum degree is more than 6 × 10-3Pa
When start power transmission heating, be heated to 800 DEG C keep the temperature 60 minutes, be heated to 1000 DEG C keep the temperature 120 minutes, be heated to 1300 DEG C
Heat preservation 60 minutes, with jaw crushing crusher machine 80 mesh of sieving and magnetic separation after being heat-treated for the first time.
Then it carries out being heat-treated for second, treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are kept the temperature to 1000 DEG C, 1350 DEG C is heated to and keeps the temperature 30 minutes, 1500 DEG C is again heated to and keeps the temperature 60 minutes, then make
60 mesh of powder, magnetic separation.Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Magnesium amount is tantalum powder weight 1.5% is mixed, stove is evacuating
Argon-filled protection afterwards, stove pressure 9 × 104Pa, then heat to 960 DEG C heat preservation 3 hours after, the row's of vacuumizing magnesium 3 is small at 960 DEG C
When, pickling and drying, acid washing conditions 10%HNO are then carried out again3Pickling 1.5 hours.Drying condition is that vacuum is dried at 120 DEG C
It is 12 hours dry.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1450 DEG C and keeps the temperature 60 minutes, third time is broken after being heat-treated with jaw
Broken crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..Obtain reuniting compared with
Tantalum powder product good, oxidation film is good.
Embodiment 3：
Using the tantalum powder after sodium reduction as raw material, raw material selection：O≤1500ppm、C≤20ppm、N≤60ppm、Fe≤
20ppm, Fei Shi average grain diameter (FSSS)：1.5-5.0μm.Using absolute ethyl alcohol as ball-milling medium, the steel ball 30Kg of ф 4mm is selected.
Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill and is carried out
Ball milling, 200 revs/min of drum's speed of rotation, Ball-milling Time 5 hours.Then alcohol, routinely acid washing conditions pickling, pickling are filtered
Condition：First pass：Use 10%HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time：With first pass phase
Together.Third time uses 15%HNO3+ 0.7%HF+1.5%H2O2Pickling 2 hours steeps 2 hours, finally pours out supernatant, add enough water
Twice of discharging of rinsing plus pure water filter.When the conductivity of diafiltration liquid is less than 30us/cm, filters and stop, being transferred to baking oven and dried
It is dry.Vacuum drying 12 hours at 120 DEG C, vacuum degree is greater than or equal to 4 × 10 in drying course4Pa, be then sieved 100 mesh.
Original powder after ball milling carries out first time heat treatment, and first time heat treatment condition is：Vacuum degree is more than 6 × 10-3During Pa
Start power transmission heating, be heated to 800 DEG C and keep the temperature 60 minutes, be heated to 1000 DEG C and keep the temperature 120 minutes, be again heated to 1300 DEG C
Heat preservation 60 minutes, with jaw crushing crusher machine 80 mesh of sieving and magnetic separation after being heat-treated for the first time.
Then it carries out being heat-treated for second, second of heat treatment condition is：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1350 DEG C and keeps the temperature 30 minutes, is again heated to 1500 DEG C and keeps the temperature 60 points
Clock, 60 mesh of powder sieving processed, magnetic separation after second of heat treatment.Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：It is tantalum powder to mix magnesium amount
The 1.5% of weight, stove argon-filled protection after evacuation, stove pressure 9 × 104Pa, then heat to 960 DEG C heat preservation 3 hours after,
Then the row's of vacuumizing magnesium 3 hours at 960 DEG C carry out pickling and drying, acid washing conditions 10%HNO again3Pickling 1.5 hours.It dries
Dry condition is vacuum drying 12 hours at 120 DEG C.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1500 DEG C and keeps the temperature 60 minutes, third time is broken after being heat-treated with jaw
Broken crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..Obtain reuniting compared with
Tantalum powder product good, oxidation film is good.
Embodiment 4：
Using the tantalum powder after sodium reduction as raw material, raw material selection：O≤1500ppm、C≤20ppm、N≤60ppm、Fe≤
20ppm, Fei Shi average grain diameter (FSSS)：1.5-5.0μm.Using absolute ethyl alcohol as ball-milling medium, the steel ball 30Kg of ф 4mm is selected.
Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill and is carried out
Ball milling, 200 revs/min of drum's speed of rotation, Ball-milling Time 5 hours.Then alcohol, routinely acid washing conditions pickling, pickling are filtered
Condition：First pass：Use 10%HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time：With first pass phase
Together.Third time uses 15%HNO3+ 0.7%HF+1.5%H2O2Pickling 2 hours steeps 2 hours, finally pours out supernatant, add enough water
Twice of discharging of rinsing plus pure water filter.When the conductivity of diafiltration liquid is less than 30us/cm, filters and stop, being transferred to baking oven and dried
It is dry.Vacuum drying 12 hours at 120 DEG C, vacuum degree is greater than or equal to 4 × 10 in drying course4Pa, be then sieved 100 mesh.
Original powder after ball milling carries out first time heat treatment, first time heat treatment condition is：Vacuum degree is more than 6 × 10-3During Pa
Start power transmission heating, be heated to 800 DEG C and keep the temperature 60 minutes, be heated to 1000 DEG C and keep the temperature 120 minutes, be again heated to 1300 DEG C
Heat preservation 60 minutes, with jaw crushing crusher machine 80 mesh of sieving and magnetic separation after being heat-treated for the first time.
Then it carries out being heat-treated for second, second of heat treatment condition is：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1350 DEG C and keeps the temperature 30 minutes, is again heated to 1500 DEG C and keeps the temperature 60 points
Clock, 60 mesh of powder sieving processed, magnetic separation after second of heat treatment.Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：It is tantalum powder to mix magnesium amount
The 1.5% of weight, stove argon-filled protection after evacuation, stove pressure 9 × 104Pa, then heat to 960 DEG C heat preservation 3 hours after,
Then the row's of vacuumizing magnesium 3 hours at 960 DEG C carry out pickling and drying, acid washing conditions 10%HNO again3Pickling 1.5 hours.It dries
Dry condition is vacuum drying 12 hours at 120 DEG C.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1520 DEG C and keeps the temperature 60 minutes, third time is broken after being heat-treated with jaw
Broken crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..Obtain reuniting compared with
Tantalum powder product good, oxidation film is good.
Comparative example 5：
Using the tantalum powder after sodium reduction as raw material, raw material selection：O≤1500ppm、C≤20ppm、N≤60ppm、Fe≤
20ppm, Fei Shi average grain diameter (FSSS)：1.5-5.0μm.Using absolute ethyl alcohol as ball-milling medium, the steel ball 30Kg of ф 4mm is selected.
Ensure that ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted tantalum powder 5Kg is added in the ball milling bucket of ball mill and is carried out
Ball milling, 200 revs/min of drum's speed of rotation, Ball-milling Time 5 hours.Then alcohol, routinely acid washing conditions pickling, pickling are filtered
Condition：First pass：Use 10%HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time：With first pass phase
Together.Third time uses 15%HNO3+ 0.7%HF+1.5%H2O2Pickling 2 hours steeps 2 hours, finally pours out supernatant, add enough water
Twice of discharging of rinsing plus pure water filter.When the conductivity of diafiltration liquid is less than 30us/cm, filters and stop, being transferred to baking oven and dried
It is dry.Vacuum drying 12 hours at 120 DEG C, vacuum degree is greater than or equal to 4 × 10 in drying course4Pa, be then sieved 100 mesh.
Original powder after ball milling carries out first time heat treatment, first time heat treatment condition is：Vacuum degree is more than 6 × 10-3During Pa
Start power transmission heating, be heated to 800 DEG C and keep the temperature 60 minutes, be heated to 1000 DEG C and keep the temperature 120 minutes, be again heated to 1300 DEG C
Heat preservation 60 minutes, with jaw crushing crusher machine 80 mesh of sieving and magnetic separation after being heat-treated for the first time.Then it carries out being heat-treated for second,
Second of heat treatment condition be：Vacuum degree is more than 6 × 10-3Start power transmission heating during Pa, be heated to 1000 DEG C and keep the temperature 60 minutes, then
Be heated to 1350 DEG C and keep the temperature 30 minutes, then 60 minutes are kept the temperature from being heated to 1500 DEG C, second be heat-treated after powder processed be sieved 60 mesh,
Magnetic separation.Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Magnesium amount is tantalum powder weight 1.5% is mixed, stove argon filling after evacuation is protected
Shield, stove pressure 9 × 104Pa, then heat to 960 DEG C heat preservation 3 hours after, the row's of vacuumizing magnesium 3 hours, Ran Houzai at 960 DEG C
Secondary progress pickling and drying, acid washing conditions 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Finally obtain tantalum powder product.
Embodiment 6：
Using the fine grained tantalum powder of tantalum ingot hydrogenation as raw material, raw material selection：O≤1000ppm、C≤15ppm、N≤40ppm、Fe
≤ 10ppm, Fei Shi average grain diameter (FSSS)：3.0-6.5μm.Pickling impurity removal, acid washing conditions are carried out first：First pass：With 10%
HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time with 15%HNO3+ 0.7%HF+1.0%H2O2Acid
It washes 2 hours, steeps 2 hours, finally pour out supernatant, enough water is added to rinse twice of discharging plus pure water suction filtration.When the conductance of diafiltration liquid
When rate is less than 30us/cm, filters and stop, being transferred to baking oven and dried.Vacuum drying 12 hours at 120 DEG C, it is true in drying course
Reciprocal of duty cycle is greater than or equal to 4 × 104Pa, be then sieved 100 mesh.
Then first time heat treatment is carried out, first time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 600 DEG C and keeps the temperature 60 minutes, is heated to 800 DEG C and keeps the temperature 120 minutes, is again heated to 1050 DEG C and keeps the temperature 120 points
Clock, with jaw crushing crusher machine 60 mesh of sieving and magnetic separation after primary heat treatment
It then carries out being heat-treated for second, treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are kept the temperature to 1000 DEG C, 1480 DEG C is heated to and keeps the temperature 60 minutes, powder processed crosses 60 mesh sieve, magnetic separation after second of heat treatment.
Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Mix magnesium amount is tantalum powder weight 1.0%, stove argon-filled protection after evacuation, stove
Sub- pressure 9 × 104Pa, then heat to 980 DEG C heat preservation 3 hours after, then the row's of vacuumizing magnesium 3 hours at 980 DEG C carry out again
Pickling and drying, acid washing conditions 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1450 DEG C and keeps the temperature 60 minutes, third time is broken after being heat-treated with jaw
Broken crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..The group of finally obtaining
Poly- tantalum powder product preferable, oxidation film is good.
Embodiment 7：
Using the fine grained tantalum powder of tantalum ingot hydrogenation as raw material, raw material selection：O≤1000ppm、C≤15ppm、N≤40ppm、Fe
≤ 10ppm, Fei Shi average grain diameter (FSSS)：3.0-6.5μm.Pickling impurity removal, acid washing conditions are carried out first：First pass：With 10%
HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time with 15%HNO3+ 0.7%HF+1.0%H2O2Acid
It washes 2 hours, steeps 2 hours, finally pour out supernatant, enough water is added to rinse twice of discharging plus pure water suction filtration.When the conductance of diafiltration liquid
When rate is less than 30us/cm, filters and stop, being transferred to baking oven and dried.Vacuum drying 12 hours at 120 DEG C, it is true in drying course
Reciprocal of duty cycle is greater than or equal to 4 × 104Pa, be then sieved 100 mesh.
Then first time heat treatment is carried out, first time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 600 DEG C and keeps the temperature 60 minutes, is heated to 800 DEG C and keeps the temperature 120 minutes, is again heated to 1050 DEG C and keeps the temperature 120 points
Clock, with jaw crushing crusher machine 60 mesh of sieving and magnetic separation after being heat-treated for the first time.
It then carries out being heat-treated for second, treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are kept the temperature to 1000 DEG C, 1480 DEG C is heated to and keeps the temperature 60 minutes, powder processed crosses 60 mesh sieve, magnetic separation after second of heat treatment.
Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Mix magnesium amount is tantalum powder weight 1.0%, stove argon-filled protection after evacuation, stove
Sub- pressure 9 × 104Pa, then heat to 980 DEG C heat preservation 3 hours after, then the row's of vacuumizing magnesium 3 hours at 980 DEG C carry out again
Pickling and drying, acid washing conditions 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1420 DEG C and keeps the temperature 60 minutes, third time is broken after being heat-treated with jaw
Broken crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..The group of finally obtaining
Poly- tantalum powder product preferable, oxidation film is good.
Embodiment 8：
Using the fine grained tantalum powder of tantalum ingot hydrogenation as raw material, raw material selection：O≤1000ppm、C≤15ppm、N≤40ppm、Fe
≤ 10ppm, Fei Shi average grain diameter (FSSS)：3.0-6.5μm.Pickling impurity removal, acid washing conditions are carried out first：First pass：With 10%
HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time with 15%HNO3+ 0.7%HF+1.0%H2O2Acid
It washes 2 hours, steeps 2 hours, finally pour out supernatant, enough water is added to rinse twice of discharging plus pure water suction filtration.When the conductance of diafiltration liquid
When rate is less than 30us/cm, filters and stop, being transferred to baking oven and dried.Vacuum drying 12 hours at 120 DEG C, it is true in drying course
Reciprocal of duty cycle is greater than or equal to 4 × 104Pa, be then sieved 100 mesh.
Then first time heat treatment is carried out, first time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 600 DEG C and keeps the temperature 60 minutes, is heated to 800 DEG C and keeps the temperature 120 minutes, is again heated to 1050 DEG C and keeps the temperature 120 points
Clock, with jaw crushing crusher machine 60 mesh of sieving and magnetic separation after being heat-treated for the first time.
It then carries out being heat-treated for second, treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are kept the temperature to 1000 DEG C, 1480 DEG C is heated to and keeps the temperature 60 minutes, powder processed crosses 60 mesh sieve, magnetic separation after second of heat treatment.
Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Mix magnesium amount is tantalum powder weight 1.0%, stove argon-filled protection after evacuation, stove
Sub- pressure 9 × 104Pa, then heat to 980 DEG C heat preservation 3 hours after, then the row's of vacuumizing magnesium 3 hours at 980 DEG C carry out again
Pickling and drying, acid washing conditions 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1480 DEG C and keeps the temperature 60 minutes, third time is broken after being heat-treated with jaw
Broken crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..The group of finally obtaining
Poly- tantalum powder product preferable, oxidation film is good.
Embodiment 9：
Using the fine grained tantalum powder of tantalum ingot hydrogenation as raw material, raw material selection：O≤1000ppm、C≤15ppm、N≤40ppm、Fe
≤ 10ppm, Fei Shi average grain diameter (FSSS)：3.0-6.5μm.Pickling impurity removal, acid washing conditions are carried out first：First pass：With 10%
HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time with 15%HNO3+ 0.7%HF+1.0%H2O2Acid
It washes 2 hours, steeps 2 hours, finally pour out supernatant, enough water is added to rinse twice of discharging plus pure water suction filtration.When the conductance of diafiltration liquid
When rate is less than 30us/cm, filters and stop, being transferred to baking oven and dried.Vacuum drying 12 hours at 120 DEG C, it is true in drying course
Reciprocal of duty cycle is greater than or equal to 4 × 104Pa, be then sieved 100 mesh.
Then first time heat treatment is carried out, first time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 600 DEG C and keeps the temperature 60 minutes, is heated to 800 DEG C and keeps the temperature 120 minutes, is again heated to 1050 DEG C and keeps the temperature 120 points
Clock, with jaw crushing crusher machine 60 mesh of sieving and magnetic separation after being heat-treated for the first time.
It then carries out being heat-treated for second, treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are kept the temperature to 1000 DEG C, 1480 DEG C is heated to and keeps the temperature 60 minutes, 60 mesh of powder sieving processed, magnetic separation after second of heat treatment.
Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Mix magnesium amount is tantalum powder weight 1.0%, stove argon-filled protection after evacuation, stove
Sub- pressure 9 × 104Pa, then heat to 980 DEG C heat preservation 3 hours after, then the row's of vacuumizing magnesium 3 hours at 980 DEG C carry out again
Pickling and drying, acid washing conditions 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.
Third time heat treatment is finally carried out again, and third time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start to send during Pa
Electrical heating is heated to 1000 DEG C and keeps the temperature 60 minutes, is heated to 1500 DEG C and keeps the temperature 60 minutes, third time is broken after being heat-treated with jaw
Broken crusher machine be sieved 60 mesh, with magnetic separator magnetic separation, remove ferromagnetic material such as iron brought into shattering process etc..The group of finally obtaining
Poly- tantalum powder product preferable, oxidation film is good.
Comparative example 10：
Using the fine grained tantalum powder of tantalum ingot hydrogenation as raw material, raw material selection：O≤1000ppm、C≤15ppm、N≤40ppm、Fe
≤ 10ppm, Fei Shi average grain diameter (FSSS)：3.0-6.5μm.Pickling impurity removal, acid washing conditions are carried out first：First pass：With 10%
HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant.Second time with 15%HNO3+ 0.7%HF+1.0%H2O2Acid
It washes 2 hours, steeps 2 hours, finally pour out supernatant, enough water is added to rinse twice of discharging plus pure water suction filtration.When the conductance of diafiltration liquid
When rate is less than 30us/cm, filters and stop, being transferred to baking oven and dried.Vacuum drying 12 hours at 120 DEG C, it is true in drying course
Reciprocal of duty cycle is greater than or equal to 4 × 104Pa, be then sieved 100 mesh.
Then first time heat treatment is carried out, first time heat treatment condition is：Vacuum degree is more than 6 × 10-3Start power transmission during Pa
Heating is heated to 600 DEG C and keeps the temperature 60 minutes, is heated to 800 DEG C and keeps the temperature 120 minutes, is again heated to 1050 DEG C and keeps the temperature 120 points
Clock, with jaw crushing crusher machine 60 mesh of sieving and magnetic separation after being heat-treated for the first time.
It then carries out being heat-treated for second, treatment conditions are：Vacuum degree is more than 6 × 10-3Start power transmission heating, heating during Pa
60 minutes are kept the temperature to 1000 DEG C, 1480 DEG C is heated to and keeps the temperature 60 minutes, 60 mesh of powder sieving processed, magnetic separation after second of heat treatment.
Drop oxygen is carried out after being heat-treated twice, drops oxygen condition：Mix magnesium amount is tantalum powder weight 1.0%, stove argon-filled protection after evacuation, stove
Sub- pressure 9 × 104Pa, then heat to 980 DEG C heat preservation 3 hours after, then the row's of vacuumizing magnesium 3 hours at 980 DEG C carry out again
Pickling and drying, acid washing conditions 10%HNO3Pickling 1.5 hours.Drying condition is vacuum drying 12 hours at 120 DEG C.Finally
To high pressure tantalum powder product.
Since the embodiment of the present invention relates to two grade tantalum powders, the content of analysis is slightly different, therefore is divided into two groups
It is analyzed.
Embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example 5 (first group) are analyzed, it is as a result as follows：
Table 1：The physical properties of tantalum powder
| Sample | Fsss(μm) | SBD(g/cc) | + 80 mesh (%) | - 325 mesh (%) |
| Embodiment 1 | 5.72 | 2.09 | 2.86 | 49.40 |
| Embodiment 2 | 5.86 | 2.16 | 3.00 | 48.20 |
| Embodiment 3 | 6.05 | 2.23 | 3.26 | 42.10 |
| Embodiment 4 | 6.24 | 2.26 | 5.12 | 38.80 |
| Comparative example 5 | 5.06 | 2.20 | 1.02 | 56.32. |
Table 2：Major impurity content (unit in tantalum powder：ppm)
Tantalum powder sample compression moulding prepared by embodiment 1-4 and comparative example 5, the density of briquet is 6.5g/cm3, fuse
Powder weight be 2.0g, mold：Ф 6.0mm are detected according to standard (GBT3137-2007 tantalum powder electrical performance tests method).
10-330 minutes obtained agglomerates are sintered in the phosphoric acid solution of 0.01% (mass percent) at 1850 DEG C in the vacuum drying oven of Pa
240V energizes, and energize time 120min, temperature of energizing：90 DEG C, current density 35mA/g.The electrical property for measuring each sample is listed in table
In 3.
Table 3：Electrical Property Correlation
SHV (%) represents the cubical contraction of capacitor anode block in table 3.
The introducing being heat-treated for the third time after oxygen is dropped by magnesium-reduced by embodiment 1-4 it can be seen from the data of table 1 to table 3,
The leakage current of product is greatly reduced, improves product quality.As can be seen from Table 3 since third time is heat-treated in embodiment 4
Temperature is higher than second of heat treatment temperature, and leakage current (K values) is larger, and effect is undesirable, it is advantageous to solution be the
Relatively low 0~150 DEG C of than second heat treatment temperature of heat treatment temperature three times is 20~100 DEG C preferably low.
Embodiment 6, embodiment 7, embodiment 8, embodiment 9 and comparative example 10 (second group) are analyzed, it is as a result as follows：
Table 4：The physical properties of tantalum powder
| Sample | Fsss(μm) | SBD(g/cc) | + 80 (%) | - 325 (%) |
| Embodiment 6 | 5.62 | 3.65 | 12.72 | 52.80 |
| Embodiment 7 | 6.72 | 3.70 | 12.86 | 50.12 |
| Embodiment 8 | 7.12 | 3.72 | 13.20 | 49.60 |
| Embodiment 9 | 7.25 | 3.86 | 14.60 | 48.20 |
| Comparative example 10 | 5.02 | 3.62 | 2.34 | 58.60 |
Table 5：Major impurity content (unit in tantalum powder：ppm)
Tantalum powder sample compression moulding prepared by embodiment 6-9 and comparative example 10, the density of briquet is 6.5g/cm3, fuse
Powder weight be 2.0g, mold：Ф 6.0mm are detected according to standard (GBT3137-2007 tantalum powder electrical performance tests method).
10-330 minutes obtained agglomerates are sintered in the phosphoric acid solution of 0.01% (mass percent) at 1950 DEG C in the vacuum drying oven of Pa
270V energizes, and energize time 120min, temperature of energizing：90 DEG C, current density 35mA/g.The electrical property for measuring each sample is listed in table
In 6.
Table 6：Electrical Property Correlation
The conclusion identical with first group is at second group (embodiment 6, embodiment 7, embodiment 8, embodiment 9 and comparative example 10)
Comparative result in it is also seen that come, referring to table 4 to table 6, in contrast, preparation method of the invention (i.e. third time it is hot at
The introducing of reason) so that product improves significantly in electric leakage performance, capacity is also improved.As can be seen from Table 6 in embodiment 9
Since heat treatment temperature is higher than secondary heat treatment temperature three times, leakage current (K values) is larger, and effect is undesirable, it is advantageous to
Solution is 0~150 DEG C more relatively low than secondary heat treatment temperature of heat treatment temperature three times, 20~100 DEG C preferably low.
The preparation method of the present invention meets requirement of the capacitor product to tantalum powder proof voltage and leakage current etc..The system
The appropriate products of Preparation Method are the Ta powder used in capacitor of the μ FV/g of 2500 μ FV/g~15000, preferably specific volume 4000 μ FV/g~
The Ta powder used in capacitor of 10000 μ FV/g.
The specification and embodiment of the open present invention in this article is exemplary illustrated, it is obvious that for this field
For technical staff, the present invention also has other embodiments, and essential scope of the invention and spirit are defined in the patent claims.
Claims (26)
1. a kind of preparation method of high pressure tantalum powder, this method include the following steps：
Tantalum powder original powder is processed slabbing, obtains flaked tantalum powder original powder by flaking step；
Flaked tantalum powder original powder is carried out to carry out drop oxygen after being heat-treated twice, then carries out third time heat treatment；
The treatment conditions of heat treatment are for the first time：Vacuum degree is more than 6 × 10-3Pa, 500~1500 DEG C are heat-treated 60~360 minutes；
The treatment conditions of heat treatment are for the second time：Vacuum degree is more than 6 × 10-3Pa, 800~1500 DEG C are heat-treated 60~200 minutes；
The treatment conditions of heat treatment are for the third time：Vacuum degree is more than 6 × 10-3Pa, 800~1500 DEG C are heat-treated 60~200 minutes；
The drop oxygen condition includes：Mix magnesium amount is tantalum powder weight 1.5%, stove argon-filled protection after evacuation, stove pressure 9 ×
104Pa, after then heating to 960 DEG C of heat preservations 3 hours, the row of vacuumizing magnesium 3 hours at 960 DEG C, then progress pickling and baking again
It is dry；
The fine grained tantalum powder that the tantalum powder original powder is hydrogenated for sodium reduction tantalum powder or tantalum ingot, impurity content in the sodium reduction tantalum powder
Impurity content is in the fine grained tantalum powder hydrogenated for O≤1500ppm, C≤20ppm, N≤60ppm, Fe≤20ppm, the tantalum ingot
O≤1000ppm、C≤15ppm、N≤40ppm、Fe≤10ppm；
The step of pickling being further included in the flaking step；
When the tantalum powder original powder is sodium reduction tantalum powder, the acid washing conditions in flaking step include：First pass：Use 10%HNO3+
0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant；Second time：It is identical with first pass；Third time uses 15%HNO3+
0.7%HF+1.5%H2O2Pickling 2 hours steeps 2 hours, finally pours out supernatant, and enough water is added to rinse twice of discharging plus pure water pumping
Filter；
When the fine grained tantalum powder that the tantalum powder original powder is hydrogenated for tantalum ingot, the acid washing conditions in flaking step include：First pass：With
10%HNO3+ 0.3%HF pickling 3 hours steeps 2 hours, pours out supernatant；Second time with 15%HNO3+ 0.7%HF+1.0%
H2O2Pickling 2 hours steeps 2 hours, finally pours out supernatant, and enough water is added to rinse twice of discharging plus pure water suction filtration.
2. the preparation method of claim 1, wherein the temperature of third time heat treatment is lower by 0~150 than the temperature of second of heat treatment
℃。
3. the preparation method of claims 1 or 2, wherein the temperature of third time heat treatment is 20 DEG C lower than the temperature of second of heat treatment
~150 DEG C.
4. the preparation method of claim 1, wherein the temperature of third time heat treatment is lower by 20~100 than the temperature of second of heat treatment
℃。
5. the preparation method of claim 1, processing method is ball milling.
6. the preparation method of claim 5, using absolute ethyl alcohol as ball-milling medium.
7. the preparation method of claim 5, the weight ratio of ball material is 3:1~8:1.
8. the preparation method of claim 5, drum's speed of rotation is 80~200 revs/min.
9. the preparation method of claim 5, Ball-milling Time is 12~18 hours.
10. the preparation method of claim 1, wherein, with crusher in crushing 50~80 mesh of sieving and magnetic after being heat-treated in first time
Choosing.
11. the preparation method of claim 1, wherein, jaw crusher in crushing is sieved 50~80 mesh simultaneously after being heat-treated in first time
Magnetic separation.
12. the preparation method of claim 10 or 11, after magnetic separation plus water carries out pre- dough, adds in tantalum powder weight 10-30%'s
Water is uniformly mixed, and be sieved 30~60 mesh, then dries.
13. the preparation method of claim 12, drying condition is vacuum drying 10~15 hours at 100~120 DEG C.
14. the preparation method of claim 12, vacuum degree is greater than or equal to 4 × 10 in drying course4Pa。
15. the preparation method of claim 1, the mesh of 60 mesh of sieving~100 is crushed after being heat-treated at second.
16. the preparation method of claim 1 carries out pickling and drying again after arranging magnesium.
17. the preparation method of claim 16, it is 8~12%HNO to arrange the acid washing conditions after magnesium3Pickling 1~2 hour.
18. the preparation method of claim 16, it is vacuum drying 8~14 hours at 100~140 DEG C to arrange the drying condition after magnesium.
19. the preparation method of claim 1, with crusher in crushing 50~80 mesh of sieving and magnetic separation after third time is heat-treated.
20. a kind of high pressure tantalum powder is obtained by the preparation method of any one of claim 1 to 19.
21. the high pressure tantalum powder of claim 20, the specific volume of the high pressure tantalum powder is the μ FV/g of 2500 μ FV/g~15000.
22. the high pressure tantalum powder of claim 20, the specific volume of the high pressure tantalum powder is the μ FV/g of 3000 μ FV/g~10000.
23. a kind of electrolytic capacitor is prepared by the high pressure tantalum powder of any one of claim 20 to 22.
24. the electrolytic capacitor of claim 23, the electrolytic capacitor is solid capacitor or liquid tantalum capacitor.
25. the electrolytic capacitor of claim 24, the operating voltage of the solid capacitor is 30~63V.
26. the electrolytic capacitor of claim 24, the operating voltage of the liquid tantalum capacitor is 50~150V.
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| CN104148654B (en) * | 2014-07-08 | 2019-08-16 | 宁夏东方钽业股份有限公司 | A kind of preparation method of the high-purity tantalum powder of target-grade |
| CN104209512B (en) * | 2014-09-05 | 2018-01-16 | 宁夏东方钽业股份有限公司 | Tantalum powder and preparation method thereof is pressed in one kind |
| CN105583406B (en) * | 2016-03-29 | 2018-12-11 | 宁夏东方钽业股份有限公司 | A kind of preparation method of low oxygen content metal powder |
| CN106392060B (en) * | 2016-10-12 | 2019-02-12 | 宁夏东方钽业股份有限公司 | A kind of mixing tantalum powder and preparation method thereof |
| CN112404439A (en) * | 2020-11-18 | 2021-02-26 | 贵州振华电子信息产业技术研究有限公司 | High-voltage tantalum powder for capacitor, preparation method thereof and capacitor |
| CN114472883B (en) * | 2022-01-27 | 2024-01-30 | 长沙南方钽铌有限责任公司 | Manufacturing process of tantalum particles |
| CN115132497B (en) * | 2022-08-09 | 2023-06-02 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Capacitor manufacturing method and device |
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| "用于中高压电解电容器的片状钽粉";杨国启等;《中国材料科技与设备》;20060630(第3期);第39-42页 * |
| "电容器用钽粉的高比容化";程越伟;《宁夏工程技术》;20060331;第5卷(第1期);第99-101页 * |
| "碳还原-电子轰击制取高压钽粉工艺研究";黄烈如;《稀有金属》;19911031(第25期);第392-395页 * |
| "钽粉降氧工艺研究与应用";潘伦桃;《稀有金属》;19900831(第4期);第259-263页 * |
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| CN103894601A (en) | 2014-07-02 |
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