RU2267182C2 - Niobium powder, sintered niobium material and capacitor made from this sintered material - Google Patents

Abstract

FIELD: niobium powder for manufacture of capacitors of high specific capacitance.

SUBSTANCE: proposed niobium powder includes at least one element of group containing chromium, molybdenum, tungsten, boron, aluminum, gallium, indium, thallium, cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic, bismuth, rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium; sintered material is made from niobium powder; capacitor includes sintered material as one electrode, dielectric material formed on surface of sintered material and counter-electrode located on dielectric material.

EFFECT: enhanced heat stability of capacitor and high capacitance per unit of mass at low leakage current.

48 cl, 29 tbl, 231 ex

Description

Technical field

The present invention relates to a niobium powder having a large capacity per unit mass and good leakage current characteristics, to sintered material obtained using the above niobium powder, and to a capacitor made using the above sintered material.

State of the art

Capacitors for use in electronic devices such as a portable telephone and personal computer must be small in size and have a large capacity. Among these capacitors, a tantalum capacitor is preferably used, due to its considerable capacitance with small size and good performance. In a tantalum capacitor, sintered material obtained from tantalum powder is usually used as an anode. In order to increase the capacity of the tantalum capacitor, it is necessary to increase the mass of the sintered material or use sintered material with an increased surface area resulting from the grinding of tantalum powder.

An increase in the mass of sintered material inevitably leads to an increase in the size of the capacitor, which does not satisfy the requirement of reducing the size of the capacitor. On the other hand, with fine grinding of tantalum powder to increase the specific surface area, the pore diameter in the sintered material based on tantalum decreases, and the number of closed pores increases at the sintering stage. As a result of this, impregnation with a cathode agent in a subsequent step becomes difficult.

As one of the approaches to solving these problems, a capacitor can be considered that uses sintered material from a powder material, which has a higher dielectric constant than the dielectric constant of tantalum powder. One of the powder materials that has such a higher dielectric constant is niobium powder.

JP 55-157226 discloses a method for producing a sintered element for a capacitor. This method includes the following stages: a niobium powder containing various particles, from agglomerates to fine particles with a size of 2.0 μm or less, is molded under pressure and then sintered, the molded sintered material is ground finely, the resulting finely ground particles are mixed with a portion of lead and after this sinter the resulting mixture. However, in the above application, the characteristics of the obtained capacitor are not described in detail.

US Pat. No. 4,084,965 discloses a capacitor made using sintered material of niobium powder having a particle size of 5.1 μm, said powder obtained from a niobium ingot by hydrogenation and pulverization. However, such a capacitor has a high leakage current (hereinafter referred to as the LC value) and is of little practical interest.

As shown in JP 10-242004, Patent Application Laid-Open, the LC value improves with partial nitriding of the niobium powder. However, in the case where a capacitor having a large capacity is made of niobium powder with a small particle diameter, the LC value of the manufactured capacitor can become extremely high.

US Pat. No. 6,051,044 discloses a niobium powder that has a specific specific surface area, determined by adsorption isotherms by the Braunauer-Emet-Teller method (BET surface), and which contains a certain amount of nitrogen. A method for reducing leakage current is also disclosed. However, no suggestions are made regarding the niobium powder containing other elements that can form an alloy with niobium. In addition, this patent does not disclose or suggest what kind of heat resistance is needed to solder capacitors and the like, and how to stabilize the LC value if the capacitor is subjected to heat treatment.

SUMMARY OF THE INVENTION

The aim of the present invention is to obtain a niobium powder suitable for capacitors having good heat resistance along with a large capacity per unit mass and characterized by a low leakage current; The aim of the invention is also to obtain sintered material obtained using the above niobium powder, and to obtain a capacitor using the above sintered material.

As a result of extensive research aimed at solving the above problems, the inventors of the present invention have found that a low LC value and good heat resistance can be achieved even when a capacitor having a large capacity is obtained by reducing the particle diameter of the niobium powder when added to niobium at least one element selected from various elements that can form an alloy with niobium. This is the meaning of the present invention. Namely, the present invention essentially provides the ability to obtain niobium powder according to the following items (1) to (29), sintered material according to items (30) and (31), obtained by sintering niobium powders, a capacitor according to items (32) to (42), and also provides a method for producing niobium powders according to paragraphs (43) to (46), an electronic circuit according to paragraph (47), and an electronic device according to paragraph (48). The term "alloy" in the description of this application includes a solid solution with other components of the alloy. The terms "parts by weight" per million "and% in the description of this application mean" mass parts per million "and"% by weight ", respectively, unless otherwise indicated.

(1) Niobium powder for capacitors comprising at least one element selected from the group consisting of chromium, molybdenum, tungsten, boron, aluminum, gallium, indium, thallium, cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium silver, zinc, silicon, germanium, tin, phosphorus, arsenic, bismuth, rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium , ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and bodies lura.

(2) The niobium powder for capacitors according to (1) above, comprising at least one element selected from the group consisting of chromium, molybdenum and tungsten.

(3) The niobium powder for capacitors according to (2) above, wherein said at least one element is tungsten.

(4) The niobium powder for capacitors according to (2) above, wherein said at least one element is chromium and tungsten.

(5) The niobium powder for capacitors according to (1) above, comprising at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium.

(6) The niobium powder for capacitors according to (5) above, wherein said at least one element is boron.

(7) The niobium powder for capacitors according to (5) above, wherein said at least one element is aluminum.

(8) The niobium powder for capacitors according to (1) above, comprising at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium , tin, phosphorus, arsenic and bismuth.

(9) The niobium powder for capacitors according to (8) above, comprising at least one element selected from the group consisting of rhenium, zinc, arsenic, phosphorus, germanium, tin and neodymium.

(10) The niobium powder for capacitors according to (9) above, wherein said at least one element is rhenium.

(11) The niobium powder for capacitors according to (9) above, wherein said at least one element is neodymium.

(12) The niobium powder for capacitors according to (9) above, wherein said at least one element is zinc.

(13) The niobium powder for capacitors according to (1) above, comprising at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium , gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium.

(14) The niobium powder for capacitors according to (13) above, comprising at least one element selected from the group consisting of lanthanum, yttrium, erbium, ytterbium and lutetium.

(15) The niobium powder for capacitors according to (14) above, wherein said at least one element is lanthanum.

(16) The niobium powder for capacitors according to (14) above, wherein said at least one element is yttrium.

(17) The niobium powder according to any one of paragraphs 1 to 16 above, wherein said at least one element is contained in the niobium powder in an amount of 10 mol% or less.

(18) The niobium powder according to (17) above, wherein said at least one element is contained in said niobium powder in an amount of from 0.01 to 10 mol%.

(19) The niobium powder according to (18) above, wherein said at least one element is contained in said niobium powder in an amount of from 0.1 to 7 mol%.

(20) The niobium powder according to any one of 1 to 16 above, the average particle size of which is from 0.05 to 5 μm.

(21) The niobium powder according to (20) above, the average particle size of which is from 0.2 to 4 microns.

(22) The niobium powder according to any one of items 1 to 16 above, the specific surface of which, determined by the adsorption isotherms by the Braunauer-Emet-Teller method (BET surface), is from 0.5 to 40 m ² / g.

(23) The niobium powder according to paragraph 22 above, the specific BET surface of which is from 1 to 20 m / g.

(24) The niobium powder according to any one of paragraphs 2, 3, 4, 7, 8, 9, 10, 11, 12, 13, 14, 15, and 16 above, further comprising at least one element selected from the group consisting of nitrogen, carbon, boron and sulfur.

(25) The niobium powder according to paragraph 5 or 6 above, further comprising at least one element selected from the group consisting of nitrogen, carbon and sulfur.

(26) The niobium powder according to paragraph 24 or 25 above, wherein at least one element selected from the group consisting of nitrogen, carbon, boron and sulfur is contained in an amount of 200,000 parts by weight. per million or less.

(27) The niobium powder according to paragraph 26 above, wherein at least one element selected from the group consisting of nitrogen, carbon, boron and sulfur is contained in an amount of from 50 parts by weight. per million up to 200,000 parts by weight per million

(28) A granular niobium product obtained by granulating said niobium powder according to any one of 1 to 27 above, the average particle size of which is from 10 μm to 500 μm.

(29) The granular niobium product according to paragraph 28 above, the average particle size of which is from 30 μm to 250 μm.

(30) Sintered material made using niobium powder according to any one of items 1 to 27 above.

(31) Sintered material made using the specified granular niobium product according to paragraph 28 or 29 above.

(32) A capacitor including an electrode made using said sintered niobium material according to paragraph 30 or 31 above, wherein a dielectric material is formed on the surface of said electrode and a counter electrode is formed on said dielectric material.

(33) The capacitor according to paragraph 32 above, wherein said dielectric material includes niobium oxide as a main component.

(34) The capacitor according to paragraph 33 above, wherein said niobium oxide is obtained by electrolytic oxidation.

(35) The capacitor according to paragraph 32 above, wherein said counter electrode comprises at least one material selected from the group consisting of an electrolyte solution, an organic semiconductor, and an inorganic semiconductor.

(36) The capacitor according to paragraph 32 above, wherein said counter electrode includes an organic semiconductor, which includes at least one material selected from the group consisting of an organic semiconductor including a tetramer of benzopyrroline and chloranil, an organic semiconductor including, as a main component tetratiotetracene, an organic semiconductor comprising tetracyanoquinodimethane as the main component, and an electrically conductive polymer.

(37) The capacitor according to paragraph 36 above, wherein said electrically conductive polymer is at least one polymer selected from the group consisting of polypyrrole, polythiophene, polyaniline and substituted derivatives thereof.

(38) The capacitor according to paragraph 36 above, wherein said electrically conductive polymer is obtained by introducing a dopant into a polymer containing a repeating unit represented by the general formula (1) or (2):

in which the radicals from R ¹ to R ⁴ each may be the same or different, and each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a linear or branched alkyl, alkoxyl group or an alkyl substituted ester group containing from 1 to 10 carbon atoms, which may be saturated or unsaturated, a halogen atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, and a substituted or unsubstituted phenyl group, each of the pairs R ¹ and R ² , R ³ and R ⁴ can independently form a bivalent chain in combination, forming a saturated or unsaturated cyclic hydrocarbon structure containing at least one 3-7-membered ring system, together with carbon atoms, substituted when combined in an arbitrary position of the hydrocarbon chains represented by radicals R ¹ and R ² radicals, or R ³ and R ^4, said cyclic obtained when combined chain may contain a bond of carbonyl, ether, ester, amide, sulfide group, sous finilom, sulfonyl or imino at an arbitrary position; X represents an oxygen atom, a sulfur atom or a nitrogen atom; R ⁵ , which is present only when X represents a nitrogen atom, independently represents a hydrogen atom or a linear or branched alkyl group containing from 1 to 10 carbon atoms, wherein said group may be saturated or unsaturated.

(39) The capacitor according to paragraph 38 above, wherein said electrically conductive polymer includes a repeating unit represented by the general formula (3):

in which R ⁶ and R ⁷ , which may be the same or different, each independently represents a hydrogen atom, a linear or branched alkyl group containing from 1 to 6 carbon atoms, which may be saturated or unsaturated, or a substituent group forming at at least one 5-, 6- or 7-membered saturated hydrocarbon cyclic structure containing two oxygen atoms, obtained by combining the alkyl groups represented by the radicals R ⁶ and R ⁷ at an arbitrary position, where the cyclic structure may incl chat substituted or unsubstituted vinylene linkage or a substituted or unsubstituted phenylene structure.

(40) The capacitor according to paragraph 39 above, in which the electrically conductive polymer containing said recurring unit represented by formula (3) is

poly (3,4-ethylenedioxythiophene).

(41) The capacitor according to paragraph 36 above, wherein the counter electrode includes an organic semiconductor having a layered structure.

(42) The capacitor according to paragraph 36 above, wherein said counter electrode is an organic semiconductor material that contains an organic sulfonic acid anion as a dopant.

(43) The method for producing the nitrogen-containing niobium powder according to paragraph 24 or 25 above, wherein the niobium powder is surface-treated using at least one method selected from the group consisting of liquid-phase nitriding, ion nitriding and gas-phase nitriding.

(44) The method for producing a carbon-containing niobium powder according to paragraph 24 or 25 above, wherein the niobium powder is surface-treated using at least one method selected from the group consisting of gas-phase carbonization, solid-phase carbonization, and liquid phase carbonization.

(45) The method for producing a boron-containing niobium powder according to paragraph 24 above, wherein the niobium powder is surface-treated using at least one method selected from the group consisting of gas-phase boronization and solid-phase boronation.

(46) The method for producing a niobium powder containing sulfur according to paragraph 24 or 25 above, wherein the niobium powder is surface-treated using at least one method selected from the group consisting of gas phase sulfidation, ionic sulfidation and solid phase sulfidation.

(47) An electronic circuit made using a capacitor according to any one of the above 32 to 42.

(48) An electronic device made using a capacitor according to any one of the above 32 to 42.

DETAILED DESCRIPTION OF THE INVENTION

The capacitor, which is the subject of the present invention, having a large capacity and good characteristics of the leakage current, niobium powder and sintered material for its manufacture, which provide these good characteristics, will be described in more detail, divided into the following four groups ((1) ~ (4) ):

(1) Niobium powder for the manufacture of capacitors, comprising at least one element selected from the group consisting of chromium, molybdenum and tungsten, and sintered material obtained from such a powder (First group according to the present invention);

(2) Niobium powder for the manufacture of capacitors, comprising at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium, and sintered material obtained from the specified powder (Second group according to the present invention);

(3) Niobium powder for the manufacture of capacitors, comprising at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth, and sintered material obtained from this powder (Third group of inventions);

(4) Niobium powder for the manufacture of capacitors, comprising at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium, and sintered material obtained from the specified powder (Fourth group of inventions).

The first group (niobium powder and sintered material)

The first group that is part of the present invention relates to niobium powder and sintered material made from it, containing at least one element selected from transition elements of the sixth group of the Periodic system, that is, from chromium, molybdenum and tungsten.

Chromium, molybdenum and tungsten are elements that can form an alloy with niobium. Tungsten is most effective at reducing leakage current, while the efficiency of molybdenum and chromium decreases in that order. Therefore, it is most preferred that the niobium powder belonging to the first group included in the present invention contains tungsten. Such a tungsten-containing niobium powder may further comprise molybdenum and / or chromium, preferably chromium. The total amount of these elements in the niobium powder may be 10 mol% or less, preferably in the range of 0.01 mol% to 10 mol%, more preferably in the range of 0.1 mol% to 7 mol%.

According to the present invention, it is preferable to use sintered material from niobium powder for capacitors, and use niobium powder containing at least one element selected from the group consisting of chromium, molybdenum and tungsten in an amount of 10 mol% or less, preferably in the range from 0.01 mol.% to 10 mol.% of the amount of niobium powder.

If the content of the above cell is less than 0.01 mol%, it is not possible to impede the tendency for oxygen in the dielectric film formed during electrolytic oxidation, which will be described below, to be prone to diffusion towards niobium metal. Therefore, the stability of the film formed during electrolytic oxidation, i.e. the dielectric film cannot be preserved, as a result of which the LC value cannot be effectively reduced. If the content of the above element is more than 10 mol%, then the amount of niobium itself in the niobium powder is reduced. As a result, the capacitance of the capacitor decreases.

In light of the foregoing, the most preferred amount of at least one element selected from the group consisting of chromium, molybdenum and tungsten is in the range from 0.01 mol.% To 10 mol.%. In order to further reduce the leakage current, it is preferable that the above element is contained in a niobium powder in an amount of 3 mol% or less, and more preferably in the range from 0.05 to 3 mol%.

In order to increase the specific surface area of the powder, it is preferable that the average particle size of the niobium powder (average particle diameter) is 5 μm or less, more preferably 4 μm or less. Most preferably, the average particle size of the niobium powder of the present invention is 0.2 μm or more and 5 μm or less. The reasons for this are listed below.

The capacitance C of the capacitor is usually expressed by the following equation:

C = ε × (S / d),

in which C means capacitance, ε means dielectric constant, S means specific surface area, and d means the distance between the electrodes.

Since d = k × V, where k is constant and V means applied voltage, C = ε × (S / (k × V)); whence it follows that C × V = (ε / k) × S.

According to the equation, the capacitance of the capacitor will only increase with increasing specific surface area. Assuming that the particles of the niobium powder have a spherical shape, we can conclude that the smaller the particle diameter of the niobium powder, the greater the capacitance of the resulting capacitor. However, in reality, all powder particles do not have a perfectly spherical shape, and sometimes flocculent particles are contained in the powder.

As described above, the capacitor, which is the subject of the present invention, must have not only a large capacity, but also good characteristics of the leakage current. This cannot be achieved only by increasing the specific surface of the powder.

According to the present invention, when used as a raw material for the manufacture of a sintered material of niobium powder, which contains at least one element selected from the group consisting of chromium, molybdenum and tungsten, it becomes possible to manufacture a capacitor having most of the above characteristics and obtain a niobium sintered material which provides such capacitor characteristics.

Table 1 shows the particle diameter and specific surface area of the corresponding tungsten-containing niobium powders prepared by the authors of the present invention by grinding and which are one embodiment of the invention.

Table 1 The average particle size (D ₅₀ ) Specific Surface Area (S) 5 microns 0.6 m ² / g 2 microns 1.3 m ² / g 0.9 μm 2.3 m ² / g 0.5 μm 4.2 m ² / t 0.2 μm 10.0 m ² / t 0.1 μm 20.8 m ² / g 0.05 μm 38.8 m ² / g

The average particle size is indicated as a D ₅₀ value that corresponds to the particle diameter determined by measuring the particle size using a Microtrac device (trade name) manufactured by Microtrac Corporation when the weight percent reaches 50% of the cumulative mass distribution. The specific surface is a value measured by the BET method (Braunauer-Emet-Teller method).

In the case where the average particle size of the niobium powder containing at least one element selected from the group consisting of chromium, molybdenum and tungsten is less than 0.05 μm, the sintered material made from such niobium powder has a small pore size and contains many closed pores. Therefore, it may be difficult to impregnate with the agent used to obtain the cathode, as described below. This leads to the fact that the capacitance of the manufactured capacitor cannot be increased and, therefore, the above sintered material is not suitable for the manufacture of capacitors. In the case where the average particle size exceeds 5 μm, a large capacity cannot be obtained.

In light of the foregoing, according to the present invention, a large capacity can be obtained using niobium powder, the average particle size of which is preferably 0.05 μm or more and 5 μm or less.

Preferably, the specific BET surface of the niobium powder o according to the present invention is at least 0.5 m ² / g, more preferably at least 1.0 m ² / t, and even more preferably 2.0 m ² / g. It is further preferred that the niobium powder according to the present invention has a specific BET surface that is from 0.5 to 40 m ² / g, more preferably from 1 to 20 m ² / g, and particularly preferably from 1 to 10 m ² / g .

It is known that the dielectric constant (ε) of niobium is approximately two times higher than the dielectric constant of tantalum. However, it is known that chromium, molybdenum, and tungsten are valve-acting metals, which is one of the characteristics of a capacitor. Thus, it was not known that the dielectric constant ε of niobium powder containing at least one element selected from the group consisting of chromium, molybdenum and tungsten will increase.

According to the present invention, when the average particle size of a niobium powder containing at least one element selected from the group consisting of chromium, molybdenum and tungsten is controlled so that the particle size is small, and a sintered material is made from this powder with large capacity, the LC value does not especially increase.

It is assumed that this effect is as follows. The bond strength of niobium with oxygen is higher than the bond strength of tantalum with oxygen. Therefore, oxygen in the film obtained by electrolytic oxidation, i.e. in a dielectric film, has a tendency to diffusion towards metallic niobium. However, since part of the niobium and at least one element selected from the group consisting of chromium, molybdenum and tungsten are bonded together in the sintered material, oxygen has fewer possibilities for binding to niobium in the film obtained by electrolytic oxidation, which prevents the diffusion of oxygen into the metal .

As a result of this, it is possible to maintain the stability of the film obtained by electrolytic oxidation, and thus, it is believed that in the case of a large capacitor obtained from niobium powder with a small particle diameter, the effect of reducing the LC value and minimizing the dispersion of the LC value can be achieved.

The present invention will now be described for the case of using tungsten as an example of a transition metal of the 6th group of the Periodic System. The present invention is not limited to this example, and also extends to the use of chromium and molybdenum.

It is particularly preferred that the tungsten-containing niobium powder used to produce the sintered material has an average particle size of 0.2 μm or more and 5 μm or less, as mentioned above.

A tungsten-containing niobium powder having such an average particle size can be obtained, for example, from a niobium-tungsten alloy hydride in the form of an ingot, granules or powder by grinding and dehydrogenation. Alternatively, the niobium powder obtained by grinding and dehydrogenating an ingot, granules or powder of niobium hydride, or obtained by grinding into a powder a sodium-reduced form, which is potassium fluorobiobate, is mixed with tungsten carbide, tungsten oxide or tungsten powder. Or a mixture of niobium oxide and tungsten oxide can be subjected to carbon reduction.

For example, in the case when a tungsten-containing niobium powder is obtained by grinding and dehydrogenation from a niobium-tungsten alloy hydride in the form of an ingot, then by controlling the hydride content in the niobium-tungsten alloy and the grinding time, as well as by selecting the type of grinder, tungsten-containing niobium can be obtained powder with the required average particle size.

In addition, niobium powder with an average particle size of 0.2 μm or more to 5 μm or less can be added to the tungsten-containing niobium powder thus obtained. The niobium powder used for the addition can be obtained, for example, by grinding into a powder the sodium reduced form of potassium fluorobiobate or by grinding and dehydrogenating the hydrogenation product of a niobium ingot, or by reducing carbon with niobium oxide.

In order to further improve the leakage current characteristics of the sintered material obtained from the tungsten-containing niobium powder, at least one of the following elements selected from nitrogen, carbon, boron or sulfur can be partially attached to the tungsten-containing niobium powder. Any of the products, such as tungsten-containing niobium nitride, tungsten-containing niobium carbide, tungsten-containing niobium boride, tungsten-containing niobium sulfide, obtained by reacting with nitrogen, carbon, boron and sulfur, respectively, can be added separately, or can optionally be added from two to four kinds of specified products.

The amount of the bound element, i.e. the total content of carbon, nitrogen, boron or sulfur, which depends on the shape of the tungsten-containing niobium powder, can be more than 0 parts by weight per million, not more than 200,000 parts by weight per million, preferably, the specified amount should be in the range from 50 parts by weight per million to 100,000 parts by weight per million, more preferably from 200 wt. hours per million up to 20,000 parts by weight million, in the case when the tungsten-containing niobium powder has an average particle size of from 0.05 microns to 5 microns. If the total amount exceeds 200 parts by weight million, the characteristics of the capacitance deteriorate to such an extent that such a niobium powder becomes unsuitable for capacitors.

Nitrogenation of a tungsten-containing niobium powder can be carried out by any of the following methods: liquid-phase nitriding, ion nitriding and gas-phase nitriding, or by combining these methods. Gas phase nitriding in an atmosphere of gaseous nitrogen is preferred since the apparatus for this can be quite simple, and the method is easy to implement.

For example, when performing gas-phase nitriding in an atmosphere of gaseous nitrogen, a tungsten-containing niobium powder is kept in an atmosphere of gaseous nitrogen. A tungsten-containing niobium powder, partially nitrided to the required degree, can be obtained at a temperature of a nitriding gaseous medium of 2000 ° C or less, with holding for one hundred hours. Raising the processing temperature can reduce the processing time.

The tungsten-containing niobium powder may be carbonized by any of the following methods: gas phase carbonization, solid phase carbonization, or liquid phase carbonization. For example, a tungsten-containing niobium powder can be exposed together with a carbon source — a carbon-containing organic material such as carbon material or methane at 2000 ° C. or less under reduced pressure for one minute to one hundred hours.

Tungsten-containing niobium powder can be subjected to boronation by gas-phase boronization or by solid-phase boronation. For example, a tungsten-containing niobium powder may be subjected to exposure together with a boron source, such as boron granules or boron halide, such as boron trifluoride, under reduced pressure at a temperature of 2000 ° C or less for one minute to one hundred hours.

The tungsten-containing niobium powder may be subjected to sulfidation by any of the following methods: gas phase sulfidation, ionic sulfidation or solid phase sulfidation. For example, when conducting gas-phase sulfidation in an atmosphere of sulfur gas, a tungsten-containing niobium powder is kept in the atmosphere for sulfidation. A tungsten-containing niobium powder with a necessary degree of sulfidation can be obtained at a temperature of 2000 ° C or less, and a holding time of one hundred hours or less. The higher the processing temperature, the shorter the processing time.

In accordance with the present invention, a tungsten-containing niobium powder can be used for capacitors after granulation to achieve the desired configuration. Alternatively, the granular powder after granulation can be mixed with a suitable amount of non-granulated niobium powder.

With regard to granulation methods, the tungsten-containing niobium powder, not subjected to granulation, is kept in high vacuum, heated to a suitable temperature and then crushed. Alternatively, the non-granulated tungsten-containing niobium powder is mixed with a suitable binder such as camphor, polyacrylic acid, polymethyl methacrylate or polyvinyl alcohol, and a solvent such as acetone, alcohol, acetic acid ester or water, and then the resulting mixture is subjected crushing.

The use of a tungsten-containing niobium powder granulated in the same manner as described above can improve the formability during pressing carried out in the manufacture of the sintered material. In this case, it is preferable that the granular powder have an average particle size of from 10 μm to 500 μm. In the case where the granular powder has an average particle size of 10 μm or less, partial adhesion occurs, which reduces fluidity when filling the mold. In the case where the granular powder has an average particle size of 500 μm or more, after molding by pressing, the pointed parts of the molded product are easily split off. Preferably, the granular powders have an average particle size of from 30 μm to 250 μm, and particularly preferably from 60 μm to 250 μm, since in this case the sintered material is easily impregnated with the counter electrode material after forming the niobium powder under pressure.

The above nitriding, carbonization, boronation or sulfidation can be carried out not only in the case of niobium powder, but also in the case of granular niobium powder, as well as niobium sintered material.

A tungsten-containing niobium sintered material for manufacturing capacitors according to the present invention is obtained by sintering the aforementioned tungsten-containing niobium powder or granular tungsten-containing niobium powder. An example illustrating a method for manufacturing sintered material will be given below, but this example does not limit the invention. For example, a tungsten-containing niobium powder is subjected to injection molding to give a predetermined shape, and the molded material is heated at a temperature of from 500 ° C to 2000 ° C, preferably from 900 ° C to 1500 ° C, more preferably from 900 ° C to 1300 ° C, applying pressure from 10 ^-5 to 10 ² Pa (Pascal) for one minute to ten hours.

(2) The second group (niobium powder and sintered material)

The second group included in the composition of the present invention relates to a niobium powder containing at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium, said powder being used as a starting material.

Boron, aluminum, gallium, indium and thallium used in accordance with the present invention are elements that can form an alloy with niobium. Among these elements, boron and aluminum are the most effective in reducing the leakage current, gallium, indium, and thallium are the next most effective, and the efficiency decreases in this order. Accordingly, according to the present invention, it is particularly preferable to introduce boron and aluminum into the composition of the niobium powder. Boron-containing niobium powder may additionally contain aluminum, gallium, indium and thallium. The total amount of these elements in the niobium powder may be 10 mol% or less, preferably in the range of 0.01 mol% to 10 mol%, more preferably in the range of 0.1 mol% to 7 mol%. In other words, the niobium powder, which is subjected to molding to obtain a sintered material and which is used to make the capacitors according to the present invention, preferably contains at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium, in an amount of 10 mol% or less, more preferably in the range from 0.01 mol% to 10 mol%, particularly preferably in the range from 0.1 mol% to 7 mol%.

If the cell content is less than 0.01 mol%, it is difficult to prevent the diffusion of oxygen in the dielectric film formed by electrolytic oxidation, which will be described below, in the depth direction, into the mass of niobium metal, as a result of which the stability of the oxide film formed during electrolytic oxidation (dielectric film), it does not persist, and the effect of lowering the LC value is unlikely to be achieved. On the other hand, if the element content exceeds 10 mol%, then the amount of niobium proper in the niobium powder decreases, and as a result, the capacitance of the capacitor decreases.

Accordingly, the most preferred amount of at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium is in the range from 0.01 mol.% To 10 mol.%. In order to further reduce the leakage current, it is preferable that the content of the above element in the niobium powder is 7 mol% or less, more preferably from 0.10 to 7 mol%.

In order to reduce the specific surface area of the powder, it is preferred that the average particle size of the niobium powder is 5 μm or less, more preferably 4 μm or less. Thus, it is preferable that the average particle size of the niobium powder of the invention be from 0.05 to 4 μm. The reasons for this are described above in the description of niobium powder included in the first group.

According to the present invention, the niobium powder starting material used to make the sintered material is a niobium powder comprising at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium, whereby both a capacitor that meets the requirements described above, and a niobium sintered material capable of providing such properties of a capacitor.

The average particle size (D ₅₀ ; μm) and the specific surface (S, m ² / g) of boron-containing niobium powder, made as one example by the authors of the present invention (obtained by grinding into powder) are shown below in table 2.

table 2 The average particle size (D ₅₀ ) (microns) Specific Surface Area (S) (m ² / g) 5,0 0.60 2.0 1.3 0.9 2,4 0.5 4.3 0.2 10.0 0.1 20.9 0.05 39.2

The average particle size (D ₅₀ , μm) shown in Table 2 above is a value that is determined according to the particle size distribution measured using the Microtrac device (trade name manufactured by Microtrac Company), (D ₅₀ value means the particle size in the case when the cumulative mass% corresponds to 50% of the mass). The specific surface is a value measured by the BET method.

In the case when the average particle size of the niobium powder containing at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium exceeds 5 μm, a capacitor with a large capacity cannot be manufactured, while as if the average particle size is less than 0.05 μm, the sintered material made from such a niobium powder has a small pore size and contains many closed pores, therefore, the cathode material described below will be difficult to impregnate, and as a result of the niobium powder can not be made capacitor, characterized by high capacity, and sintered material made from such a powder, is not suitable for capacitors.

For these reasons, the niobium powder intended for use in accordance with the present invention preferably has an average particle size of 0.05 μm to 4 μm, and a large capacitor can be manufactured.

The niobium powder of the present invention is preferably a powder with a specific BET surface area of at least 0.5 m ² / g, more preferably at least 1 m ² / g, even more preferably 2 m ² / g. Also, the niobium powder of the present invention preferably has a specific BET surface that is from 0.5 to 40 m ² / g, more preferably from 1 to 20 m ² / g, and particularly preferably from 1 to 10 m ² / g.

As for the dielectric constant (ε), it is known that niobium has a dielectric constant of about two times higher than the dielectric constant of tantalum, but in any case it is not known whether boron, gallium, indium and thallium are valve-valued metals that are necessary for capacitor properties. Aluminum is a metal valve action, but it is known that its dielectric constant is less than the dielectric constant of niobium. Thus, even if at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium is introduced into the niobium powder, it is not known whether ε of niobium powder containing at least one of these elements will increase .

In accordance with the studies carried out by the inventors of the present invention, even when the average particle size of the niobium powder is reduced and a sintered material with a large capacity is made from it, the LC value does not especially increase, since at least one element selected from the group is contained consisting of boron, aluminum, gallium, indium and thallium.

The reasons for this are supposed to be as follows.

Compared to tantalum, niobium has a higher bond strength with oxygen, and therefore, oxygen in an oxide film obtained by electrolytic oxidation (a film of dielectric material) tends to diffuse in the direction of niobium metal, into the material, however, in the sintered material according to the present invention part of niobium is associated with at least one element selected from the group consisting of boron, aluminum, gallium, indium and thallium, and therefore, the binding of oxygen to m in the inner part, it is difficult for niobium, and thus, oxygen diffusion to the metal side is inhibited, as a result of which the stability of the oxide film obtained by electrolytic oxidation can be preserved, and the effect of reducing the LC value and its dispersion can be achieved even in the case of a capacitor of significant capacity niobium powder with a small particle diameter.

Hereinafter, the present invention will be described for the case of using boron as an example, however, the present invention is not limited to this example, and the following also applies to the use of aluminum, gallium, indium or thallium.

The boron-containing niobium powder used to obtain the sintered material preferably has an average particle size of from 0.05 μm to 4 μm, as mentioned above.

A boron-containing niobium powder having such an average particle size can be obtained, for example, by using the method of grinding into powder and dehydrogenation of a niobium-boron alloy hydride in the form of an ingot, granules or powder.

Boron-containing niobium powder can also be obtained by mixing boric acid, boron oxide and boron powder with niobium powder obtained by grinding and dehydrogenating an ingot, granules or powder of niobium hydride or by grinding the product of sodium potassium fluorobiobate with reduction or by grinding the product into powder, obtained by the reduction of niobium oxide using at least one substance selected from hydrogen, carbon, magnesium, aluminum, or using and carbon recovery mixture of niobium oxide and boron oxide.

For example, in the case when the niobium powder is obtained from the hydrogenation product of an ingot of niobium-boron alloy by grinding and dehydrogenation, a boron-containing niobium powder with the required average particle size can be obtained by controlling the degree of hydrogenation of the niobium-boron alloy, grinding time into powder, and also through the selection of equipment for grinding, etc. The boron-containing niobium powder thus obtained can be mixed with niobium powder having an average particle size of 5 μm or less, in order to control the boron content. The niobium powder used for the addition can be obtained, for example, by grinding into a powder the product of sodium potassium fluorobiobate reduction or by grinding into a powder and dehydrogenating a niobium ingot hydroxide, or by reducing a niobium oxide using at least one substance selected from hydrogen, carbon, magnesium , aluminum, or using a method for reducing niobium halide with hydrogen.

In order to further improve the leakage current characteristics of the thus obtained boron-containing niobium powder, a part of the boron-containing niobium powder can be subjected to surface treatment by nitriding, carbonization, sulfidation and further boronation. The powder may include any of these products obtained by surface treatment by nitriding, carbonization, sulfidation or boronation, more specifically, the powder may include any of such products as niobium boron nitride, niobium boron carbide, niobium boron sulfide and niobium boron boride. The powder may also include two, three or four such products in combination.

The total number of related items, i.e. the total content of nitrogen, carbon, boron or sulfur varies depending on the shape of the boron-containing niobium powder, however, in the case of a powder with an average particle size of from about 0.05 μm to 5 μm, the total content is more than 0 wt.h. per million and not more than 200,000 parts by weight per million, preferably from 50 parts by weight per million up to 200,000 parts by weight per million and more preferably from 200 parts by weight per million up to 20,000 parts by weight per million. If the total content exceeds 200,000 parts by weight. ppm, capacitance deteriorates and the resulting product is unsuitable for capacitors.

Nitriding of boron-containing niobium powder can be carried out by any of the following methods: liquid-phase nitriding, ion nitriding and gas-phase nitriding, or by combining these methods. Among these methods, gas phase nitriding in an atmosphere of gaseous nitrogen is preferable since the apparatus for this is quite simple and the method is easy to implement. For example, gas-phase nitriding in an atmosphere of gaseous nitrogen can be carried out by exposure of the above boron-containing niobium powder in an atmosphere of gaseous nitrogen. A boron-containing niobium powder, nitrided to the necessary degree, can be obtained at a temperature of a gaseous medium of 2000 ° C or less, and exposure for one hundred hours or less. The processing time can be reduced when carrying out such processing at a higher temperature.

Carbonization of boron-containing niobium powder can be carried out by any of such methods as gas phase carbonization, solid phase carbonization or liquid phase carbonization. For example, a boron-containing niobium powder can be carbonized by exposure together with a carbon material or with a carbon source, such as an organic material containing carbon (e.g. methane) at 2000 ° C or less under reduced pressure for one minute to one hundred hours.

Sulphidation of boron-containing niobium powder can be carried out by any of the following methods: gas-phase sulfidation, ionic sulfidation or solid-phase sulfidation. For example, gas-phase sulfidation in an atmosphere of sulfur gas can be carried out by exposure to boron-containing niobium powder in a sulfidation atmosphere. A boron-containing niobium powder with the necessary degree of sulfidation can be obtained at a temperature of 2000 ° C or less, and a holding time of one hundred hours or less. The processing time can be reduced when processing at a higher temperature.

Boronation of boron-containing niobium powder can be carried out either by gas-phase boronation or by solid-phase boronation. For example, a boron-containing niobium powder can be boronated by exposure together with a boron source such as boron granules or boron halide (e.g. boron trifluoride) under reduced pressure at a temperature of 2000 ° C or less for one minute to one hundred hours.

The boron-containing niobium powder for the manufacture of capacitors, which is the subject of the present invention, can be used after granulation of the boron-containing niobium powder to obtain the desired shape, or can be used by mixing with a suitable amount of non-granulated niobium powder after the granulation described above.

Examples of granulation methods include a method in which non-granulated boron-containing niobium powder is kept in high vacuum, heated to a suitable temperature and then crushed, and also include a method in which non-granulated boron-containing niobium powder is mixed with a suitable binder such as camphor, polyacrylic acid, polymethyl methacrylate or polyvinyl alcohol, and a solvent such as acetone, alcohols, acetic ester slots or water, and then subjected to crushing.

The use of boron-containing niobium powder, granulated in the manner described above, improves the characteristics necessary for injection molding carried out in the manufacture of sintered material. The average particle size of the granular powder is preferably from 10 to 500 microns. If the granular powder has an average particle size of 10 μm or less, partial adhesion occurs, which impairs the fluidity of the powder when it is poured into a metal mold, while if the average particle size exceeds 500 μm, the molded product after molding during compression is easy breaks around the edges. More preferably, the average particle size of the granular powder is from 30 μm to 250 μm, since in this case, when the capacitor is manufactured after sintering the pressure-molded niobium powder, the sintered material can be easily impregnated with a cathode agent.

Sodium boron-containing niobium material for the manufacture of capacitors according to the present invention is obtained by sintering the aforementioned boron-containing niobium powder or granular boron-containing niobium powder. The method for producing the sintered material is not particularly limited, however, the sintered material can be obtained by injection molding to give a predetermined shape and subsequent heating at a temperature of from 500 ° C to 2000 ° C, preferably from 900 ° C to 1300 ° C, more preferably from 900 ° C to 1300 ° C, for from one minute to ten hours at a pressure of 10 ^-5 to 10 ² Pa.

(3) Third group (niobium powder and sintered material)

The third group included in the composition of the present invention includes niobium powder comprising at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin , phosphorus, arsenic and bismuth, the specified powder can be used as niobium powder - the starting material.

Cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth, used in accordance with the present invention, are elements that can form an alloy with niobium. In particular, niobium powder comprising at least one element selected from the group consisting of rhenium, neodymium, zinc, arsenic, phosphorus, germanium and tin is preferred, and niobium powder comprising at least one element selected is more preferred. from the group consisting of rhenium, neodymium and zinc.

According to one embodiment, the niobium powder is a rhenium-containing niobium powder comprising at least one element selected from the group consisting of cerium, neodymium, titanium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth. In accordance with the present invention, the total amount of these elements in the niobium powder is 10 mol% or less, preferably from 0.01 mol% to 10 mol%, more preferably from 0.1 mol% to 7 mol%.

If the total content of the element is less than 0.01 mol%, it is impossible to inhibit the diffusion of oxygen in the dielectric film formed by electrolytic oxidation, which will be described below, in the direction of niobium metal, therefore, the stability of the oxide film (dielectric film) cannot be maintained. ) formed during electrolytic oxidation, and the effect of lowering the LC value is unlikely to be achieved. On the other hand, if the total content of the above element exceeds 10 mol%, then the amount of niobium proper in the niobium powder decreases, and as a result, the capacitance of the capacitor decreases.

Accordingly, the total content of at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth is preferably from 0.01 to 10 mol.%.

In order to further reduce the leakage current, the cell content is preferably 7 mol% or less, more preferably 0.1 to 7 mol%.

In order to increase the specific surface area of the powder, it is preferred that the average particle size of the niobium powder is 5 μm or less, more preferably 4 μm or less. Also, the average particle size of the niobium powder is preferably from 0.05 μm to 4 μm.

The reasons for this are described above in the description of niobium powder included in the first group.

According to the present invention, the raw material niobium powder used for the manufacture of sintered material is niobium powder, which contains at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth, it becomes possible to manufacture a capacitor having most of the above characteristics or to obtain a niobium sintered material that provides such Characteristics of the capacitor.

The average particle size (D ₅₀ , μm) and the specific surface (S, m ² / g) of rhenium-containing niobium powder prepared as an example by the authors of the present invention (obtained by grinding) are shown in table 3 below.

Table 3 The average particle size (D ₅₀ ) (microns) Specific Surface Area (S) (m ² / g) 4.9 0.63 2.0 1.3 0.9 2.6 0.5 4.9 0.2 11.0 0.1 20.7 0.05 38,4

The average particle size (D ₅₀ ; μm) shown in Table 3 is a value that is determined according to the particle size distribution measured using the Microtrac device (trade name manufactured by Microtrac Company), (d50 means size particles in the case when the cumulative mass% corresponds to 50% of the mass). The specific surface is the value measured by the BET method.

In the case where the average particle size of the niobium powder containing at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth, exceeds 5 microns, a capacitor with a large capacity cannot be manufactured, while if the average particle size is less than 0.05 microns, the sintered material obtained from the powder has a small pore size and contains many closed pores, due to this makes impregnation difficult cathode material, which will be described later, and as a result, a capacitor with a high capacity cannot be made from niobium powder, and sintered material made from such a powder is not suitable for capacitors.

For these reasons, the niobium powder intended for use in accordance with the present invention has an average particle size of 0.05 to 5 μm, in which case a large capacitor can be obtained.

The niobium powder of the present invention is preferably a powder whose specific BET surface is at least 0.5 m ² / g, more preferably at least 1 m ² / g, even more preferably 2 m ² / g . Also, the niobium powder of the present invention preferably has a specific BET surface that is from 0.5 to 40 m ² / g, more preferably from 1 to 20 m ² / g, and particularly preferably from 1 to 10 m ² / g .

As for the dielectric constant (ε), it is known that niobium has a dielectric constant of about two times higher than the dielectric constant of tantalum, but in any case it is not known that cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver , zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth are valvular metals with the properties necessary for a capacitor. Thus, if at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth is introduced into niobium powder, it is not known whether ε of niobium powder containing such an element will increase.

According to the studies of the present inventors, even when the average particle size of the niobium powder is reduced and a sintered material with a high capacity is made from it, the LC value does not especially increase if at least one element selected from the group is contained, consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth.

The reasons for this are supposed to be as follows.

Niobium is characterized by a higher bond strength with oxygen compared with tantalum, and therefore, oxygen in an oxide film obtained electrochemically (film of a dielectric material) tends to diffuse in the direction of niobium metal, into the material, however, in the sintered material according to the present invention part of niobium is associated with at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth, therefore, the binding of oxygen to the niobium located in the inner part is difficult and thus diffusion of oxygen towards the metal is prevented, as a result of which the stability of the oxide film obtained electrochemically can be maintained and the effect of reducing the LC value and its dispersion can be achieved even in the case of a large capacitor obtained from a fine powder.

Hereinafter, the present invention will be described for the case of using rhenium as an example, but the present invention is not limited to this example, and the following also applies to cases of using cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium , tin, phosphorus, arsenic and bismuth.

The rhenium-containing niobium powder used to produce the sintered material preferably has an average particle size of from 0.05 μm to 4 μm, as mentioned above.

A rhenium-containing niobium powder having such an average particle size can be obtained, for example, using the method of grinding and dehydrogenation of a niobium-rhenium alloy hydride in the form of an ingot, granules or powder. Rhenium-containing niobium powder can also be obtained by mixing rhenium or oxide powder, sulfide, sulfate, halide salt, nitrate, organic acid salt or a complex of rhenium salt with niobium powder obtained by grinding and dehydrogenation of an ingot, granules or powder of niobium hydride or by grinding potassium fluorobiobate reduction product into a powder, or by grinding into a powder the product obtained from the reduction of niobium oxide using at least one substance va selected from hydrogen, carbon, magnesium, aluminum or the like; or when using the method of magnesium reduction of a mixture of niobium oxide and rhenium oxide.

Niobium powder containing rhenium, zinc and germanium can be obtained, for example, by grinding into a powder and dehydrogenating a hydrogenation product of a niobium-rhenium-zinc-germanium alloy in the form of an ingot, granules or powder. The specified niobium powder can also be obtained by mixing rhenium powder, zinc powder and germanium powder, or oxides, sulfides, sulfates, halide salts, nitrates or organic acid salts of rhenium, zinc, germanium with niobium powder obtained by grinding and dehydrogenation of the niobium hydrogenation product an ingot, granules or powder of niobium, by grinding into a powder the product of sodium potassium fluorobiobate reduction or by grinding the product obtained from the reduction of niobium oxide using at least one substance selected from hydrogen, carbon, magnesium, aluminum, or a similar substance; or when using the method of magnesium reduction of a mixture of niobium oxide, rhenium oxide, zinc oxide and germanium oxide.

For example, in the case of obtaining a rhenium-containing niobium powder by grinding and dehydrogenating the hydrogenation product of the niobium-rhenium alloy in the form of an ingot, rhenium-containing niobium powder with the required average particle size can be obtained by controlling the content of the hydrogenation product in the niobium-rhenium alloy and grinding time, as well as selecting the type of chopper or similar device.

The rhenium-containing niobium powder thus obtained can be mixed with niobium powder having an average particle size of 5 μm or less, in order to control the rhenium content. The niobium powder used for the addition can be obtained, for example, by grinding into a powder the product of sodium potassium fluorobiobate reduction or by grinding into a powder and dehydrogenating a hydrogenation product of a niobium ingot, or by reducing a niobium oxide using at least one substance selected from the group consisting of hydrogen , carbon, magnesium, aluminum, or a method for hydrogen reduction of niobium halide. In order to further improve the leakage current characteristics of the rhenium-containing niobium powder thus obtained, a part of the rhenium-containing niobium powder can be subjected to surface treatment by nitriding, boronation, carbonization or sulfidation. The powder may include any of such products as rhenium-containing niobium nitride, rhenium-containing niobium boride, rhenium-containing niobium carbide and rhenium-containing niobium sulfide obtained by surface treatment by nitriding, boronation, carbonization or sulfidation, the powder may also include two, three or four such products in combination.

The number of related items, i.e. the total content of nitrogen, carbon, boron or sulfur varies depending on the form of the rhenium-containing niobium powder, however, in the case of a powder with an average particle size of approximately 0.05 μm to 5 μm, the total content is more than 0 parts by weight. per million, and not more than 200,000 parts by weight per million, preferably from 50 to 100,000 parts by weight per million, particularly preferably from 200 to 20,000 parts by weight per million. If the total content exceeds 200,000 parts by weight. ppm, capacitance deteriorates and the resulting product is unsuitable for capacitors.

Nitrogenation of rhenium-containing niobium powder can be accomplished by any of the following methods: liquid-phase nitriding, ion nitriding and gas-phase nitriding, or by combining these methods. Among these methods, gas phase nitriding in an atmosphere of gaseous nitrogen is preferable since the apparatus for this is quite simple and the method is easy to implement. For example, gas phase nitriding in an atmosphere of gaseous nitrogen can be carried out by exposure of the above rhenium-containing niobium powder in an atmosphere of gaseous nitrogen. The rhenium-containing niobium powder, nitrided to the necessary degree, can be obtained at a temperature of a gaseous medium of 2000 ° C or less, and exposure for one hundred hours or less. The processing time can be reduced when carrying out such processing at a higher temperature.

Boronation of rhenium-containing niobium powder can be carried out either by gas-phase boronation or by solid-phase boronation. For example, a rhenium-containing niobium powder can be borated by holding the rhenium-containing niobium powder together with a boron source such as boron granules or boron halide (e.g. boron trifluoride) under reduced pressure at a temperature of 2000 ° C or less for one minute to one hundred hours.

Carbonization of a rhenium-containing niobium powder can be carried out by any of such methods as gas phase carbonization, solid phase carbonization or liquid phase carbonization. For example, a rhenium-containing niobium powder can be carbonized by exposure together with a carbon source, such as a carbon material or organic material containing carbon (e.g. methane) at 2000 ° C or less under reduced pressure for one minute to one hundred hours.

Sulphidation of rhenium-containing niobium powder can be carried out by any of the following methods: gas-phase sulfidation, ionic sulfidation or solid-phase sulfidation. For example, gas phase sulphidation in an atmosphere of sulfur gas can be carried out by holding rhenium-containing niobium powder in a sulphidation atmosphere. Rhenium-containing niobium powder with the required degree of sulfidation can be obtained at a gas temperature of 2000 ° C and a holding time of one hundred hours or less. Processing time can be reduced when processing at a higher temperature.

The rhenium-containing niobium powder for the manufacture of capacitors, which is the subject of the present invention, can be used after granulation of the rhenium-containing niobium powder to obtain the desired shape, or can be used by mixing with a suitable amount of non-granulated niobium powder after carrying out the granulation described above.

Examples of granulation methods include a method in which the granular rhenium-containing niobium powder is kept under high vacuum, heated to a suitable temperature and then crushed, and also include a method in which the granular or granular rhenium-containing niobium powder is mixed with a suitable binder, such like camphor, polyacrylic acid, polymethyl methacrylate or polyvinyl alcohol, and a solvent such as acetone, alcohols, esters, acetic th acid or water, and then subjected to crushing.

The use of rhenium-containing niobium powder, granulated in the manner described above, improves the characteristics necessary for injection molding carried out in the manufacture of sintered material. The average particle size of the granular powder is preferably from 10 to 500 microns. If the granular powder has an average particle size of 10 μm or less, partial adhesion occurs and the fluidity of the powder worsens when it is poured into a metal mold, while if the average particle size exceeds 500 μm, then the molded product is easily broken after molding to the edges. The average particle size of the granular powder is more preferably from 30 μm to 250 μm, since in this case, after sintering the pressure-molded article in the manufacture of the capacitor, the sintered material is easily impregnated with a cathode agent.

Rhenium-containing niobium sintered material for the manufacture of capacitors according to the present invention is obtained by sintering the above rhenium-containing niobium powder or granular rhenium-containing niobium powder. The choice of the method for producing the sintered material is not particularly limited, however, the sintered material can be obtained, for example, by molding under pressure a rhenium-containing niobium powder to give it a predetermined shape and subsequent heating at a temperature of from 500 ° C to 2000 ° C, preferably from 900 ° C up to 1500 °, more preferably from 900 ° C to 1300 ° C, for from one minute to one hundred hours at a pressure of from 10 ^-5 to 10 ² Pa (Pascal).

(4) Fourth group (niobium powder and sintered material)

The fourth group of the present invention includes niobium powder comprising at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium , holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium, this powder is used as niobium powder - the starting material with properties suitable for capacitors.

Rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, gold, platinum Cadmium, mercury, lead, selenium and tellurium are elements that can form an alloy with niobium. In particular, a niobium powder comprising at least one element selected from the group consisting of lanthanum, yttrium, erbium, ytterbium and lutetium is preferred, and niobium powder comprising at least one element selected from the group consisting of from lanthanum and yttrium.

In accordance with one embodiment of the invention, the niobium powder is, for example, a lanthanum-containing niobium powder comprising at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium. In accordance with the present invention, the total content of these elements in the niobium powder is 10 mol% or less, preferably from 0.01 to 10 mol%, more preferably from 0.1 to 7 mol%.

If the total element content is less than 0.01 mol%, then oxygen diffusion cannot be prevented in the dielectric film formed during electrolytic oxidation, which will be described later, in the direction toward the metal niobium, and therefore, the stability of the oxide film cannot be maintained. formed during electrolytic oxidation (dielectric film), and it is unlikely that the effect of reducing the value of LC will be achieved. On the other hand, if the total element content exceeds 10 mol%, then the amount of niobium per se in the niobium powder decreases, and as a result, the capacitance of the capacitor decreases.

Accordingly, the total content of at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium is preferably from 0.01 to 10 mol%.

In order to further reduce the leakage current, the element content in the niobium powder is preferably 7 mol% or less, more preferably from 0.1 to 7 mol%.

In order to increase the specific surface area of the powder, it is preferred that the average particle size of the niobium powder is 5 μm or less, more preferably 4 μm or less. Also, the average particle size of the niobium powder is preferably 0.05 μm to 4 μm. The reasons for this are described above in the description of niobium powder included in the first group.

According to the present invention, the niobium powder feedstock used to make the sintered material is niobium powder, which contains at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium, while it becomes possible to manufacture a capacitor satisfying most of the above requirements, or obtain a niobium sintered material that provides such characteristics of a capacitor.

The average particle size (D ₅₀ , μm) and specific surface area (S, m ² / g) of a lanthanum-containing niobium powder (obtained by grinding into powder), prepared as an example by the authors of the present invention, are shown below in table 4.

Table 4 The average particle size (D ₅₀ ) (microns) Specific Surface Area (S) (m ² / g) 5.1 0.61 1.9 1.4 0.9 2,5 0.5 5.1 0.2 11.1 0.1 20.8 0.05 38.7

The average particle size (D ₅₀ ; μm) shown in Table 4 is a value that is determined according to the particle size distribution measured using the Microtrac device (trade name manufactured by Microtrac Company) (D ₅₀ means size particles in the case when the cumulative mass% corresponds to 50% of the mass). The specific surface is the value measured by the BET method.

If the average particle size of a niobium powder containing at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium, exceeds 5 μm, a capacitor with a large capacity cannot be manufactured, and if the average particle size is less than 0, 05 microns, sintered material obtained from such a powder has t is a small pore size and contains many closed pores, as a result of which it is difficult to impregnate the cathode material, which will be described later, and as a result, a capacitor with a high capacity cannot be made from niobium powder, and sintered material made from such a powder is not suitable for capacitors .

For these reasons, the niobium powder intended for use in accordance with the present invention preferably has an average particle size of from 0.05 μm to 5 μm, in which case a capacitor having a large capacity can be obtained.

The niobium powder of the present invention is preferably a powder with a specific BET surface area of at least 0.5 m ² / g, more preferably at least 1 m ² / g, even more preferably at least 2 m ² / g Also, the niobium powder of the present invention preferably has a specific BET surface that is from 0.5 to 40 m ² / g, more preferably from 1 to 20 m ² / g, particularly preferably from 1 to 10 m ² / g .

As for the dielectric constant (ε), it is known that niobium has a dielectric constant of about two times higher than the dielectric constant of tantalum, but in any case it is not known that rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum , praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium are valve-valued metals necessary for conden sator properties. Thus, if at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium is introduced into niobium powder Since erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium, it is not known whether ε of niobium powder containing such an element will increase.

In accordance with the studies conducted by the inventors of the present invention, even when the average particle size of the niobium powder is reduced and a sintered material with a large capacity is made from it, the LC value does not especially increase if at least one element selected from the group is contained consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samaria, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum gold to dmiya, mercury, lead, selenium and tellurium.

The reasons for this are supposed to be as follows.

Niobium is characterized by a higher bond strength with the element oxygen, compared with tantalum, and therefore, the oxygen in the oxide film obtained by electrolytic oxidation (film of a dielectric material) has a tendency to diffusion towards metallic niobium, inside the material, however, in the sintered material according to this the invention, a part of niobium is associated with at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, itself Riya, Europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium, therefore, the interaction of oxygen with that located in the inner parts of it is hindered by niobium, and thus the diffusion of oxygen in the direction of the metal is inhibited, as a result of which the stability of the oxide film obtained by electrolytic oxidation can be preserved, and it is possible to obtain the effect of decreasing the LC value and its dispersion even in the case of a capacitor th capacity obtained from a powder with a small particle diameter.

Hereinafter, the present invention will be described for the case of using mainly lanthanum as an example, however, the present invention is not limited to this example, and the following also applies to the use of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium , europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium.

The lanthanum-containing niobium powder used to obtain the sintered material preferably has an average particle size of from 0.05 μm to 4 μm, as mentioned above.

Lanthanum-containing niobium powder having such an average particle size can be obtained, for example, by using the method of grinding and dehydrogenation of a hydride of a niobium-lanthanum alloy in the form of an ingot, granules or powder. Lanthanum-containing niobium powder can also be obtained by mixing lanthanum or hydride powder, oxide, sulfide, sulfate, halide, nitrate, organic acid salts or a complex of lanthanum salts with niobium powder obtained by grinding into a powder and dehydrogenation of an ingot, granules or hydride powder niobium, or by grinding into a powder the product of sodium potassium fluorobiobate reduction, or by grinding into a powder the product obtained by reducing niobium oxide using m nshey least one substance selected from hydrogen, carbon, magnesium, aluminum or the like material, or when using a method of recovering magnesium mixture of niobium oxide and lanthanum oxide.

Niobium powder containing lanthanum, hafnium and iridium can be obtained, for example, by pulverizing and dehydrogenating the hydrogenation product of a niobium-lanthanum-hafnium-iridium alloy in the form of an ingot, granules or powder. Said niobium powder can also be obtained by mixing lanthanum powder, hafnium powder and iridium powder, or hydrides, oxides, sulfides, sulfates, halide salts, nitrates or organic acid salts of lanthanum, hafnium and iridium with niobium powder obtained by grinding into a powder and dehydrogenation of the hydrogenation product of a niobium ingot, granules or niobium powder, by grinding into a powder the product of sodium reduction of potassium fluorobiobate or by grinding into a powder the product obtained When restoring a niobium oxide using at least one substance selected from hydrogen, carbon, magnesium, aluminum or the like; or when using the method of magnesium reduction of a mixture of niobium oxide and lanthanum oxide, hafnium oxide and iridium oxide.

For example, in the case of obtaining a lanthanum-containing niobium powder by grinding into powder and dehydrogenating the product of hydrogenation of the niobium-lanthanum alloy in the form of an ingot, a lanthanum-containing niobium powder with the required average particle size can be obtained by controlling the content of the hydrogenation product in the niobium-lanthanum alloy and the grinding time, as well as by selecting the type of grinder, etc.

In a niobium ingot, usually used as a feedstock for the lanthanum-containing niobium powder thus obtained, the content of tantalum and each metal element other than the element described above (namely, rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium) is 1000 parts by weight per million or less, and the oxygen content is from 3000 to 60,000 wt.h. per million

These values have the same values as for the niobium powder containing the element described above (namely, containing at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, selenium and tellurium).

The lanthanum-containing niobium powder thus obtained can be mixed with niobium powder having an average particle size of 5 μm or less, in order to control the lanthanum content. The niobium powder used for the addition can be obtained, for example, by grinding into a powder the product of sodium potassium fluorobiobate reduction or by grinding into a powder and dehydrogenating the hydrogenation product of a niobium ingot, or by reducing niobium oxide using at least one substance selected from the group consisting of hydrogen, carbon , magnesium, aluminum, or using a method for reducing niobium halide with hydrogen.

The lanthanum-containing niobium powder for the manufacture of capacitors, which is the subject of the present invention, can be used after granulation of the lanthanum-containing niobium powder, which allows to give the necessary shape, or can be used for mixing with a suitable amount of non-granulated niobium powder after the granulation described above.

Examples of granulation methods include a method in which a non-granulated lanthanum-containing niobium powder is kept under high vacuum, heated to a suitable temperature and then crushed, and also include a method in which a non-granulated or granular lanthanum-containing niobium powder is mixed with a suitable binder, such like camphor, polyacrylic acid, polymethyl methacrylate or polyvinyl alcohol, and a solvent such as acetone, alcohols, vinegar esters acid or water, and then subjected to crushing; a method in which a non-granulated or granular lanthanum-containing niobium powder is mixed with a suitable binder, such as camphor, polyacrylic acid, polymethyl methacrylate or polyvinyl alcohol, and a solvent, such as acetone, alcohols, esters of acetic acid or water, the resulting mixture is sintered at significantly reduced pressure until a vapor phase forms and thus the added binder and solvent are removed by evaporation, sublimation or thermal decomposition, and then the canted lanthanum-containing niobium mass is crushed; a method in which a non-granulated or granular lanthanum-containing niobium powder is mixed with barium oxide, magnesium oxide or a similar substance and solvent such as acetone, alcohols, esters of acetic acid or water, the resulting mixture is sintered under significantly reduced pressure, the sintered mass is crushed, and then dissolved in an acid solution, for example, such as nitric acid or hydrochloric acid, or in a solution containing a complexing agent.

The use of lanthanum-containing niobium powder subjected to granulation in the manner described above improves the characteristics necessary for pressure molding carried out in the manufacture of sintered material. The average particle size of the granular powder is preferably from 10 to 500 microns. If the granular powder has an average particle size of less than 10 microns, partial adhesion occurs and the fluidity of the powder deteriorates when it is poured into a metal mold, while if the average particle size exceeds 500 microns, then the molded product is easily broken along the edges after molding under pressure . More preferably, the average particle size of the granular powder is from 30 μm to 250 μm, since in this case, when the capacitor is manufactured after sintering the pressure-molded niobium powder, the sintered material is easily impregnated with a cathode agent.

The lanthanum-containing niobium sintered material for the manufacture of capacitors according to the present invention is obtained by sintering the aforementioned lanthanum-containing niobium powder or granular lanthanum-containing niobium powder. The method for producing sintered material is not particularly limited, and sintered material can be obtained, for example, by molding under pressure a lanthanum-containing niobium powder to give it a predetermined shape, and then heating it at a temperature of from 500 to 2000 ° C, preferably from 900 to 1500 ° , more preferably from 900 ° C. to 1300 ° C., for from one minute to ten hours at a pressure of from 10 ⁻⁵ to 10 ² Pa (Pascal).

In order to further improve the leakage current characteristics of the thus obtained lanthanum-containing niobium powder, a part of the lanthanum-containing niobium powder can be subjected to surface treatment by nitriding, boronation, carbonization or sulfidation, or by many such treatments.

The powder may include any of such products as lanthanum-containing niobium nitride, lanthanum-containing niobium boride, lanthanum-containing niobium carbide and lanthanum-containing niobium sulfide obtained, or also two or more such products may be contained in combination.

The number of related items, i.e. the total content of nitrogen, boron, carbon, or sulfur, varies depending on the form of the lanthanum-containing niobium powder, however, the total content may be more than 0 parts by weight per million and not more than 200,000 parts by weight per million, preferably from 50 to 100,000 parts by weight per million, particularly preferably from 200 to 20,000 parts by weight per million. If the total content exceeds 200,000 parts by weight. million, capacitive characteristics deteriorate and the resulting product is unsuitable for capacitors.

Nitriding of a lanthanum-containing niobium powder, granular powder or sintered material can be carried out by any of the following methods: liquid-phase nitriding, ion nitriding and gas-phase nitriding, or by combining these methods. Among these methods, gas phase nitriding in an atmosphere of gaseous nitrogen is preferable since the apparatus for this is quite simple and the method is easy to implement. For example, gas phase nitriding in an atmosphere of gaseous nitrogen can be carried out by holding the above lanthanum-containing niobium powder, granular powder or sintered material in an atmosphere of gaseous nitrogen. Lanthanum-containing niobium powder, granular powder, or sintered material, nitrided to the necessary extent, can be obtained at a gaseous temperature of 2000 ° C or less and a holding time of 100 hours or less. The processing time can be reduced when carrying out such processing at a higher temperature.

Boronation of lanthanum-containing niobium powder, granular powder or sintered material can be carried out either by gas-phase boronation or by solid-phase boronation. For example, a lanthanum-containing niobium powder, granular powder or sintered material can be boronated by exposure together with a boron source such as boron granules or boron halide (e.g. boron trifluoride) under reduced pressure at a temperature of 2000 ° C or less for about 1 minute up to 100 hours.

Carbonization of a lanthanum-containing niobium powder, granular powder or sintered material can be carried out by any of such methods as gas phase carbonization, solid phase carbonization or liquid phase carbonization. For example, lanthanum-containing niobium powder, granular powder or sintered material can be carbonized by exposure together with a carbon material or with a carbon source, such as an organic substance containing carbon (e.g. methane) at 2000 ° C or less under reduced pressure for approximately from 1 minute to 100 hours.

Sulphidation of a lanthanum-containing niobium powder, granular powder or sintered material can be carried out by any of the following methods: gas-phase sulfidation, ionic sulfidation or solid-phase sulfidation. For example, gas phase sulphidation in an atmosphere of sulfur gas can be carried out by exposing the lanthanum-containing niobium powder in a sulphidation atmosphere. Niobium powder, granular powder or sintered material with the required degree of sulfidation can be obtained at a gas temperature of 2000 ° C or less, and a holding time of 100 hours or less. The processing time can be reduced when processing at a higher temperature.

(5) Capacitor device

The manufacture of a capacitor device is described below.

For example, a lead wire is prepared comprising a valve metal such as niobium or tantalum, and having an appropriate volume and length, and this lead wire is pressed together as a unit when pressed under pressure of niobium powder, so that part of the lead wire is inside the molded product moreover, the lead wire leaves the main part of the sintered material.

When using such a sintered material as one of the electrodes, a capacitor can be made by placing a dielectric substance between this electrode and another electrode (counter electrode). The dielectric material used in this case for capacitors is preferably a dielectric material, mainly consisting of niobium oxide. A dielectric material, mainly including niobium oxide, can be obtained, for example, by chemical treatment of a lanthanum-containing niobium sintered material as one of the electrodes in an electrolyte solution. For the chemical treatment of a lanthanum-containing niobium electrode in an electrolyte solution, an aqueous protic acid solution, such as an aqueous 0.1% phosphoric acid solution or an aqueous solution of sulfuric acid, or a 1% acetic acid solution, or an adipic acid aqueous solution, is usually used. In the case of a chemical treatment of a lanthanum-containing niobium electrode in an electrolyte solution to produce a dielectric material, niobium oxide, the capacitor of the present invention is an electrolyte capacitor, and the niobium electrode serves as an anode.

In the capacitor that is the subject of the present invention, the choice of another electrode (counter electrode) with respect to the sintered niobium material is not particularly limited and, for example, at least one material (compound) selected from solutions of electrolyte, organic semiconductors and inorganic semiconductors can be used, known from the prior art for aluminum electrolyte capacitors.

Specific examples of an electrolyte solution include a solution in a mixture of dimethylformamide-ethylene glycol in which 5 wt.% Of an electrolyte, isobutyltropropylammonium tetrafluoride, is dissolved in a solution in a mixture of propylene carbonate-ethylene glycol in which 7 wt.% Of an electrolyte, boron tetraethylammonium tetrafluoride, is dissolved.

Specific examples of an organic semiconductor include an organic semiconductor containing a benzopyrroline tetramer and chloranil, an organic semiconductor mainly comprising tetratiotetracene, an organic semiconductor mainly comprising tetracyanoquinodimethane, and an electrically conductive polymer containing a repeating unit represented by the following formulas (1) or (2):

in which the radicals R ¹ to R ⁴ each independently represent a monovalent group selected from the group consisting of a hydrogen atom, a linear or branched, saturated or unsaturated alkyl, alkoxy or alkyl-containing ester group containing from 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group or a substituted phenyl group; each of the pairs R ¹ and R ² , R ³ and R ⁴ can be combined arbitrarily with the formation of a bivalent chain to obtain at least one 3-, 4-, 5-, 6- or 7-membered saturated or unsaturated cyclic hydrocarbon structure together with carbon atoms substituted by radicals R ¹ and R ² or radicals R ³ and R ⁴ ; the combined cyclic chain may contain a bond with a carbonyl, ether group, ester group, amide group, sulfide group, sulfinyl, sulfonyl or imino in an arbitrary position; X represents an oxygen atom, a sulfur atom or a nitrogen atom; R ^{5 is} present only when X represents a nitrogen atom, and independently represents a hydrogen atom or a linear or branched, saturated or unsaturated alkyl group containing from 1 to 10 carbon atoms.

In accordance with the present invention, in the formula (1) or (2), the radicals R ¹ to R ⁴ each independently preferably represent hydrogen, a linear or branched, saturated or unsaturated alkyl or alkoxy group containing from 1 to 6 carbon atoms, and each of the pairs R ¹ and R ² , R ³ and R ⁴ may be combined with each other to form a ring.

In accordance with the present invention, an electrically conductive polymer containing a repeating unit represented by the above formula (1) is preferably an electrically conductive polymer comprising, as a repeating unit, a structural unit represented by the following formula (3):

in which R ⁶ and R ⁷ each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated alkyl group containing from 1 to 6 carbon atoms, or a substituent allowing to form at least one 5-, 6- or 7-membered a saturated cyclic hydrocarbon structure containing two oxygen moieties derived from alkyl groups that combine with each other in an arbitrary position; the cyclic structure includes a structure containing a vinylene bond, which may be substituted, and a phenylene structure, which may be substituted.

An electrically conductive polymer having the indicated chemical structure is electrically charged and a dopant is introduced into it. As a dopant, without limitation, known dopants can be used.

Specific examples of an inorganic semiconductor include an inorganic semiconductor containing mainly lead dioxide or manganese dioxide, and an inorganic semiconductor comprising ferric tetraoxide. These semiconductors can be used individually or in combination of two of them or more.

Examples of a polymer containing a repeating unit that is represented by formula (1) or (2) include polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole and their substituted derivatives and copolymers. Among these compounds, polypyrrole, polythiophene and their substituted derivatives (e.g. poly (3,4-ethylenedioxythiophene)) are preferred.

In the case when the used organic or inorganic semiconductors have an electrical resistance of 10 to 10 cm · cm ^-1 , the manufactured capacitor has a lower impedance, and its capacitance at high frequencies can be increased.

A layer of an electrically conductive polymer is formed, for example, by polymerization of a polymerizable compound, such as aniline, thiophene, furan, pyrrole, methylpyrrole or their substituted derivatives, when exposed to an oxidizing agent capable of providing an oxidation reaction - dehydrogenating two-electron oxidation. Examples of the polymerization reaction of the polymerizable compound (monomer) include vapor polymerization and solution polymerization. A layer of conductive polymer is formed on the surface of the sintered niobium material on which there is a dielectric material. In the case where the electrically conductive polymer is an organic solvent soluble polymer suitable for coating from a solution in order to form a layer of an electrically conductive polymer, a method for producing a polymer coating on the surface of a sintered material is used.

One preferred example of a manufacturing process using solution polymerization is a method of immersing a sintered niobium material on which there is a layer of dielectric material in a solution containing an oxidizing agent (solution 1), and then immersing the sintered material in a solution containing monomer and dopant (solution 2), with the formation of an electrically conductive polymer on the surface of the sintered material. Also, the sintered material can be immersed in solution 1 after it has been immersed in solution 2. As a solution 2 used in accordance with the method described above, a dopant-free monomer solution can be used. In the case of using a dopant in a solution containing an oxidizing agent, a dopant may be present together with the oxidizing agent.

Such an operation at the polymerization stage is repeated once or more, preferably from 3 to 20 times, for one sintered niobium material on which the dielectric material is located, and a dense and layered layer of an electrically conductive polymer can easily be formed.

According to the present invention, in accordance with the method of manufacturing a capacitor, any oxidizing agent can be used, provided that it does not adversely affect the performance of the capacitor, the reducing agent of the oxidizing agent can deplete the dopant and increase the conductivity of the electrically conductive polymer. Preferred for use is an inexpensive commercially available compound that is easy to work with.

Specific examples of oxidizing agents include Fe (III) ferric compounds, such as FeCl ₃ , FeCl _4, and salts of the Fe structure (organic anion); anhydrous aluminum chloride / copper chloride (I); alkali metal persulfates; ammonium persulfates, peroxides; manganese compounds such as potassium permanganate; quinone derivatives such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDC), tetrachloro-1,4-benzoquinone and tetracyano-1,4-benzoquinone; halogens such as iodine and bromine; peracids; sulfonic acids such as sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid, fluorosulfonic acid and amidosulfuric acid; ozone, etc. and mixtures of these oxidizing agents.

Examples of the most typical compounds with an organic acid anion suitable for forming the above-described compounds of the Fe structure (organic anion) include organic sulfonic acid, organic carboxylic acid, organic phosphoric acid and organic boron acid, and the like. Specific examples of organic sulfonic acid include benzenesulfonic acid, n-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, α-sulfonaphthalene, β-sulfonaphthalene, naphthalenedisulfonic acid and alkylnaphthalenesulfonic acid (examples of alkyl include butyl, tri-butyl and triisopropyl. P.

Specific examples of organic carboxylic acids include acetic acid, propionic acid, benzoic acid and oxalic acid. In addition, anions of polymer electrolytes such as polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, polyvinyl sulfonic acid, poly-a-methyl sulfonic acid, polyvinyl sulfate, polyethylene sulfonic acid and polyphosphoric acid can also be used in accordance with the present invention. These organic sulfonic acids and organic carboxylic acids are given only as an illustration of the invention, and the present invention is not limited to them. Examples of the counterion for the anions described above include alkali metal ions such as H ⁺ , Na ⁺ and K ⁺ , as well as ammonium ions substituted with a hydrogen atom, tetramethyl group, tetraethyl group, tetrabutyl group or tetraphenyl group, but the present invention is not limited to this. Among these oxidizing agents, ferric compounds and oxidizing agents including copper (I) chloride, alkali metal persulfate, ammonium persulfate, acid or quinone are preferred.

As an anion which has the property of a dopant and which may be present together, if necessary, upon receipt of a polymer composition for an electrically conductive polymer (an anion other than an anion reducing agent of an oxidizing agent), an electrolyte anion containing an anion of an oxidizing agent as a counterion can be used (an oxidizing agent reducing agent) produced by the oxidizing agent described above, or another electrolyte anion. Specific examples of such anions include protic acid anions, including halide anions of group 5B elements, such as PF ₆ ^- , SbF ₆ ^- , PF ₆ ^- and AsF ₆ ^- . halide anions of group 3B elements, such as BF4; halogen anions such as I ^- (I ₃ ^- ), Br ^- and Cl ^- ; a perhalogenate anion such as ClO ₄ ^- , a Lewis acid anion such as AlCl ₄ ^- , FeCl ₄ ^- , SnCl ₅ ^- , an inorganic acid anion such as NO ₃ ^- and SO ₄ ^2- ; a sulfonate anion, such as the anion of n-toluenesulfonic acid, naphthalenesulfonic acid and the anion of an alkyl substituted naphthalenesulfonic acid containing from 1 to 5 carbon atoms (hereinafter referred to simply as “C1-5”); organic sulfonate anions such as CF ₃ ^- SO ₃ ^- and CH ₃ SO ₃ ^- ; and carboxylate anions such as CH ₃ COO ^- and C ₆ H ₅ COO ^- .

Similarly to the foregoing, anions of polymer electrolytes such as polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, polyvinyl sulfonic acid, polyvinyl sulfonic acid, poly-α-methyl sulfonic acid, polyethylene sulfonic acid and polyphosphoric acid can be used, however, the present invention is not limited to this. A preferred anion is an anion of an organic sulfonic acid derivative of a polymer type or oligomeric type, or an anion of a polyphosphoric acid derivative. Preferably, aromatic sulfonic acid derivatives (e.g. sodium dodecylbenzenesulfonate, sodium naphthalenesulfonate) are used as anion-forming compounds.

Among organic sulfonate anions, more effective dopants are sulfoquinone derivatives, in the molecule of which there is one or more sulfoanionic groups (-SO ₃ ^- ) and which have a quinone structure, as well as anthracene sulfonate anion.

Typical examples of the skeleton of the sulfoquinone anion of the above sulfoquinone derivatives include n-benzoquinone, o-benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 2,6-naphthoquinone, 9,10-anthraquinone, 1,4-anthraquinone, 1,2 -anthraquinone, 1,4-chrysenquinone, 5,6-chrysenquinone, 6,12-chrysenquinone, acenaphthoquinone, acenaphthenoquinone, camphoroquinone, 2,3-boronandion, 9,10-phenanthrenquinone and 2,7-pirenoquinone.

In the case where the other electrode (counter electrode) is solid, an electrically conductive layer may be formed on it, so as to achieve good electrical contact with the outer lead wire (e.g., lead frame), if necessary.

An electrically conductive layer may be formed, for example, by curing the electrically conductive paste, cladding, metallizing, or forming a film of a heat-resistant electrically conductive polymer. Preferred examples of the electrically conductive paste include silver paste, copper paste, aluminum paste, carbon paste and nickel paste, these pastes can be used individually or in combination of two or more pastes. In the case of using two or more kinds of pastes, these pastes can be mixed or applied alternately on top of each other in separate layers. The applied electrically conductive paste is then cured by holding it in air or by heating. Examples of cladding include nickel cladding, silver cladding and aluminum cladding. Examples of metals from which the vapor deposited film is formed include aluminum, nickel, copper and silver.

More specifically, for example, a carbon paste and a silver paste are applied in the indicated order to the second electrode and pressed with a material such as, for example, epoxy resin, thereby obtaining a capacitor. This capacitor may contain lead with the addition of niobium or tantalum, which is sintered and molded as a whole with sintered niobium material or welded later.

The condenser made in this way, which is the subject of the present invention, is used in a closed casing, for example, a polymer melt, a surface polymer shell, a metal casing, a polymer film or a laminating film obtained by immersion are used, and then used as a finished condenser product for various goals.

When the other electrode (counter electrode) is liquid, the capacitor made includes the two electrodes described above and the dielectric material disposed therein, for example, this material can be electrically connected to the other part of the counter electrode in order to form a capacitor. In this case, the electrode side of the sintered lanthanum-containing niobium material has a lead out through lead with the addition of niobium or tantalum described above, and at the same time, the electrode side is isolated from the housing by insulating with a resin or the like.

By manufacturing a sintered material for capacitors using niobium powder obtained in accordance with the embodiment of the present invention described on the previous pages and manufacturing a capacitor from sintered material, a capacitor having a low leakage current and high reliability can be obtained.

The capacitor of the present invention has a higher capacity per unit volume than commonly used tantalum capacitors, and thus a more compact product can be manufactured using a capacitor.

A capacitor according to the present invention having the above properties can be used, for example, as a blocking capacitor or as an isolation capacitor, which is often used in analog circuits and in digital circuits, and can also be used in the same way as well-known tantalum capacitors.

Typically, such a capacitor is in most cases used in electronic circuits, and thus, when a capacitor is used that is the subject of the present invention, the restrictions arising from the installation of electronic parts or due to heat generation can be removed, and can be made electronic circuit, occupying a smaller volume than circuits made by known methods.

In addition, when a capacitor of the present invention is used, an electronic device having a smaller size and higher reliability, such as a computer, peripheral computer equipment (e.g., PC Card), mobile devices, e.g. such as a portable telephone, household appliances, equipment installed in automobiles, artificial satellites and communications.

Most preferred embodiment of the invention

Below the present invention is described in more detail with examples, however, the present invention is not limited to these examples.

The capacity and leakage current of a sintered material made of niobium powder containing at least one element selected from the group consisting of chromium, molybdenum, tungsten, boron, aluminum, gallium, indium, thallium, cerium, neodymium, titanium, rhenium , ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic, bismuth, rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium , holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iri Ia, platinum, gold, cadmium, mercury, lead, selenium and tellurium (hereinafter referred to as "niobium sintered body" or simply "sintered body") was measured using the following methods.

Sintered material capacity measurement

The niobium sintered material was immersed in 30% sulfuric acid and combined with a tantalum electrode in sulfuric acid using a measuring device manufactured by Hewlett Packard Co, Ltd under the trade name Precision LCR meter HP4284A for measuring capacitance at room temperature. Capacitance (unit: μF · V / g) at 120 Hz is considered as the capacity of the sintered material.

Sintered material leakage current measurement

A voltage of 70% of the molding voltage (direct current) supplied during the formation of the dielectric is constantly applied for 3 minutes at room temperature between the sintered material immersed in a 20% aqueous solution of phosphoric acid and the electrode in an aqueous solution of phosphoric acid. The measured current value is considered as the value of the leakage current (i.e., as the LC value, unit: μA / g) of the sintered material. In accordance with the present invention, a voltage of 14 V is applied.

The capacitance and magnitude of the capacitor leakage current for a chip manufactured according to the examples is measured as follows.

Capacitor Capacitance Measurement

An HCR instrument manufactured by Hewlett Packard is installed between the two outputs of the fabricated chip in order to measure capacitance at room temperature. Capacitance at 120 Hz is considered as the capacitance of the capacitor for the chip.

Capacitor leakage current measurement

The DC voltage is selected from a nominal voltage of 2.5 V, 4 V, 6.3 V, 10 V, 16 V and 25 V, so that the selected voltage is as close as possible to a value of approximately 1/3 up to about 1/4 of the molding voltage applied during the formation of the dielectric, and continuously applied between two outputs of the chip capacitor for one minute at room temperature. The current value measured one minute later is defined as the value of the leakage current of the capacitor for the chip. In accordance with the present invention, a voltage of 6.3 V is applied.

Example 1

92 g of a niobium ingot and 1.8 g of tungsten powder are fused under the influence of an electric arc to obtain a tungsten-containing niobium ingot (alloy) containing 1 mol.% Tungsten, 50 g of this ingot is placed in a reaction vessel made of stainless steel (SUS 304), and hydrogen is continuously supplied at 400 ° C. for 10 hours. Hydrogenated tungsten-containing niobium in the form of a sintered mass is cooled and ground for 10 hours into a powder in a container made of stainless steel (SUS 304) using stainless steel balls (SUS).

An aqueous suspension is prepared from the hydrogenation product with a content of the specified product of 20 volume% by placing in a wet grinding device made of stainless steel (SUS304) (trade name "Atritor", manufactured by Atlanta Corporation) together with zirconium balls and wet grinding is carried out in within 7 hours. The suspension is subjected to sedimentation by centrifugation, and the powdered particles are separated by decantation. The crushed particles are dried at 50 ° C in a vacuum of 133 Pa.

After that, the hydrogenated tungsten-containing niobium powder is heated at 400 ° C for dehydrogenation at a pressure of 1.33 × 10 ^-2 Pa for one hour. The average particle size of the obtained tungsten-containing niobium powder is 1.0 μm, and the tungsten content, as found by the measurement by atomic absorption analysis, is 1 mol.%. The tungsten-containing niobium powder obtained as described above is granulated at 1150 ° C in a vacuum of 3.99 × 10 ^-3 Pa, and then subjected to grinding. Thus, a powder with an average particle size of 150 μm is obtained.

The tungsten-containing niobium powder subjected to granulation in this way is molded together with a lead wire containing niobium with a diameter of 0.3 mm, thereby obtaining a molded product whose size is approximately 0.3 cm × 0.18 cm × 0.45 cm and the mass is approximately 0.1 g.

The molded product is kept at 1200 ° C in a vacuum of 3.99 × 10 ^-3 Pa for 30 minutes, while obtaining sintered material. The obtained sintered material is subjected to processing in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage of 20 V for 200 minutes, so that a dielectric layer forms on the surface of the sintered material. Then, the capacity of the sintered material in 30% sulfuric acid and the leakage current of the sintered material (hereinafter referred to as “LC”) in a 20% aqueous solution of phosphoric acid are separately measured. The results are shown in table 5.

Examples 2-9

In order to obtain a niobium sintered material containing at least one of the above transition elements of the 6th group of the Periodic system, that is, at least one element selected from the group consisting of chromium, molybdenum and tungsten, a transition element (s) 6 -th group of the Periodic system in the form of a powder and a niobium ingot are mixed in an arbitrary ratio. Thus, a niobium ingot containing a transition element of the 6th group of the Periodic system is obtained by fusion under the influence of an electric arc. A niobium ingot, the mass of which is 50 g, is ground into powder using the same apparatus as in Example 1, changing the grinding time. Using the obtained niobium powder containing a transition element of the 6th group of the Periodic system, sintered material is obtained. Separately measure the capacity and LC value of the sintered material. The results are shown in table 5.

Comparative Examples 1-4

In order to compare the results according to examples 1-9, receive niobium powder, which does not contain a transition element of the 6th group of the Periodic system. Using niobium powder, sintered material is obtained in accordance with the same procedure as described in Example 1, and the capacitance and LC value of the sintered material are measured. The results are shown in table 5.

Table 5 Composition (molar ratio) The average particle size (microns) Capacitance (μF · V / g) LC (μA / g) Nb Cr Mo W Example 1 99 - - 1 1,0 120,000 36 Example 2 99 - 1 - 1,0 118,000 42 Example 3 99 1 - - 1,0 115,000 52 Example 4 99 - 0.5 0.5 1,0 121,000 42 Example 5 99 0.2 - 0.8 1,0 119000 40 Example 6 99 - - 1 0.5 240000 132 Example 7 99 - - 1 0.7 169000 97 Example 8 99 - - 1 1.3 99000 27 Example 9 99 - - 1 3.2 31000 3 Comparative Example 1 100 - - - 0.5 210000 2210 Reference Example 2 100 - - - 0.7 139000 1570 Reference Example 3 100 - - - 1,0 101000 592 Reference Example 4 100 - - - 1.3 85000 389

Examples 10-15

The amount of niobium and tungsten is varied prior to fusion under the influence of an electric arc in order to change the tungsten content in the resulting tungsten-containing niobium product. Thus, a niobium ingot is obtained containing tungsten in an amount of from 0.01 to 10 mol%. Sintered material is obtained from 50 g of a tungsten-containing niobium ingot, the tungsten content of which is as described in example 1. Separately measure the capacity and LC value of the sintered material. The results are shown in table 6.

Comparative example 5 and example 16

A niobium ingot containing 0 mol% tungsten and a niobium ingot containing 15.5 mol% tungsten are obtained in order to compare with the results according to Examples 10-15. Sintered material is obtained from 50 g of a tungsten-containing niobium ingot, the tungsten content of which in all cases is the same as described in example 1. Separately measure the capacity and LC value of the sintered material. The results are shown in table 6.

Table 6 The tungsten content (mol.%) The average particle size (microns) Capacitance (μF · V / g) LC (μA / g) Example 10 0.02 1,0 111,000 79 Example 11 0.05 1,0 113000 71 Example 12 0.5 1,0 121,000 39 Example 13 3,1 1,0 119000 39 Example 14 6.2 1,0 117000 63 Example 15 10.0 1,0 109,000 76 Reference Example 5 0,0 1,0 101000 592 Example 16 15,5 1,0 67000 89

Examples 17-22

100 g of the niobium ingot was placed in a stainless steel reaction vessel (SUS 304) and hydrogen was continuously fed at 400 ° C. for 10 hours. Hydrogenated niobium in the form of a sintered mass is cooled and pulverized using stainless steel balls (SUS) for 10 hours in a container made of stainless steel (SUS304).

A suspension in water is prepared from the hydrogenation product with a content of the specified product of 20 volume%, placed together with zirconium balls in a wet grinding apparatus made of stainless steel (SUS304) (trade name "Atritor"), and wet grinding is carried out for 7 hours. The suspension is sedimented by centrifugation, and the crushed particles are separated by sedimentation in a centrifuge. The crushed particles are dried at 50 ° C in a vacuum of 133 Pa.

After that, the hydrogenated niobium powder is heated at 400 ° C for dehydrogenation under a pressure of 1.33 × 10 ^-2 Pa for one hour. The average particle size of the obtained niobium powder is 1.3 μm.

Any of the following substances is added to the niobium powder in an arbitrary ratio: tungsten carbide, tungsten oxide or tungsten metal, the average particle size of each of which is approximately 1 μm. Thus obtained, a tungsten-containing niobium powder was granulated at 1150 ° C in a vacuum of 3.99 × 10 ^-3 Pa and then subjected to grinding. A powder with an average particle size of 190 microns is obtained. The tungsten-containing niobium powder subjected to granulation is molded as a unit with a lead wire containing niobium with a diameter of 0.3 mm, thereby obtaining a molded product whose size is approximately 0.3 cm × 0.18 cm × 0.45 cm and the mass is approximately 0.1 g.

The molded product is kept at 1230 ° C in a vacuum of 3.99 × 10 ^-3 Pa for 30 minutes, while obtaining sintered material. The obtained sintered material is subjected to processing in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage of 20 V for 200 minutes, so that a dielectric layer forms on the surface of the sintered material. Then separately measure the capacity of the sintered material in 30% sulfuric acid and the LC value in a 20% aqueous solution of phosphoric acid. The results are shown in table 7.

Table 7 The form in which tungsten is The tungsten content (mol.%) Capacitance (μF · V / g) LC (μA / g) Example 17 WC 0.2 100,000 35 Example 18 WC 1,0 98000 26 Example 19 Wo ₂ 0.5 99000 27 Example 20 Wo ₂ 2.2 97000 28 Example 21 W 0.05 101000 40 Example 22 W 0.7 99000 29th

Examples 23-27

To obtain a tungsten-containing niobium nitride, 10 g of a tungsten-containing niobium powder with an average particle size of 0.9 μm containing tungsten in an amount of 1.2 mol% and obtained by the same procedure as described in example 15, was placed in a reaction vessel made of stainless steel (SUS304). Feeding nitrogen into the reaction vessel at 300 ° C for 0.5 to 20 hours, a tungsten-containing niobium nitride is obtained. The amount of nitrogen in niobium nitride is determined using a device manufactured by LECO Corporation to determine the nitrogen content based on thermal conductivity. The ratio of the amount of nitrogen to the mass of the powder is determined separately and is indicated as the nitride content. In accordance with the results, the nitride content is from 0.02 to 0.89 wt.%.

The tungsten-containing niobium nitride thus obtained is subjected to the same granulation, molding and sintering operations as described in Example 1, whereby sintered material is obtained. The obtained sintered material is subjected to processing in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage of 20 V for 200 minutes, so that a dielectric layer forms on the surface of the sintered material. Then separately measure the capacity of the sintered material in 30% sulfuric acid and the LC value of the sintered material in a 20% aqueous phosphoric acid solution. The results are shown in table 8.

Table 8 The tungsten content (mol.%) The amount of nitrogen (% by weight) Capacitance (μF · V / g) LC (μA / g) Example 23 1,2 0.02 140,000 65 Example 24 1,2 0.10 136000 58 Example 25 1,2 0.28 138000 55 Example 26 1,2 0.43 141000 63 Example 27 1,2 0.89 139000 71

Examples 28-30

To obtain a sintered material, including a mixture of tungsten-containing niobium powder and niobium powder, a tungsten-containing niobium powder with an average particle size of 1.0 μm, containing tungsten in an amount of 10 mol%, is obtained according to the same procedure as described in example 1. Separately from of this, sodium is added to 20 g of potassium fluorobiobate completely dried at 80 ° C in a vacuum placed in a crucible made of nickel, while the amount of sodium is 10 times the molar amount of potassium fluorobiobate. Then carry out the restoration at 1000 ° C in an argon atmosphere for 20 hours. After completion of the reduction reaction, the reduced product is cooled and washed successively with water, 95% sulfuric acid and water, and then dried in vacuum. The resulting product is ground into powder for 40 hours using a ball mill, i.e. aluminum tank equipped with aluminosilicate balls. After this, the powdery product is immersed with stirring in a liquid mixture of 50% nitric acid and 10% aqueous hydrogen peroxide in a mass ratio of 3: 2. The powdery product is thoroughly washed with water to remove impurities until the pH of the product reaches 7, and dried in vacuum. The average particle size of the obtained niobium powder is 1.2 μm.

The tungsten-containing niobium powder and the niobium powder obtained by the above method are thoroughly mixed in the required ratio, and the resulting mixture is subjected to the same granulation, molding and sintering operations as in Example 15, thereby obtaining a sintered material. Then separately measure the capacitance and LC value of the sintered material. The results are shown in table 9.

Examples 31-33

To obtain a sintered material from a tungsten-containing niobium nitride, including a mixture of a tungsten-containing niobium powder and a niobium powder, a tungsten-containing niobium powder with an average particle size of 1.0 μm containing tungsten in an amount of 10 mol% was obtained by the same procedure as described in example 15 Separately, 50 g of a niobium ingot is placed in a stainless steel reaction vessel (SUS304), and hydrogen is continuously fed into it at 400 ° C. for 12 hours. Hydrogenated niobium in the form of a sintered mass is cooled and ground into powder using steel balls for 10 hours in a container made of stainless steel (SUS304).

After this, the powdery product is placed in the same reaction vessel made of stainless steel (SUS304), as described above, and again hydrogenated under the same conditions as described above. The hydrogenation product is used to prepare an aqueous suspension containing 20 volume% of the indicated product and is placed in a wet grinding device made of stainless steel (SUS304) (trade name "Atritor"), together with zirconium balls and wet grinding for 6 hours .

The suspension is subjected to sedimentation by centrifugation, and the crushed particles are separated by decantation. The crushed particles are dried at 50 ° C in a vacuum of 133 Pa. After that, the hydrogenated niobium powder is heated at 400 ° C for dehydrogenation under a pressure of 1.33 × 10 ^-2 Pa for one hour. The average particle size of the obtained niobium powder is 1.3 μm.

The tungsten-containing niobium powder and the thus obtained niobium powder are sufficiently mixed in the required ratio and the nitride is obtained by the same procedure as in Example 25. The tungsten-containing niobium nitride is granulated, molded and sintered to obtain a sintered material. Then separately measure the capacitance and LC value of the sintered material. The results are shown in table 9.

Table 9 Type of Niobium Powder Mixing ratio (tungsten-containing niobium powder / niobium powder) Capacitance (μF · V / g) LC (μA / g) Example 28 Reconstituted powder 90:10 110000 73 Example 29 Reconstituted powder 50:50 117000 55 Example 30 Reconstituted powder 10:90 119000 38 Example 31 Ground powder 80:20 111,000 68 Example 32 Ground powder 40:60 118,000 52 Example 33 Ground powder 20:80 121,000 41

Examples 34 and 35

According to example 34 and example 35 receive 50 units of sintered material in the same manner as described in example 1 and example 11, respectively. Each of the sintered materials is subjected to processing in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V for 200 minutes, thereby obtaining a dielectric layer on the surface of the sintered material by electrolytic molding. After this, the operations of immersing the sintered material, on the surface of which a dielectric film is formed, are repeated in a 60% aqueous solution of manganese nitrate and subsequent heating at 220 ° C for 30 minutes, so that a layer of manganese dioxide is formed on the dielectric oxide film serving as a counter electrode layer. Then, a carbon layer and a silver paste layer are successively applied to the counter electrode layer. After mounting the lead case, the material as a whole is sealed with epoxy resin for chip capacitors. The average capacitance and average LC capacitor value for the chip (n = 50 units in each case) are given in Table 10. The LC value is the value obtained at room temperature with a voltage of 6.3 V applied for one minute.

Examples 36 and 37

According to examples 36 and 37 receive 50 units of sintered material in the same manner as described in example 8 and in example 15, respectively. Each of the sintered materials is subjected to processing in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V for 200 minutes, thereby obtaining a dielectric layer on the surface of the sintered material by electrochemical molding. After this, the operations of immersing the sintered material, on the surface of which a dielectric film is repeated, are repeated in a 1: 1 mixture of a 35% aqueous solution of lead acetate and a 35% aqueous solution of ammonium persulfate and initiating the reaction at 40 ° C for one hour so that a layer of lead dioxide and lead sulfate is formed on the dielectric oxide film, which serves as a counter electrode layer. Then, a carbon layer and a silver paste layer are successively applied to the counter electrode layer.

After mounting the lead case, the material as a whole is sealed with epoxy resin, while manufacturing a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (in each case n = 50 units) are given in Table 10. The LC value is the value obtained at room temperature at 6.3 V for one minute.

Examples 38-40

According to example 38, example 39 and example 40, 50 units of sintered material are obtained in the same manner as described in example 7, example 12 and example 25, respectively. Each of the sintered materials is subjected to processing in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V for 200 minutes, thereby forming a dielectric oxide film on the surface of the sintered material by electrolytic molding. After this, the operations of bringing into contact the sintered material, on the surface of which a dielectric film is formed, are repeated at least 5 times with a liquid mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonsulfonic acid in a volume ratio of 1: 1 and subsequent exposure of the dielectric oxide film in pyrrole vapor, so that in this case another electrode (counter electrode) of polypyrrole is formed on the dielectric oxide film.

Then, a carbon layer and a silver paste layer are successively applied to the counter electrode. After mounting the lead case, the material as a whole is sealed with epoxy resin, while manufacturing a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (in each case n = 50 units) are given in Table 10. The LC value is the value obtained at room temperature for one minute at a voltage of 6.3 V.

Comparative Examples 6-8

In a nickel crucible, sodium is added to 20 g of potassium fluorobiobate completely dried at 80 ° C in vacuo, while the amount of sodium is 10 times the molar amount of potassium fluorobiobate. Then carry out the restoration at 1000 ° C in an argon atmosphere for 20 hours. After completion of the reduction reaction, the reduced product is cooled and washed successively with water, 95% sulfuric acid and water, and then dried in vacuum. The resulting product is ground into powder for 40 hours using a ball mill, i.e. aluminum tank equipped with aluminosilicate balls. After this, the powdery product is immersed with stirring in a liquid mixture of 50% nitric acid and 10% aqueous hydrogen peroxide in a mass ratio of 3: 2. The powdery product is thoroughly washed with water to remove impurities until the pH of the product reaches 7, and dried in vacuum. The average particle size of the obtained niobium powder is 1.3 μm. 30 g of the thus obtained niobium powder was placed in a reaction vessel made of stainless steel (SUS304), and nitrogen was supplied to it at 300 ° C. for 0.5 to 4 hours. Thus, niobium nitride is obtained.

The amount of nitrogen in niobium nitride is determined using a device manufactured by LECO Corporation by determining the nitrogen content based on thermal conductivity. The ratio of the amount of nitrogen to the mass of the powder is determined separately and is indicated as the nitride content. As a result, the nitride content is from 0.02 to 0.30 wt.%. The niobium nitride thus obtained is subjected to the same granulation, molding and sintering operations as described in Example 1, whereby sintered material is obtained. 50 units of the sintered material thus obtained are subjected to electrolytic treatment in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V to each sintered material for 200 minutes and forming a dielectric oxide film on the surface of the sintered material. After this, the operations of immersing the sintered material, on the surface of which a dielectric film is formed, are repeated in a 60% aqueous solution of manganese nitrate and subsequent heating at 220 ° C for 30 minutes, so that a layer of manganese dioxide is formed on the dielectric oxide film serving as a counter electrode layer. Then, a carbon layer and a silver paste layer are successively applied to the counter electrode. After mounting the lead case, the material as a whole is sealed with epoxy resin, making a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (in each case n = 50 units) are given in Table 10. The LC value is the value obtained at room temperature for one minute at a voltage of 6.3 V.

Comparative Examples 9-11

50 g of a niobium ingot was placed in a stainless steel reaction vessel (SUS304) and hydrogen was continuously fed into it at 400 ° C. for 12 hours. Hydrogenated niobium in the form of a sintered mass is cooled and ground into powder using steel balls for 10 hours in a container made of stainless steel (SUS304). The powdery product is placed in the same reaction vessel made of stainless steel (SUS304), as indicated above, and again subjected to hydrogenation under the same conditions as above. A suspension in water is prepared from the hydrogenation product with a content of the specified product of 20 volume%, and placed together with zirconium balls in a wet grinding apparatus made of stainless steel (SUS304) (trade name "Atritor"), wet grinding for 6 hours. The suspension is subjected to sedimentation by centrifugation, and the crushed particles are separated by decantation. The crushed particles are dried at 50 ° C in a vacuum of 133 Pa.

After that, the hydrogenated niobium powder is heated at 400 ° C for dehydrogenation under a pressure of 1.33 × 10 ^-2 Pa for one hour. The average particle size of the obtained niobium powder is 1.0 μm. 30 g of niobium powder was placed in a reaction vessel made of stainless steel (SUS304) and nitrogen was supplied to it at 300 ° C for 0.5 to 3 hours. The amount of nitrogen in niobium nitride is determined using a device manufactured by LECO Corporation by determining the nitrogen content based on thermal conductivity. The ratio of the amount of nitrogen to the mass of the powder is determined separately and is indicated as the nitride content. According to the results, the nitride content is from 0.03 to 0.28 wt.%. The niobium nitride thus obtained is subjected to the same granulation, molding and sintering operations as described in Example 1, thereby obtaining a sintered material. 50 units of the sintered material thus obtained are subjected to electrolytic treatment in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V to each sintered material for 200 minutes and forming a dielectric oxide film on the surface of the sintered material. After this, the operation of contacting the sintered material, on the surface of which a dielectric film, with a liquid mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid in a volume ratio of 1: 1 is repeated at least 5 times and subsequent exposure of the dielectric oxide film in pyrrole vapor, so that a polypyrrole counter electrode is formed on the dielectric oxide film. Then, a carbon layer and a silver paste layer are successively applied to the counter electrode.

After mounting the lead case, the material as a whole is sealed with epoxy resin, making a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (in each case n = 50 units) are given in Table 10. The LC value is the value obtained at room temperature for one minute at a voltage of 6.3 V.

Example 41

According to Example 41, fifty units of sintered material are obtained by the same procedure as described in Example 25. The sintered material is subjected to electrolytic treatment in a 0.1% aqueous solution of phosphoric acid by applying a voltage of 20 V to each sintered material for 200 minutes and forming this dielectric oxide film on the surface of the sintered material. Then, the sintered niobium material is immersed in an aqueous solution containing 25 wt% ammonium persulfate (solution 1A), removed from solution 1A and dried for 30 minutes at 80 ° C, thereby forming a dielectric. Then, the sintered material coated with a dielectric is immersed in an isopropanol solution containing 18% by weight of 3,4-ethylenedioxythiophene (solution 2), removed from solution 2 and kept at 60 ° C for 10 minutes, thereby performing oxidative polymerization .

The resulting product is re-immersed in solution 1A and subjected to the same operations as described above. After the procedure, starting from immersion in solution 1A and up to oxidative polymerization, is performed 8 times, the resulting product is washed with hot water at a temperature of 50 ° C for 10 minutes and then dried at 100 ° C for 30 minutes, thus forming another an electrode (counter electrode) comprising an electrically conductive poly (3,4-ethylenedioxythiophene). Then, a carbon layer and a silver paste layer are successively applied to the counter electrode.

After mounting the lead case, the material as a whole is sealed with epoxy resin, making a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (n = 50 units) are given in Table 10. The LC value is the value obtained at room temperature for one minute at a voltage of 6.3 V.

Example 42

50 units of sintered material are obtained according to the same procedure as described in Example 12. The sintered material is subjected to electrolytic treatment in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V to each sintered material for 200 minutes and forming on the surface of the sintered material, a dielectric oxide film. Then, the sintered niobium material is immersed in an aqueous solution containing ammonium persulfate in an amount of 25 wt.% And anthraquinone-2-sulfonate (solution 1B) in an amount of 3 wt.%, Removed from solution 1B and dried at 80 ° C for 30 minutes thus forming a dielectric. Then, the sintered material coated with a dielectric is immersed in an isopropanol solution containing 18% by weight of 3,4-ethylenedioxythiophene (solution 2), removed from solution 2 and kept at 60 ° C for 10 minutes, thereby performing oxidative polymerization .

The resulting product is re-immersed in solution 1B and subjected to the same operations as described above. After the procedure, starting from immersion in solution 1A and up to oxidative polymerization, is performed 8 times, the resulting product is washed with hot water at a temperature of 50 ° C for 10 minutes and then dried at 100 ° C for 30 minutes, thus forming another an electrode (counter electrode) comprising an electrically conductive poly (3,4-ethylenedioxythiophene). Then, a carbon layer and a silver paste layer are successively applied to the counter electrode.

After mounting the lead case, the material as a whole is sealed with epoxy resin, making a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (in each case n = 50 units) are shown in Table 10. The LC value is a value measured at room temperature for one minute at a voltage of 6.3 V.

Table 10 The nitrogen content (wt.%) Capacitance (μF) LC (μA) The number of samples with an LC value greater than 100 μA Example 34 - 539 25 0/50 Example 35 - 506 fifty 0/50 Example 36 - 440 17 0/50 Example 37 - 491 69 0/50 Example 38 - 763 67 0/50 Example 39 - 548 26 0/50 Example 40 0.28 621 40 0/50 Reference Example 6 0.02 399 46 1/50 Reference Example 7 0.09 393 42 1/50 Reference Example 8 0.30 384 thirty 0/50 Reference Example 9 0,03 454 48 1/50 Reference Example 10 0.14 449 44 0/50 Reference Example 11 0.28 459 40 0/50 Example 41 0.28 619 38 0/50 Example 42 - 545 23 0/50

Example 43

Using 93 g of a niobium alloy and 0.25 g of boron powder, a boron-containing niobium ingot (alloy) containing 2 mol% boron is obtained by fusion under the influence of an electric arc. 50 g of this ingot are placed in a reactor made of SUS 304 stainless steel and hydrogen is continuously fed into the reactor at 400 ° C. for 10 hours. After cooling, the hydrogenated boron-containing niobium sintered mass is placed in a container made of SUS 304 and containing stainless steel balls (SUS), and ground into powder for 10 hours. Then, a suspension in water is prepared from this hydrogenation product with a content of the specified product of 20 volume%, placed together with zirconium balls in a wet grinding device made of SUS 304 stainless steel and wet grinding at 10 ° C or less for 7 hours, The resulting suspension is subjected to sedimentation by centrifugation and then decanted in order to separate the powdery product. The powdery product is dried at 50 ° C in a vacuum of 1.33 × 10 ² PA.

After that, the hydrogenated boron-containing niobium powder is dehydrated by heating at 400 ° C and a pressure of 1.33 × 10 ^-2 Pa for one hour. The average particle size of the obtained boron-containing niobium powder is 1.0 μm, and the boron content, measured by atomic absorption analysis, was found to be 2 mol%. Thus obtained boron-containing niobium powder was granulated at 1000 ° C in a vacuum of 3.99 × 10 ^-3 Pa. After that, the granular mass is subjected to grinding into a powder, thereby obtaining granular powder with an average particle size of 100 μm.

Thus obtained boron-containing granular niobium powder is molded together with lead wire containing niobium, the diameter of which is 0.3 mm, while obtaining a molded product, the size of which is approximately 0.3 cm × 0.18 cm × 0.45 cm (mass approximately 0.1 g).

The molded product is kept at 1200 ° C in a vacuum of 3.99 × 10 ^-3 Pa for 30 minutes, while obtaining sintered material. The obtained sintered material is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage of 20 V for 200 minutes, so that a dielectric layer forms on the surface of the sintered material. Then measure the capacity of the sintered material in 30% sulfuric acid and the leakage current of the sintered material LC in a 20% aqueous phosphoric acid solution. The results are shown in table 11.

Examples 44-55

In accordance with the above procedure for the manufacture of sintered niobium material containing boron and aluminum, in order to obtain niobium ingots containing boron, aluminum, gallium indium or thallium by fusion using an electric arc, boron, aluminum, gallium powder taken in arbitrary proportions is used , indium or thallium and niobium ingot. Then 50 g of each ingot is pulverized using the same apparatus as in Example 43, changing the grinding time. Using the niobium powder thus obtained containing boron and aluminum, sintered materials are made and the capacitance and LC value are measured for each material. The results are shown in table 11.

Comparative Examples 12-15

In order to compare the results obtained according to examples 43-45, by the same procedure as described in example 43, four types of niobium powder are obtained that do not contain any of the following elements: boron, aluminum, gallium, indium and thallium, and with different average particle sizes.

Using the obtained niobium powder, sintered material is made and the capacitance and LC value are measured. The results are shown in table 11.

Table 11 Composition (molar ratio) The average particle size (microns) Capacitance (μF · V / g) LC (μA / r) Nb IN Al Ga In Tl Example 43 98 2.0 - - - - 1,0 115,000 28 44 99 - 1,0 - - - 1,0 114000 33 45 99 - - 1,0 - - 1,0 115,000 37 46 99 - - - 1,0 - 1,0 116000 39 47 99 - - - - 1,0 1,0 114000 39 48 98 1,0 1,0 - - - 1,0 115,000 32 49 98 0.5 1,5 - - - 1,0 114000 33 fifty 98 1,5 0.5 - - - 1,0 116000 thirty 51 98 2.0 - - - - 0.1 540000 344 52 98 2.0 - - - - 0.5 240000 153 53 98 2.0 - - - - 0.7 155,000 75 54 98 2.0 - - - - 1.3 95000 eighteen 55 98 2.0 - - - - 3.2 35,000 2 Comparative example 12 100 - - - - - 0.5 182000 2120 thirteen 100 - - - - - 0.7 120,000 1074 14 100 - - - - - 1,0 87000 424 fifteen 100 - - - - - 1.3 74000 233

Examples 56-63

In order to change the boron content in the resulting boron-containing niobium powder, the amount of niobium and boron in the powder is varied prior to fusion under the influence of an electric arc, thereby obtaining boron-containing niobium ingots with boron content from 0.02% to 9.8 mol%. Then, using 50 g of each of the boron-containing niobium ingots having an appropriate concentration of boron, sintered materials are made by the same procedure as described in Example 43, and the capacity and LC value are measured for each material. The results are shown in table 12.

Comparative Examples 16-18

In order to compare the results obtained according to examples 56-63, boron-containing niobium ingots with a boron content of 0 mol%, 13.3 mol% or 17.5 mol% are obtained. Thereafter, using 50 g of each of the boron-containing niobium ingots having the corresponding boron content, sintered materials were made in the same manner as described in Example 43, and the capacity and LC value were measured for each material. The results are shown in table 12.

Table 12 The content of boron (mol.%) The average particle size (microns) Sintering temperature, (° С) Capacitance (μF · V / g) LC (μA / g) Example 56 0.02 1,0 1200 105000 52 57 0.10 1,0 1200 112000 43 58 1,1 1,0 1200 113000 36 43 2.0 1,0 1200 115,000 28 59 3.0 1,0 1200 117000 28 60 4.1 1,0 1200 116000 29th 61 5.2 1,0 1200 112000 32 62 7.5 1,0 1200 105000 38 63 9.8 1,0 1200 98000 43 Comparative example 16 0,0 1,0 1200 88000 420 17 13.3 1,0 1200 85000 49 eighteen 17.5 1,0 1200 79000 52

Examples 64-69

100 g of a niobium ingot are placed in a reactor made of SUS 304 and hydrogen is continuously fed into the reactor at 400 ° C. for 10 hours. After cooling, the hydrogenated sintered niobium mass is placed in a container made of SUS 304 and containing steel balls (SUS), and ground into powder for 10 hours. Then, a suspension in water is prepared from this hydrogenation product with a content of the specified product of 20 volume%, placing it together with zirconium balls in a wet grinding device made of SUS 304 stainless steel and wet grinding for 7 hours. The resulting suspension is subjected to sedimentation by centrifugation and then decanted to obtain a powdery product. The powdery product is dried at 50 ° C in a vacuum of 1.33 × 10 ² PA. After that, the hydrogenated niobium powder is dehydrated under heating at a pressure of 1.33 × 10 ^-2 Pa at 400 ° C for one hour. The average particle size of the obtained niobium powder is 1.1 μm. This powder is mixed in an arbitrary ratio with any of such substances as niobium diborate, boron oxide and metallic boron, each with an average particle size of about 1 μm. The resulting boron-containing niobium powder was granulated at 1050 ° C. in vacuo 3.99 × 10 ^-3 Pa. After that, the granular sintered mass is subjected to grinding into a powder, thereby obtaining granular powder with an average particle size of 90 μm. The boron-containing granular niobium powder thus obtained is formed together with a lead wire containing niobium with a diameter of 0.3 mm, to thereby obtain a molded product whose size is approximately 0.3 cm × 0.18 cm × 0.45 cm (mass approximately 0.1 g). Then these molded products are kept at 1200 ° C in a vacuum of 3.99 × 10 ^-3 Pa for 30 minutes, while obtaining sintered material. Each of the obtained sintered materials was subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage of 20 V for 200 minutes, so that a dielectric layer was formed on the surface of the sintered material. Then measure the capacity of the sintered material in 30% sulfuric acid and the LC value in a 20% aqueous solution of phosphoric acid. The results are shown in table 13.

Table 13 The form in which boron is located The content of boron (mol.%) Capacitance (μF · V / g) LC (μA / g) Example 64 Nbb ₂ 2.9 117000 thirty 65 Nbb ₂ 1,2 112000 38 66 VO ₃ 3.8 113000 34 67 VO ₃ 2.2 112000 32 68 IN 0.5 112000 38 69 IN 1,1 114000 39

Examples 70-74

In order to obtain a boron-containing niobium nitride, 10 g of boron-containing niobium powder containing 3.2 mol.% Boron and having an average particle size of 0.9 μm was obtained by the same procedure as described in example 43 and placed in a reactor, made of stainless steel SUS 304, nitrogen is continuously fed into it at 300 ° C for 0.5 to 20 hours, while receiving boron-containing niobium nitrides. The amount of nitrogen in each of the niobium nitrides is determined using a thermal conductivity nitrogen meter manufactured by LECO Corporation. The ratio of the measured value to the separately measured powder mass is determined and indicated as the nitride content. The nitride content in accordance with the results is from 0.02 to 0.89 wt.%.

Each of the niobium boron nitrides thus obtained was granulated, molded and sintered in the same manner as described in Example 43, and each sintered material obtained was subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage 20 V for 200 minutes, so that a dielectric layer forms on the surface of the sintered material. Then measure the capacity of the sintered material in 30% sulfuric acid and the LC value of the sintered material in a 20% aqueous phosphoric acid solution. The results are shown in table 14.

Table 14 The content of boron (mol.%) The nitrogen content (wt.%) Capacitance (μF · V / g) LC (μA / g) Example 70 3.2 0.02 129,000 31 71 3.2 0.10 128,000 thirty 72 3.2 0.28 128,000 28 73 3.2 0.43 127000 33 74 3.2 0.89 128,000 39

Examples 75 and 76

To obtain a sintered material, including a mixture of boron-containing niobium powder and niobium powder, according to the same procedure as described in example 43, receive boron-containing niobium powder containing boron in the amount of 6.9 mol.% And having an average particle size of 1.0 μm .

Separately, 20 g of potassium fluorniobate carefully dried at 80 ° C in vacuum and sodium are placed in a crucible made of nickel, while the amount of sodium is 10 times the molar amount of potassium fluorobiobate and reduction is carried out at 1000 ° C in argon atmosphere within 20 hours. After completion of the reaction, the reduction product is cooled and washed successively with water, 95% sulfuric acid and water, then dried in vacuum and ground into powder for 40 hours using a ball mill, which is an aluminum tank containing aluminosilicate balls. The powdery product is immersed and mixed in a liquid mixture of 50% nitric acid and 10% aqueous hydrogen peroxide in a ratio of 3: 2 (by weight). After that, the powdery product is thoroughly washed with water to remove impurities until the pH reaches 7, and dried in vacuum. The average particle size of the obtained niobium powder is 1.2 μm.

Thus obtained boron-containing niobium powder is thoroughly mixed with niobium powder in the ratio shown in table 15, and each of the mixtures obtained is subjected to granulation, molding and sintering, in the same manner as described in example 43, while obtaining sintered materials. The capacitance and LC value of each of the sintered materials is measured, the results are shown in table 15.

Examples 77-80

To obtain a sintered material from boron-containing niobium nitride, including a mixture of boron-containing niobium powder and niobium powder, using the same procedure as described in example 43, a boron-containing niobium powder is obtained containing 6.9 mol.% Boron and having an average particle size of 1, 0 microns. Separately, 50 g of a niobium ingot was placed in a reactor made of SUS 304, and hydrogen was continuously fed into it at 400 ° C. for 12 hours. After cooling, the hydrogenated niobium sintered mass is placed in a container made of SUS 304 containing steel balls and ground into powder for 10 hours. This powdery product is placed in the same reactor made of SUS 304, as described above, and once again hydrogenated under the same conditions as described above. Then, an aqueous suspension containing 20 volume% of this product is prepared from the hydrogenation product, placed together with zirconium balls in a wet grinding device made of SUS 304, and wet grinding is carried out for 6 hours to obtain a powder.

The resulting suspension is subjected to centrifugation and decantation, while obtaining a powdery product. The powdery product is dried at 50 ° C in vacuo 1.3 3 × 10 ^-2 PA. After that, the hydrogenated niobium powder is dehydrogenated by heating in a vacuum of 1.33 × 10 ^-2 Pa at 400 ° C for one hour. The average particle size of the obtained niobium powder is 1.1 μm.

The boron-containing niobium powder thus obtained is thoroughly mixed with the niobium powder in an arbitrary ratio, and after nitride production by the same procedure as in Example 72, each of the nitrides is granulated, molded and sintered to obtain sintered material. The capacitance and LC value of each of the sintered materials is measured, the results are shown in table 15.

Table 15 Type of Niobium Powder Mixing ratio (boron-containing niobium powder: niobium powder) Capacitance (μF · V / g) LC (μA / g) Example 75 Reconstituted powder 90:10 109,000 36 76 Reconstituted powder 50:50 117000 28 77 Reconstituted powder 10:90 111,000 41 78 Ground powder 80:20 113000 33 79 Ground powder 40:60 116000 27 80 Ground powder 20:80 114000 36

Examples 81 and 82

According to each of Examples 81 and 82, 50 units of sintered material are obtained in the same manner as described in Example 43 and Example 44, respectively. Each of these sintered materials is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V for 200 minutes, forming a dielectric layer on the surface of the sintered material. After this, the operations of immersing each sintered material in a 60% aqueous solution of manganese nitrate and subsequent heating at 220 ° C for 30 minutes are repeated, so that a layer of manganese dioxide is formed on the dielectric oxide film, which serves as another electrode (counter electrode) . Then, a carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead casing, the whole material is sealed with epoxy resin for capacitors suitable for the chip. The average capacitance and the average LC value of the capacitor suitable for the chip (in each example n = 50 units) are shown in Table 16. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 83 and 84

According to each of Examples 83 and 84, 50 units of sintered material are obtained in the same manner as described in Example 53 and Example 48, respectively. Each of the sintered materials is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V for 200 minutes, forming a dielectric layer on the surface of the sintered material. After this, the operation of immersing each sintered material in a mixture of a 35% aqueous solution of lead acetate and a 35% aqueous solution of ammonium persulfate, taken in a ratio of 1: 1, is repeated, and the reaction is carried out upon exposure for one hour at 40 ° C, so that a mixed layer of lead dioxide and lead sulfate forms on the dielectric oxide film, which serves as another electrode (counter electrode). A carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead case, the device is molded as a whole with epoxy resin, while manufacturing a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (in each example n = 50 units) are given in Table 16. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 85-88

According to example 85, example 86, example 87 and example 88, 50 units of sintered material are obtained in the same manner as described in example 58, in example 49, example 67 and in example 71, respectively. Each of the sintered materials is subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes, thereby forming a dielectric oxide film on the surface of the sintered material. After this, the operations of bringing into contact of the dielectric oxide film with a liquid mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid in an equivalent (by weight) ratio are repeated at least 5 times, followed by exposure in pairs pyrrole, so that in this case another electrode (counter electrode), including polypyrrole, is formed on the dielectric oxide film.

Then, a carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead casing, the device as a whole is pressed with epoxy resin, while manufacturing a capacitor for the chip. The average capacitance and the average LC capacitor value for the chip (in each example n = 50 units) are given in Table 16. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 89-93

According to example 89, example 90, example 91, example 92 and example 93, 50 units of sintered material are obtained in the same manner as described in example 59, example 50, example 65, example 72 and example 76, respectively. Each of these sintered materials is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V for 200 minutes, thereby forming a dielectric oxide film on the surface of the sintered material. Then, the sintered niobium material is immersed in an aqueous solution containing ammonium persulfate in an amount of 25 wt.% (Solution 1), then removed and dried at 80 ° C for 30 minutes. After that, the sintered material coated with a dielectric is immersed in an isopropanol solution containing 18 wt.% 3,4-ethylenedioxythiophene (solution 2), after which it is removed and maintained at 60 ° C for 10 minutes, thereby performing oxidative polymerization.

The resulting sintered material is re-immersed in solution 1 and then subjected to the same operations as described above. Operations from immersion in solution 1 to oxidative polymerization are repeated 8 times. Then, the sintered material is washed with hot water at 50 ° C. for 10 minutes and dried at 100 ° C. for 30 minutes, thereby forming another electrode (counter electrode) including electrically conductive poly (3,4-ethylenedioxythiophene).

Then, a carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead case, the material as a whole is filled with epoxy resin, making a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (n = 50 units in each example) are shown in Table 16. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Comparative Examples 19-21

In a nickel crucible, 20 g of potassium fluorobiobate completely dried at 80 ° C in vacuum are placed, and sodium is added in a molar amount, which is 10 times the molar amount of potassium fluorobiobate, a reduction reaction is carried out at 1000 ° C in argon atmosphere for 20 hours. After completion of the reaction, the reconstituted product is cooled and washed successively with water, 95% sulfuric acid and then water, dried in vacuum and ground into powder for 40 hours using a ball mill containing an aluminum tank equipped with aluminosilicate balls. The powdery product is immersed and mixed in a solution, which is a mixture of 50% nitric acid and 10% aqueous hydrogen peroxide in a mass ratio of 3: 2. After that, the powdery product is thoroughly washed with water to remove impurities, until the pH of the product reaches 7, and dried in vacuum. The average particle size of the obtained niobium powder is 1.3 μm. 30 g of the niobium powder thus obtained are placed in a reactor made of SUS 304 and nitrogen is supplied to the reactor at 300 ° C. for 0.5 to 4 hours in order to obtain niobium nitride. The amount of nitrogen in each of the niobium nitriding products is determined using a nitrogen quantity meter manufactured by LECO Corporation by determining the amount of nitrogen based on thermal conductivity. The ratio of the measured value to the separately measured powder mass is indicated as the nitride content, and according to the results obtained, the nitride content is from 0.02 to 0.30 wt.%. Each of the niobium nitrides is subjected to granulation, molding and sintering, in the same manner as described in example 43, while obtaining sintered material. Thus obtained 50 units of sintered material are subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes, forming a dielectric oxide film on the surface of the sintered material. After this, the operations of immersing the sintered material in a 60% aqueous solution of manganese nitrate and then heating it at 220 ° C for 30 minutes are repeated, forming a layer of manganese dioxide on the dielectric oxide film, which serves as another electrode (counter electrode). A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead case, the material as a whole is filled with epoxy resin, making a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (n = 50 units in each example) are shown in Table 16. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Comparative Examples 21-23

50 g of a niobium ingot is placed in a reactor made of SUS 304 steel, and hydrogen is continuously fed into it at 400 ° C. for 12 hours. After cooling, the hydrogenated sintered niobium mass is placed in a container made of SUS 304 steel, which contains steel balls, and ground into powder for 10 hours. This powdery product is placed in the same reactor made of SUS 304, as described above, and once again hydrogenated under the same conditions as described above. Then, a 20% (by volume) aqueous suspension is prepared from the hydrogenation product, which is placed together with zirconium balls in a wet grinding device made of SUS 304 (trade name "Atritor"), and wet grinding is carried out for 6 hours to receiving powder. The resulting suspension is subjected to sedimentation by centrifugation and decantation, while obtaining a powdery product. The powdery product is dried at 50 ° C in a vacuum of 1.33 × 10 ² PA. After that, the hydrogenated niobium powder is dehydrogenated by heating in a vacuum of 1.33 × 10 ^-2 Pa at 400 ° C for one hour. The average particle size of the obtained niobium powder is 1.0 μm. 30 g of the obtained niobium powder were placed in a reactor made of SUS304 steel and nitrogen was continuously fed at 300 ° C. for 0.5 to 3 hours in order to obtain niobium nitrides. The amount of nitrogen in each of the nitrides is determined using a device for determining the nitrogen content, the device is manufactured by LECO Corporation and allows you to determine the amount of nitrogen by thermal conductivity. The ratio of the measured value to the separately measured mass of the powder is indicated as the nitride content, in accordance with the results obtained, the nitride content in this case is from 0.03 to 0.28 wt.%. Each of the niobium nitrides is subjected to granulation, molding and sintering in the same manner as described in example 43, while obtaining sintered material. 50 units of each of the sintered materials thus obtained are subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes so that a dielectric oxide film is formed on the surface of the sintered material. After that, the operation of contacting the dielectric oxide film and a mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid in an equivalent (by weight) ratio is repeated at least 5 times, followed by exposure to pyrrole vapor , so that in this case another counter electrode, including polypyrrole, is formed on the dielectric oxide film. A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead casing, the device as a whole is pressed with epoxy resin, while manufacturing a capacitor for the chip. The average capacitance and average LC capacitor value for the chip (n = 50 units in each example) are shown in Table 16. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Table 16 The nitrogen content (wt.%) Capacitance (μF) LC (μA) The number of samples for which the LC value exceeds 100 μA Example 81 - 529 17 0/50 82 - 513 23 0/50 83 690 53 0/50 84 - 500 22 0/50 85 - 480 21 0/50 86 - 513 23 0/50 87 - 520 25 0/50 88 0.10 557 22 0/50 89 - 521 twenty 0/50 90 - 528 22 0/50 91 - 493 28 0/50 92 - 589 twenty 0/50 93 0.28 527 eighteen 0/50 Comparative example eighteen 0.02 399 46 1/50 19 0.09 393 42 1/50 twenty 0.30 384 thirty 0/50 21 0,03 454 48 1/50 22 0.14 449 44 0/50 23 0.28 459 40 0/50

Example 94

Using 92 g of a niobium ingot and 1.9 g of rhenium powder by fusion under the influence of an electric arc, a rhenium-containing niobium ingot (alloy) containing 1 mol.% Rhenium is obtained. 50 g of the obtained ingot was placed in a reactor made of SUS 304 steel, and hydrogen was continuously fed into the reactor at 400 ° C. for 10 hours. After cooling, the hydrogenated rhenium-containing niobium sintered mass is placed in a container made of stainless steel (SUS304) using SUS steel balls and pulverized for 10 hours. After that, a 20% (by volume) aqueous suspension is prepared from the hydrogenation product, placed together with zirconium balls in a wet grinding device made of SUS 304 stainless steel, and wet grinding is carried out at 10 ° C or less for 7 hours. The resulting suspension is subjected to sedimentation by centrifugation and decanted in order to obtain a powdery product. The powdery product is dried at 50 ° C in a vacuum of 1.33 × 10 ² PA.

After that, the hydrogenated rhenium-containing niobium powder is dehydrated when heated under a pressure of 1.33 × 10 ^-2 Pa at 400 ° C for one hour. The average particle size of the obtained rhenium-containing niobium powder is 1 μm, and the content of rhenium in it, as measured by atomic absorption analysis, is 1 mol.%. The rhenium-containing niobium powder thus obtained was granulated at 1000 ° C. in a vacuum of 4 × 10 ⁻³ Pa. After that, the granular sintered mass is subjected to grinding into a powder, thereby obtaining granular powder with an average particle size of 100 μm.

Thus obtained rhenium-containing niobium granular powder is molded together with lead wire containing niobium, the diameter of which is 0.3 mm, while obtaining a molded product, the size of which is approximately 0.3 cm × 0.18 cm × 0.45 cm (mass approximately 0.1 g).

The specified molded product is maintained at 1200 ° C in a vacuum of 4 × 10 ^-3 Pa for 30 minutes, while obtaining sintered material. The obtained sintered material is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage of 20 V for 200 minutes in order to form a dielectric layer on the surface of the sintered material. Then measure the capacity of the sintered material in 30% sulfuric acid and the leakage current of the sintered material (hereinafter referred to simply as “LC”) in a 20% aqueous phosphoric acid solution. The results are shown in table 17.

Examples 95-117

In accordance with the method described above for the manufacture of sintered material containing at least one element, such as cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth, powder of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic or bismuth and a niobium ingot are mixed in an arbitrary ratio and obtained by fusion under the influence of an electric arc a niobium ingot containing at least least dynes element such as cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic or bismuth. Then 50 g of each ingot is pulverized using the same apparatus as in Example 94, changing the grinding time. Using the niobium powder thus obtained containing cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic or bismuth, sintered materials are obtained and the capacitance and LC value of each sintered material are measured . The results are shown in table 17.

Using rhenium allows to achieve the effect of the greatest reduction in leakage current, and the effect of zinc, arsenic, phosphorus, germanium and tin is reduced in this order. The leakage current is approximately the same for cerium, neodymium, titanium, ruthenium, rhodium, palladium, silver, silicon and bismuth, and is smaller than that of tin. According to the present invention, it is most preferred that the niobium powder contains rhenium and the next most preferred is zinc.

Comparative Examples 24-27

In order to compare the results obtained according to examples 94-117, four types of niobium powder, which do not contain any of the elements, such as cerium, neodymium, titanium, rhenium, ruthenium, rhodium, are obtained in the manner described in example 94 , palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth, and which have different average particle sizes. Using the obtained niobium powder, sintered materials are made and the capacitance and LC value are measured. The results are shown in table 17.

Table 17 Composition (molar ratio) The average particle size (microns) Capacitance (μF · V / g) LC (μA / g) Example 94 Nb (99.0), Re (1.0) 1,0 113000 25 95 Nb (99.9), Zn (0.1) 1,0 105000 25 96 Nb (99.0), As (1.0) 1,0 104000 26 97 Nb (98.0), P (2.0) 1,0 105000 29th

98 Nb (99.0), Ge (1.0) 1,0 100,000 38 99 Nb (99.0), Sn (1.0) 1,0 101000 39 100 Nb (99.0), Ce (1.0) 1,0 92000 43 101 Nb (99.0), Nd (1.0) 1,0 94000 40 102 Nb (99.7), Ti (0.3) 1,0 89000 39 103 Nb (99.9), Ru (0.1) 1,0 90,000 44 104 Nb (99.8), Rh (0.2) 1,0 92000 39 105 Nb (99.8), Pd (0.2) 1,0 88000 40 106 Nb (99.9), Ag (0.1) 1,0 90,000 42 107 Nb (94.0), Si (6.0) 1,0 95000 44 108 Nb (99.8), Bi (0.2) 1,0 91000 42 109 Nb (95.0), Re (1.0), P (4.0) 1,0 115,000 29th 110 Nb (97.0), Re (0.5), As (2.5) 1,0 111,000 27 111 Nb (99.0), Re (0.3), Ge (0.7) 1,0 113000 26 112 Nb (98.5), Re (1.0), Sn (0.5) 1,0 112000 29th 113 Nb (92.0), Re (0.5), Si (7.5) 1,0 118,000 44 114 Nb (98.0), Re (0.8), Zn (0.2), Ge (1.0) 1,0 113000 22 115 Nb (99.0), Re (1.0) 0.5 246000 126 116 Nb (99.0), Re (1.0) 0.7 162000 55 117 Nb (99.0), Re (1.0) 1.3 96000 12 Comparative example 24 Nb (100) 0.5 182000 2120 25 Nb (100) 0.7 120,000 1074 26 Nb (100) 1,0 87000 424 27 Nb (100) 1.3 74000 233

Examples 118-122

In order to vary the rhenium content in the rhenium-containing niobium powder, rhenium-containing niobium ingots with rhenium content from 0.01 to 7 mol% are obtained by fusing under the influence of an electric arc, changing the amount of niobium and rhenium used for alloying. Then, using 50 g of each rhenium-containing niobium ingot with an appropriate concentration of rhenium, sintered materials are obtained by performing the same operations as in Example 94, and the capacitance and LC value of each sintered material are measured. The results are shown in table 18.

Comparative Examples 28-30

In order to compare the results obtained according to example 94 and examples 118-122, get rhenium-containing niobium ingots containing 0 mol.%, 11 mol.% Or 18 mol.% Rhenium. After that, using 50 g of each rhenium-containing niobium ingot, with an appropriate concentration of rhenium, sintered are made by performing the same operations as in Example 94, and the capacitance and LC value of each sintered material are measured. The results are shown in table 18.

Table 18 The content of rhenium (mol.%) The average particle size (microns) Sintering temperature (° C) Capacitance (μF · V / g) LC (μA / g) Example 118 0.01 1,0 1200 95000 65 Example 119 0.10 1,0 1200 106000 39 Example 94 1,0 1,0 1200 113000 25 Example 120 2.0 1,0 1200 112000 28 Example 121 3.0 1,0 1200 113000 26 Example 122 7.0 1,0 1200 109,000 32 Reference Example 28 0,0 1,0 1200 86000 420 Reference Example 29 11.0 1,0 1200 85000 59 Reference Example 30 18.1 1,0 1200 80,000 62

Examples 123-128

100 g of the niobium ingot was placed in a reactor made of SUS 304 steel, and hydrogen was continuously fed into the reactor at 400 ° C. for 10 hours. After cooling, the hydrogenated niobium sintered mass is placed in a container made of SUS 304 stainless steel and containing SUS steel balls and ground into powder for 10 hours. Then, from this hydrogenation product, a 20% (by volume) aqueous suspension is prepared, placed together with zirconium balls in a wet grinding device made of SUS 304 steel, and wet grinding is carried out for 7 hours. The resulting suspension is subjected to sedimentation by centrifugation and decanted in order to obtain a powdery product. The powdery product is dried at 50 ° C in a vacuum of 1.33 × 10 ² PA. After that, the hydrogenated rhenium-containing niobium powder is dehydrated when heated under a pressure of 1.33 × 10 ^-2 Pa at 400 ° C for one hour. The average particle size of the manufactured niobium powder is 1.1 μm.

This powder is mixed in an arbitrary ratio with any of the following substances: rhenium oxide, rhenium sulfide and metallic rhenium, each of which has an average particle size of approximately 1 μm. The resulting rhenium-containing niobium powder was granulated at 1050 ° C in a vacuum of 4 × 10 ^-3 Pa. After that, the granular sintered mass is subjected to grinding, while obtaining granular powder with an average particle size of 90 μm. Thus obtained rhenium-containing niobium granular powder is pressed together with a lead wire containing niobium, the diameter of which is 0.3 mm, while obtaining a molded product, the size of which is approximately 0.3 cm × 0.18 cm × 0.45 cm (mass approximately 0.1 g). After that, the obtained molded products are kept at 1200 ° C in a vacuum of 4 × 10 ^-3 Pa for 30 minutes, while obtaining sintered materials. The obtained sintered materials are subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at a temperature of 80 ° C, applying a voltage of 20 V for 200 minutes in order to form a dielectric layer on the surface of the sintered material. Then measure the capacity in 30% sulfuric acid and LC in a 20% aqueous solution of phosphoric acid. The results are shown in table 19.

Table 19 The form in which rhenium is The content of rhenium (mol,%) Capacitance (μF · V / g) LC (μA / g) Example 123 ReO ₂ 2,8 115,000 27 Example 124 ReO ₃ 1,2 112000 25 Example 125 Re ₂ O ₇ 3,5 114000 26 Example 126 Res ₂ 2,3 115,000 29th Example 127 Re ₂ S ₇ 0.5 112000 31 Example 128 Re 1,0 114000 25

Examples 129-133

In order to obtain rhenium-containing niobium nitride, 10 g of rhenium-containing niobium powder was prepared containing 0.9 mol% of rhenium and having an average particle size of 0.9 μm, using the same procedure as in Example 94, this powder was placed in a reactor made of SUS 304 steel, and nitrogen is supplied to the reactor at 300 ° C. for 0.5 to 20 hours, thereby obtaining niobium nitride. The amount of nitrogen in each of the niobium nitrides is determined using a nitrogen quantity meter manufactured by LECO Corporation by determining the amount of nitrogen based on thermal conductivity. The ratio of the measured value to the separately measured powder mass is indicated as the nitride content, and according to the results obtained, the nitride content is from 0.02 to 0.79 wt.%.

Each of the rhenium-containing niobium nitrides thus obtained was subjected to granulation, molding and sintering in the same manner as described in Example 94, and each sintered material obtained was subjected to electrochemical treatment at a temperature of 80 ° C in a 0.1% aqueous solution of phosphoric acid, applying a voltage of 20 V for 200 minutes, thereby forming a dielectric oxide film on the surface of the sintered material. Then measure the capacity in 30% sulfuric acid and the value of LC in a 20% aqueous solution of phosphoric acid. The results are shown in table 20.

Table 20 The content of rhenium (mol.%) The nitrogen content (wt.%) Capacitance (μF · V / g) LC (μA / g) Example 129 0.9 0.02 124000 28 Example 130 0.9 0.11 125000 25 Example 131 0.9 0.27 125000 22 Example 132 0.9 0.45 124000 22 Example 133 0.9 0.79 125000 35

Examples 134-136

In order to produce a sintered material comprising a mixture of rhenium-containing niobium powder and niobium powder, using the same procedure as in Example 94, rhenium-containing niobium powder containing 10 mol% rhenium and having an average particle size of 1.0 was obtained microns.

Separately, 2,000 g of potassium fluorobiobate carefully dried at 80 ° C in vacuum and sodium are placed in a crucible made of nickel, while the molar amount of sodium is 10 times the molar amount of potassium fluorobiobate and a reduction reaction is carried out at 1000 ° C argon atmosphere for 20 hours. After completion of the reaction, the reduction product is cooled and washed successively with water, 95% sulfuric acid and water, dried in vacuum and ground into powder for 40 hours using a ball mill, which is an aluminum reservoir containing aluminosilicate balls. The powdery product is immersed and mixed in a liquid mixture of 50% nitric acid and 10% aqueous hydrogen peroxide in a ratio of 3: 2 (by weight). After that, the powdery product is thoroughly washed with water to remove impurities until the pH reaches 7, and dried in vacuum. The average particle size of the obtained niobium powder is 1.2 μm.

Thus obtained rhenium-containing niobium powder is thoroughly mixed with niobium powder in the ratio shown in table 21, and each of the mixtures obtained is subjected to granulation, molding and sintering, in the same manner as described in example 94, while obtaining sintered materials. The capacitance and LC value of each sintered material is measured, the results are shown in table 21.

Examples 137-139

In order to produce a sintered material comprising rhenium-containing niobium nitride, which includes a mixture of rhenium-containing niobium powder and niobium powder, using the same procedure as in Example 94, rhenium-containing niobium powder containing 10 mol% rhenium and having an average particle size equal to 1.0 microns. Separately, 50 g of a niobium ingot was placed in a reactor made of SUS 304 steel, and hydrogen was continuously fed into the reactor at 400 ° C. for 12 hours. After cooling, the hydrogenated niobium sintered mass is placed in a container made of SUS 304 steel containing steel balls and ground into powder for 10 hours. This powdery product is charged into the same reactor made of SUS 304 steel, as described above, again hydrogenated under the conditions described above. Then, from this hydrogenation product, a 20% (by volume) aqueous suspension is prepared, placed together with zirconium balls in a wet grinding device made of SUS 304 steel, and wet grinding is carried out for 6 hours.

The resulting suspension is subjected to sedimentation by centrifugation and decanted in order to obtain a powdery product. The powdery product is dried at 50 ° C in a vacuum of 1.33 × 10 ² PA. After that, the hydrogenated rhenium-containing niobium powder is dehydrogenated by heating in a vacuum of 1.33 × 10 ^-2 Pa at 400 ° C for one hour. The average particle size of the manufactured niobium powder is 1.1 μm.

The rhenium-containing niobium powder thus obtained is thoroughly mixed in an arbitrary ratio with the niobium powder, and after receiving the nitrides in the same manner as in Example 131, each of the nitrides is granulated, molded and sintered to obtain sintered materials. The capacitance and LC value for each of the sintered materials is measured, the results are shown in table 21.

Table 21 Type of Niobium Powder Mixing ratio (rhenium-containing niobium powder: niobium powder) Capacitance (μF · V / g) LC (μA / g) Example 134 Reconstituted powder 90:10 104000 45 Example 135 Reconstituted powder 50:50 110000 41 Example 136 Reconstituted powder 10:90 114000 26 Example 137 Ground powder 80:20 104000 46 Example 138 Ground powder 40:60 111,000 38 Example 139 Ground powder 20:80 115,000 25

Examples 140 and 141

According to Example 140 and Example 141, 50 units of sintered material are obtained in the same manner as described in Example 94 and Example 116, respectively. Each of these sintered materials is subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes, thereby forming a dielectric oxide film on the surface of the sintered material. After this, the operations of immersing each sintered material in a 60% aqueous solution of manganese nitrate and then heating this material at 220 ° C for 30 minutes are repeated, forming a layer of manganese dioxide on the dielectric oxide film, which serves as another electrode (counter electrode). Then, a carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead case, the material is molded as a whole with epoxy resin for capacitors for the chip. The average capacitance and the average LC capacitor value for the chip (in each example n = 50 units) are given in Table 22. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 142 and 143

According to Example 142 and Example 143, 50 units of sintered material are obtained in the same manner as described in Example 95 and Example 128, respectively. Each of these sintered materials is subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes, thereby forming a dielectric film on the surface of the sintered material. After this, the operation of immersing each sintered material in a mixture of a 35% aqueous solution of lead acetate and a 35% aqueous solution of ammonium persulfate (in a volume ratio of 1: 1) is repeated, followed by a reaction at a temperature of 1 hour at 40 ° C. , in order to form on the dielectric oxide film a mixed layer of lead dioxide and lead sulfate, which serves as another electrode (counter electrode). A carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead case, the device is molded as a whole with epoxy resin, while manufacturing a capacitor for the chip. The average capacitance and the average LC capacitor value for the chip (in each example n = 50 units) are given in Table 22. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 144-147

According to example 144, example 145, example 146 and example 147, 50 units of sintered material are obtained in the same manner as described in example 96, example 115, example 132 and example 97, respectively. Each of the sintered materials is subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes, thereby forming a dielectric oxide film on the surface of the sintered material. After this, the operation of contacting the dielectric oxide film with a liquid mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid in an equivalent (by weight) ratio is repeated at least 5 times, followed by exposure in pairs pyrrole, so that in this case another electrode (counter electrode), including polypyrrole, is formed on the dielectric oxide film.

A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead case, the device as a whole is pressed with epoxy resin, while manufacturing a capacitor for the chip. The average capacitance and the average LC capacitor value for the chip (in each example n = 50 units) are given in Table 22. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 148-153

According to example 148, example 149, example 150, example 151, example 152 and example 153, 50 units of sintered material are obtained in the same manner as described in example 114, example 122, example 123, example 124, example 124, example 131 and in example 136, respectively. Each of these sintered materials is subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes, thereby forming a dielectric oxide film on the surface of the sintered material. Then, the sintered niobium material is immersed in an aqueous solution containing ammonium persulfate in an amount of 25 wt.% (Solution 1), then removed and dried at 80 ° C for 30 minutes. Then, the sintered material coated with a dielectric is immersed in an isopropanol solution containing 18 wt.% 3,4-ethylenedioxythiophene (solution 2), after which it is removed and maintained at 60 ° C for 10 minutes, thereby performing oxidative polymerization. The resulting sintered material is re-immersed in solution 1, and then subjected to the same operations as described above. Operations starting from immersion in solution 1 and ending with oxidative polymerization are repeated 8 times. Then, the sintered material is washed with hot water at 50 ° C. for 10 minutes and dried at 100 ° C. for 30 minutes, thereby forming another electrode (counter electrode) including electrically conductive poly (3,4-ethylenedioxythiophene).

A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead casing, the material as a whole is pressed with epoxy resin, making a capacitor for the chip. The average capacitance and the average LC capacitor value for the chip (in each example n = 50 units) are given in Table 22. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Comparative Examples 32-34

2,000 g of potassium fluorobiobate carefully dried in vacuo at 80 ° C are placed in a nickel crucible, sodium is added in a molar amount that is 10 times the molar amount of potassium fluorobiobate, and the reduction reaction is carried out in an argon atmosphere at 1000 ° C for 20 hours. After completion of the reaction, the reconstituted product is cooled and washed successively with water, 95% sulfuric acid and then water, dried in vacuum and ground into powder for 40 hours using a ball mill, which is an aluminum tank equipped with aluminosilicate balls. The powdery product is immersed and mixed in a solution, which is a mixture in a ratio of 3: 2 (by weight) of 50% nitric acid and 10% aqueous hydrogen peroxide solution. After that, the powdery product is thoroughly washed with water to remove impurities until the pH reaches 7, and dried in vacuum. The average particle size of the manufactured niobium powder is 1.3 μm. 30 g of the niobium powder thus obtained are charged into a reactor made of SUS 304 steel and nitrogen is supplied thereto at 300 ° C. for 0.5 to 4 hours, thereby producing niobium nitrides. The amount of nitrogen in each of the niobium nitrides is determined using a LECO nitrogen measuring device based on thermal conductivity. The ratio of the measured value to the separately measured powder mass is indicated as the nitride content, according to the results obtained, the nitride content is from 0.02 to 0.30 wt.%. Each of the niobium nitrides is subjected to granulation, molding and sintering, in the same manner as described in example 94, while obtaining sintered material.

Thus obtained 50 units of each sintered material is subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes, forming a dielectric oxide film on the surface of the sintered material. After that, the operations of immersing the sintered material in a 60% aqueous solution of manganese nitrate are repeated, followed by heating the sintered material at 220 ° C for 30 minutes, forming a layer of manganese dioxide on the dielectric oxide film, which serves as another electrode (counter electrode). A carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead casing, the material as a whole is pressed into the epoxy resin, making a capacitor suitable for the chip. The average capacitance and average LC capacitor value for the chip (in each example n = 50 units) are given in Table 22. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Comparative Examples 33-35

50 g of a niobium ingot was placed in a reactor made of SUS 304 steel, and hydrogen was continuously fed into the reactor at 400 ° C. for 12 hours. After cooling, the hydrogenated sintered niobium mass is placed in a container made of SUS 304 steel, which contains steel balls, and ground into powder for 10 hours. This powdery product is placed in the same reactor made of SUS 304, as described above, and once again hydrogenated under the same conditions as described above. Then, a 20% (by volume) aqueous suspension is prepared from the hydrogenation product, which is placed together with zirconium balls in a wet grinding device made of SUS 304 (trade name "Atritor"), and wet grinding is carried out for 6 hours to receiving powder. The resulting suspension is subjected to sedimentation by centrifugation and decantation, while obtaining a powdery product. The powdery product is dried at 50 ° C in a vacuum of 1.33 × 10 ² PA. After that, the hydrogenated niobium powder is dehydrogenated by heating in a vacuum of 1.33 × 10 ^-2 Pa at 400 ° C for one hour. The average particle size of the obtained niobium powder is 1.0 μm. 30 g of the obtained niobium powder are charged into a reactor made of SUS 304 steel, and nitrogen is continuously fed into the reactor at 300 ° C. for 0.5 to 3 hours in order to obtain niobium nitrides. The amount of nitrogen in each of the nitrides is determined using a nitrogen analyzer manufactured by LECO, which allows determining the amount of nitrogen by thermal conductivity. The ratio of the measured value to the separately measured powder mass is indicated as the nitride content, the nitride content in this case is from 0.03 to 0.28 wt.%. Each of the niobium nitrides is subjected to granulation, molding and sintering in the same manner as described in example 94, while obtaining sintered material.

50 units of each of the sintered materials thus obtained are subjected to electrochemical treatment using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 200 minutes so that a dielectric oxide film is formed on the surface of the sintered material. After that, the operation of contacting the dielectric oxide film and a mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid in an equivalent (by weight) ratio is repeated at least 5 times, followed by exposure to pyrrole vapor , so that in this case another electrode (counter electrode), including polypyrrole, is formed on the dielectric oxide film. A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead housing, the device as a whole is pressed into place with an epoxy resin, while manufacturing a capacitor suitable for the chip. The average capacitance and the average LC value of the capacitor suitable for the chip (in each example n = 50 units) are given in Table 22. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Table 22 The nitrogen content (wt.%) Capacitance (μF) LC (μA) The number of samples for which the LC value exceeds 100 μA Example 140 - 502 17 0/50 Example 141 - 689 39 0/50 Example 142 - 473 16 0/50 Example 143 - 507 fifteen 0/50 Example 144 - 447 eighteen 0/50 Example 145 - 1058 83 0/50 Example 146 0.45 558 fifteen 0/50 Example 147 - 468 twenty 0/50 Example 148 - 497 14 0/50 Example 149 - 474 22 0/50 Example 150 - 483 19 0/50 Example 151 - 498 twenty 0/50 Example 152 0.28 544 16 0/50 Example 153 - 473 19 0/50 Reference Example 30 0.02 399 46 1/50 Reference Example 31 0.09 393 42 1/50 Reference Example 32 0.30 384 thirty 0/50 Reference Example 33 0,03 454 48 1/50 Reference Example 34 0.14 449 44 0/50 Reference Example 35 0.28 459 40 0/50

Example 154

By fusion under the influence of an electric arc, using 184 g of a niobium ingot and 2.8 g of lanthanum powder, a lanthanum-containing niobium ingot (alloy) containing 1 mol,% lanthanum is obtained. 50 g of the obtained ingot was placed in a reactor made of SUS 304 steel, and hydrogen was continuously fed into the reactor at 400 ° C. for 10 hours. After cooling, the hydrogenated lanthanum-containing niobium sintered mass is placed in a container made of SUS 304 steel and containing balls made of SUS steel and ground into powder for 10 hours. After this, a 20% (by volume) aqueous suspension is prepared from this hydrogenation product, loaded with zirconium balls into a wet grinding device made of SUS 304 stainless steel, and wet grinding is carried out for 7 hours. The resulting suspension is subjected to sedimentation by centrifugation and decanted in order to obtain a powdery product. The powdery product is dried under reduced pressure of 1.33 × 10 ² Pa at 50 ° C.

After that, the hydrogenated lanthanum-containing niobium powder is dehydrated when heated at 1.33 × 10 ^-2 Pa and a temperature of 400 ° C for one hour. The average particle size of the obtained lanthanum-containing niobium powder is 1.0 μm, and the content of lanthanum in it is 1 mol.%. The lanthanum-containing niobium powder thus obtained was granulated at 1100 ° C. and under a reduced pressure of 4 × 10 ⁻³ Pa. After that, the granular sintered mass is subjected to grinding into a powder, thereby obtaining granular powder with an average particle size of 100 μm.

The lanthanum-containing niobium granular powder thus obtained is pressed together with a lead wire containing niobium, the diameter of which is 0.3 mm, to thereby obtain a molded product whose size is approximately 0.3 cm × 0.18 cm × 0.45 cm (weight approximately 0 , 1 g).

The specified molded product is maintained at 1200 ° C and a reduced pressure of 4 × 10 ^-3 Pa for 30 minutes, while receiving sintered material. The obtained sintered material is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at 80 ° C, applying a voltage of 20 V for 200 minutes in order to form a dielectric layer on the surface of the sintered material. Then measure the capacity of the sintered material in 30% sulfuric acid and the leakage current of the sintered material (hereinafter referred to simply as “LC”) in a 20% aqueous phosphoric acid solution. The results are shown in table 23 (No. 1 and No. 2).

Examples 155-195

In accordance with the methodology described above for the manufacture of sintered material containing at least one element, such as rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium. europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, sulfur, selenium and tellurium, rubidium powder, cesium, magnesium, strontium , barium, scandium, yttrium, lanthanum, praseodymium, samaria, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, sulfur , selenium and tellurium, and niobium powder are used in an arbitrary ratio for fusion under the influence of an electric arc, p while radiating niobium ingots containing at least one element, such as rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium , ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, sulfur, selenium and tellurium. Then, 500 g of each ingot is pulverized using the same apparatus as in Example 154, changing the grinding time. Using the niobium powder thus obtained containing at least one element selected from the group consisting of rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium , erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, sulfur, selenium and tellurium, sintered materials are made and the capacity and LC value of each sintered material are measured. The results are shown in table 23 (No. 1 and No. 2).

Comparative Examples 36-39

For comparison with the results obtained according to examples 154-195, four types of niobium powder, which do not contain any of the elements, such as rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, are obtained in the same manner as described in example 154 , lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead, sulfur, selenium and tellurium, and which have different average particle sizes. Using the obtained niobium powder, sintered materials are made and the capacitance and LC value are measured. The results are shown in table 23 (No. 1 and No. 2).

Table 23 (No. 1) Composition The average particle size (microns) Capacitance (μF · V / g) LC (μA / g) Items Molar ratio Example 154 Nb: la 99: 1 1,0 108,000 21 Example 155 Nb: la 99: 1 0.5 228000 125 Example 156 Nb: la 99: 1 0.7 151000 55 Example 157 Nb: la 99: 1 1.3 92000 eleven Example 158 Nb: Sc 99.9: 0.1 1,0 106000 36 Example 159 Nb: Y 97: 3 1,0 106000 23 Example 160 Nb: Pr 99: 1 1,0 105000 32 Example 161 Nb: Sm 99: 1 1,0 107,000 37 Example 162 Nb: Eu 99.5: 0.5 1.0 104000 39 Example 163 Nb: gd 98.5: 1.5 1,0 103000 40 Example 164 Nb: Tb 99.8: 0.2 1,0 105000 41 Example 165 Nb: Dy 99: 1 1,0 107,000 39 Example 166 Nb: ho 99.7: 0.3 1,0 106000 44 Example 167 Nb: Er 99.5: 0.5 1,0 106000 25 Example 168 Nb: Tm 99.8: 0.2 1,0 103000 37 Example 169 Nb: Yb 97: 3 1,0 105000 26 Example 170 Nb: Lu 95: 5 1,0 104000 27 Example 171 Nb: Hf 93: 7 1,0 105000 35 Example 172 Nb: V 99.9: 0.1 1,0 109,000 48 Example 173 Nb: os 99.9: 0.1 1,0 107,000 43 Example 174 Nb: Ir 99.9: 0.1 1,0 107,000 44 Example 175 Nb: Pt 99.8: 0.2 1,0 102000 37 Example 176 Nb: Au 99.8: 0.2 1.0 101000 41 Example 177 Nb: Cd 99.7: 0.3 1,0 109,000 35 Example 178 Nb: Hg 99.9: 0.1 1,0 101000 43 Example 179 Nb: Pb 99.9: 0.1 1,0 102000 36 Example 180 Nb: s 95: 5 1,0 108,000 35

Table 23 (No. 2) Composition The average particle size (microns) Capacitance (μF · V / g) LC (μA / g) Items Molar ratio Example 181 Nb: Se 99: 1 1,0 108,000 35 Example 182 Nb: Te 98: 2 1,0 107,000 28 Example 183 Nb: Hf: Lu 92.9: 7: 0.1 0.7 145000 75 Example 184 Nb: Cs 99.95: 0.05 0.7 153000 120 Example 185 Nb: Y: Mg 97.99: 2: 0.01 0.7 150,000 81 Example 186 Nb: Er: Sr 95.9: 4: 0.1 0.7 146000 132 Example 187 Nb: Yb: Ba 96.9: 3: 0.1 0.7 151000 143 Example 188 Nb: La: Hf 93: 1: 6 0.5 210000 133 Example 189 Nb: Y: La: Lu 97.5: 1: 1: 0.5 0.5 225,000 156 Example 190 Nb: La: Er: Yb 96.5: 2: 0.5: 1 0.5 208000 161 Example 191 Nb: Sm: Hf: Te 93: 1: 5: 1 0.5 213000 171 Example 192 Nb: Y: Os: Ir 96.5: 2: 0.5: 1 1,0 107,000 45 Example 193 Nb: La: Cd: S 93.4: 1.5: 0.1: 5 1,0 106000 39 Example 194 Nb: Er: Hf: Te 95: 0.5: 4: 0.5 0.7 154000 66 Example 195 Nb: Gd: Yb: Lu: Se 98: 0.5: 0.5: 0.5: 0.5 0.7 143000 78 Reference Example 36 Nb 100 0.5 182000 2120 Reference Example 37 Nb 100 0.7 120,000 1074 Reference Example 38 Nb 100 1,0 87000 424 Reference Example 39 Nb 100 1.3 74000 233

Examples 196-202

In order to vary the lanthanum content in a lanthanum-containing niobium powder, fusion under the influence of an electric arc produces lanthanum-containing niobium ingots with rhenium content from 0.01 to 20 mol%, changing the amount of niobium and lanthanum used for alloying. Then, using 500 g of each lanthanum-containing niobium ingot with the corresponding concentration of lanthanum, sintered materials are obtained by performing the same operations as in Example 154, and the capacitance and LC value of each obtained material are measured. The results are shown in table 24.

Table 24 The content of lanthanum (mol.%) The average particle size (microns) Sintering Temperature (° C) Capacitance (μF · V / g) LC (μA / g) Reference Example 38 0.00 1,0 1200 87000 424 Example 196 0.01 1,0 1200 95000 65 Example 197 0.1 1,0 1200 106000 33 Example 154 1 1,0 1200 108,000 21 Example 198 2 1,0 1200 110000 23 Example 199 3 1,0 1200 109,000 23 Example 200 7 1,0 1200 109,000 thirty Example 201 eleven 1,0 1200 85000 59 Example 202 twenty 1,0 1200 79000 66

Examples 203-207

1,000 g of a niobium ingot is placed in a reactor made of SUS 304 steel, and hydrogen is continuously fed into the reactor at 400 ° C. for 10 hours. After cooling, the hydrogenated niobium sintered mass is placed in a container made of SUS 304 stainless steel containing SUS steel balls and ground into powder for 10 hours. Then, from this hydrogenation product, a 20% (by volume) aqueous suspension is prepared, loaded together with zirconium balls into a wet grinding device made of SUS 304 steel, and wet grinding is carried out for 7 hours. The resulting suspension is subjected to sedimentation by centrifugation and decanted in order to obtain a powdery product. The powdery product is dried under reduced pressure of 1.3 × 10 ² Pa and 50 ° C. After that, the hydrogenated niobium powder is dehydrated by heating at 1.3 × 10 ⁻² Pa and 400 ° C. for one hour.

The average particle size of the manufactured niobium powder is 1.0 μm. This powder is mixed in an arbitrary ratio with any of the following substances: lanthanum oxide, lanthanum oxalate, hydrogenated lanthanum, lanthanum nitrate and lanthanum (metal), each of which has an average particle size of approximately 1 μm. The obtained lanthanum-containing niobium powder is granulated under reduced pressure of 4 × 10 ^-3 Pa and 1050 ° C. After that, the granular sintered mass is subjected to grinding, thereby obtaining granular powder with an average particle size of 90 μm. The lanthanum-containing niobium granular powder thus obtained is pressed together with a niobium wire 0.3 mm in diameter to obtain a molded product whose size is approximately 0.3 cm × 0.18 cm × 0.45 cm (weight approximately 0, 1 g). After that, the obtained molded products are kept under reduced pressure of 4 × 10 ^-3 Pa and 1250 ° C for 30 minutes, while obtaining sintered materials. Each sintered material obtained is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at a temperature of 80 ° C for 200 minutes, applying a voltage of 20 V, in order to form a dielectric layer on the surface of the sintered material. Then measure the capacity in 30% sulfuric acid and the value of LC in a 20% aqueous solution of phosphoric acid. The results are shown in table 25.

Table 25 The form in which lanthanum is located The content of lanthanum (mol.%) Capacitance (μF · V / g) LC (μA / g) Example 203 lanthanum oxide 0.5 109,000 29th Example 204 lanthanum oxalate 1,2 112000 23 Example 205 hydrogenated lanthanum 3,5 113000 22 Example 206 lanthanum nitrate 0.8 108,000 29th Example 207 lanthanum 1,1 108,000 26

Examples 208-212

In order to obtain lanthanum-containing niobium nitride, 10 g of lanthanum-containing niobium powder containing 0.9 mol% of lanthanum and having an average particle size of 0.9 μm were prepared using the same procedure as in Example 154, and then this powder is placed in a reactor made of SUS 304 steel, nitrogen is supplied to the reactor at 300 ° C for 0.5 to 20 hours, thereby obtaining lanthanum-containing niobium nitrides. The amount of nitrogen in each of the niobium nitrides is determined using a nitrogen quantity meter manufactured by LECO Corporation by determining the amount of nitrogen by thermal conductivity. The ratio of the measured value to the separately measured powder mass is indicated as the nitride content. In this case, the nitride content is from 0.02 to 0.81 wt.%.

Each of the lanthanum-containing niobium nitrides thus obtained is subjected to granulation, molding and sintering, in the same manner as described in Example 154, and each sintered material obtained is subjected to electrochemical treatment in a 0.1% aqueous solution of phosphoric acid at a temperature of 80 ° C. for 200 minutes, applying a voltage of 20 V and thus forming a dielectric layer on the surface of the sintered material. Then measure the capacity in 30% sulfuric acid and the value of LC in a 20% aqueous solution of phosphoric acid. The results are shown in table 26.

Table 26 The content of lanthanum (mol.%) The nitrogen content (wt.%) Capacitance (μF · V / g) LC (μA / g) Example 208 0.9 0.02 120,000 29th Example 209 0.9 0.12 122000 19 Example 210 0.9 0.26 121,000 19 Example 211 0.9 0.45 124000 23 Example 212 0.9 0.81 120,000 24

Examples 213-215

In order to produce a sintered material containing a mixture of lanthanum-containing niobium powder and niobium powder in the same manner as in Example 154, a lanthanum-containing niobium powder containing 10 mol% of lanthanum and having an average particle size of 1.0 μm was obtained.

Separately, 2,000 g of potassium fluorobiobate carefully dried under reduced pressure and a temperature of 80 ° C, and sodium are placed in a crucible made of nickel, and sodium, while the molar amount of sodium is 10 times the molar amount of potassium fluorobiobate, a reduction reaction is carried out at 1000 ° C in an argon atmosphere for 20 hours. After completion of the reaction, the reduction product is cooled and washed successively with water, 95% sulfuric acid and water, dried under reduced pressure, and pulverized for 40 hours using a ball mill, which is an aluminum tank containing aluminosilicate balls. The powdery product is immersed and mixed in a mixture of 50% nitric acid and 10% aqueous hydrogen peroxide in a ratio of 3: 2 (by weight). After that, the powdery product is thoroughly washed with water to remove impurities until the pH reaches 7, and dried under reduced pressure. The average particle size of the obtained niobium powder is 1.2 μm.

The lanthanum-containing niobium powder thus obtained was thoroughly mixed with niobium powder in the ratio shown in Table 27, and each of the resulting mixtures was granulated, molded and sintered in the same manner as described in Example 154 to obtain sintered materials. The capacitance and LC value of each sintered material is measured, the results are shown in table 27.

Examples 216-218

In order to produce sintered material based on lanthanum-containing niobium nitride, including a mixture of lanthanum-containing niobium powder and niobium powder, receive in the same manner as in example 154, lanthanum-containing niobium powder containing 10 mol.% Lanthanum and having an average particle size of 1 , 0 μm. Separately, 50 g of a niobium ingot was placed in a reactor made of SUS 304 steel, and hydrogen was continuously fed into the reactor at 400 ° C. for 12 hours. After cooling, the hydrogenated niobium sintered mass is placed in a container made of SUS 304 steel containing steel balls and ground into powder for 10 hours. This powdery product is charged into the same reactor made of SUS 304 steel as described above, and again hydrogenated under the conditions described above. Then, from this hydrogenation product, a 20% (by volume) aqueous suspension is prepared, placed together with zirconium balls in a wet grinding device made of SUS 304 steel, and wet grinding is carried out for 6 hours.

The resulting suspension is subjected to sedimentation by centrifugation and decanted in order to obtain a powdery product. The powdery product is dried under reduced pressure of 1.3 × 10 ² Pa and 50 ° C. After that, the hydrogenated niobium powder is dehydrated under reduced pressure of 1.33 × 10 ^-2 Pa and heating at 400 ° C for one hour. The average particle size of the manufactured niobium powder is 1.1 μm.

The lanthanum-containing niobium powder thus obtained is thoroughly mixed in an arbitrary ratio with the niobium powder, and after receiving the nitrides in the same manner as in Example 210, each of the nitrides is granulated, molded and sintered to obtain sintered materials. The capacitance and LC value of each of the sintered materials is measured, the results are shown in table 27.

Table 27 Mixing ratio (lanthanum-containing niobium powder / niobium powder) Capacitance (μF · V / g) LC (μA / g) Example 213 90:10 91000 41 Example 214 50:50 102000 thirty Example 215 10:90 108,000 22 Example 216 80:20 94000 34 Example 217 40:60 102000 25 Example 218 20:80 108,000 19

Examples 219 and 220

According to example 219 and example 220 receive 50 units of sintered material in the same manner as described in example 154 and in example 182, respectively. Each of these sintered materials is subjected to electrochemical oxidation using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 6 hours, thereby forming a dielectric oxide film on the surface of the sintered material. After this, the operations of immersing each sintered material in a 60% aqueous solution of manganese nitrate and then heating this material at 220 ° C for 30 minutes are repeated, forming a layer of manganese dioxide on the dielectric oxide film, which serves as another electrode (counter electrode). Then, a carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead case, the material as a whole is sealed with epoxy resin for chip capacitors. The average capacitance and the average LC value of the capacitor for the chip (in each example n = 50 units) are shown in Table 28. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 221 and 222

According to example 221 and example 222 receive 50 units of sintered material in the same manner as described in example 159 and in example 204, respectively. Each of these sintered materials is subjected to electrochemical oxidation using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 6 hours, thereby forming an oxide dielectric film on the surface. After this, the operation of immersing each sintered material in a mixture of a 35% aqueous solution of lead acetate and a 35% aqueous solution of ammonium persulfate (in a volume ratio of 1: 1) is repeated, followed by a reaction at a temperature of 1 hour at 40 ° C. , in order to form on the dielectric oxide film a mixed layer of lead dioxide and lead sulfate, which serves as another electrode (counter electrode). A carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead housing, the device is molded as a whole with epoxy resin, while manufacturing a capacitor suitable for the chip. The average capacitance and the average LC value of the capacitor for the chip (in each example n = 50 units) are shown in Table 28. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 223-226

According to Example 223, Example 224, Example 225 and Example 226, 50 units of sintered material are obtained in the same manner as described in Example 167, Example 189, Example 211 and Example 215, respectively. Each of the sintered materials is electrochemically oxidized using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 6 hours, forming a dielectric oxide film on the surface of the sintered material. After that, the operation of contacting the dielectric oxide film and a mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid in an equivalent (by weight) ratio is repeated at least 5 times, followed by exposure to pyrrole vapor , so that in this case another electrode (counter electrode), including polypyrrole, is formed on the dielectric oxide film.

A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead casing, the device as a whole is pressed with epoxy resin, while manufacturing a capacitor of the type used for the chip. The average capacitance and the average LC value of the type of capacitor used for the chip (in each example n = 50 units) are given in Table 28. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Examples 227-231

According to example 227, example 228, example 229, example 230 and example 231, 50 units of sintered material are obtained in the same manner as described in example 170, in example 191, in example 205, in example 210 and in example 218, respectively. Each of these sintered materials is electrochemically oxidized using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 6 hours, forming a dielectric oxide film on the surface of the sintered material. Then, the sintered niobium material is immersed in an aqueous solution containing 25 wt.% Ammonium persulfate (solution 1), then removed and dried at 80 ° C for 30 minutes. Then, the sintered material coated with a dielectric is immersed in an isopropanol solution containing 18 wt.% 3,4-ethylenedioxythiophene (solution 2), after which it is removed and maintained at 60 ° C for 10 minutes, thereby performing oxidative polymerization. The resulting sintered material is re-immersed in solution 1 and then processed in the manner described above. Operations starting from immersion in solution 1 and ending with oxidative polymerization are repeated 8 times. Then, the sintered material is washed with hot water at 50 ° C. for 10 minutes and dried at 100 ° C. for 30 minutes, thereby forming another electrode (counter electrode) including electrically conductive poly (3,4-ethylenedioxythiophene).

A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead case, the material as a whole is filled with epoxy resin, making a capacitor of the type used for the chip. The average capacitance and the average LC value of the capacitor for the chip (in each example n = 50 units) are shown in Table 28. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Comparative Examples 40-42

2,000 g of potassium fluorobiobate carefully dried under reduced pressure at 80 ° C and sodium in a molar amount that is 10 times the molar amount of potassium fluorobiobate are placed in a nickel crucible, and a reduction reaction is carried out in an argon atmosphere at 1000 ° C for 20 hours . After completion of the reaction, the reduction product is cooled and washed successively with water, 95% sulfuric acid and then water, dried in vacuum and ground into powder for 40 hours using a ball mill, which is an aluminum tank equipped with aluminosilicate balls. The powdery product is immersed and mixed in a solution, which is a mixture in a ratio of 3: 2 (by weight) of 50% nitric acid and 10% aqueous hydrogen peroxide solution. After that, the powdery product is thoroughly washed with water to remove impurities until the pH reaches 7, and dried in vacuum. The average particle size of the manufactured niobium powder is 1.3 μm. 30 g of the niobium powder thus obtained are charged into a reactor made of SUS 304 steel and nitrogen is supplied thereto at 300 ° C. for 0.5 to 4 hours, thereby producing niobium nitrides. The amount of nitrogen in each of the niobium nitrides is determined using a LECO nitrogen measuring device based on thermal conductivity. The ratio of the measured value to the separately measured powder mass is indicated as the nitride content, according to the results obtained, the nitride content is from 0.02 to 0.30 wt.%. Each of the niobium nitrides is subjected to granulation, molding and sintering in the same manner as described in example 154, while obtaining sintered material. Thus obtained 50 units of each sintered material is subjected to electrochemical oxidation using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 6 hours, forming a dielectric oxide film on the surface of the sintered material. After that, the operations of immersing the sintered material in a 60% aqueous solution of manganese nitrate are repeated, followed by heating the sintered material at 220 ° C for 30 minutes, forming a layer of manganese dioxide on the dielectric oxide film, which serves as another electrode (counter electrode). A carbon layer and a silver paste layer are applied to this counter electrode layer in this order. After mounting the lead casing, the material as a whole is pressed into the epoxy resin, making a capacitor suitable for the chip. The average capacitance and the average LC value of the capacitor for the chip (in each example n = 50 units) are shown in Table 28. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Comparative Examples 43-45

50 g of a niobium ingot are placed in a reactor made of SUS 304 steel, and hydrogen is continuously fed into the reactor at 400 ° C. for 12 hours. After cooling, the hydrogenated sintered niobium mass is placed in a container made of SUS 304 steel, which contains steel balls, and ground into powder for 10 hours. This powdery product is charged into the same reactor made from SUS 304 as described above, and once again hydrogenated under the same conditions as described above. Then, a 20% (by volume) aqueous suspension is prepared from the hydrogenation product, which is placed together with zirconium balls in a wet grinding device made of SUS 304 (trade name "Atritor"), and wet grinding is carried out for 6 hours to obtain powder. The resulting suspension is subjected to sedimentation by centrifugation and decanted, while receiving a powdery product. The powdery product is dried at 50 ° C. under reduced pressure of 1.33 × 10 ² Pa. After that, the hydrogenated niobium powder is dehydrated by heating under reduced pressure of 1.33 × 10 ^-2 Pa and 400 ° C for one hour. The average particle size of the obtained niobium powder is 1.0 μm. 30 g of the obtained niobium powder are charged into a reactor made of SUS 304 steel, and nitrogen is continuously fed into the reactor at 300 ° C. for 0.5 to 3 hours in order to obtain niobium nitrides. The amount of nitrogen in each of the nitrides is determined using a nitrogen analyzer manufactured by LECO, which allows determining the amount of nitrogen by thermal conductivity. The ratio of the measured value to the separately measured powder mass is indicated as the nitride content, the nitride content in this case is from 0.03 to 0.28 wt.%. Each of the niobium nitrides is subjected to granulation, molding and sintering in the same manner as described in example 154, while obtaining sintered material. 50 units of each of the sintered materials thus obtained are subjected to electrochemical oxidation using a 0.1% aqueous solution of phosphoric acid at a voltage of 20 V for 6 hours so that a dielectric oxide film is formed on the surface of the sintered material. After that, the operation of contacting the dielectric oxide film and a mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid in an equivalent (by weight) ratio is repeated at least 5 times, followed by exposure to pyrrole vapor , so that in this case another electrode (counter electrode), including polypyrrole, is formed on the dielectric oxide film. A carbon layer and a silver paste layer are applied to this counter electrode in this order. After mounting the lead casing, the device as a whole is pressed with epoxy resin, while manufacturing a capacitor suitable for use in the chip. The average capacitance and average LC capacitor value for the chip (in each example n = 50 units) are given in Table 28. The LC value is a value measured at room temperature with a voltage of 6.3 V for one minute.

Table 28 The nitrogen content (wt.%) Capacitance (μF) LC (μA) The number of samples for which the LC value exceeds 100 μA Example 219 - 486 fifteen 0/50 Example 220 - 471 twenty 0/50 Example 221 - 482 16 0/50 Example 222 - 504 17 0/50 Example 223 - 480 eighteen 0/50 Example 224 - 1012 109 0/50 Example 225 0.45 546 16 0/50 Example 226 - 488 fifteen 0/50 Example 227 - 463 19 0/50 Example 228 - 937 119 0/50 Example 229 - 509 fifteen 0/50 Example 230 0.26 532 12 0/50 Example 231 - 491 thirteen 0/50 Reference Example 40 0.02 398 47 4/50 Reference Example 41 0.08 392 41 3/50 Reference Example 42 0.30 383 40 0/50 Reference Example 43 0,03 455 47 2/50 Reference Example 44 0.15 444 43 0/50 Reference Example 45 0.28 460 41 0/50

Examples 232-238, comparative examples 46-48

The heat resistance of the capacitor is measured as follows. Capacitors in the amount of 50 pieces, obtained in accordance with the examples and comparative examples shown in table 29, were placed on a multilayer substrate of an integrated circuit having a width of 1.5 mm, and soldered. This substrate was passed through a melting furnace at 230 ° C, the transmission time was 30 seconds, repeating the operation three times, and the actual thermal background was evaluated (for example, the previous heat treatment for three types of soldering: soldering of parts placed on the surface of the substrate, soldering of parts placed on back side of the substrate and soldering of parts placed later).

The LC capacitor value was measured before passing through the melting furnace and after triple passing through the melting furnace, the average values and the increase rate (LC value after passing through the melting furnace / LC value before passing through the melting furnace) are shown in Table 29. According to the results obtained, the capacitor which is the subject of the present invention, is characterized by such an indicator of increasing characteristic LC, which corresponds to an increase of less than an increase of 5 times, preferably less than 3 times, and none of the capacitors had an LC value of more than 100 μA.

Table 29 Capacitor device Chip manufacturing examples (comparative examples) LC value before / after melting furnace (μA) LC increase indicator The number of samples for which the LC value exceeds 100 μA Anode Type / Cathode Type Example 232 Nb-W / MnO ₂ Example 34 25/55 2.2 times 0/50 Example 233 Nb-B / MnO ₂ Example 81 17/39 2.3 times 0/50 Example234 Nb-B-Al / Polypyrrole Example 86 23/51 2.2 times 0/50 Example235 Nb-Re-Zn-Ge / Polythiophene Example 148 14/35 2.3 times 0/50 Example236 Nb-Y / PbO ₂ Example 221 16/38 2.4 times 0/50 Example237 Nb-La / Polythiophene Example 230 12/30 2.5 times 0/50 Example 238 Nb-Nd / polythiophene *1 21/39 1.9 times 0/50 Reference Example 46 Nb / MnO ₂ Reference Example 40 47/277 5.9 times 50/50 Reference Example 47 Nb / MnO ₂ Reference Example 42 40/208 5.2 times 50/50 Reference Example 48 Nb / polypyrrole Reference Example 45 41/209 5.1 times 50/50

* 1 The used sintered material was obtained in the same manner as in Example 101, and the capacitor for the chip was obtained in the same manner as in Example 148.

Claims (52)

1. A powder for the manufacture of capacitors, including niobium and at least one element selected from the group consisting of chromium, molybdenum, tungsten, boron, gallium, indium, thallium, cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic, bismuth, rubidium, cesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury and lead. 2. The powder for capacitors according to claim 1, comprising at least one element selected from the group consisting of chromium, molybdenum and tungsten. 3. The capacitor powder of claim 2, wherein said at least one element is tungsten. 4. The powder for capacitors according to claim 2, wherein said at least one element is chromium and tungsten. 5. The powder for capacitors according to claim 1, comprising at least one element selected from the group consisting of boron, gallium, indium and thallium. 6. The capacitor powder of claim 5, wherein said at least one element is boron. 7. The powder for capacitors according to claim 1, comprising at least one element selected from the group consisting of cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic and bismuth. 8. The powder for capacitors according to claim 7, comprising at least one element selected from the group consisting of rhenium, zinc, arsenic, phosphorus, germanium, tin and neodymium. 9. The capacitor powder of claim 8, wherein said at least one element is rhenium. 10. The capacitor powder of claim 8, wherein said at least one element is neodymium. 11. The capacitor powder of claim 8, wherein said at least one element is zinc. 12. The powder for capacitors according to claim 1, comprising at least one element selected from the group consisting of rubidium, cesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium , erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, and lead. 13. The capacitor powder of claim 12, comprising at least one element selected from the group consisting of lanthanum, yttrium, erbium, ytterbium, and lutetium. 14. The capacitor powder of claim 13, wherein said at least one element is lanthanum. 15. The capacitor powder of claim 13, wherein said at least one element is yttrium. 16. The powder for capacitors according to any one of claims 1 to 15, further comprising at least one element selected from the group consisting of aluminum, magnesium, selenium and tellurium. 17. A powder according to any one of claims 1-16, wherein said at least one element is contained in an amount of 10 mol% or less. 18. The powder according to 17, in which the specified at least one element is contained in an amount of 0.01-10 mol.%. 19. The powder according to claim 18, wherein said at least one element is contained in an amount of 0.1-7 mol%. 20. Powder for the manufacture of capacitors, including niobium and at least one element from the group consisting of chromium, molybdenum, tungsten, boron, aluminum, gallium, indium, thallium, cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin ,, phosphorus, arsenic, bismuth, rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium , ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead selenium and those llura, wherein said niobium powder has an average particle size of 0.05-5 microns. 21. The powder according to claim 20, the average particle size of which is 0.2-4 microns. 22. Powder for the manufacture of capacitors, including niobium and at least one element from the group consisting of chromium, molybdenum, tungsten, boron, aluminum, gallium, indium, thallium, cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic, bismuth, rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium, osmium, iridium, platinum, gold, cadmium, mercury, lead selenium and those Loor, whose specific surface area determined by Brunauer adsorption isotherms emet-Teller (BET-surface) of 0.5-40 m ² / g. 23. The powder according to item 22, the specific BET surface of which is 1-20 m ² / g 24. The powder according to any one of paragraphs.2, 3, 4, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16, further comprising at least one element selected from the group consisting of nitrogen, carbon, boron and sulfur. 25. The powder according to claim 5 or 6, further comprising at least one element selected from the group consisting of nitrogen, carbon and sulfur. 26. The powder according to paragraph 24 or 25, in which at least one element selected from the group consisting of nitrogen, carbon, boron and sulfur, is contained in an amount of 200,000 wt.h. per million or less. 27. The powder according to p. 26, in which at least one element selected from the group consisting of nitrogen, carbon, boron and sulfur, is contained in an amount of 50-200000 wt.h. per million 28. A granulated niobium product obtained by granulating a powder for the manufacture of capacitors, including niobium and at least one element from the group consisting of chromium, molybdenum, tungsten, boron, aluminum, gallium, indium, thallium, cerium, neodymium, titanium, rhenium, ruthenium, rhodium, palladium, silver, zinc, silicon, germanium, tin, phosphorus, arsenic, bismuth, rubidium, cesium, magnesium, strontium, barium, scandium, yttrium, lanthanum, praseodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, vanadium , osmium, iridium, platinum, gold, cadmium, mercury, lead selenium and tellurium, and having an average particle size of 10-500 microns. 29. The granular niobium product according to claim 28, wherein the average particle size is 30-250 microns. 30. Sintered material made using powder for the manufacture of capacitors according to any one of claims 1 to 27. 31. Sintered material made using the granular niobium product according to p. 28 or 29. 32. A capacitor comprising an electrode made using sintered niobium material according to claim 30 or 31, wherein a dielectric material is formed on the surface of said electrode, and a counter electrode is formed on said dielectric material. 33. The capacitor according to claim 32, in which the dielectric material includes niobium oxide as a main component. 34. The capacitor according to claim 33, wherein the niobium oxide is produced by electrolytic oxidation. 35. The capacitor according to claim 32, wherein the counter electrode includes at least one material selected from the group consisting of an electrolyte solution, an organic semiconductor, and an inorganic semiconductor. 36. The capacitor according to claim 32, wherein said counter electrode includes an organic semiconductor, which includes at least one material selected from the group consisting of an organic semiconductor including a tetramer of benzopyrroline and chloranil, an organic semiconductor including tetratiotetracene, an organic component a semiconductor, including tetracyanoquinodimethane as a main component, and an electrically conductive polymer. 37. The capacitor according to clause 36, in which the electrically conductive polymer is at least one polymer selected from the group consisting of polypyrrole, polythiophene, polyaniline and their substituted derivatives. 38. The capacitor according to clause 36, in which the electrically conductive polymer is obtained by introducing a dopant into the polymer containing a repeating unit represented by the General formula (1) or (2):

in which the radicals from R ¹ to R ⁴ each can be the same or different and each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group, an alkoxyl group or an alkyl substituted ester group containing 1-10 carbon atoms, which may be saturated or unsaturated, a halogen atom, a nitro group, a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a substituted or unsubstituted phenyl group, and R ¹ and R ² , R ³ and R ⁴ may Independently combine a bivalent chain, forming a saturated or unsaturated cyclic hydrocarbon structure containing at least one 3-7-membered ring system, together with carbon atoms substituted in the arbitrary position of the hydrocarbon chains represented by the radicals R ¹ and R ² or radicals R ³ and R ⁴ , and the resulting cyclic chain may contain a bond with a carbonyl, ether group, ester group, amide group, sulfide group, sulfinyl, sulfonyl and whether imino is in an arbitrary position; X represents an oxygen atom, a sulfur atom or a nitrogen atom; R ⁵ , which is present only when X represents a nitrogen atom, independently represents a hydrogen atom or a linear or branched alkyl group containing 1-10 carbon atoms, wherein said group may be saturated or unsaturated. 39. The capacitor according to claim 38, wherein said electrically conductive polymer comprises a repeating unit represented by the general formula (3):

in which R ⁶ and R ⁷ , which may be the same or different, each independently represents a hydrogen atom, a linear or branched alkyl group containing 1-6 carbon atoms, which may be saturated or unsaturated, or a substituent group forming at least at least one 5-, 6- or 7-membered saturated cyclic hydrocarbon structure containing two oxygen atoms, obtained by combining the alkyl groups represented by the radicals R ⁶ and R ⁷ in an arbitrary position, where the cyclic structure may include a substituted or unsubstituted vinylene bond or a substituted or unsubstituted phenylene structure. 40. The capacitor according to § 39, in which the electrically conductive polymer containing the specified repeating unit represented by formula (3), is a poly (3,4-ethylenedioxythiophene). 41. The capacitor according to clause 36, in which the counter electrode includes an organic semiconductor having a layered structure. 42. The capacitor according to clause 36, wherein said counter electrode is an organic semiconductor material that contains as an dopant an organic anion of sulfonic acid. 43. The method for producing a nitrogen-containing niobium powder according to claim 24 or 25, wherein the niobium powder is surface-treated using at least one method selected from the group consisting of liquid-phase nitriding, ion nitriding and gas-phase nitriding. 44. The method for producing a carbon-containing niobium powder according to claim 24 or 25, wherein the niobium powder is surface-treated using at least one method selected from the group consisting of gas-phase carbonization, solid-phase carbonization and liquid-phase carbonization. 45. The method of producing boron-containing niobium powder according to paragraph 24, according to which niobium powder is subjected to surface treatment using at least one method selected from the group consisting of gas-phase boronization and solid-phase boronation. 46. A method for producing a sulfur-containing niobium powder according to claim 24 or 25, wherein the niobium powder is surface-treated using at least one method selected from the group consisting of gas-phase sulfidation, ionic sulfidation and solid-phase sulfidation. 47. An electronic circuit manufactured using a capacitor according to any one of claims 32-42. 48. An electronic device manufactured using a capacitor according to any one of claims 32-42. Point priority 08/10/2000 - claims 1-3, 15-21, 24-44; 12/19/2000 - claims 4-6, 22-23; 03/09/2001 - claims 7-10; 06/08/2001 - pp. 11-14, 45-48.