CN105051225A - Wet ball-milling method for tantalum powder and tantalum powder prepared therefrom - Google Patents
Wet ball-milling method for tantalum powder and tantalum powder prepared therefrom Download PDFInfo
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- CN105051225A CN105051225A CN201480018132.5A CN201480018132A CN105051225A CN 105051225 A CN105051225 A CN 105051225A CN 201480018132 A CN201480018132 A CN 201480018132A CN 105051225 A CN105051225 A CN 105051225A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
A wet ball-milling method for a tantalum powder, which method uses a grinding aid containing a ball-milling medium and a surfactant. The method has a simple process and strong controllability, and the product obtained has a lower content of metallic impurities.
Description
A kind of wet ball-milling method of tantalum powder and the tantalum powder technical field prepared by this method
The invention belongs to rare metal field of smelting, it is related to the process technology of tantalum powder powder, the wet ball-milling method of more particularly to a kind of tantalum powder and the tantalum powder prepared by this method.Background technology
Tantalum powder is widely used in a variety of industries, such as mobile phone, computer industry mainly for the manufacture of the solid electrolytic capacitor of high reliability.When tantalum metal is as electrolytic condenser anode material, powder is thinner, then specific surface area is bigger, and specific volume is higher.With the miniaturization miniaturization of electronic product, tantalum capacitor constantly requires increase capacity and reduces equivalent series resistance（ESR), in order to further increase tantalum capacitor capacity, and good leakage current, less ESR and higher reliability are kept, the fundamental characteristics of tantalum powder must be improved.It is well known that the chemical analysis and physical arrangement of tantalum powder have influence on the performance of final tantalum electrolytic capacitor, including leakage current, ESR and reliability.At present, the challenge faced is tantalum powder of the production with Fabrication of High Specific Capacitance, high resistance to burning and resistance to pressure.
It is well known that the most of tantalum powder largely produced is chemically reacted by potassium floutaramite with sodium in a reactor.In this process, the particle diameter and specific surface area of the physical property of tantalum powder such as tantalum powder are controlled by controlling reducing condition to be such as not involved in diluting salt KC1, KF ratio of reaction etc..Adjustment reducing condition makes tantalum powder attenuate, and the specific surface area of tantalum powder will increase.The tantalum powder obtained using this method is combined the porous aggregate of the high-specific surface area constituted by many tiny primary particals, and its is complicated, and specific surface area is big.In general, above-mentioned tantalum powder is big due to specific surface area, specific volume is higher, but its corresponding breakdown voltage, than relatively low, resistance to pressure and poor reliability, such tantalum powder is difficult to work under high voltages.In order to obtain the tantalum powder that reliability, proof voltage are high, it is necessary to from primary partical structure and morphology is changed, obtain a kind of simple tantalum powder of particle shape.
Flaked tantalum powder is the tantalum powder that a kind of primary partical is sheet.From three-dimensional angle, the size in mono- direction of sheet ^ is smaller than the size of other both directions, that is, has certain compression or so-called radius-thickness ratio.The fcl of tantalum powder one of this type is passed through as other tantalum powders grinds to form flake powder again by obtained from the subsequent treatments such as drop oxygen, hot dough.This tantalum powder is relative to reduced powder, and it compares surface
The smaller, particle shape of product is simpler, and corresponding specific volume is relatively low.
Currently known tablet making technology is by granular tantalum powder (such as EB powder obtained after the hydrogenated powder processed of sodium reduction tantalum powder or electron bombardment ingot（Electron bombardment powder）) in a ball mill grinding it is flattened.In order to reduce pollution and aoxidize, tantalum particle is ground in a kind of organic solvent, then, it is purified by the method for pickling.The surface area and final specific volume of flaked tantalum powder uniqueness are determined by the thickness and size of piece.Its piece is thinner, smaller, and specific surface area is bigger, and corresponding specific volume is also higher.
In order to obtain thinner, thinner piece, most straightforward approach is exactly to extend Ball-milling Time, and tantalum powder particle diameter is gradually reduced with the extension of time, but not！Limit reduces, after certain particle size is ground to, it may appear that inverse grinding phenomenon, so that particle diameter can be prevented to continue to reduce, particle diameter increases on the contrary.Because material is constantly extruded in mechanical milling process, crushed, increasing chemistry ^ L lifes are broken, and many unsaturated bonds, many fresh Free Surfaces of generation are formed in surface of material.Particle inside material is interacted by surrounding particle, energy is in poised state, and it is located at the particle inward direction on top layer by strong active force, but the active force that outward direction is received is extremely weak, so, the particle on material top layer just shows remaining bond energy (i.e. surface free energy) and existed, and grain graininess is smaller, specific surface area is bigger, and surface free energy is also bigger.In terms of thermodynamic consideration, due to there is unsaturated bond in surface of material, ambient substance must be adsorbed to be allowed to be compensated to drop low-surface-energy, so that forming cohesiveness between material particles particle, so that the chemical bond being broken regroups, this occurs as soon as granularity after material grinding to a certain extent and no longer diminished there is becoming big phenomenon on the contrary.Further, since the indefinite extension of Ball-milling Time, can cause metals content impurity and o, C content to greatly increase.
Patent US6706240 B2, WO00/56486 disclose a kind of manufacture niobium and the method for other metal dusts, and this method is that sheet metal is made by the way that metal dust to be carried out to wet-milling in the presence of at least a kind of fluoride or the liquid solution of perfluoro-compound.It is advantageous in that using fluoride or the liquid flux for crossing Gas compounds：Obtained final piece is for traditional spirit solvent, the content with relatively low 0, Fe and C, but waste liquid must be difficult due to that containing substantial amounts of fluorine, can be brought to liquid waste processing after final ball milling.
A kind of method that United States Patent (USP) US5580367 discloses sheet improved and production flaked tantalum powder, the production method of the sheet is to use large stretch of made from above-mentioned conventional method, so
Sheet is carried out afterwards to use Mechanical Crushing mode the size of piece is diminished after hydrogenation treatment.Its purpose, which is mainly, improves mobility, briquetting intensity and the mouldability of tantalum powder, but to increase CV values（Specific capacitance, abbreviation specific volume）Contribution it is little.Further, since the hardness of hydrogenated material is higher, it can bring substantial amounts of metal impurities into accordingly in the shattering process in later stage, cause final products impurity content higher.Because its processing procedure needs to carry out hydrogenation treatment, and hydrogen belongs to hazardous chemical, and production process has the potential safety hazard of hydrogen Fire explosion.
In summary, flaked tantalum powder is prepared, existing skill ^ is in following shortcoming：First, with requiring specific volume is higher and higher, using the production technology of traditional flaked tantalum powder, receive and must limit in terms of the production of more high specific capacitance tantalum powder is realized.Simultaneously, it is contemplated that ball milling waste liquid, the influence to environment, the selection of medium is also vital.Second, using crushing process is hydrogenated after first film-making, complex technical process, process route length, cost are high.And hydrogenation process hydrogen content is whard to control, the selection to later stage crumbling method requires higher, and metals content impurity is higher, and production process has the potential safety hazard of hydrogen Fire explosion, there is a definite limitation in terms of practical application.The content of the invention
The purpose of the present invention is：There is provided a kind of distribution of prepared sizes more it is thin evenly, the method for the lower mesohigh tantalum powder of impurity content.This method technique is simple and controllability is strong, and production process security risk is low.This method can obtain the flaked tantalum powder with high specific surface area, the electrolytic capacitor a obtained after being processed further, with relatively low impurity content, higher specific volume, at higher voltages using with relatively low leakage current and higher breakdown voltage.
The first aspect of the present invention provides a kind of wet ball-milling method of tantalum powder, it is characterised in that contain ball-milling medium and surfactant in grinding aid used in this method.
In a preferred embodiment, in the wet ball-milling method described in first aspect present invention, the consumption of surfactant is 1 ~ 50%, 1.5 ~ 50% or the 10 ~ 50% of the 0.001-50%, preferably tantalum powder weight of tantalum powder weight,（Such as 1%, 1.5%, 2%, 3%, 5%, 8%, 9%, 10%, 15%, 20%, 30%, 40% or 50%).
In a preferred embodiment, in the wet ball-milling method described in first aspect present invention, described surfactant is selected from oleic acid, benzoic acid, butanone, polyethylene glycol, isopropanol, hexamethylene
Alcohol, calgon, sodium tripolyphosphate or its combination.Preferably, described surfactant is selected from oleic acid, cyclohexanol, polyethylene glycol, isopropanol, butanone, benzoic acid or its combination.
In a preferred embodiment, in the wet ball-milling method described in first aspect present invention, described ball-milling medium is water or organic solvent（Such as absolute ethyl alcohol）.
In a specific embodiment, in the wet ball-milling method described in first aspect present invention, described surfactant is oleic acid, and its consumption is 10 ~ 50 % (such as 10 %, 20 %, 50 %) of tantalum powder weight.
In another specific embodiment, in wet ball-milling method described in first aspect present invention, described surfactant is selected from isopropanol, butanone, benzoic acid, cyclohexanol, polyethylene glycol or its combination, and its consumption is 0.5 ~ 15 % (such as 1 %, 1.5 %, 5 %, 10 %, 15 %) of tantalum powder weight.
In the wet ball-milling method of tantalum powder described in first aspect present invention, the tantalum powder that the tantalum powder or electron bombardment tantalum ingot that can be selected after sodium reduction are obtained after break process is as raw material, ball-grinding machine can select agitating ball mill or vibrator, using stainless steel ball as mill ball, stainless steel ball diameter typically selects l-10mm, preferably 3-6 mm.
, can be 1-50 hours to tantalum powder continuous ball milling in above-mentioned wet ball-milling method, preferably ball milling 18-30 hours, such as 20 hours, 25 hours.
The second aspect of the present invention provides a kind of grinding aid for tantalum powder wet ball-milling, including ball-milling medium and surfactant, wherein described ball-milling medium is water or organic solvent（Such as absolute ethyl alcohol）, described surfactant is selected from oleic acid, benzoic acid, butanone, polyethylene glycol, isopropanol, cyclohexanol, calgon, sodium tripolyphosphate or its combination；Preferably, wherein described surfactant is selected from oleic acid, cyclohexanol, polyethylene glycol, isopropanol, butanone, benzoic acid or its combination.
In a preferred embodiment, grinding aid described in second aspect of the present invention, wherein the consumption of surfactant is the 0.001-50% (such as 1 %, 1.5 %, 5 %, 10 %, 15 %, 20 %, 50 %) of tantalum powder weight, preferably 1 ~ 50 % of weight, 1.5 ~ 50 % or 10 ~ 50 %.
In another preferred embodiment, the grinding aid described in second aspect of the present invention, wherein surfactant are oleic acid, and its consumption is 10 ~ 50 % (such as 10 %, 20 %, 50 %) of tantalum powder weight；Or, wherein surfactant be selected from isopropanol, butanone, benzoic acid, cyclohexanol,
Polyethylene glycol or its combination, its consumption is 0.5 ~ 15 % (such as 1 %, 1.5 %, 5 %, 10 %, 15 %) of tantalum powder weight.
The third aspect of the present invention provides a kind of sheet S, and it is prepared by the wet ball-milling method of any one of first aspect present invention.Preferably, the metals content impurity ∑ Fe+Ni+Cr of described flaked tantalum powder<50PPm, C content<50ppm.Described flaked tantalum powder passes through pelletizing granulation, high temperature hypertonic solutions, mixes the combined treatment of one of which processing or a variety of processing in oxygen processing, can obtain highly reliable Fabrication of High Specific Capacitance electrolytic capacitor tantalum powder.
The fourth aspect of the present invention provides a kind of highly reliable Fabrication of High Specific Capacitance electrolytic capacitor tantalum powder, and it is obtained as the flaked tantalum powder described in third aspect present invention after a kind of processing in pelletizing granulation, high temperature hypertonic solutions, oxygen processing or the combined treatment of a variety of processing.
Fifth aspect present invention provides a kind of electrolytic capacitor anode, and it is made up of the tantalum powder described in fourth aspect present invention.Preferably, the specific capacitance of described electrolytic capacitor anode is that (^FV/g, its voltage of energizing is in 50-270V by 5000-6000.Detailed description of the invention
In order to obtain size distribution more it is thin evenly, and the lower mesohigh tantalum powder of impurity content, the present inventor's research is found, face activating agent is added to carry out ball milling film-making processing into organic solvent in logical i ± early stage ball milling tablet making technologies, while Ball-milling Time is reduced, gained tantalum powder granularity is more uniformly distributed, and metal impurities and content are relatively low, the resistance to sparking of final products can be improved, and leakage current is improved.Technique thinking proposed by the present invention is as follows：The tantalum powder obtained after break process from the tantalum powder after sodium reduction or electron bombardment tantalum ingot is as raw material, from agitating ball mill or vibrator, using not Recording steel balls as mill ball, steel ball size typically selects l-10mm, it is preferred that 3-6 mm, using water or organic solvent as ball-milling medium, generally select absolute ethyl alcohol, while the 0.001-50%'s of addition tantalum powder weight can improve the surfactant of tantalum powder dispersion effect in decentralized medium, to improve film-making efficiency, improve flaked tantalum powder pattern, carbon and metals content impurity in reduction, surfactant often selects preferred oleic acid, benzoic acid, butanone, polyethylene glycol, isopropanol, cyclohexanol, calgon, sodium tripolyphosphate etc., but not limited to this.Continuous ball milling 1-50 hours.Afterwards by washing, pickling, sieving, the former powder of the sheet of granularity and pattern required for finally giving us.Pelletizing granulation, high temperature hypertonic solutions, magnesium are carried out also to the former powder of sheet obtained above
The combined treatment of one of which processing or a variety of processing, obtains electrolytic capacitor mesohigh a in original drop oxygen processing.
Sheet original powder passes through pelletizing granulation, high temperature hypertonic solutions, mixes the combined treatment of one of which processing or a variety of processing in magnesium deoxidation treatment, obtains highly reliable Fabrication of High Specific Capacitance electrolytic capacitor tantalum powder.Any of ratio required by can adding in processes is conducive to tantalum powder to suppress to shrink in high temperature sintering and reduces the chemical substance of specific surface area loss as resistance burning agent.Such as one or more in phosphorous, nitrogen, boron.High temperature hypertonic solutions temperature general control is in 1300-1600.C, is incubated 15-200 minutes.Cooled after terminating, Passivation Treatment is obtained condensing tantalum block, then crushed.Specific heat treatment method can be carried out using the method described in Chinese patent CN 102120258A.Deoxidation treatment generally carries out deoxidation treatment in reducing atmosphere.General, a small amount of reducing agent bigger than the affinity of tantalum and oxygen with oxygen affinity is mixed into tantalum powder, such as alkaline-earth metal, rare earth metal and its hydride, weight 0.2-6.0% metal magnesium powder is most commonly mixed into, sabot is carried out using the method described in Chinese patent CN 102120258A.Then heated in the case of inert gas shielding, in 800-1000.C is incubated 2-4 hours, then vacuumizes again, is incubated 2-4 hours again under vacuumized conditions.Then cool, be passivated.Tantalum powder after deoxidation treatment must carry out pickling, washing, drying, sieving processing.
The above method can obtain metals content impurity ∑ Fe+M+Cr<50PPm, C content<50ppm flaked tantalum powder, the electrolytic capacitor anode being made from it, its specific capacitance is that (its voltage of energizing of ^FV/g. is in 50-270V by 5000-6000.
In the present invention, for describing the specific surface area that the physical quantity of metallic thickness has nitrogen absorption under low temperature BET to determine（ m2/ g), the Fei Shi average grain diameters (FSSS/ μ π ι) that Fei Shi Asias pulp classifier is determined.Fei Shi average grain diameters are that the flow velocity that the sub- pulp classifiers of Yong Feishi determine the powder being seated in metal tube by gas permeable method is obtained, on the one hand relevant with the size of particle, relevant also with the cohesive strength of powder；The former powder obtained for same process, the smaller specific surface area of Fei Shi average grain diameters is bigger；And for the metal dust after cohesion, the powder of different specific surface areas can have close Fei Shi average grain diameters；For the powder of same grade, the powder Fei Shi average grain diameters condensed are larger.The beneficial effect of invention
The wet ball-milling method for the tantalum powder that the present invention is provided, its technique is simple, and controllability is strong；Products obtained therefrom metals content impurity is relatively low.The flaked tantalum powder that this method is obtained has the mobility and mouldability having had after high specific surface area, and dough, with higher specific volume, at higher voltages using with relatively low leakage current and higher breakdown voltage.
Sheet prepared by ^ provided by the present invention wet ball-milling method has the size distribution being more uniformly distributed and more low impurity content.The present invention is by adding surfactant into ball-milling medium to carrying out ball milling, obtain sheet a, while Ball-milling Time is reduced, gained sheet § ^ granularities are more uniformly distributed, and tantalum powder metal impurities and content are lower, the resistance to sparking of final products can be improved, and leakage current is improved.The advantage of this method is during ball milling film-making to add a certain amount of surfactant, improves ^ of the powder in ball-milling medium：Property, the secondary agglomeration compared with fine powder is prevented, ^ size distribution is more uniformly distributed and controllable.Simultaneously, material is in the presence of ^^ power, surface can form many crackles, in ball-milling medium plus after the activating agent of face, surfactant molecule can enter and adsorb along these crackles, prevent the chemical bond being broken from regrouping, substantially increase grinding efficiency, shorten milling time.Also, also reduce the metal impurities caused due to regrouping for chemical bond and c elements are wrapped in inside tantalum powder particle（Usual this mechanical entrainment is difficult to be removed in subsequent treatment processing）, greatly reduce the impurity content in tantalum powder.Further, since the addition of surfactant, SURFACTANT ADSORPTION forms layer protective layer in particle surface, material particles is realized surface passivation levigate while, can effectively suppress the oxidation in powder ^ mechanical milling processes, effectively control oxygen ^ *.In capacitor use, low iron, carbon content and oxygen content is necessary, and because carbon, iron content are lower, the leakage current for the capacitor being made of this flake powder is lower, and breakdown voltage is higher.Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, it will be appreciated by those skilled in the art that the following example is merely to illustrate the present invention, and be should not be taken as limiting the scope of the invention.In the examples where no specific technique or condition is specified, carried out according to the technology or condition described by document in the art or according to product description.The unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.
The analytical equipment and model of involved parameters are as shown in the table in the present invention:
Embodiment 1:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O < 2000ppm、 C < 20ppm、 N < 150ppm、 Fe < 20ppm.Using absolute ethyl alcohol as ball-milling medium, oleic acid is added as surfactant, the addition of oleic acid is the 50% of tantalum powder weight, selected（|) 4mm steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.By load weighted tantalum powder 10KgIt is added in the ball milling bucket of ball mill and carries out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.Powder HN0 after ball milling3With HF mixed acid（By the HN0 that concentration is 69 %3Solution, concentration add water for 40 % HF solution and are formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical properties and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out secondary heat treatment and deoxidation treatment, and specific implementation condition is under vacuo 1300 processing insulation 60 minutes, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, are finally 20% (mass percent with concentration）HN03Pickling removes magnesia and unnecessary magnesium, and drying, sieve powder make it obtain sample A by 50 mesh sieves completely.Sample A main performance and chemical impurity content is shown in Table 2.Embodiment 2:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O < 2000ppm、
C < 20ppm、 N < 150ppm、 Fe < 20ppm.Using absolute ethyl alcohol as ball-milling medium, oleic acid is added as surfactant, the addition of oleic acid is the 20% of tantalum powder weight.From（|) 5mm steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.By load weighted tantalum powder 10KgIt is added in the ball milling bucket of ball mill and carries out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.The mixed acid of powder HN03 and HF after ball milling（By the HN0 that concentration is 69 %3Solution, concentration add water for 40 % HF solution and are formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out secondary heat treatment and deoxidation treatment, are embodied as 1300 processing insulation 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, are finally 20% (mass percent with concentration）HN03 pickling remove magnesia and unnecessary magnesium, drying, sieve powder it is obtained sample B by 50 mesh sieves completely.Sample B main performance and chemical impurity content is shown in Table 2.Embodiment 3:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O < 2000ppm、 C < 20ppm、 N < 150ppm、 Fe < 20ppm.Using absolute ethyl alcohol as ball-milling medium, oleic acid is added as surfactant, the addition of oleic acid is the 10% of tantalum powder weight, selected（|) 3mm steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.By load weighted tantalum powder 10KgIt is added in the ball milling bucket of ball mill and carries out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.The mixed acid of powder HN03 and HF after ball milling（By the HN0 that concentration is 69 %3Solution, concentration add water for 40 % HF solution and are formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property of gained sheet original powder is shown in is shown in Table 1 with chemical impurity content.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out secondary heat treatment and deoxidation treatment, are embodied as 1300 processing insulation 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, finally with the (mass percent of concentration 20%）HN03Pickling removes magnesia and unnecessary magnesium, drying,
Sieve powder makes it obtain sample C by 50 mesh sieves completely.Sample C main performance and chemical impurity content is shown in Table 2.
Embodiment 4:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O<2000ppm、 C<20ppm、 N<150ppm、 Fe<20ppm.Using absolute ethyl alcohol as ball-milling medium, cyclohexanol is added as surfactant, the addition of cyclohexanol is the 1.5% of tantalum powder weight, from the π π η of φ 4 steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted tantalum powder 10Kg is added in the ball milling bucket of ball mill and carries out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.Powder HN0 after ball milling3With HF mixed acid（By the HN0 that concentration is 69%3The HF solution that solution, concentration are 40%, which adds water, to be formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out secondary heat treatment and deoxidation treatment, are embodied as 1300 processing insulation 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, are finally 20% (mass percent with concentration）HN03Pickling removes magnesia and unnecessary magnesium, and drying, sieve powder make it obtain sample D by 50 mesh sieves completely.Sample D main performance and chemical impurity content is shown in Table 2.
Embodiment 5:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O<2000ppm、 C<20ppm、 N<150ppm、 Fe<20ppm.Using absolute ethyl alcohol as ball-milling medium, polyethylene glycol is added as surfactant, the addition of polyethylene glycol is the 1.5% of tantalum powder weight, from the π ι ι η of φ 6 steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.By load weighted tantalum powder 10KgIt is added in the ball milling bucket of ball mill and carries out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.Powder HN0 after ball milling3With HF mixed acid（By the HN0 that concentration is 69%3The HF solution that solution, concentration are 40%, which adds water, to be formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, and then Hubei Province is broken
To -50 mesh, secondary heat treatment and deoxidation treatment are then carried out, 1300 processing insulation 60 minutes under vacuo are embodied as, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, are finally 20% (mass percent with concentration）HN03Pickling removes magnesia and unnecessary magnesium, and drying, sieve powder make it obtain sample E by 50 mesh sieves completely.Sample E main performance and chemical impurity content is shown in Table 2.
Embodiment 6:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O<2000ppm、 C<20ppm、 N<150ppm、 Fe<20ppm.Using absolute ethyl alcohol as ball-milling medium, isopropanol and butanone are added as surfactant, and the addition of isopropanol and butanone is respectively the 5% and 1.5% of tantalum powder weight.From the π π η of φ 6 steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted S 10Kg are added in the ball milling bucket of ball mill and carry out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.Powder HN0 after ball milling3With HF mixed acid（By the HN0 that concentration is 69%3The HF solution that solution, concentration are 40%, which adds water, to be formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out secondary heat treatment and deoxidation treatment, are embodied as 1300 processing insulation 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, are finally 20% (mass percent with concentration）HN03Pickling removes magnesia and unnecessary magnesium, and drying, sieve powder make it obtain sample F by 50 mesh sieves completely.The main performance and chemical impurity content of sample F are shown in Table 2.
Embodiment 7:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O<2000ppm、 C<20ppm、 N<150ppm、 Fe<20ppm.Using absolute ethyl alcohol as ball-milling medium, polyethylene glycol is added as surfactant, the addition of polyethylene glycol is the 15% of tantalum powder weight.From the π ι ι η of φ 6 steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.By load weighted tantalum powder 10KgIt is added in the ball milling bucket of ball mill and carries out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.Powder HN0 after ball milling3With HF mixed acid（By the HN0 that concentration is 69%3Solution, concentration add water preparation for 40% HF solution
Form, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out secondary heat treatment and deoxidation treatment, are embodied as 1300 processing insulation 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, are finally 20% (mass percent with concentration）HN03Pickling removes magnesia and unnecessary magnesium, and drying, sieve powder make it obtain sample G by 50 mesh sieves completely.Sample G main performance and chemical impurity content is shown in Table 2.
Embodiment 8:
Using the ^ after sodium reduction as raw material, every impurity content in raw material： O<2000ppm、 C<20ppm、 N<150ppm、 Fe<20ppm.Using absolute ethyl alcohol as ball-milling medium, benzoic acid is added as surfactant, the addition of benzoic acid is the 10% of tantalum powder weight.From the π π η of φ 3 steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted tantalum powder lOKg is added in the ball milling bucket of ball mill and carries out ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.Powder HN0 after ball milling3With HF mixed acid（By the HN0 that concentration is 69%3The HF solution that solution, concentration are 40%, which adds water, to be formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out secondary heat treatment and deoxidation treatment, are embodied as 1300 processing insulation 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then carry out 900 to it.C deoxidation treatments, are finally 20% (mass percent with concentration）HN03Pickling removes magnesia and unnecessary magnesium, and drying, sieve powder make it obtain sample H by 50 mesh sieves completely.Sample H main performance and chemical impurity content is shown in Table 2.
Comparative example 9:
Using the tantalum powder after sodium reduction as raw material, every impurity content in raw material： O<2000ppm、 C<20ppm、 N<150ppm、 Fe<20ppm.Using absolute ethyl alcohol as ball-milling medium, any surfactant is not added with, from the π π η of φ 4 steel ball 150Kg.Ensure ball milling bucket, stirring slurry and steel ball are rustless, clean.Load weighted S 10Kg are added in the ball milling bucket of ball mill and carried out
Ball milling, 130 revs/min of drum's speed of rotation, Ball-milling Time makes its in blocks in 20 hours.Powder HN0 after ball milling3With HF mixed acid（By the HN0 that concentration is 69 %3Solution, concentration add water for 40 % HF solution and are formulated, HN03The volume ratio of solution, HF solution and water is 4:1:20) pickling removes metal impurities, and drying sieving obtains the former powder of sheet.The physical property and chemical impurity content of gained sheet original powder are shown in Table 1.By the former powder of above-mentioned sheet, 1150 processing are incubated 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, then secondary heat treatment and deoxidation treatment are carried out, it is embodied as 1300 processing insulation 60 minutes under vacuo, then -50 mesh are broken in Hubei Province, 900 °C of deoxidation treatments are carried out to it again, are finally 20% (mass percent with concentration）HN03Pickling removes magnesia and unnecessary magnesium, and drying, sieve powder make it obtain sample I by 50 mesh sieves completely.Sample I main performance and chemical impurity content is shown in Table 2.
Table 1:The physical properties and chemical impurity content of sheet original powder
Table 2:Final sample main performance and chemical impurity content
The notes of 2.01 1.72 53.02 2,210 25 34 43 88 sample I of sample F 2.05 1.55 48.92 2,070 30 26 65 86 sample G, 2.18 1.62 50.02 1,980 32 29 55 90 sample H 2.74 1.85 52.14 2,800 72 75 10 10 75：When showing the granularity of powder with mesh, "+" or "-" before mesh number number represents the screen cloth of " not by " or " by " described mesh number respectively.Such as " -325 mesh " is represented by 325 eye mesh screens, and "+325 mesh " represents not pass through 325 eye mesh screens."-200 -+325 mesh " represents not passing through 325 eye mesh screens by 200 eye mesh screens.
Sample A ~ I that above-described embodiment is obtained is compressing, and pressed density is 5.0g/cm3, fuse powder weight is 0.15g, and according to standard（GBT 3137-2007 tantalum powder electrical performance test methods）Detected.In l (T3Sintered 30 minutes under 1400 °C respectively in Pa vacuum drying oven, obtain agglomerate.By agglomerate concentration be 0.01% (mass percent）Phosphoric acid solution in energized under 70V voltage, obtain capacitor anode.Its every electrical performance indexes is determined to be listed in Table 3 below.
Table 3:Electrical Property Correlation
SHD (%) represents shrinkage factor of the capacitor anode block in radial direction in table 3, and SHV (%) represents the cubical contraction of capacitor anode block.
Can significantly it be found out by the data comparison in table 3, different surfactants are added in mechanical milling process compared with being not added with surfactant, and film-making efficiency, final products performance make moderate progress.
It can also be seen that there is high specific volume and low leakage current under high sintering temperature, high voltage of energizing by the electrolytic capacitor anode of the tantalum powder manufacture obtained by the present invention by the data in table 3.
Although the embodiment of the present invention has obtained detailed description, it will be understood to those of skill in the art that.According to disclosed all teachings, various modifications and replacement can be carried out to those details, these change within protection scope of the present invention.The four corner of the present invention is provided by appended claims and its any equivalent.
Claims (1)
- Claim1. a kind of wet ball-milling method of tantalum powder, it is characterised in that contain ball-milling medium and surfactant in grinding aid used in this method.2. the wet ball-milling method of claim 1, wherein the consumption of described surfactant is the 0.001-50%, preferably 1 ~ 50 % of weight, 1.5-50 % or 10-50 % of tantalum powder weight.3. the wet ball-milling method of claim 1 or 2, wherein described surfactant is selected from oleic acid, benzoic acid, butanone, polyethylene glycol, isopropanol, cyclohexanol, calgon, sodium tripolyphosphate or its combination；Preferably, wherein described surfactant is selected from oleic acid, cyclohexanol, polyethylene glycol, isopropanol, butanone, benzoic acid or its combination.4. any one of claim 1-3 3 wet ball-milling method, wherein described ball-milling medium is water or organic solvent（Such as absolute ethyl alcohol）.5. any one of claim 1-4 wet ball-milling method, wherein described surfactant is oleic acid, its consumption is 10 ~ 50% (such as 10%, 20%, 50%) of tantalum powder weight；Or, wherein described surfactant is cyclohexanol or polyethylene glycol, its consumption is the 0.5 ~ 2.5% of tantalum powder weight, preferably the 1.5% of the 1% ~ 2% of tantalum powder weight, more preferably tantalum powder weight.6. a kind of grinding aid for wet ball-milling, including ball-milling medium and surfactant, wherein described ball-milling medium is water or organic solvent（Such as absolute ethyl alcohol）, described surfactant is selected from oleic acid, benzoic acid, butanone, polyethylene glycol, isopropanol, cyclohexanol, calgon, sodium tripolyphosphate or its combination；Preferably, wherein described surfactant is selected from oleic acid, cyclohexanol, polyethylene glycol, isopropanol, butanone, benzoic acid or its combination.7. the consumption of the grinding aid of claim 6, wherein surfactant is 1 ~ 50%, 1.5 ~ 50% or the 10 ~ 50% of the 0.001-50%, preferably weight of tantalum powder weight.8. the grinding aid of claim 6, wherein surfactant are oleic acid, its consumption is 10 ~ 50% (such as 10%, 20%, 50%) of tantalum powder weight； Or, wherein surfactant is selected from isopropanol, butanone, benzoic acid, cyclohexanol, polyethylene glycol or its combination, and its consumption is 0.5 ~ 15 % of tantalum powder weight.9. a kind of flaked tantalum powder, it is prepared by any one of claim 1-5 wet ball-milling method；Preferably, the metal impurities of described sheet>^J:∑Fe+M+Cr<50PPm, C contain:<50ppm.10.-kind of highly reliable Fabrication of High Specific Capacitance electrolytic capacitor a, it is obtained as the flaked tantalum powder described in claim 9 after pelletizing granulation, high temperature hypertonic solutions, the combined treatment of a kind of processing or a variety of processing mixed in the processing of M ^ oxygen.11. a kind of electrolytic capacitor anode, it is made up of the tantalum powder described in claim 10；Preferably, the specific capacitance of described electrolytic capacitor anode is 5000-6000 (^FV/g, its voltage of energizing is in 50-270V.
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| 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 |
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| CN114410276B (en) * | 2021-12-13 | 2023-06-13 | 长安大学 | Preparation method of ball milling process control agent |
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