CN108607987B - Method and equipment for reducing oxygen content of anode tantalum core - Google Patents
Method and equipment for reducing oxygen content of anode tantalum core Download PDFInfo
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- CN108607987B CN108607987B CN201810461400.0A CN201810461400A CN108607987B CN 108607987 B CN108607987 B CN 108607987B CN 201810461400 A CN201810461400 A CN 201810461400A CN 108607987 B CN108607987 B CN 108607987B
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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Abstract
The invention provides a method and equipment for reducing the oxygen content of an anode tantalum core, and relates to the technical field of electronic component manufacturing. The method for reducing the oxygen content of the anode tantalum core comprises the following steps: (a) plasmatizing the inert gas with the alkaline metal steam to form an alkaline metal-containing inert gas plasma; (b) placing the tantalum core in an inert gas plasma containing an alkali metal; (c) and (4) isolating the alkali metal steam source, and introducing inert gas to place the tantalum core in the inert gas plasma. The method of the invention accelerates the reaction speed of oxygen atoms and alkali metal ions, and reduces the treatment time of the deoxidation process; the required environmental temperature and pressure are lower, and the controllability and the safety of the production process are improved; effectively reduces the oxygen concentration in the tantalum core and improves the voltage resistance and other performances of the final tantalum capacitor.
Description
Technical Field
The invention relates to the technical field of electronic component manufacturing, in particular to a method and equipment for reducing the oxygen content of an anode tantalum core.
Background
Tantalum capacitor anodes are typically made from capacitor grade tantalum powder by compression molding and high temperature sintering. The impurity oxygen atoms in the tantalum powder in the manufacturing raw material and the oxygen atoms mixed in the tantalum powder in the production process can have great influence on the performance of the tantalum capacitor. When the oxygen impurity concentration in the anode tantalum core is higher, the voltage resistance of the final tantalum capacitor is affected, or the leakage current and the loss angle of the tantalum capacitor are larger.
The most direct solution to this problem is to use high-purity and low-oxygen tantalum powder to compact capacitor-grade tantalum powder, and care to maintain high vacuum in the high-temperature sintering process to volatilize volatile oxides as much as possible. However, the former scheme of passing through tantalum powder greatly increases the procurement cost and difficulty of raw materials, and the latter scheme of passing through a sintering process is limited by technical conditions and sintering temperature.
In the prior art, alkaline metal steam is adopted to react with oxygen in a tantalum core at high temperature to reduce the oxygen content in the tantalum core. This method is subject to various limitations in practical use. Firstly, the reaction temperature must be controlled below the high-temperature sintering temperature of the tantalum core, otherwise, the excessive reaction temperature can modify the tantalum capacitance, so that the capacitance value changes. Secondly, the method of direct heating reaction is inefficient and the reaction rate is not fast enough. For this reason, the treatment time of the tantalum core is required, and usually 10 hours or more is required. Another method to speed up the process is by increasing the temperature and pressure in the reaction chamber, but this results in a difficult manufacturing of the apparatus and a difficult process control. Therefore, the following technical defects exist in the prior art: (1) the direct heating reaction has low efficiency and slow reaction speed; (2) high temperature and high pressure have high requirements on equipment, and the controllability and safety are low.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a method for reducing the oxygen content in the anode tantalum core, so as to alleviate the technical problems of low direct heating reaction efficiency, low reaction speed, high reaction temperature and pressure in the chamber, low controllability and safety, etc. existing in the prior art.
The method for reducing the oxygen content of the anode tantalum core provided by the invention comprises the following steps:
(a) under the conditions that the temperature is higher than the melting point and lower than the boiling point of the alkali metal and the pressure is 700-45000Pa, the inert gas with the alkali metal steam is plasmatized to form inert gas plasma containing the alkali metal;
(b) placing the tantalum core in inert gas plasma containing alkali metal to enable oxygen in the tantalum core to react with the alkali metal to generate alkali metal oxide;
(c) isolating the alkali metal steam source, introducing inert gas, placing the tantalum core in the inert gas plasma, and discharging the generated alkali metal oxide along with the inert gas;
optionally, performing step (d): and cooling the system to finish cooling.
Further, the alkali metal is selected from at least one of magnesium, aluminum and calcium, and is preferably magnesium.
Further, the temperature is 650-1000 ℃, preferably 700-950 ℃, and more preferably 750-900 ℃; the pressure is 2000-35000Pa, preferably 10000-20000 Pa.
Further, the inert gas with the alkali metal vapor is obtained by passing the inert gas through an alkali metal vapor source, and preferably the alkali metal vapor source is obtained by heating the alkali metal to a temperature higher than the melting point to form a liquid and volatilizing the liquid.
Further, the temperature of the inert gas is 650-.
Further, the inert gas is argon.
Further, in the step (b), the tantalum core is placed in the inert gas plasma containing the alkali metal for 5-1000min, preferably 50-800min, and more preferably 200-600 min.
Further, in the step (c), the tantalum core is placed in the inert gas plasma for 1 to 100min, preferably 10 to 80min, and more preferably 40 to 60 min.
Further, the plasma is magnetized plasma; preferably a capacitively coupled plasma, an inductively coupled plasma or a magnetic field enhanced CCP radio frequency plasma.
The second purpose of the invention is to provide equipment for reducing the oxygen content of the anode tantalum core, which has the advantages of low equipment investment, low operation cost, stability, reliability, convenient operation and management, obviously reduced oxygen content of the treated anode tantalum core and improved voltage resistance of the tantalum capacitor.
The equipment for reducing the oxygen content of the anode tantalum core comprises a heat insulation pipeline, wherein the heat insulation pipeline is communicated with a heat insulation container, an inlet is formed in one end of the heat insulation pipeline, an outlet is formed in the bottom of the heat insulation container, the heat insulation pipeline is internally provided with the container and a liftable cover plate, the cover plate is positioned above the container, an induction heater is arranged on the container, an upper electrode and a lower electrode are arranged in the heat insulation container, and the upper electrode and the lower electrode are connected with a high-frequency power supply.
The invention has the following beneficial effects:
the method adopts the tantalum powder which is conventionally used as a raw material to press the capacitance-grade tantalum powder, activates alkaline metal plasma under the conditions that the reaction temperature is higher than the melting point and lower than the boiling point of alkaline metal and the pressure is 700-45000Pa, and the activated alkaline metal ions react with oxygen in the tantalum core to generate alkaline metal oxide which is finally discharged along with inert gas, thereby completing the deoxidation process of the anode tantalum core. According to the method, the conventionally used tantalum powder is used as the raw material to press the capacitor-grade tantalum powder, and the high-purity and low-oxygen-content tantalum powder is not needed to press the capacitor-grade tantalum powder, so that the purchase cost of the raw material is greatly saved, and the purchase difficulty is reduced; the method of the invention adopts the plasma to activate the alkali metal to obtain the activated alkali metal ions, thereby accelerating the reaction speed of oxygen atoms and the alkali metal ions and reducing the treatment time of the deoxidation process; the required environment temperature is above the melting point and below the boiling point of the alkali metal, the pressure is 700-45000Pa, the reaction temperature is controlled above the melting point and below the boiling point of the alkali metal, the alkali metal vapor can be kept to volatilize but not to boil, meanwhile, the plasma releases heat, the alkali metal vapor can be prevented from being condensed on the inner wall of the equipment, and the controllability and the safety of the production process are improved; the method can effectively reduce the oxygen concentration in the tantalum core and improve the pressure resistance and other performances of the final tantalum capacitor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic representation of the results of the apparatus for reducing the oxygen content of an anodic tantalum core provided by the present invention;
FIG. 2 is a schematic structural diagram of a seal ring provided in the present invention;
fig. 3 is a schematic structural diagram of the carrier support provided by the present invention.
Icon: 1-magnesium as metallic material; 2-a container; 3-an induction heater; 4-heat preservation of pipelines; 5-a heat-preservation container; 6-inlet; 7-cover plate; 8-plasma; 9-a high frequency power supply; 10-an outlet; 11-a lower electrode; 12-an upper electrode; 14-a through hole; 15-a drive rod; 16-a sealing ring; 17-carrying support.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
According to one aspect of the present invention, there is provided a method for reducing the oxygen content of an anodic tantalum core, comprising the steps of:
(a) under the conditions that the temperature is higher than the melting point and lower than the boiling point of the alkali metal and the pressure is 700-45000Pa, the inert gas with the alkali metal steam is plasmatized to form inert gas plasma containing the alkali metal;
(b) placing the tantalum core in inert gas plasma containing alkali metal to enable oxygen in the tantalum core to react with the alkali metal to generate alkali metal oxide;
(c) isolating the alkali metal steam source, introducing inert gas, placing the tantalum core in the inert gas plasma, and discharging the generated alkali metal oxide along with the inert gas.
The method adopts the tantalum powder which is conventionally used as a raw material to press the capacitance-grade tantalum powder, activates alkaline metal plasma under the conditions that the reaction temperature is higher than the melting point and lower than the boiling point of alkaline metal and the pressure is 700-45000Pa, and the activated alkaline metal ions react with oxygen in the tantalum core to generate alkaline metal oxide which is finally discharged along with inert gas, thereby completing the deoxidation process of the anode tantalum core. According to the method, the conventionally used tantalum powder is used as the raw material to press the capacitor-grade tantalum powder, and the high-purity and low-oxygen-content tantalum powder is not needed to press the capacitor-grade tantalum powder, so that the purchase cost of the raw material is greatly saved, and the purchase difficulty is reduced; the method of the invention adopts the plasma to activate the alkali metal to obtain the activated alkali metal ions, thereby accelerating the reaction speed of oxygen atoms and the alkali metal ions and reducing the treatment time of the deoxidation process; the required environment temperature is above the melting point and below the boiling point of the alkali metal, the pressure is 700-45000Pa, the reaction temperature is controlled above the melting point and below the boiling point of the alkali metal, the alkali metal vapor can be kept to volatilize but not to boil, meanwhile, the plasma releases heat, the alkali metal vapor can be prevented from being condensed on the inner wall of the equipment, and the controllability and the safety of the production process are improved; the method can effectively reduce the oxygen concentration in the tantalum core and improve the pressure resistance and other performances of the final tantalum capacitor.
In a preferred embodiment, step (d) is carried out: and cooling the system to finish cooling. After the tantalum core is deoxygenated, the system temperature is lowered to facilitate system maintenance and removal of the tantalum core.
In a preferred embodiment, the alkali metal is selected from at least one of magnesium, aluminum, calcium.
In a more preferred embodiment, the alkali metal is magnesium, and the temperature is 650-1000 ℃, preferably 700-950 ℃, and more preferably 750-900 ℃; the pressure is 2000-35000Pa, preferably 10000-20000Pa, which can ensure that the magnesium vapor can be kept to volatilize but not to boil, thus improving the controllability and safety of the production process, and the plasma is not easy to form when the pressure is too high or too low.
Optionally, the temperature is 650 ℃, 700 ℃, 750 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃.
Optionally, the pressure is 700Pa, 2000Pa, 4500Pa, 10000Pa, 15000Pa, 20000Pa, 35000Pa, or 45000 Pa.
In a preferred embodiment, the inert gas with the alkali metal vapor is obtained by passing an inert gas through an alkali metal vapor source, preferably the alkali metal vapor source is obtained by heating an alkali metal to a temperature above its melting point to form a liquid and volatilizing the liquid.
In a preferred embodiment, the temperature of the inert gas is 650-. The inert gas is preheated to 650-1200 ℃, so that the required temperature condition can be provided for the reaction, and the alkali metal vapor can be prevented from being condensed on the inner wall of the equipment.
Optionally, the temperature is 650 deg.C, 750 deg.C, 800 deg.C, 900 deg.C, 1000 deg.C, 1050 deg.C, 1100 deg.C or 1200 deg.C.
In a preferred embodiment, the inert gas is argon. In the inert gas, nitrogen is not strictly an inert gas, and is easy to react with oxygen to form nitrogen oxide under the activation action; helium and neon are expensive and are generally not used in order to reduce cost; the argon gas is cheap and has stable property under the action of activation.
In a preferred embodiment, in the step (b), the tantalum core is placed in the inert gas plasma containing the alkali metal for 5-1000min, preferably 50-800min, and more preferably 200-600min, so that the oxygen in the tantalum core reacts with the alkali metal to form the alkali metal oxide. The anode tantalum core is pressed by powder, and if the pressed powder is compact, the capacity of the formed capacitor is smaller, the effect is more difficult, and the acting time is longer; if the pressing is loose, the capacity of the formed capacitor is large, the action is easy, and the action time is short.
Optionally, the time is 5min, 50min, 200min, 400min, 500min, 600min, 800min, 900min or 1000 min.
In a preferred embodiment, in the step (c), the tantalum core is exposed to the inert gas plasma for 1 to 100min, preferably 10 to 80min, and more preferably 40 to 60min, and the generated alkali metal oxide is discharged with the inert gas.
Optionally, the time is 1min, 10min, 40min, 50min, 60min, 80min or 100 min.
In a preferred embodiment, the plasma is a magnetized plasma; preferably a capacitively coupled plasma, an inductively coupled plasma or a magnetic field enhanced CCP radio frequency plasma. The magnetized plasma is different from high-temperature plasma, and forms plasma under the action of high-frequency oscillation electromagnetism at lower temperature, so that the anode material is not denatured.
According to a second aspect of the invention, the invention provides equipment for reducing the oxygen content of an anode tantalum core, which comprises a heat insulation pipeline, wherein the heat insulation pipeline is communicated with a heat insulation container, an inlet is formed in one end of the heat insulation pipeline, an outlet is formed in the bottom of the heat insulation container, a container and a liftable cover plate are arranged in the heat insulation pipeline, the cover plate is positioned above the container, an induction heater is arranged on the container, an upper electrode and a lower electrode are arranged in the heat insulation container, and the upper electrode and the lower electrode are connected with a high-frequency power supply.
The equipment for reducing the oxygen content of the anode tantalum core provided by the invention has the working process that: the magnesium metal material is placed in a container and melted into a liquid by an induction heater around the container. In the case of low ambient pressure, magnesium vapor is generated. High-purity argon preheated to a temperature higher than the melting point of magnesium is introduced from the inlet, and when the high-purity argon flows over the container, magnesium steam is brought into the heat-insulating pipeline by the argon and finally enters the heat-insulating container.
In the center of the heat-insulating container, the argon with magnesium vapor is ionized into plasma through discharge between an upper electrode and a lower electrode of a high-frequency power supply. A tantalum core to be treated is placed in the plasma region. After the tantalum core is subjected to plasma treatment for a period of time, the opening of the container is closed by the upper cover plate. After the cover plate is closed, the plasma will not carry magnesium vapor any more, and the magnesium and oxides in the tantalum core will diffuse into the argon plasma and be carried away through the outlet. After the pure argon gas ventilation process lasts for a period of time, stopping inputting argon gas, closing a high-frequency power supply of the plasma source, gradually cooling the system, and finishing cooling.
The equipment has the advantages of low investment, low operating cost, stability, reliability and convenient operation and management.
It should be noted that the cover plate is vertically provided with a driving rod, the heat preservation pipeline is provided with a through hole, and the driving rod penetrates through the through hole and can move up and down in the through hole. The cover plate moves downwards to close the opening of the container, and the magnesium vapor is not carried by the plasma any more; the cover plate moves upwards to open the opening of the container, magnesium vapor volatilizes out, and the plasma carries the magnesium vapor. The setting of through-hole, easy to assemble and dismantlement also can avoid the apron to produce when reciprocating and rock.
It should be noted that the driving rod is driven by a driving unit, and the driving unit is driven by a hand, a hydraulic cylinder, a pneumatic cylinder or a motor.
It should also be noted that the through hole and the driving rod are sealed by a sealing structure. The purpose of sealing is to avoid the magnesium vapor in the insulated pipeline from reacting with the external oxygen. Preferably, the sealing structure is a sealing ring, the sealing ring is located in the through hole, and the driving rod is in contact with the sealing ring. The sealing ring has the advantages of simple structure, convenient installation and disassembly and good sealing effect.
It should also be noted that the sealing can also be performed by blowing argon gas, that is, argon gas is blown at the contact position of the through hole and the driving rod, and the sealing is isolated from the external oxygen by argon gas. It should also be noted that a carrier support is arranged on the lower electrode. The carrying support is used for placing the tantalum core, and the tantalum core is subjected to deoxidation treatment on the carrying support, so that the damage to the lower electrode caused by direct contact of the tantalum core and the lower electrode is avoided. The carrier support may be in direct contact with the lower electrode or may be disposed on the lower electrode via other support structures.
It should be noted that the material of the carrying bracket is a high temperature resistant material. The material of the carrier support can be, but is not limited to, molybdenum, tungsten, tantalum and other metals. In order to facilitate a clearer understanding of the present invention, the technical solution of the present invention will be further described below with reference to examples and comparative examples.
Example one
The embodiment provides a method for reducing the oxygen content of an anode tantalum core, which comprises the following steps:
(a) heating a magnesium material to obtain magnesium steam under the conditions that the temperature is 750 ℃ and the pressure is 10000Pa, passing high-purity argon gas flow which is preheated to 800 ℃ and has the purity of more than 5N through a magnesium steam source, wherein the magnesium steam generates steam pressure of about 2000Pa, plasmatizing the argon gas with the magnesium steam to form argon gas plasma containing the magnesium steam, and the plasma is capacitively coupled plasma;
(b) placing the tantalum core in argon plasma containing magnesium steam to keep for 400min, so that oxygen in the tantalum core reacts with magnesium ions to generate magnesium oxide;
(c) isolating a magnesium metal steam source, introducing argon, placing the tantalum core in an argon plasma for 50min, and discharging generated alkaline metal oxide along with inert gas;
(d) stopping inputting argon, closing a high-frequency power supply of the plasma source, and cooling the system to finish the deoxidation process operation of the tantalum core.
As shown in fig. 1-3, this embodiment further provides an apparatus for reducing oxygen content in an anode tantalum core, which includes a thermal insulation pipe 4, a thermal insulation pipe 4 communicated with a thermal insulation container 5, an inlet 6 disposed at one end of the thermal insulation pipe 4, an outlet 10 disposed at the bottom of the thermal insulation container 5, a container 2 and a liftable cover plate 7 disposed in the thermal insulation pipe 4, the cover plate 7 being disposed above the container 2, a driving rod 15 vertically disposed on the cover plate 7, the driving rod 15 passing through the through hole 14, the induction heating device can move up and down in the through hole 14, the through hole 14 and the driving rod 15 are sealed through the sealing ring 16, the sealing ring 16 is located in the through hole 14, the driving rod 15 is in contact with the sealing ring 16, the induction heater 3 is arranged on the container 2, the upper electrode 12 and the lower electrode 11 are arranged in the heat preservation container 5, the lower electrode 11 is provided with a carrying support 17, the carrying support 17 is made of tantalum, and the upper electrode 12 and the lower electrode 11 are connected with the high-frequency power supply 9.
The equipment for reducing the oxygen content of the anode tantalum core provided by the embodiment has the working process that: a metal material magnesium 1 is placed in a container 2, and the magnesium material is melted into a liquid by a heater 3. The cover 7 is manually driven to move upwards to open the opening of the container 2, and magnesium vapour is generated at low ambient pressure. High-purity argon preheated to a temperature exceeding the melting point of magnesium is introduced from the inlet 6, and when the high-purity argon flows over the container 2, magnesium steam is brought into the heat-insulating pipeline 4 by the argon and finally enters the heat-insulating container 5.
In the center of the heat-insulating container 5, the argon gas with magnesium vapor is ionized into plasma 8 by capacitive coupling discharge between the upper electrode 12 and the lower electrode 11 of the high-frequency power supply 9. The tantalum core to be treated is placed on the carrier support 17 and is located in the plasma region. After the tantalum core is subjected to plasma treatment for a period of time, the cover plate 7 is manually driven to move downwards to close the opening of the container 2, after the cover plate 7 is closed, magnesium steam is not carried by the plasma any more, and magnesium and oxides in the tantalum core are diffused into the argon plasma and taken away through the outlet 10. After the pure argon gas ventilation process lasts for a period of time, stopping inputting the argon gas, closing the high-frequency power supply 9 of the plasma source, gradually cooling the system and finishing cooling.
Example two
The embodiment provides a method for reducing the oxygen content of an anode tantalum core, which comprises the following steps:
(a) heating a magnesium material to obtain magnesium vapor under the conditions that the temperature is 900 ℃ and the pressure is 20000Pa, passing a high-purity argon gas flow with the purity of more than 5N which is preheated to 1000 ℃ through a magnesium vapor source, wherein the magnesium vapor generates vapor pressure of about 14000Pa, plasmatizing the argon gas with the magnesium vapor to form argon plasma containing the magnesium vapor, and the plasma is induction coupling plasma;
(b) placing the tantalum core in argon plasma containing magnesium steam to keep for 200min, so that oxygen in the tantalum core reacts with magnesium ions to generate magnesium oxide;
(c) isolating a magnesium metal steam source, introducing argon, placing the tantalum core in an argon plasma for 60min, and discharging generated alkaline metal oxide along with inert gas;
(d) stopping inputting argon, closing a high-frequency power supply of the plasma source, and cooling the system to finish the deoxidation process operation of the tantalum core.
EXAMPLE III
The embodiment provides a method for reducing the oxygen content of an anode tantalum core, which comprises the following steps:
(a) heating a magnesium material to obtain magnesium vapor under the conditions that the temperature is 650 ℃ and the pressure is 2000Pa, passing a high-purity argon gas flow with the purity of more than 5N which is preheated to 650 ℃ through a magnesium vapor source, wherein the magnesium vapor generates vapor pressure of about 360Pa, plasmatizing the argon gas with the magnesium vapor to form argon plasma containing the magnesium vapor, and the plasma is magnetic field enhanced CCP radio frequency plasma;
(b) placing the tantalum core in argon plasma containing magnesium steam to keep for 600min, so that oxygen in the tantalum core reacts with magnesium ions to generate magnesium oxide;
(c) isolating a magnesium metal steam source, introducing argon, placing the tantalum core in an argon plasma for 40min, and discharging generated alkaline metal oxide along with inert gas;
(d) stopping inputting argon, closing a high-frequency power supply of the plasma source, and cooling the system to finish the deoxidation process operation of the tantalum core.
Example four
The embodiment provides a method for reducing the oxygen content of an anode tantalum core, which comprises the following steps:
(a) heating a magnesium material to obtain magnesium vapor under the conditions that the temperature is 850 ℃ and the pressure is 15000Pa, passing high-purity argon gas flow with the purity of more than 5N which is preheated to 900 ℃ through a magnesium vapor source, wherein the magnesium vapor generates the vapor pressure of about 7800Pa, plasmatizing the argon gas with the magnesium vapor to form argon plasma containing the magnesium vapor, and the plasma is capacitively coupled plasma;
(b) placing the tantalum core in argon plasma containing magnesium steam for 500min to enable oxygen in the tantalum core to react with magnesium ions to generate magnesium oxide;
(c) isolating a magnesium metal steam source, introducing argon, placing the tantalum core in an argon plasma for 80min, and discharging generated alkaline metal oxide along with inert gas;
(d) stopping inputting argon, closing a high-frequency power supply of the plasma source, and cooling the system to finish the deoxidation process operation of the tantalum core.
EXAMPLE five
The embodiment provides a method for reducing the oxygen content of an anode tantalum core, which comprises the following steps:
(a) heating a magnesium material to obtain magnesium vapor under the conditions that the temperature is 950 ℃ and the pressure is 35000Pa, passing a high-purity argon gas flow with the purity of more than 5N which is preheated to 1050 ℃ through a magnesium vapor source, wherein the magnesium vapor generates vapor pressure of about 25000Pa, and plasmatizing the argon gas with the magnesium vapor to form argon plasma containing the magnesium vapor, wherein the plasma is inductively coupled plasma;
(b) placing the tantalum core in argon plasma containing magnesium steam for 800min to enable oxygen in the tantalum core to react with magnesium ions to generate magnesium oxide;
(c) isolating a magnesium metal steam source, introducing argon, placing the tantalum core in an argon plasma for 10min, and discharging generated alkaline metal oxide along with inert gas;
(d) stopping inputting argon, closing a high-frequency power supply of the plasma source, and cooling the system to finish the deoxidation process operation of the tantalum core.
EXAMPLE six
The embodiment provides a method for reducing the oxygen content of an anode tantalum core, which comprises the following steps:
(a) heating a magnesium material to obtain magnesium vapor under the conditions that the temperature is 700 ℃ and the pressure is 4500Pa, passing high-purity argon gas with the purity of more than 5N which is preheated to 750 ℃ through a magnesium vapor source, wherein the magnesium vapor generates vapor pressure of about 900Pa, plasmatizing the argon gas with the magnesium vapor to form argon plasma containing the magnesium vapor, and the plasma is magnetic field enhanced CCP radio frequency plasma;
(b) placing the tantalum core in argon plasma containing magnesium steam to keep for 1000min, so that oxygen in the tantalum core reacts with magnesium ions to generate magnesium oxide;
(c) isolating a magnesium metal steam source, introducing argon, placing the tantalum core in an argon plasma for 1min, and discharging generated alkaline metal oxide along with inert gas;
(d) stopping inputting argon, closing a high-frequency power supply of the plasma source, and cooling the system to finish the deoxidation process operation of the tantalum core.
EXAMPLE seven
The embodiment provides a method for reducing the oxygen content of an anode tantalum core, which comprises the following steps:
(a) heating a magnesium material to obtain magnesium vapor under the conditions that the temperature is 1000 ℃ and the pressure is 45000Pa, passing high-purity argon gas with the purity of more than 5N which is preheated to 1200 ℃ through a magnesium vapor source, wherein the magnesium vapor generates vapor pressure of about 40000Pa, plasmatizing the argon gas with the magnesium vapor to form argon plasma containing the magnesium vapor, and the plasma is capacitively coupled plasma;
(b) placing the tantalum core in argon plasma containing magnesium steam for 50min to enable oxygen in the tantalum core to react with magnesium ions to generate magnesium oxide;
(c) isolating a magnesium metal steam source, introducing argon, placing the tantalum core in an argon plasma for 100min, and discharging generated alkaline metal oxide along with inert gas;
(d) stopping inputting argon, closing a high-frequency power supply of the plasma source, and cooling the system to finish the deoxidation process operation of the tantalum core.
Comparative example 1
The comparative example provides a method for reducing the oxygen content of an anodic tantalum core comprising the steps of:
(a) heating a magnesium material to obtain magnesium vapor under the conditions that the temperature is 750 ℃ and the pressure is 10000Pa, and passing a high-purity argon gas stream which is preheated to 800 ℃ and has the purity of more than 5N through a magnesium vapor source, wherein the magnesium vapor generates the vapor pressure of about 2000 Pa;
(c) placing the tantalum core in magnesium steam for 400 min;
(d) isolating a magnesium metal steam source, introducing argon, and placing the tantalum core in the argon for 50 min;
(d) stopping inputting argon, cooling the system and finishing the deoxidation process operation of the tantalum core.
Comparative example No. two
The comparative example provides a method for reducing the oxygen content of an anodic tantalum core comprising the steps of:
(a) passing magnesium vapor at a pressure of 0.1MPa through a tantalum core at a temperature of 2000 deg.C;
(c) placing the tantalum core in magnesium steam for 1000 min;
(d) isolating a magnesium metal steam source, introducing argon, and placing the tantalum core in the argon for 50 min;
(d) stopping inputting argon, cooling the system and finishing the deoxidation process operation of the tantalum core.
Comparative example No. three
The comparative example provides a method for reducing the oxygen content of an anodic tantalum core comprising the steps of:
(a) passing magnesium vapor at a pressure of 0.2MPa through the tantalum core at a temperature of 2000 deg.C; (ii) a
(c) Placing the tantalum core in magnesium steam for 400 min;
(d) isolating a magnesium metal steam source, introducing argon, and placing the tantalum core in the argon for 50 min;
(d) stopping inputting argon, cooling the system and finishing the deoxidation process operation of the tantalum core.
Comparative example No. four
Without any treatment.
The tantalum cores produced in the same batch are treated according to the methods of the examples and the comparative examples respectively, sintering is completed at 1400 ℃ by the same equipment and process after treatment, then the formation process is completed for 2 hours under the voltage of 30V and 0.02% phosphoric acid solution, and finally the electrical property test of the tantalum cores is carried out, and the test results are shown in Table 1.
The results of the tantalum core performance tests in each of the examples and comparative examples are shown in table 1.
TABLE 1 tantalum core Performance test results
As can be seen from the table, the capacitance value of the tantalum core treated by the process of the invention is not obviously changed relative to the capacitance value of the tantalum core not treated by any process in the comparative example IV, but the relative leakage current is reduced, the breakdown voltage is improved, and the performance is obviously improved. The capacitance value of the tantalum core treated in the first embodiment of the invention is not obviously changed relative to the capacitance value of the tantalum core which is not treated by any process in the fourth comparative example, but the relative leakage current is reduced by 40.6%, and the breakdown voltage is improved by 42.1%. The method in the first comparative example does not carry out plasma treatment on magnesium vapor, so that the tantalum core and the magnesium vapor directly react, and the result shows that the capacity value of the tantalum core is not obviously changed, the relative leakage current is only reduced by 18.7%, and the breakdown voltage is only improved by 15.7%. The method in the second comparative example does not carry out plasma treatment on the magnesium vapor, so that the tantalum core and the magnesium vapor directly carry out high-temperature and long-time reaction, and the capacitance value of the tantalum core is obviously reduced due to the high-temperature reaction although the relative leakage current is reduced and the breakdown voltage is improved. In the method of the third comparative example, the magnesium vapor is not subjected to plasma treatment, so that the tantalum core and the magnesium vapor are directly subjected to high-temperature and high-pressure reaction, and although the relative leakage current is reduced and the breakdown voltage is improved, the capacitance value of the tantalum core is obviously reduced due to the high-temperature reaction, the manufacturing difficulty of equipment is high due to the high temperature and high temperature, and the control on the process is also difficult.
In conclusion, the method of the invention activates the alkali metal ions through the plasma, accelerates the reaction speed of oxygen atoms and the alkali metal ions, and reduces the treatment time of the deoxidation process; compared with the traditional method, the method of the invention needs lower environmental temperature and pressure, and improves the controllability and safety of the production process; the method can effectively reduce the oxygen concentration in the tantalum core and improve the pressure resistance and other performances of the final tantalum capacitor.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (18)
1. A method for reducing the oxygen content of an anodic tantalum core, comprising the steps of, in order:
(a) the method comprises the following steps Under the conditions that the temperature is higher than the melting point and lower than the boiling point of the alkali metal and the pressure is 700-45000Pa, the inert gas with the alkali metal steam is plasmatized to form inert gas plasma containing the alkali metal;
wherein the inert gas with the alkali metal steam is obtained by flowing the inert gas through an alkali metal steam source; the alkaline metal vapor source is obtained by heating an alkaline metal to a temperature above the melting point to form a liquid and volatilizing the liquid; the alkali metal is selected from at least one of magnesium, aluminum or calcium;
(b) the method comprises the following steps Placing the tantalum core in inert gas plasma containing alkali metal to enable oxygen in the tantalum core to react with the alkali metal to generate alkali metal oxide;
(c) the method comprises the following steps Isolating an alkaline metal vapor source, continuously introducing the inert gas in the step (a), placing the tantalum core in an inert gas plasma, and discharging the generated alkaline metal oxide along with the inert gas;
(d) the method comprises the following steps And cooling the system to finish cooling.
2. The method as claimed in claim 1, wherein the alkali metal is magnesium, the temperature is 650-1000 ℃, and the pressure is 2000-35000 Pa.
3. The method as claimed in claim 2, wherein the temperature is 700 ℃ to 950 ℃.
4. The method as claimed in claim 2, wherein the temperature is 750-900 ℃.
5. The method for reducing the oxygen content in the tantalum core of the anode as claimed in claim 2, wherein the pressure is 10000-.
6. The method as claimed in claim 1, wherein the inert gas is at a temperature of 650-1200 ℃.
7. The method as claimed in claim 1, wherein the inert gas is at a temperature of 750-1050 ℃.
8. The method as claimed in claim 1, wherein the inert gas is at a temperature of 800-1000 ℃.
9. The method of reducing the oxygen content of an anodic tantalum core of claim 1 wherein said inert gas is argon.
10. The method for reducing the oxygen content of the anode tantalum core according to claim 1, wherein in the step (b), the tantalum core is placed in the inert gas plasma containing the alkali metal for 5-1000 min.
11. The method for reducing the oxygen content of the anode tantalum core according to claim 1, wherein in the step (b), the tantalum core is placed in the inert gas plasma containing the alkali metal for 50-800 min.
12. The method as claimed in claim 1, wherein the step (b) of subjecting the tantalum core to the alkali metal-containing inert gas plasma is performed for 200-600 min.
13. The method for reducing the oxygen content of the anode tantalum core as claimed in claim 1, wherein in the step (c), the tantalum core is exposed to the inert gas plasma for 1-100 min.
14. The method for reducing the oxygen content of the anode tantalum core as claimed in claim 1, wherein in the step (c), the tantalum core is exposed to the inert gas plasma for a time period of 10-80 min.
15. The method for reducing the oxygen content of the anode tantalum core as claimed in claim 1, wherein in the step (c), the tantalum core is exposed to the inert gas plasma for 40-60 min.
16. The method for reducing the oxygen content of an anode tantalum core according to claim 1, wherein said plasma is a magnetized plasma.
17. The method for reducing the oxygen content of the anode tantalum core according to claim 1, wherein the plasma is a capacitively coupled plasma, an inductively coupled plasma or a magnetic field enhanced CCP radio frequency plasma.
18. The equipment used for realizing the method for reducing the oxygen content of the anode tantalum core in any one of claims 1 to 17 is characterized by comprising a heat insulation pipeline, wherein the heat insulation pipeline is communicated with a heat insulation container, one end of the heat insulation pipeline is provided with an inlet, the bottom of the heat insulation container is provided with an outlet, the heat insulation pipeline is internally provided with a container and a liftable cover plate, the cover plate is positioned above the container, the container is provided with an induction heater, the heat insulation container is internally provided with an upper electrode and a lower electrode, and the upper electrode and the lower electrode are connected with a high-frequency power supply;
placing alkali metal in a container, melting the alkali metal into liquid through an induction heater, driving a liftable cover plate to move upwards, opening an opening of the container, generating alkali metal steam under the condition of low pressure, introducing inert gas preheated to the temperature exceeding the melting point of the alkali metal from an inlet of a heat preservation pipeline, introducing the alkali metal steam into the heat preservation pipeline by the inert gas when the alkali metal steam flows above the container, introducing the alkali metal steam into the heat preservation pipeline and then into the heat preservation container, in the heat preservation container, carrying out capacitive coupling discharge between an upper electrode and a lower electrode through a high-frequency power supply to ionize the inert gas with the alkali metal steam into plasma, placing a tantalum core between the upper electrode and the lower electrode and locating in a plasma area, driving the liftable cover plate to move downwards after the tantalum core is subjected to plasma treatment, closing the opening of the container, and diffusing the alkali metal and oxides in the tantalum core into the inert gas plasma and bringing the alkali metal and the oxides into the inert gas plasma through an outlet of the And (4) walking.
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| US6171363B1 (en) * | 1998-05-06 | 2001-01-09 | H. C. Starck, Inc. | Method for producing tantallum/niobium metal powders by the reduction of their oxides with gaseous magnesium |
| CN102965525B (en) * | 2012-12-05 | 2013-11-27 | 江门富祥电子材料有限公司 | Device and method for carrying out magnesium reduction and deoxidization on tantalum powder |
| CN202954080U (en) * | 2012-12-05 | 2013-05-29 | 江门富祥电子材料有限公司 | Magnesium reduction and deoxygenation device of tantalum powder |
| CN203245360U (en) * | 2012-12-05 | 2013-10-23 | 江门富祥电子材料有限公司 | A device used for reducing tantalum powder by using magnesium to reduce oxygen content and provided with conic heat shields |
| CN103084568B (en) * | 2012-12-05 | 2014-12-03 | 江门富祥电子材料有限公司 | Device used for reducing tantalum powder by using magnesium to reduce oxygen content and provided with cooler and method for reducing tantalum powder by using magnesium to reduce oxygen content |
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