CA2331707C - Reduction of nb or ta oxide powder by a gaseous light metal or a hydride thereof - Google Patents

Abstract

Metal powder Ta and/or Nb, with or without one or metals from the group Ta, Nb, Ti, Mo, W, V, Zr and Hf, is made in a fine powder form by reduction of metal oxide by contact with a gaseous reducing agent, preferably an alkaline earth metal, to near complete reduction, leaching, further deoxidation and agglomeration, the powder so produced being sinterable to capacitor anode form and processable to other usages.

Description

REDUCTION OF Nb OR Ta OXIDE POWDER BY

A GASEOUS LIGHT METAL OR A HYDRIDE THEREOF
Field and L'aclcoround of the Invention This invention relates to (he production of tantalum, niobium and other metal powders and their alloys by the reduction of the corresponding metal oxide with gaseous active metals such as Mg, Ca and ofher elemental and compound reducing materials, in gaseous form.

Tantalum and niobium are members of a group of inetals that are difficult to isolate in the free state because of the stability of their compounds, especially some of their oxides. A review of the methods developed to produce tantalum will serve to illustrate the history of a typical manufacturing process for these metals.
Tantalum metal powder was first produced on a commercial scale in Germany at the beginning of the 20`h Century- by the reduction of the double salt, potassium heptafluorotantalate (K-)TaF7) with sodium. Small pieces of sodium were mixed with the tantalum containing salt and sealed into a steel tube. The tube was heated at the top with a ring burner and, after ignition, the reduction proceeded quickly down the tube. The reaction mixture was allowed to cool and the solid mass, consisting of tantalum metal powder, unreacted K2TaF7 and sodium, and other products of the reduction was removed by hand using a chisel. The mixture was crushed and then leached with dilute acid to separate the tantalum from the components. The process was difficult to control, dan-erous, and produced a coarse, contaniinated powder, but neverthcless pointed the %vav to what beeamc- the principal mearu cif produetion of llit'lh purity tantaluni in later years.

-2-Comniercial production of tantalum metal in the United States began in the 1930's. A
molten mixture of K2TaF7 containing tantalum oxide (Ta205) was electrolyzed at 700 C in a steel retort. When the reduction was conlpleted, the system was cooled and the solid mass removed from the electrolysis cell, and then crushed and leached to separate the coarse tantalum powder froni the other reaction products. The dendritic powder was not suitable for use directly in capacitor applications.

The modern method for manufacturing tantalum was developed in the late 1950's by Hellier and Martin (Hellier, E.G. and Martin, G.L., US Patent 2950185, 1960).
Fol-lowing Hellier and Martin, and llundreds of subsequently described implementations or variatioiis, a molten mixture of K2TaF7 and a diluent salt, typically NaCI, is re-duced with molten sodium in a stirred reactor. Using this system, control of the in1-portant reaction variables, such as reduction temperature, reaction rate, and reaction composition, was feasible. Over the years, the process was reftned and perfected to the point wliere high quality powders with surface area exceeding 20,000 cm2/gm are produced and materials with surface area in the 5000-8000 cm2/gm range being typi-cal. The manufacturing process still requires the renioval of the solid reaction pro-ducts from the retort, separation of the tantalum powder from the salts by leaching, and treatments like agglomeration to improve the physical properties. Most capacitor grade tantalum powders are also deoxidized with magnesium to minimize the oxygen content (Albrecht, W.W., Hoppe, H., Papp, V. and Wolf, R., US Patent 4537641, 1985). Artifacts of preagglomeration of primary particles to secondary particle form and doping with inaterials to enhance capacitance (e.g. P, N, Si, and C) are also known todav.

-3-While the reduction of K2TaF7 with sodium has allowed the industry to make high performance, high quality tantalum powders thus, according to Ullmann's Encyclo-pedia of Industrial Chemistry, 5"' Edition, Volume A 26, p. 80, 1993, the consump-tion of tantalum for capacitors had already reached a level of more than 50%
of the world production of tantalum of about 1000 tons per annum, whereas there had essentially been no use of niobium for capacitors, even though the raw material base for niobium is considerably broader than that for tantalum and most of the publications on powder preparation and capacitor manufacturing methods mention niobium as well as tantalum.

Some of the difficulties of applying that process to niobium are as follows:

While the manufacturing process of the type shown in Hellier and Martin (US
2,950,185) for the reduction of potassium heptaflorotantalate by means of sodium in a salt melt is available in principle for the production of high purity niobium powders via potassium heptafluoroniobate, it doesn't work well in practice. This is due, in part, to the difficulti of precipitating the corresponding heptafluoroniobate salts and is due, in part, to the aggressively reactive and corrosive nature of such salts, such that niobium produced by that process is very impure. Further, niobium oxide is usually unstable. See, e.g., N.F. Jackson et al, Electrocomponent Science &
Technology, Vol. 1, pp. 27-37 (1974).

Accordingly, niobium has only been used in the capacitor industry to a very minor extent, predominantly in areas with lower quality requirements.

-4-However, niobium oxide dielectric constant is about 1.5 times as high as that of a similar tantalum oxide layer, which should allow in principle, for higher capacitance of niobium capacitors, subject to considerations of stability and other factors.

As for tantalum itself, despite the success of the K2TaF7/sodium reduction process, there are several drawbacks to this method.

It is a batch process subject to the inherent variability in the system; as a result, batch to batch consistency is difficult. Post reduction processing (mechanical and hydro-metallurgical separations, filtering) is complex, requiring considerable human and capital resources and it is time consuming. The disposal of large quantities of reaction products containing fluorides and chlorides can be a problem. Of fundamental significance, the process has evolved to a state of maturity such that the prospects for significant advances in the performance of the tantalum powder produced are limited.

Over the years, numerous attempts were made to develop alternate ways for reducing tantalum and similar metal compounds, including Nb-compounds, to the metallic state (Miller, G.L. "Tantalum and Niobium," London, 1959, pp. 188-94; Marden, J.W. and Rich, M.H., US Patent 1728941, 1927; and Gardner, D., US Patent 2516863 1946; Hurd, U.S. Patent 4687632). Among these were the use of active metals other than sodium, such as calcium, magnesium and aluminum and raw mate-rials such as tantalum pentoxide and tantalum chloride. As seen in Table I, below, the negative Gibbs free energy changes indicate that the reduction of the oxides of Ta, Nb and otlier metals with magnesiuin to the metallic state is favorable;
reaction rate and method detertnine the feasibility of using this approach to produce high quality powders on a coniinercial scale. To date, none of these approaches were

-5-commercialized significantly because they did not produce high quality powders.
Apparently, the reason these approaches failed in the past was because the reductions were carried out by blending the reducing agents with the metal oxide. The reaction took place in contact with the niolten reducing agent and under conditions of inability to control the temperature of highly exothermic reactions.
Tlierefore, one is unable to control morpltology of the produets and residual reducing metal content.
Table 1 Gibbs Free Energy Change for Reduction of Metal Oxides with Magnesiuni MxOy(s) + yMg (g) ~ yMgO(s) + xM(s) Temperature Gibbs Free Energy Change (KcaUmole oxide) C

Ta205 Nb205 Ti02 V2O3 Zr02 The use of inagnesium to deoxidize or reduce the oxygen content of tantalum metal is well known. The process involves blending the metal powder with 1-3 percent magnesiuni and lieating to achieve the reduction process. The magnesium is in the

- 6 -molten state during a portion of the heating time. In this case, the objective is to remove 1000-3000 ppm oxygen and only a low concentration of MgO is produced. However, when a much greater quantity of tantalum oxide is reduced a large quantity of magnesium oxide is generated. The resulting mixture of magnesium, tantalum oxide and magnesium oxide can under conditions of poorly controlled temperature, form tantalum-magnesium-oxygen complexes that are difficult to separate from the tantalum metal.

Summary of the Invention The invention provides a new approach to production of high performance, capacitor grade tantalum and niobium powders that provides a means of eliminating one or more, preferably all, the problems of traditional double salt reduction and follow on processing. The invention enables a continuous production process. Further, the invention provides improved metal forms. The invention also provides niobium/tantalum alloy powders of capacitor grade quality and morphology.

We have discovered that the prior art problems can be eliminated or at least mitigated when metal oxides such as Ta205 and Nbz05 and suboxides in massive amounts are reduced with magnesium in gaseous form, substantially or preferably entirely. The oxide source should be substantially or preferably entirely in solid. The oxide is provided in the

-7-form of a porous solid with high access throughout its mass by the gaseous reducing agent.

The metals that can be effectively produced singly or in multiples (co-produced) through the present invention are in the group of Ta, Nb, and Ta/Nb alloy, any of these alone or with further inclusion of added or co-produced Ti, Mo, V, W, Hf and/or Zr. The metals can also be mixed or alloyed during or after production and/or formed into useful compounds of such ntetals. The respective stable and unstable oxide forms of these metals can be used as sources. Metal alloys may be produced from alloyed oxide precursors, e.g. resulting from coprecipitation of a suitable precursor for the oxide.

Vapor pressures of some of the reducing agents are given as follows:
Temperature ( C) Aluminum P (Atmospheres) 2,000 53 x 10-2 2,100 1.0 x 10-1 2,200 1.9 x 10- 1 2,300 3.3 x 10-1 2,400 5.6 x 10-1 2,500 9.0 x 10-1 2,600 1.4 Temperature ( C) Magnesium P (Atmospheres) 800 4.7 x 10-2 850 8.9 x 10-2

-8-900 1.6 x 10" 1 950 2.7 x 10' 1 1000 4.8 x 10- 1 1050 7.2 x 10-1 1100 1.1 + _

-9-Temperature ( C) Calcium P (Atmospheres) 1,000 1.7 x 10-2 1,100 5.1 x 10-2 1,200 1.3 x 10- h 1,300 2.9 x 10-1 1,400 6.0 x 10-1 1,500 1.1 Temperature ( C) Lithium P (Atmospheres) i 1,000 5.1 x 10-2 ~
1,100 1.4x10-1 1,200 3.8 x 10-1 1,300 7.2 x 10-1 1,400 1.4 The temperature of reduction varies significantly depending on the reducing agent used. The temperature ranges for reduction of (Ta, Nb) oxide are:

with Mg(gas)-800-1,100 C, Al(gas)- 1,100-1,500 C, Li(gas)- 1,000-1,400 C, 13a(,,as) 1,300-1,900 C.

Different physical properties as well as morphology of the metal powder produced by reduction can be achieved by variations of temperature and other conditions of processing v;ithin the effective reduction range.

10-One embodiment of the invention includes a first step of reducing an oxide source of selected metal(s) substantially to free 80-100% (by weight) of the metal values therein as priniary powder particles, then leaching or other steps of hydrometallurgy to separate the metal fronl residual reducing agent oxide and other byproducts of the reduction reaction and from residual condensed reducing agent (optionally), followed by one or nlore deoxidation steps under less concentrated reagent conditions than in the first gross reduction step (and with better tolerance of molten state of the reducing agent), then further separation as might be needed.

In accordance with this first embodiment the invention provides for a single stage reduction process for the production of metal powders as cited above, coniprising the steps of:

(a) providing an oxide or mixed oxides of the metal(s), the oxide itself being in a forni that is traversable by gas, (b) generating a gaseous reducing agent at a site outside the oxide mass and passing the gas through the mass at an elevated temperature, (c) the reactants selection, porosity of the oxide, temperature and time of the reduction reaction beiiig selected for substantially coniplete reduction of the oxide(s) to free the metal portion thereof, the residual oxide of reducing agent formed in the reaction being easily removable, whereby a high surface area, flowable metal powder is formed in a process that es-sentially avoids use of molten state reducing agent in production of metal or alloy powder.

- 11 -More particularly, the first embodiment of the invention provides a process for producing (i) a Ta or Nb metal powder, (ii) a Ta/Nb alloy powder or (iii) the powder of (i) or (ii) further alloyed with one or more metals selected from the group consisting of Ti, Mo, W, Hf, V and Zr, comprising the steps of: (a) providing a powdered oxide or mixed oxides of the metal or metals defined in (i), (ii) or (iii), the powdered oxide or mixed oxides being in a porous solid form with high access throughout the mass thereof by a gaseous reducing agent as defined in (b);

(b) generating a gaseous reducing agent selected from the group consisting of Mg, Ca, Al, Li, Ba, Sr and a hydride thereof at a site outside the powdered oxide or mixed oxides mass and passing the gaseous reducing agent through the mass at an elevated temperature; and (c) selecting the gaseous reducing agent and the powdered oxide or mixed oxides, porosity of the powdered oxide or mixed oxides, temperature and time of the reduction reaction for substantially complete reduction of the powdered oxide or mixed oxides to free the metal (i) or alloy (ii) or (iii), wherein the residual oxide formed in the reaction is removed by leaching; whereby a high surface area powder is formed in a process that essentially avoids use of a molten state reducing agent in the production of the metal (i) or alloy (ii) or (iii) powder.

Preferred reducing agents used in this reduction process of the first embodiment are Mg, Ca and/or their hydrides. Particularly preferred is Mg.

Preferred is the production of Nb and/or Ta metals, optionally alloyed with each other and/or with alloying elements, selected from the group consisting of Ti, Mo, W, Hf, V and Zr.

- lla -A second embodiment of the invention provides for a two-stage reduction process, comprising the steps of:

(a) providing an oxide or mixed oxide of the metal(s), the oxide being in a form that is traversible by gas, (b) passing a hydrogen containing gas, alone or with gaseous diluent, through the mass at an elevated temperature in a manner for partial reduction of the oxide (s) , (c) the porosity of the oxide, temperature and time of reduction reaction being selected to remove at least 20% of the oxygen contained in the oxide to produce a suboxide, (d) reducing the suboxide with reducing metal(s) and/or hydrides of one or more reducing metals, thereby substantially completely reducing the oxide to free the metal portion thereof.

More particularly, the second embodiment of the invention provides a process for producing (i.) a Nb metal powder or (ii) the powder of (i) alloyed with one or more metals selected from the group consisting of Ti, Mo, W, Hf, V and Zr, comprising the steps of: (a) providing a powdered oxide or mixed oxides of the metal or metals defined in (i) or (ii), the powdered oxide or mixed oxides being in a porous solid form with high access throughout the mass thereof by a hydrogen containing gas; (b) passing the hydrogen containing gas through the mass at an elevated temperature; (c) selecting the porosity of the powdered oxide or mixed oxides, temperature and time of the reduction reaction to remove at least 20% of the oxygen contained in the powdered oxide or mixed oxides to produce a suboxide;

- lib -and (d) further reducing the suboxide in a second stage with a reducing agent as defined in step (b) above, thereby substantially completely reducing the suboxide to free the metal (i) or alloy (ii).

Preferably, the oxide mass provides a void volume of 90%.

Preferably the reducing metals and/or metal hydrides are brought into contact with the suboxide in gaseous form.

- 12 -Preferred reducing metals in the second reduction step of this second embodiment are Mg and/or Ca and/or their hydrides. Particularly preferred is Mg.

Reduction temperature preferably (for Mg) is selected between 850 C up to normal boiling point (1150 C) The process according to the present invention (both embodiments) specifically has been developed to provide capacitor grade tantalum and niobium and tantalum nio-bium alloy powders and Ta/Nb materials or application of equivalent purity and/or morphology needs. The greatest gap of the state of the art is filled in part by the availability of capacitor grade niobium enabled by this invention, but a segment of the tantalum art is also enhanced thereby. In all cases the tantaluni and/or niobium may be enhanced by alloying or compounding with other materials during the reduction reaction production of the tantalum/niobium or thereafter. Among the requirements for such powders is the need for a high specific surface presintered agglomerate structure of approximately spherical prin-ary particles which after pressing and sintering results in a coherent porous mass providing an interconilected system of pore channels with gradually narrowing diameter to allow easy entrance of the forming electrolyte for anodization and nlanganese nitrate solution [Mn(NO3)2]
for manganization.

The reduction of oxides with gaseous reducing agents at least during the initial re-duction phase allows for easy control of temperature during reduction to avoid excessive presintering. Furthermore, as compared to prior art proposals using liquid reducing metals, the controlled reduction with gaseous reducing nietals does not lead to contamination of the reduced nietal with the reducing metal by incorporation into

- 13-the reduced metal lattice. It has been found that such contamination mainly occurs during the initial reduction of (in case of Nb) Nb205 to NbO,. This at first appeared surprising because niobium suboxide (Nb02) contains only 20% less oxygen than niobium pentoxide (Nb02.5). This effect was traced back to the fact that the suboxide forms a considerably more dense crystal lattice than the pentoxide.
The density of NbO2.5 is 4.47 g/cm3, whilst that of Nb02 is 7.28 g/cm3, i.e., the density is increased by 1.6 times by the removal of only 20% of the oxygen. Taking into account the different atomic weights of niobium and oxygen, a reduction in volume of 42% is associated with the reduction of Nb02.5 to Nb02. Accordingly, Applicants state (without limiting the scope of the invention thereby or being bound by any theory) that the effect according to the invention can be explained in that during the reduction of the pentoxide magnesium in contact with the oxide is able to diffuse relatively easily into the lattice, where it has a high mobility, whereas the mobility of magnesium in the suboxide lattice is significantly reduced. Accordingly, during the reduction of the suboxide the niaanesium substantially remains on the surface and remains accessible to attack by washing acids.

This even applies in case of a controlled reduction with gaseous magnesium.
Obvi-ously in this case reduction occurs also during the critical initial reduction to. sub-oxide only at the surface of the oxide, and magnesium oxide formed during reduction does not enter the oxide or suboxide powder. Preferred temperature during reduction with magnesium gas is between 900 and 1100 C, particularly preferred between and 1000 C.

Temperature may be increased up to 1200 C after at least 20% of the oxygen is removed to improve presintering.

! =

-14-The reduction of the pentoxide with hydrogen produces a suboxide which is already sintered with the formation of agglomerates comprising stable sintered bridges, wliich llave a favorable structure for use as a capacitor material.

Lower temperatures necessitate longer times of reduction. Moreover, the degree of sintering of the metal powders to be produced can be adjusted in a predeterminable manner by the choice of reduction temperature and reduction time. The reactors are preferably lined with molybdenum slleet or by a ceramic which is not reduced by H2, in order to prevent contamination.

Furthermore, the reduction time and reduction temperature should be selected so that at least 20% of the oxygen is removed from the pentoxide. Higher degrees of reduction are not harmful. However, it is generally not possible to reduce more than 60% of the oxygen within practicable time scales and at tolerable temperature.

After a degree of reduction of 20% or more has been reached, the suboxide is present. According to this process embodiment the reduction product is preferably still held (annealed) for some tinie, most preferably for about 60 to 360 minutes, at a temperature above 1000 C. It appears that this enables that the new, dense, crystal structure can be formed and stabilized. Since the rate of reduction decreases very considerably with the degree of reduction, it is sufficient to heat the suboxide at the { reduction temperature under hydrogen, optionally with a slight decrease in temperature. Reduction and annealing times of 2 to 6 hours within the temperature range from I 100 to I500 C are typically sufficient. Moreover, reduction witll hydrogen llas the advantage that impurities such as F, Cl and C, which are critical for capacitor applications, are reduced to less than 10 ppm, preferably less than 2 ppm.

- 15-The suboxide is subsequently cooled to room temperature (<100 C) in the reduction apparatus, the suboxide powder is mixed with finely divided powders of the reducing metals or metal hydrides and the mixture is heated under an inert gas to the reduction temperature of the second stage. The reducing metals or metal hydrides are preferably used in a stoichiometric amount with respect to residual oxygen of the acid earth metal suboxide, and are most preferably used in an amount which is slightly in excess of the stoichiometric amount.

One particularly preferred procedure consists of using an agitated bed in the first stage and of carrying out the second stage, without intermediate cooling, in the same reactor by introducing the reducing metals or metal hydrides. If magnesium is used as the reducing metal, the magnesium is preferably introduced as magnesium gas, since in this manner the reaction to form metal powder can readily be controlled.

After the reduction whether according to the one-stage or to the two-stage reduction process to metal is complete, the metal is cooled, and the inert gas is subsequently passed through the reactor with a gradually increasing content of oxygen in order to deactivate the metal powder. The oxides of the reducing metals are removed in the manner known in the art by washing with acids.

Tantalum and niobium pentoxides are preferably used in the form of finely divided powders. The primary grain size of the pentoxide powders should approximately correspond to 2 to 3 times the desired primary grain size of the metal powders to be produced. The pentoxide particles preferably consist of free-flowing agglomerates with average particle sizes of 20 to 1000 m, including a specific preference of a narrower range of most preferably 50 to 300 pm particle size. The oxide may also be provided in the form of agglomerated primary oxide particles with diameters of between 100 to 1000 nm and an average agglomerate size of 10 to 1000 m (Mastersizer D50).

-16-~ Reduction of niobium oxide with gaseous reducing agents can be conducted in an agitated or static bed, such as a rotary kiln, a fluidized bed, a rack kiln, or in a sliding batt kiln. If a static bed is used, the bed deptli should not exceed 5 to 15 cm, so that the reducing gas can penetrate the bed. Greater bed depths are possible if a bed packing is employed tlirougli which the gas flows froni below. For tantalunl, preferred equipment choices are described in Exanlple 2 and the paragrapli between Examples 2 and 3, below, with reference to FIGS. 1-4.

Niobium powders which are particularly preferred according to the invention are obtained in the form of agglomerated primary particles with a primary particle size of 100 to 1000 nn1, wherein ttle agglomerates have a particle size distribution as determined by Mastersizer (ASTM-B822) corresponding to D 10 = 3 to 80 m, particularly preferred 3 to 7 m, D50 = 20 to 250 Ftm, particularly preferred 70 to 250 m, most preferably 130 to 180gm and D90 = 30 to 400, particularly preferred 230 to 400 in, most preferably 280 to 350 m. The powders according to the invention exhibit outstanding flow properties and pressed strengths, which determine their processability to produce capacitors. The agglomerates are characterized by stable sintered bridges, which ensure a favorable porosity after processing to fornl capacitors.

Preferably niobium powder according to the invention contains oxygen in amounts of 2500 to 4500 ppm/m2 surface and is otherwise low in oxygen, up to 10,000 ppm nitrogen and up to 150 ppm carbon, and without taking into account a content of alloying metals has a maximum content of 350 ppm of other metals, wherein the metal content is mainly that of the reducing metal or of the hydrogenation catalyst metal. The total content of other metals amounts to not more than 100 ppm. The total content of F, Cl, S is less than 10 ppm.

-17-Capacitors can be produced from the niobium powders which are preferred according to the invention, immediately after deactivation and sieving through a sieve of mesh size 400 m. After sintering at a pressed density of 3.5 g/cm3 at 1100 C and forming at 40 V these capacitors have a specific capacitance of 80,000 to 250,000 FV/g (as measured in phosphoric acid) and a specific leakage current density of less than 2 nA/ FV. After sintering at 1150 C and forming at 40 V, the specific capacitor capacitance is 40,000 to 150,000 FV/g with a specific leakage current density of less than 1 nA,' FV. After sintering at 1250 C and forming at 40 V, capacitors are obtained which have a specific capacitor capacitance (as measured in phosphoric acid) of 30,000 to 80,000 FV/g and a specific leakage current density of less than 1 nA/ FV.

The niobium powders which are preferred according to the invention have a BET
specific surface of 1.5 to 30 m2/g, preferably of 2 to 10 m2/g.

Surprisingly it has been found that capacitors can be made from Nb/Ta-alloy powders in way that the capacitors have an appreciably higher specific capacitance obtained from capacitors made from pure Nb-and pure Ta-powers or anticipated for an alloy be simple linear interpolation. Capacitances ( FV) of capacitors with sintered Nb-powder anodes and sintered Ta-powder anodes having the same surface area are approximately equal. The reason is that the higher dielectric constant of the insulating niobium oxide layer (41 as compared to 26 of tantalum oxide) is compensated by the larger thickness of the oxide layer per volt (anodization voltage) formed durino anodization. The oxide layer thickness per volt of Nb is about twice as thick as that formed on Ta (about 1.8 nm/V in the case of Ta and about 3.75 nm/V

-18-in the case of Nb). The present invention can provide a surface related capacitancc ( FV/m2) of alloy powder capacitors which is up to about 1.5 to 1.7 higher than the expected value from linear interpolation between Nb powder capacitors and Ta powder capacitors. This seems to indicate that oxide layer thickness per volt of anodization voltage of alloy powders of the invention is closer to ttiat of Ta, whereas the dielectric constant of the oxide layer is closer to that of Nb. The foregoing surprisingly lligh capacitance of the alloy may be associated with a different structural form of oxide of alloy components compared to structure of oxides on surfaces of pure Nb powders. Indeed, preliminary measurements have revealed that oxide layer growth of a 15 at. -%Ta -- 85 at.-% Nb alloy is almost 2.75 nm/volt.

The present invention accordingly further comprises an alloy powder for use in the manufacture of electrolyte capacitors consisting primarily of niobium and containing up to 40 at.-% of tantalum based on the total content of Nb and Ta. Alloy powder in accordance with the present invention shall mean that the minor Ta-component shall be present in an amount greater than the amount of ordinary impurity of niobium ~ nietal, e.g. in an amount of more than 0.2% by weight (2000 ppm, corresponding to 2 at.-% for Ta).

Preferrably, the content of Ta is at least 2 at.-% of tantalum, particularly preferred at least 5 at.-% of tantalum, most preferably at least 12 at.-% of tantalum, based on the total content of Nb and Ta.

Preferably the content of tantalum in the alloy powders in accordance with the in-vention is less than 34 at.-% of tantalum. The effect of capacitance increase is gradually increasing up to a ratio of Nb- to Ta-atoms of about 3. Higher than 25 at.-, .

-19-% Ta based on the total content of Nb and Ta does only slightly furtlier increase the effect.

The alloy powders according to the invention preferably have BET'-surfaces multi-plied with the alloy density of between 8 and 250 (m2/g) x(g/cm3), particularly preferred between 15 and 80 (m2/g) x (g/cm3). The density of the alloy material may be calculated from the respective atomic ratio of Nb and Ta multiplied by the densities of Nb and Ta respectively.

The effect of capacitance increase of alloying is not limited to powders having the structure of agglomerated spherical grains. Accordingly the alloyed powders in accordance of the invention may have a morphology in the form agglomerated flakes preferably haviiig liave a BET-surface times density of between 8 and 45 (m2/g) x (g/cm3).

Particularly preferred alloy powders are agglomerates of substantially spherical pri-niary particles having a BET-surface times density of 15 to 60 (m2/g) x(g/cm3). The primary alloy powders (grains) may have mean diameters of between 100 to 1500 nm, preferrably 100 to 300 nm. Preferrably the deviation of dianleter of primary particles from mean diameter is less than a factor 2 in both directions.

The agglomerate powders may have a mean particle size as determined in accordance with ASTM-B 822 (Mastersizer) as disclosed for niobium powders above.

Particularly preferred alloy powders have a ratio of Scott density and alloy density of between 1.5 and 3 (g/inch3)!(g/cm3).

-20-Any production method known in the art for the production of capacitor grade tan-taluni powder may be used, provided that a precursor is used which is an alloyed precursor containing niobium and tantalum approximately at the atomic ratio of Nb and Ta desired in the metal powder alloy instead of precursor containing tantalurn alone.

Useful alloy precursors may be obtained from coprecipitation of (Nb, Ta)-compounds from aqueous solutions containing water soluble Nb- and Ta-compounds e.g. coprecipitation of (Nb, Ta)-oxyhydrate from aqueous solution of heptafluoro-complexes by the addition of ammonia and subsequent calcination of the oxhydrate to oxide.

Flaked powders may be obtained by electron beani melting of a blend of high purity tantalum and niobium oxides, reducing the molten ingot, hydriding the ingot at ele-vated temperature, and comminuting the brittle alloy, dehydriding the alloy powder and forming it into flakes. The flakes are thereafter agglomerated by heating to 1100 to 1400 C in the presence of a reducing metal such as Mg, optionally witli doping with P and/or N. This process for the manufacture of "ingot derived" powder is generally knoxvn from US-A 4,740,238 for the production of tantalum flaked powder and from WO 98/19811 for niobium flaked powder.

Particularly preferred Nb-Ta-alloy powders having the morphology of agglomerated spherical grains are produced froni mixed (Nb, Ta)-oxides by reduction with gaseous reducing aoent as described herein.

~ , .

-21 -The metal powders produced are suitable for use in electronic capacitors and other applications including, e.g. the production of complex electro-optical, superconductive and other metal and ceranlic compounds, such as PMN structures and high temperatures form metals and oxide.

The invention comprises the said powders, the methods of producing such powders, certain derivative products made from such powders and methods for making such derivative products.

The capacitor usage can be accompanied by other known artifacts of capacitor pro-duction such as doping with ageitts to retard sinter densification or otherwise enllance end product capacitance, leakage and voltage breakdown.

The invention enables several distinct breakthroughs in several of its various fields of application.

First, the well known high performance tantalum powders for making computer/telecomnlunications grade solid electrolyte, small size capacitors (higll capacitance per unit volume and stable performance characteristics) can now be made with substantial net savings of cost, complexity and time.

Second, other reactive metals - especially Nb and alloys, e.g. Ta-Nb, Ta-Ti, Nb-Ti, can be introduced as replacement for Ta in capacitors in certain applications with a cost saving or as replacement for the high eiid Al market with much better performance, particularly enabling much smaller sizes for equivalent capacitance and use of solid electrolyte. Commercial aluminunl electrolytic capacitors use wet electrolyte systems.

-22-Other aspects, features and advantages will be apparent from the following detailed description of preferred embodiments taken in conjunction with the accompanying drawing in which:

Brief Description of the Drawing FIGS. 1-4 show sketch outlines of processing systems for practice of the present invention;

FIGS. 5A-12C are scanning electron micrographs (SEMs) of powders produced according to the present invention, including some SEMs of state of the art or comparison examples of metal powders made otherwise than in accordance with the present invention;

FIGS. 13 and 14 are flow charts illustrating diverse usages of the powder and derivatives; and FIG. 15 is a schematic representation of an end item according to usage as a capacitor (one of several forms of capacitor usage).

FIG. 16 is a trace of capacitance and surface area of Ta-Nb alloy powders in relation to alloy composition.

Detailed Description of Preferred Embodiments Example 1 (comparison)

-23-A mixture of Ta205 arid magnesium was loaded into a tantalum tray and covered with tantalum foil. The magnesium stoichionietry was 109% of that required to completely reduce the tantalum oxide. The mixture was heated at 1000 for six hours in an argon atniosphere. The mixture was not agitated during the reduction process. After cooling, the products were passivated by programmed addition of oxygen. The result of tiie reduction process was a black spongy material that was difficult to break up. The product was leached with dilute niineral acid to rerr-ove the magnesium oxide, dried and screened. The yield of the coarse (+40 mesh) niaterial was lligh at 25 percent. The impurity content of each (as % or ppm) and surface areas (SA, cm2/gm) of the +40 and -40 fractions are given in Table 1.1, below.
Both the magnesium and oxygen contents were high. The large percentage of coarse material and poor quality of the product made it unsuitable for use in capacitor applications.

Table 1.1 0 N C S Na K Mg Sa % ppm PPm ppni PPm PPm ppm cm2/gm +40 mesh 7.6 840 21 <5 <I <10 >7000 17,000 -40 mesh 4.7 413 57 <5 <5 <10 >7000 35,000 Example 2 Referring to FIG. 1, a bed (3) of 200 grams of tantalum pentoxide was placed on a porous tantalum plate 4 suspended above magnesium metal chips (5) contained in a tantalum boat. The container was covered with a tantalum lid and placed in a sealed retort with argon (Ar) passed through the sealed volume via nozzle (6). The boat

-24-was heated to and maintained at 1000 C for six hours in an argon/magnesium gas atmosphere utilizing a bed (5) of solid magnesium cliips maintained in a region wholly separate from the oxide bed. After cooling to rooni temperature, the product mixture was passivated by introdttcing argon-oxygen mixtures, containing 2, 4, 8, 15 inches (Hg, partial pressure) of 02 (g), respectively, into the furnace. Each mixture was in contact with powder for 30 mintttes. The liold time for the last passivation with air was 60 minutes.

The magnesium oxide was separated from the tantalum powder by leaching with dilute sulfuric acid and then rinsed with high purity water to remove acid residues.
The product was a free flowing, powder. Samples of the product (designated as Ta GR-2D) are shown in scanning electron micrographs (SEMs) at FIGS. 5A, 513, 5C
at 15,700, 30,900 and 60,300 magnifications, respectively, taken in an electron microscope operated at 15 kilovolts. A comparison is given in FIGS. 5D and 5E

which are 70,000 magnification (x) SEMs of tantalum powder made by sodium reduction. Properties of the tantalum powder of FIGS. 5A, 513, 5C are given in Table 2.1, below.

Table 2.1 Surface Content of Included Chemical Elements (ppm) area (cm 2/gm O N C Cr Fe Ni Na K Ca Si 12,900 126 75 <5 23 <5 <I <10 <2 <8 37,600 The oxygen concentration to surface area ratio was consistent with surface oxygen only, indicatino, that the tantalum oxide was completel), reduced.

-25-Alternate forms of reactor to the one shown in FIG. 1(and discussed in Example 2) are shown in FIGS. 2-4. FIG. 2 shows a flash reactor 20 with a vertical tube 22 surroun-ded by a heater 24, a feed source 25 of metal oxide and a source 26 of reducing agent (e.g. Mg) vapor (mixed in argon), an argon outlet 26' and a collector 28 for metal and oxide of the reducing agent. Valves V1, V2 are provided. Particles of the oxide drop through the tube and are flash reduced. FIG.3 shows a rotary kiln 30 with an inclined rotating tube 32, heater 34, oxide hopper 35, gas source 36 (reducing agent and diluent, e.g. argon), outlet 36', and collector 38 for metal and reducing agent oxide.

FIG. 4 shows a multiple hearth furnace 40 with a retort 42 containing rotary trays 43 and splined paddles 43', heater 44, oxide source 45, gas source 46, exit 46' and collector 48. Still other forms of reactors such as conventional per se fluid bed furnace reactors or Contop, KIVCET types can be used.

Example 3 Tantalum powder with surface area of 57,000 cm2/gm made according to the procedure in Example 2 was deoxidized by blending the powder with 2 W/W% Mg and heating at 850 C for two hours in an argon atmosphere. Separation of reducing agent source and oxide is not necessary in this follow up deoxidation step.
The deoxidized powder was allowed to cool and then passivated, leached, and dried.
A
SEM (100,000 x) of the deoxidized (finished) powder appears at FIG. 7A and a SEM
(70,000 x) of finished sodium reduced powders appears at FIG. 7B. the morphology differences are apparent. After doping with 100 ppm P by adding an appropriate amount of NH4H2PO4, the powder was pressed into pellets weighing 0.14 grams at a press density of 5.0 g/cc. A SEM of the further deoxidized powder is given at FIG.
6. The pellets were sintered in vacuum at 1200 C for 20 minutes. The pellets were

-26-anodized to 30 volts in 0.1 volume percent (V/V%) H3PO4 solution at 80 C. The formation current density was 100 mA/gm and the hold time at the formation voltage was two hours. The average capacitance of the anodized pellets was105, 000 F
(V)/gm and the leakage current nleasured after five minutes application of 21 V was 0.1 nA/ F (V).

Exaniplc 4 Powder with surface area of 133,000 cm2/gm and bulk density of 27.3 g/m3 niade as described in Example 2 was treated as in Example 3. A SEM (56,600 x) of the finished powder appears at FIG. 7C. Pellets made from the deoxidized powder were anodized to 16V using the conditions in Example 3. The average capacitance of the anodized pellets was 160,000 F (V)/gm.

Cxample 5 Nine hundred grams of Ta205 was reduced with gaseous magnesium at 900 C for two hours. The magnesium oxide was removed from the reduction product by leaching with dilute sulfuric acid. The resulting powder had a surface area of 70,000 cm2/gm and was deoxidized at 850 C for two hours using 8 W/W% magnesium.
One (1.0) W/W% NH4CI was added to the charge to nitride the tantalum. The deoxidized powder was treated as described in Example 3. The P doping level was 200 ppm. The powder was deoxidized again using the same time and temperature profile with 2.0 W/W% Mg and no NHaCI. Residual magnesium and magnesium oxide were removed by leaciiing with dilute mineral acid. The chemical properties of the poxvder are given in Table 5.1, below. The powder liad a surface area of 9,000 =

-27-cm2/gm and excellent flowability. Pressed pellets were sintered at 1,350 C for twenty minutes and anodized to 16V in 0.1 VN% H3P04 at 80 C.

The capacitance of the anodized pellets was 27,500 F (V)/gnl and the leakage was 0.43 nA/ F (V).

Table 5.1 Cliemical Element (ppm) 0 N C Cr Fe Ni Na K Ca Si 2610 2640 95 8 18 <5 1 <10 <2 41 Example 6 500 granis of Ta205 were reduced at 1,000 C for six hours witli gaseous magnesium.
Properties of the primary powder so produced are given in Table 6.1, below:

Table 6.1 0, ppm N, ppm C, ppm Na, ppm K, ppln SA, cmZ/g 19,000 1693 49 <1 <10 60,600 The primary powder was deoxidized at 850 C for two hours. 4 W/W% Mg and I
W/W% NH
4CI were added. MgO was leached with mineral acid. Then the powder was doped at 200 ppnl P by adding the equivalent amount of NH4H2PO4. The pow-der was deoxidized for the second tinie at 850 C for two hours and then nitrided at

-28-325 C by adding a gaseous mixture containing 80% argon and 20% nitrogen. Some properties of the finished powder are given in Table 6.2, below.

Table 6.2 Table 6.2 0-ppm N, ppm C, ppm Na, ppm K, ppm SA, cm2/g 6050 3430 54 <1 <10 24,300 Pellets were made from the powder at a press density of 5.0 gm/cc. The sintered pellets were anodized at 80 C to 16 volts in 0.1 W/W% H3POq solution.

Capacitances and leakages as a function of sintering temperature are given in Table 6.3, below.

Table 6.3 Sintering Capacitance Leakage Temperature ( C) F (V)/gm A/ F(V) 1,200 143,000 0.77 1,250 121,000 0.88 1,300 96,000 1.01 Example 7 (comparative) Potassium heptatluoroniobate (K2NbF7) was reduced with sodiurn using a stirred reactor molten salt process siniilar to the ones described by Hellier et al.
and 1-fildretli

-29-et al., US patent 5,442,978. The diluent salt was sodium chloride and the reactor was nlade ftom Inconel alloy. The niobium nletal powder was separated from the salt matrix by leaching with dilute nitric acid (HNO3) and then rinsing witli water.
Selected physical and chemical properties are given in Table 7. 1, below. The very high concentrations of the metallic elements, nickel, iron and chromium, make the powders unsuitable for use as capacitor grade material. The contamination resulted because of the inherent corrosive nature of the K2NbF7. This property nlakes the sodium reduction process unsuitable for making capacitor grade niobium powder.

Table 7.1 Sample SA SBD FAPD O(ppm) Ni Cr Fe 1 13820 8.7 1.76 6080 18000 2970 2660 2 11700 9.4 1.48 4930 11300 4790 2060 SBD=Scott Bulk Density (g/in'), FAPD=Fislier Average Particle Diameter ( ) Cxaniple 8 Two hundred grams of niobium pentoxide was reduced as described in Example 2.
The resulting product was a free flowing black powder and had a surface area of 200,800 cm2/gm. The passivated product was leached with dilute nitric acid solution to remove maanesium oxide and residual magnesium and then with high purity water to remove residual acid. This material was blended with ten (10.0) W/W% Mg and deoxidized at 850 C for two hours. Physical and chemical properties of the powder are listed in table 8.1, beloNti-. The powder was doped with 100 ppni P as described in Example 3.

-30-Table 8.1 Physical and Chemical Properties of Niobium Powder Surface Chemical Element (ppm) Area cm2/gm 0 N C Cr Fe Ni Na K Ca Si 13000 620 40 27 45 21 8 I 3 26 40,900 SEMs (70,000 x) appear at FIGS. 8A and 8B, respectively, for niobium powders produced by liquid sodium (Ex. 7) and magnesium gas (Ex. 8) reduction. Note the clustering of small particles as barnacles on large ones is much more pronounced in FIG. 8B than in 8A. FIGS. 8C, 8D are SEMs (2,000 x) of, respectively niobium powder as produced by sodium reduction and magnesium gas reduction.

The niobium powder produced by liquid sodium reduction has large (>700 nm) joined (300 nm+) grains protruding and facets that give the product a blocky shape and fine grain material (order of 10 nm, but some up to 75 nm) as barnacles while the niobium powder produced by magnesiuni gas reduction has a base grain_size of about 400 nm and many smaller grains of about 20 nm thereon many of which smaller grains are themselves agglomerates of up to 100 nm in size.

Example 9 Pellets weighing 0.14 gm were prepared from the niobium powder produced in Example 8. The pellets were anodized in 0.1 V/V% 143P04 solution at 80 C. The current density was 100 mA/gni and the hold time at the formation voltage was two .

`

-31-hours. Electrical results as a function of pellet press density, formation voltage and sintering temperature are given in Table 9.1, below.

Table 9.1 Sunimary of Electrical Properties (capacitance, leakage) of Niobium Powder at 3.0, 3.5 (g/cc) Press Densities Sintering Capacitance Leakage Temperature ( F (V)/gm) (nA/ F(V)) ( C) 3.0 3.5 3.0 3.5 16 V Formation 1300 29,500 20,000 1.6 4.7 1350 21,000 16,000 0.7 1.5 40 V Formation 1250 53,200 44,500 2.1 4.0 1300 31,000 22,300 1.2 4.7 1350 26,500 20,000 0.7 1.0 Example 10 Niobium oxide was reduced witli gaseous magnesium as described in Example 8.
The resulting powder was deoxidized twice. During the first deoxidation, 2.0 W/W% NH4CI was added to the charge to nitride the powder. The deoxidation conditions Nvere 850 C for two hours with 7.0 W/W% Mg. After leaching and . .

-32-drying, the powder was doped with 200 ppm P. The second deoxidation was carried out at 850 C for two hours using 2.5 W/W% Mg. The finished powder has a surface area of 22,000 cm2/gm and good flowability. The chemical properties are given in Table 10.1, below. Pellets were anodized to 16 volts in 0.1 V/V% H3PO4 solution at 80 C using a current density of 100 mA/g and a two-hour hold. The electrical properties are given in Table 10.2, below.

Table 10.1 Chemical Clenient (ppm) 0 N C S Cr Fe Ni Si Ta 7490 8600 166 9 <20 114 <20 34 <200

-33-Table 10.2 Electrical Properties Sintering Capacitanee Leakage Temperature ( C) ( F(V)/gm (nA/ F(V) 1250 68,000 0.24 1300 34,500 0.14 1350 11,300 0.32 Exatnple 11 ~

a) The Nb205 used had a particle size of 1.7 m as determined by FSSS (Fisher Sub Sieve Sizer) and comprised the following contents of impurities:

Total (Na, K, Ca, Mg) 11 ppm Total (Al, Co, Cr, Cu, Fe, Ga, Mn, Mo, Ni, Pb, Sb, Sn, Ti, V, W, Zn, Zr) 19 ppm Ta 8 ppm Si 7 ppin C <1 ppm C1 <3 ppm F 5 PPm S <1 PPm

-34-The Nb205 was passed in a molybdenum boat through a sliding batt kiln, under a slowly flowing hydrogen atmosphere, and was maintained in the hot zone of the kiln for 3.5 hours.

The suboxide obtained had a composition corresponding to Nb02.

b) The product was placed on a fine-mesli grid under which a crucible was situated which contained magnesium in 1.1 times the stoichionletric amount with respect to the oxygen content of the suboxide.

The arrangement comprising the grid and crucible was treated for 6 liours at IO00 C under an argon protective gas. In the course of this procedure, the magnesium evaporated and reacted with the overlying suboxide. The kiln was subsequently cooled (<100 C) and air was gradually introduced in order to passivate the surface of the metal powder.

The product was washed with sulfuric acid tintil magnesiunl could no longer be detected in the filtrate, and thereafter was washed tintil neutral with deionized water and dried.

Analysis of the niobium powder gave the following impurity contents:
0 20,000 ppm (3300 ppm/m2) Mg 200 ppm Fe 8 ppm Cr 13 ppm Ni 3 ppni

-35-Ta 110 ppm C 19ppm N 4150 ppm The particle size distribution, as determined by Mastersizer, corresponded to D 10 4.27 gm D50 160.90 m D90 318.33 }Lm The primary grain size was determined visually as about 500 nm. The Scott bulk density was 15.5 g/inch3. The BET specific surface was 6.08 mz/g. The flowability, determined as the Hall Flow, was 38 seconds.

c) Anodes with a diameter of 3 mm, a length of 5.66 nim, an anode mass of 0.14 g and a pressed density of 3.5 g/cm3 were produced from the niobiunl powder by sintering on a niobium wire for the times and at the temperatures given in Table 11.1.

The pressed strength of the anodes, as determined according to Chatillon, was 6.37 kg. The anodes were formed at 80 C in an electrolyte containing 0.1 %
by volume of H3PO4 at a current density of 100/150 mA at the voltage given in Table 11.1 and the capacitor characteristics were determined; see Table 11.1

-36-Table 11.1 Sample Sintering Sintered Wire draw- Forming Capacitance Leakage Temp. density ing strength voltage FV/g current /tinie g/cm' N V nA/ FV
oC

min a 1250/20 5.1 16 41,126 0.47 b 5 40 41,725 0.7 c 5 70 23,721 2.13 d 1150/20 3.9 35.6 16 111,792 0.77 e 4 35.6 40 147,292 0.43 f 1100/20 3.75 36.6 16 194,087 0.4 g 3.7 36.1 40 194,469 0.36 Example 12 Example 11 Nvas repeated, with the difference that the tenlperature in the first reduction stage was 1300 C.

The metal powder had the following properties:
Mastersizer D 10 69.67 m D50 183.57 gm D90 294.5 m Primary grain size (visual) 300 - 400 nm BET specific surface 5 rn2/g =

-37-Free-flowing.
The pressed strength was extremely high:
13 kg at a pressed density of 3.5 g/cm3, and 8 kg at a pressed density of 3 g/cm3.

After sintering at 1100 C for 20 minutes (pressed density 3 g/m3), and after forrning at 40 V, a capacitance of 222,498 FV/g and a leakage current of 0.19 nA/ FV
were measured.

Cxample13 This example shows the effect of the reduction tenlperature in the first stage on the properties of the niobium powder:

Three batches of niobiunl pentoxide were treated for 4 hours under hydrogen at 1100 C, 1300 C or 15000C, under conditions which were otherwise the same.

The batches were subsequently reduced to niobium metal witli Mg gas (6 hours, 1000 C). The MgO which was formed in the course of the reaction, together with excess Mg, were washed out with sulfuric acid. The following powder properties were obtained:

=

-38-Reduction temperature 1100 C 1300 C 1500 C
Suboxide:

BET m2/gO 1.03 0.49 0.16 Hall FlowZ) non- 25 g in 25 g in flowing 48 sec. 20 sec.
Niobium metal:

BET m2/g 9.93 7.8 5.23 FSSS m3) 0.6 0.7 6.8 Hall Flow non- 25 g in 25 g in flowing 85 sec. 19 sec.
SD g/inch4) 16.8 16.5 16.8 Mg ppm 240 144 210 O ppm 40,000 28,100 16,600 BET specific surface 2) flowability 3) particle size as determined by Fisher Sub Sieve Sizer 4) bulk density Example 14 A(Nbx, Tal-r)2O5 precursor is prepared by coprecipitation of (Nb, Ta)-oxyhydrate from mixed aqueous solution of niobium and tantalum heptafluorocomplexes by the addition of ammonia with stirring and subsequent calcination of the oxyhydrate to oxide.

-39-A lot of the mixed oxide powder having a nominal contposition of Nb: Ta =
90:10 (weight ratio) was placed in a molybdenum boat and passed tlirough a sliding batt kiln under slowly flowing hydrogen atmosphere and was maintained in the hot zone of the kiln for 4 hours at 1300 C. After cooling down to rooni temperature the composition was determined from weiglit loss to be approxiniately (Nb0.944Ta0.054)0=

The suboxide was placed on a fine mesh grid under which a crucible was situated which contained magnesiuni in 1,2 times the stoichiometric amount with respect to the oxygen content of the suboxide. The arrangement comprising grid and crucible was treated for 6 hours at 1000 C under an argon protective gas. The kiln was subsequently cooled to below 100 C and air was gradually introduced in order to passivate the surface of the metal powder.

The product was washed kvith sulfuric acid until nlagnesiuni could no longer be detected in the filtrate, and thereafter washed until neutral with deionized water and dried.

Analysis of the alloy powder gave a tantalum content of 9.73 wt.-% and the following impurity contents (ppm):

0: 20500, Mg: 24, C: 39, Fe: 11, Cr: 19, Ni: 2, Mo: 100.

The primary grain size as determined visually was roughly 450 nm. BET specific surface was 6.4 m2/g, Scott density 15.1 g/1n3, particle size (FSSS) was 0.87 m.

-40-Anodes with a diameter of 2.94 mm, a length of 3.2 mm and a pressed density of 3.23 g/cm3 were produced from the alloy powder by sintering on a niobium wire for 20 minutes at 1 150 C. Sintered density was 3.42 g/cm3. The electrodes were anodized in an electrolyte containiiig 0.25% of H3PO4 until a final voltage of 40 V.

The capacitor characteristics were determined by using a 10% H3PO4 aqueous solu-tion as follows: Capacitance: 209117 FV/g, Leakage current: 0.55 nA/ Pg.

Exam le 1~

An alloy powder was prepared as in Example 14, using an oxide powder with nominal composition of Nb:Ta = 75:25 (weiglit ratio).

Analysis of the nietal alloy powder gave a tantalunl content of 26,74 wt.-%
and the following impurity contents (ppm):

0: 15000, Mg: 25, C: 43, Fe: 9, Cr: 20, Ni: 2, Mo: 7, N: 247.

The primary grain size as deterniined visually was roughly 400 nm. BET
specific surface was 3.9 m2/g, Scott density 17.86 g/in3, particle size (FSSS) was 2.95 m, Hall Flow 27.0 s.

Anodes with a diameter of 2.99 mm, a length of 3.23 mm and a pressed density of 3.05 g/cm~ were produced from the alloy powder by sintering on a niobium wire for 20 minutes at 1,150 C. Sintered density was 3.43 g/cm3. The electrodes were anodized in an electrolyte containing 0.25% of H3PO4 until a final voltage of 40 V.

-41 The capacitor characteristics were determined by using a 10%H3PO4 aqueous solution as follows: Capacitance: 290173 FV/g, Leakage current: 0.44 nA/ Fg.
Exaninle 16 Tantalum hydroxide was precipitated from an aqueous tantalum fluorocomplex solution by addition of anlmonia. The precipitated hydroxide was calcined at for 4 hours to provide a Ta205 precursor with the following physical data:
average particle diameter with Fisher Sub Sieve Sizer (FSSS): 7.3 m, bulk density (Scott):

27.8 g/inch3, specific surface area (BET): 0.36 mz/g particle size distribution with laser diffraction on Master Sizer S, measured without ultrasound: D10 = 15.07 m, D50 = 23.65 .m, D90 = 34.03 m.

The morphology of agglomerated spheres is sllown on Fig. 9A -9C (SEM-pictures).

300 g of the precursor pentoxide was placed on the screen and 124 g Mg (1.5 times the stoichio-netric amount necessar), to reduce the pentoxide to nietal) was placed on the bottom of a retort shown in Fig. 1.

The retort was evacuated, filled with argon and heated to 950 C for 12 hours.
After cooling to below 100 C, and passivation the product was leached with an aqueous solution containing 23 wt.-% sulfuric acid and 5.5 wt.-% hydrogen peroxide and thereafter washed with water until neutral. The product was dried over night at 50 C
and screened < 400 m.

The tantalum powder showed the following analytical data:
Average particle size (FSSS): 1.21 m, bulk density (Scott): 25.5 g/inch,

-42-BET surface: 2,20 m2/g, good flowability, MasterSizer D 10 = 12.38 m, D50 = 21.47 gm, D90 = 32.38 nl, morphology: see Fig. 1 OA - 10C (SEM-pictures).

Chenlical analysis:
0: 7150 ppm N: 488 ppm H: 195 ppm C: 50 ppm Si: 30 ppm F: 2 ppm Mg: 6 ppm Na: I ppm Fe: 3 ppm Cr: <2 ppm Ni: < 3ppm.

The powder was soaked with gentle stirring with NH4H2PO4-solution containing 1 mg P per nil, dried over night at 50 C for doping with 150 ppin P and screened < 400 m.

Capacitor anodes were prepared from 0.047 g of Ta-powder each at pressed density of 5.0 g/cm3 by sintering at 1260 C with 10 minutes holding time.

Forming current density was 150 mA/g with 0,1 wt.-% H3PO4 solution as forming electrolyte at 85 C until final voltage of 16 V which was held for 100 minutes.

-43-Test results:

Sintered density: 4.6 g/cm3, capacitance: 100 577 FV/g leakage current: 0.73 nA/gFV.

Example 17 High purity optical grade Ta205 was calcined first at 1700 C for 4 hours and thereafter for 16 hours at 900 C to provide for more compact and coarser precursor particles. Pliysical properties of the pentoxide powder are:

Average particle size (FSSS): 20 m bulk density (Scott): 39 g/inch3 Screen analysis: 400-500 m 8.7 %
200-400 m 63.6 %
125-200 m 15.0%
80-125 m 7.2 %

45- 80 m 3.8%
<45 m 1.7%
Morphology is shown in Fig. I IA-1 1C (SEM-pictures).

The oxide powder was reduced to metal as described in example 16, however at 1000 C for 6 liours.

Leaching and P-doping was as in example 16.

-44-The tantalum powder showed the following analytical data:
Average particle size (FSSS): 2.8 m, bulk density (Scott): 28.9 g/inch3, BET surface: 2.11 m2/g, flowability through nonvibrated funnel with 60 -angle and 0,1 inch opening: 25 g in 35 seconds, Master Sizer D 10 = 103.29 m, D50 = 294.63 m, D90 = 508.5 m, morphology: see Fig. 12A - 12C (SEM-pictures).

Chemical analysis:
O: 7350 ppm N: 207 ppm H: 174 ppm C: 62 ppm Mg: 9 ppm Fe: 5 ppm Cr: <2 ppm Ni: < 3ppm.
P: 150 ppm Capacitor anodes were prepared and anodized as in example 16.
Test results:

Sintered density: 4.8 g/cm3 Capacitance: 89 201 FV/g I_eakage current: 0.49 nA/pFV

-45 -A second series of capacitors were prepared the same way, however with sintering temperature raised to 1310 C.

Test results:

Sintered density: 5.1 g/cm3 Capacitance: 84 201 FV/g Leakage current: 0.68 nA/ FV
Example 18 Several samples, each approximately 25 grams, of W03, Zr02, and V203 were reduced individually with gaseous magnesiunl at 950 C for 6 hours. The reduction products were leaclled with dilute sulfuric acid to remove residual magnesium oxide.
The product was a black metal powder in each case. The tungsten and zirconium powders had oxygen contents of 5.9 and 9.6 W/W% respectively, indicating that the nletal oxides were reduced to the metallic state.

The present process appears to represent the only demonstrated way of making high quality chemically reduced niobium powder. The reduction of the metal oxide with a gaseous reacting agent, such as magnesium, as shown herein is thus particularly suitable for producing powders useable as metal-metal oxide capacitor substrates.
Although the reduction process was carried out with the metal oxide in a bed in con-tact with a source of magnesium gas, the reduction can take place in a fluidized bed, rotary kiln, flash reactor, multiple hearth or similar systenls provided the magnesium or other reducing agent is in the gaseous state. The process will also work xvitli other nietal oxides or metal oxide mixtures for which the. reduction reaction with gaseous magnesium or otlier reducing agent has a negatix=e Gibbs free energy cllange.

-46-There are several advantages to the gaseous reduction processes described herei .
Treatment of the reduction products is much less complicated and expensive than post reduction work-up of tantalum powder produced by liquid phase reactions such as the sodium reduction of K2TaF7 in a molten salt system. No fluoride or cliloride residues are produced in the present process. This eliminates a potentially serious disposal problem or the need to institute an expensive waste recovery system.
The reduction of metal oxides with gaseous reducing agents gives powders witll much higher surface areas than powders produced by the molten salt/sodium reduction process. The new process easily makes powders witli very higli surface area compared to the traditional method; the potential for making very high performance capacitor grade powders is great with magnesium or other gaseous reducing agent.
The present invention further for the first time demonstrates the superiority of Ta-Nb alloy powders for use in the production of capacitors.

Fig. 16 shows the ratio of maximum obtainable capacitance ( FV/g) a.nd BET-surface of powder (m2/g) in relation to the alloy composition. A and C
represent pure Ta-, Nb-powders, respectively, as measured in present Example 16. B represents the highest known values of pure Ta powder capacitors as disclosed in Examples 2, and 7 of WO 98/37249. Line 1 represents expectable values for alloy powder capacitors from linear interpolation from pure Ta, and Nb powder capacitors. E
represents a fictive Nb-powder capacitor wherein the insulating oxide layer has the same thickness per volt as in Ta powder capacitors, however, the dielectric constant of niobium oxide differs. Line 11 represents linear interpolation between B
and E. D
represents a nieastired value of 25 %vt.-% Ta/75 wt.-% Nb alloy powder capacitor as presented in present Exaniple 15. Curve III represents the estiniated dependency of = ~

-47-capacitance on alloy composition of alloy powder capacitors in accordance with the present inventioii.

FIG. 13 is a block diagram of steps for achieving an electrolytic capacitor usage of the invention. The steps comprise reduction of metal oxide with gaseous reducing agent; separation of reduction agent oxide from a mass of resultant metal;
breakdown to powder forin and/or primary powder particle size; classification;
optionally, presinter to establish agglomerated secondary particles (controlled mechanical rnethods and control of original reduction or separation steps also being affective to establish agglomerates); deoxidation to reduce the oxygen concentration;
compaction of primary or secondary particles to a porous coherent mass by cold isostatic pressing with or without use of compacting binders or lubricants; sintering to a porous anode form (which can be an elongated cylindrical, or slab or of a short length from such as a chip); anode lead attachment by embedding in the anode before sinteriilg or welding to the sintered anode'compact; forming the exposed metal surfaces within the porous anode by electrolytic oxidation to establish a dielectric oxide layer; solid electrode impregnation by impregnating precursors into the porous mass and pyrolysis in one or more stages or other methods of impregnation; cathode completioil; and packaging. Various additional steps of cleaning and testing are not sllown. The end product is illustrated (in a cylindrical form) in FIG. 15 as a Ta or Nb (or Ta-Nb- alloy) capacitor 101 in partial cut-away form as a porous Ta or Nb (or Ta-Nb alloy) anode 102, impregnated with a solid electrolyte, surrounded by a counter-electrode (cathode) 104 and packaging sheath 105 with a dense lead wire 106 of Ta or Nb (generall), niatchin? the powder composition) that is joined to the anode by a weld joint 107. As stated above, other known per se capacitor fornis (different stlape factors, different nietals, different electrolyte systems anode lead joinder, etc.) are accessible through the present invention.

-48-PIG. 14 is a block diagram collectively illustrating production of some of the other derivative products and uses of the invention including use of the powders as slips, in molding and loose pack form for further reaction and/or consolidation by way of sintering, liot isostatic pressing (H.I.P.) or in sinter/H.I.P. methods. The powders per se and/or as consolidated can be used in making composites, in combustion, in chemical synthesis (as reactants) or in catalysis, in alloying (e.g.
ferrometallurgy) and in coatings. The consolidated powders can be used to make mill products and fabricated parts.

In some instances the end use products made using the gas reduction produced powders will resemble state of the art powders made witll state of the art (e.g.
reduced) powders and in other instances the products will be novel and have unique physical, chemical or electrical characteristics resulting from the unique forms as described lierein of the powders produced by reduction by gaseous reducing agents.
The processes of going from powder production to end product or end use are also modified to the extent the powdets, and methods of producing the same, produce inodified impurity profiles and morphology.

The mill products and fabricated parts manufacture can involve remelting, casting, annealing, dispersion strengthening and other well known per se artifacts. The end products made through further reaction of the metal powders can include high purity oxides, nitrides, silicides and still further derivatives such as complex ceramics used in ferroelectrics and in optical applications, e.g. perovskite structtire PMW
compounds.

. t.

-49-It will now be apparent to those skilled in the art that other etnbodiments, improve-ments, details, and uses can be made consistent with the letter and spirit of the fore-going disclosure and within the scope of this patent, wliich is liniited only by the following claims, construed in accordance with the patent law, including the doctrine of equivalents.

Claims (23)

CLAIMS:

1. A process for producing (i) a Ta or Nb metal powder, (ii) a Ta/Nb alloy powder or (iii) the powder of (i) or (ii) further alloyed with one or more metals selected from the group consisting of Ti, Mo, W, Hf, V and Zr, comprising the steps of:

(a) providing a powdered oxide or mixed oxides of the metal or metals defined in (i), (ii) or (iii), the powdered oxide or mixed oxides being in a porous solid form with high access throughout the mass thereof by a gaseous reducing agent as defined in (b);

(b) generating a gaseous reducing agent selected from the group consisting of Mg, Ca, Al, Li, Ba, Sr and a hydride thereof at a site outside the powdered oxide or mixed oxides mass and passing the gaseous reducing agent through the mass at an elevated temperature; and (c) selecting the gaseous reducing agent and the powdered oxide or mixed oxides, porosity of the powdered oxide or mixed oxides, temperature and time of the reduction reaction for substantially complete reduction of the powdered oxide or mixed oxides to free the metal (i) or alloy (ii) or (iii), wherein the residual oxide formed in the reaction is removed by leaching;

whereby a high surface area powder is formed in a process that essentially avoids use of a molten state reducing agent in the production of the metal (i) or alloy (ii) or (iii) powder.

2. A process for producing (i) a Nb metal powder or (ii) the powder of (i) alloyed with one or more metals selected from the group consisting of Ti, Mo, W, Hf, V and Zr, comprising the steps of:

(a) providing a powdered oxide or mixed oxides of the metal or metals defined in (i) or (ii), the powdered oxide or mixed oxides being in a porous solid form with high access throughout the mass thereof by a hydrogen containing gas;

(b) passing the hydrogen containing gas through the mass at an elevated temperature;

(c) selecting the porosity of the powdered oxide or mixed oxides, temperature and time of the reduction reaction to remove at least 20% of the oxygen contained in the powdered oxide or mixed oxides to produce a suboxide;
and (d) further reducing the suboxide in a second stage with the reducing agent as defined in step (b) of claim 1, thereby substantially completely reducing the suboxide to free the metal (i) or alloy (ii).

3. The process according to claim 2, wherein the reduction in stage (b) is carried out at least until the volume of solid matter is reduced by 35 to 50%.

4. The process according to claim 2 or 3, wherein the reduction in stage (b) is conducted as far as MeO x, wherein Me represents Nb and x is 1 to 2.

5. The process according to any one of claims 2 to 4, wherein the reduction product from stage (b) is maintained at a temperature of from 1100 to 1500°C for a further 60 to 360 minutes.

6. The process according to any one of claims 2 to 4, wherein Mg, Ca or a hydride thereof is used as the reducing agent in stage (d).

7. The process according to any one of claims 1 to 6, wherein the metal (i) or alloy (ii) or (iii) powder is processed from an agglomerated primary produced form to an agglomerated secondary form.

8. The process according to any one of claims 1 to 7, wherein the produced metal powder is further deoxidized by further exposure to the gaseous reducing agent.

9. The process according to claim 1, wherein the metal (i) consists essentially of tantalum and the oxide is tantalum pentoxide.

10. The process according to claim 1, wherein the metal consists essentially of niobium, tantalum or a mixture thereof and the oxide consists essentially of niobium pentoxide, tantalum pentoxide or a mixture thereof, or a niobium suboxide.

11. The process according to claim 10, wherein the oxide contains tantalum in an amount of up to 50 at.% based on the total content of the metal.

12. The process according to any one of claims 1 to 11, wherein the oxide mass provides a void volume of at least 90%.

13. The process according to any one of claims 1 to 12, wherein the oxide is provided in the form of agglomerated primary oxide particles with diameters of between 100 to 1000 nm and an average agglomerate size of 10 to 1000 µm (Mastersizer D50).

14. The process according to any one of claims 1 to 13, wherein the gaseous reducing agent is magnesium.

15. The process according to any one of claims 1 to 4 and 6 to 14, wherein the elevated temperature in stage (b) is below 0.5 TM, wherein TM is the melting point of the powdered oxide or mixed oxides.

16. The process according to claim 15, wherein the temperature is below 0.4 TM.

17. The process according to any one of claims 1 to 16, wherein the produced metal powder is subjected to a further deoxidation treatment to produce a finished powdered metal or alloy.

18. The process according to claim 17, wherein one or more finishing deoxidation steps are provided as an extension of the reduction reaction.

19. The process according to claim 18, wherein the finishing deoxidation is a separate treatment.

20. The process according to any one of claims 1 to 19, wherein the produced metal powder is processed to the agglomerated secondary form.

21. The process according to claim 20, wherein one of the one or more finishing deoxidation steps is applied to the agglomerated secondary form of the metal powder.

22. The process according to any one of claims 1 to 21, wherein the produced metal powder is further formed by pressing and sintering into a coherent porous mass.

23. The metal powder produced according to the process of claim 4 or 5, having a mean particle size D50-value according to Mastersizer of 20 to 250 µm.