A TI-ZR ALLOY POWDER AND AN ANODE CONTAINING THE SAME

Abstract

A Ti-Zr alloy in powder form is described. Sintered granules containing the Ti-Zr alloy powder of the present invention, as well as capacitor anodes, are also described.

Description

A Ti-Zr alloy powder and an anode containing the same CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit pursuant to 35 USC §119(e) of prior US Provisional Patent Application No. 62 / 839,807 filed on April 29, 2019, which is incorporated herein by reference in its entirety. FIELD OF INVENTION The present invention relates to titanium-zirconium (Ti-Zr) alloy powders and the use of these alloy powders to form sintered granules and capacitor anodes and the like. Methods for manufacturing these are described in further detail. BACKGROUND OF THE INVENTION Although tantalum and, occasionally, niobium have been readily used in powder form to create sintered granules and ultimately capacitor anodes, there is a desire to use alternative materials for various reasons, including cost. Another reason is to work with materials that have a higher dielectric constant compared to tantalum oxide, allowing for a higher theoretical CV / g with a comparable CV / cc. Furthermore, a metal like titanium oxide can have significant leakage, but, as shown in the present invention, a zirconium-titanium alloy can exhibit lower leakage compared to titanium alone. As described in US Patent No. 3,599,053, pure titanium has been considered for potential use as a capacitor electrode material due to the high dielectric constant of its oxide and other desirable properties such as corrosion resistance and low density. However, it has proven difficult to create a superior dielectric oxide film on the surface of titanium with respect to leakage current at high voltages. This drawback of titanium hinders its widespread use as an electrode in electrolytic capacitors, despite its high dielectric constant and good sinterability. Furthermore, a porous titanium body can exhibit inferior leakage current when formed in a solid electrolytic capacitor. US Patent No. 3,649,880 describes a mixture of titanium powder with zirconium powder used for anodes, but the material identified as an alloy in this patent is a powder metallurgy-type product that is a mixture of sintered powders and is not particles or material that has a Ti-Zr phase, which is generally ZQQ L LO / LZnZ / E / YILI is a solid solution of titanium and zirconium. Therefore, there is a need to develop true titanium and zirconium alloys and provide products made from them that overcome one or more of the problems / disadvantages described above. BRIEF DESCRIPTION OF THE INVENTION A feature of the present invention is to provide a titanium-zirconium alloy that is in powder or particle form and is a solid solution of titanium and zirconium. An additional feature of the present invention is to provide a titanium-zirconium alloy in powder or particle form that can be used in the formation of sintered granules. Furthermore, a feature of the present invention is to provide a titanium-zirconium alloy having a dendritic structure or having a nodular shape. An additional feature of the present invention is to provide a titanium-zirconium alloy powder that is useful for forming anodes for capacitors. To achieve these and other advantages, and in accordance with the purposes of the present invention, as fully implemented and described herein, the present invention provides a Ti-Zr alloy in powder form. The Ti-Zr alloy powder may have a dendritic structure and / or a nodular form. The Ti-Zr alloy powder may be substantially devoid of other elements (other than Ti and Zr). The Ti-Zr alloy powder may have one or more beneficial properties that enable the powder to be useful for forming sintered granules and ultimately anodes, thereby providing one or more suitable capacitor properties such as electrical leakage control and / or other properties associated with anodes. The present invention further relates to a titanium-zirconium (Ti-Zr) alloy powder having a Ti-to-Zr atomic ratio of 10:90 to 90:10. The Ti-Zr alloy powder may have an average primary particle size of 500 nm to 2 microns. The Ti-Zr alloy powder may further include a Ti-Zr oxide layer on the Ti-Zr alloy powder. The Ti-Zr alloy powder may also include phosphorus. Further options and details regarding the Ti-Zr alloy powder are provided herein. The additional features and advantages of the present invention will be partly set forth in the following description, and partly will be evident from the description, or can be learned through the practice of the present invention. The objectives and other 7QQ L LO / LZnZ / E / YILI The advantages of the present invention shall be realized and achieved by means of the elements and combinations indicated particularly in the description and the attached claims. It should be understood that both the above general description and the following detailed description are merely illustrative and explanatory and are intended to provide further explanation of the present invention, as claimed. The accompanying drawings, which are incorporated herein and form a part of this application, illustrate some of the features of the present invention and, together with the description, serve to explain the principles of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1A and Figure 1B are SEM photographs of an example of the Ti-Zr alloy powder of the present invention, where Figure 1B has a higher magnification. Figure 2 is a diagram showing an exemplary part of the process for forming the Ti-Zr alloy powders of the present invention. Figure 3 is a schematic diagram showing an embodiment of the various steps leading to the formation of the Ti-Zr alloy powder of the present invention. Figure 4A and Figure 4B are an XRD analysis showing a) pure zirconium, b) Ti-15 in % Zr-85 in %, c) Ti-40 in Zr-60 in d) Ti-50 in Zr-50 in % of the examples of the present invention. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to Ti-Zr alloy powders. The Ti-Zr alloy powder is not a mere physical mixture of titanium and zirconium, nor is the Ti-Zr alloy powder of the present invention considered a mechanical mixture of the two elements. Instead, the Ti-Zr alloy powder of the present invention is a powder comprising a plurality of particles, each particle or nearly all particles having at least one Ti-Zr phase, which is generally a solid solution of titanium and zirconium. Ti-Zr alloy powders can have a dendritic structure. Ti-Zr alloy powders can have a nodular shape. Ti-Zr alloy powders can have both a dendritic structure and a nodular shape. For the purposes of the present invention, a dendritic configuration or shape is understood to be a particle having branched structures and / or erratic winding paths of individual branches. The term is understood in the art and is referenced, for example, in Modeling ZQQ L LO / ίΖΠΖ / Β / ΥΙΛΙ Dendritic Shapes Using Path Planning by Lingxhu et al. In addition, Figure 1A and Figure 1B show examples of dendritic configurations and shapes. Ti-Zr alloy powder can have an atomic ratio of Ti to Zr of approximately 10:90 to approximately 90:10, such as, but not limited to, an atomic ratio of Ti to Zr of 20:80 to 80:20, or 30:70 to 70:30, or 40:60 to 60:40. As a further example, Ti-Zr alloy powder can contain 50% Zr, or approximately 20% to approximately 40% Zr, or approximately 30% to approximately 40% Zr. As an option, the Ti-Zr alloy powder has a Ti-Zr primary phase that is at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 99%. For example, the Ti-Zr alloy powder can have a Ti-Zr primary phase of approximately 10% to 99.99%, or approximately 10% to 95%, or approximately 10% to 90%, and so on. Ti-Zr alloy powder can be particles consisting of a homogeneous single-phase solid solution of Ti and Zr. As an option, titanium-zirconium alloy powder can be considered a binary Ti-Zr alloy powder. Ti-Zr alloy powder may have less than 500 ppm of individual grains of titanium or zirconium or both, such as less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm or less than 1 ppm of individual grains of titanium or zirconium or both. The Ti-Zr alloy powder of the present invention may be a powder that is in the substantial absence of elements other than Ti and Zr. For example, the non-gaseous elements (e.g., non-gaseous elements in general or non-gaseous metallic elements) present in the Ti-Zr alloy powder, other than Ti and Zr, may be present in an amount of less than 1% by weight, such as from approximately 0.1 ppm to approximately 500 ppm, or from approximately 1 ppm to 250 ppm, or from approximately 1 ppm to 100 ppm, or from approximately 1 ppm to 50 ppm, or less than 50 ppm, or less than 25 ppm, or less than 500 ppm, based on the weight of the alloy powder. Ti-Zr alloy powder can have less than 50 ppm of elemental carbon, ZQQ L Ln / ίΖΠΖ / Β / ΥΙΛΙ such as less than 40 ppm carbon, less than 30 ppm carbon, less than 20 ppm carbon, less than 10 ppm carbon, less than 5 ppm carbon, less than 1 ppm carbon, such as 0 ppm to 49 ppm or 0.1 ppm to 20 ppm or 0.1 ppm to 2 ppm. As an option, the titanium-zirconium alloy powder can have an oxygen content of approximately 0.1% by weight to approximately 5% by weight (e.g., approximately 0.1% by weight to approximately 4% by weight, approximately 0.1% by weight to approximately 3% by weight, approximately 0.1% by weight to approximately 2% by weight, approximately 0.1% by weight to approximately 1% by weight, approximately 0.2% by weight to approximately 5% by weight, approximately 0.3% by weight to approximately 5% by weight, approximately 0.5% by weight to approximately 5% by weight, approximately 1% by weight to approximately 5% by weight), based on the weight of the powder. As an option, the titanium-zirconium alloy powder can have a nitrogen content of approximately 0.01% by weight to approximately 20% by weight (e.g., approximately 0.01% by weight to approximately 15% by weight, approximately 0.01% by weight to approximately 10% by weight, approximately 0.01% by weight to approximately 5% by weight, approximately 0.01% by weight to approximately 1% by weight, approximately 0.05% by weight to approximately 20% by weight, approximately 0.1% by weight to approximately 20% by weight, approximately 0.5% by weight to approximately 20% by weight, approximately 1% by weight to approximately 20% by weight), based on the weight of the powder. As an option, the titanium-zirconium alloy powder can have a phosphorus content of approximately 0.01% by weight to approximately 5% by weight (e.g., from approximately 0.1% by weight to approximately 4% by weight, from approximately 0.1% by weight to approximately 3% by weight, from approximately 0.1% by weight to approximately 2% by weight, from approximately 0.1% by weight to approximately 1% by weight, from approximately 0.2% by weight to approximately 5% by weight, from approximately 0.3% by weight to approximately 5% by weight, from approximately 0.5% by weight to approximately 5% by weight, from approximately 1% by weight to approximately 5% by weight), based on the weight of the powder. As an option, titanium-zirconium alloy powder can have a hydrogen content of approximately 0.01% by weight to approximately 5% by weight (e.g., from approximately 0.1% by weight to approximately 4% by weight, ZQQ L LO / LZnZ / E / YILI from approximately 0.1% by weight to approximately 3% by weight, from approximately 0.1% by weight to approximately 2% by weight, from approximately 0.1% by weight to approximately 1% by weight, from approximately 0.2% by weight to approximately 5% by weight, from approximately 0.3% by weight to approximately 5% by weight, from approximately 0.5% by weight to approximately 5% by weight, from approximately 1% by weight to approximately 5% by weight), based on the weight of the powder. The use of a gas such as nitrogen, phosphorus and / or hydrogen can also serve as a passivating agent to further stabilize the Ti-Zr alloy powder. As an option, the titanium-zirconium alloy powder (excluding the optional oxide layer) may consist of less than 500 ppm of elements other than Ti, Zr, O, and P, such as less than 100 ppm of elements other than Ti, Zr, O, and P (e.g., 0 ppm to 99 ppm, 1 ppm to 75 ppm, 1 ppm to 50 ppm, 1 ppm to 25 ppm, 1 ppm to 10 ppm, less than 5 ppm). These ppm limits as set forth in the present invention may apply to one element, more than one element, or all of the elements stated. As an option, the Ti-Zr alloy powder can also include a layer of Ti-Zr oxide over the titanium-zirconium alloy powder. The Ti-Zr oxide layer can be approximately 1 nm to approximately 20 nm thick or more, such as approximately 5 nm to approximately 20 nm or approximately 10 nm to approximately 20 nm. As an option, the Ti-Zr oxide layer, if present, can partially or completely encapsulate the titanium-zirconium alloy powder. For example, more than 95% by volume, more than 99% by volume, more than 99.9% by volume, or 100% by volume of the Ti-Zr powder can have an oxide layer on its surface that encapsulates more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 95%, more than 99%, or 100% of the available external surface area of ​​the Ti-Zr powder. As an option, the Ti-Zr oxide layer may also include phosphorus. If present, phosphorus may be present at a level of approximately 1 ppm to 5,000 ppm, or approximately 50 ppm to approximately 5,000 ppm, such as approximately 100 ppm to 4,000 ppm, or 200 ppm to approximately 5,000 ppm, or approximately 100 ppm to 3,000 ppm, or approximately 100 ppm to 2,000 ppm. ZQQ L LO / LZnZ / Ε / ΥΙΛΙ ppm, or from approximately 100 ppm to 1,000 ppm or from approximately 100 ppm to 500 ppm. Regarding particle sizes and distributions, Ti-Zr can have a variety of particle sizes and / or distributions. The Ti-Zr alloy powder of the present invention may have an average primary particle size of approximately 500 nm to approximately 2 micrometers, or sizes below or above this range. Examples of sizes include, but are not limited to, approximately 600 nm to 2 micrometers, 600 nm to 1.5 micrometers, 600 nm to 1 micrometer, and the like. For example, titanium-zirconium alloy powder may have a D10 and D90 that is within 35% of D50. Titanium-zirconium alloy powder may have a D10 and D90 that is within 25% of D50. Titanium-zirconium alloy powder can have a D10 of approximately 0.3 micrometers to approximately 10 micrometers (e.g., from approximately 0.5 micrometers to approximately 7 micrometers, or from approximately 1 micrometer to approximately 5 micrometers, or from approximately 2 micrometers to approximately 8 micrometers), and / or a D50 of approximately 0.5 micrometers to approximately 400 micrometers (e.g., from approximately 0.5 micrometers to approximately 300 micrometers, from approximately 0.5 micrometers to approximately 200 micrometers, from approximately 0.5 micrometers to approximately 100 micrometers, from approximately 0.5 micrometers to approximately 50 micrometers, from approximately 1 micrometer to approximately 400 micrometers, from approximately 5 micrometers to approximately 400 micrometers, from approximately 10 micrometers to approximately 400 micrometers, from approximately 20 micrometers to approximately 400 micrometers, from approximately 50 micrometers to approximately 400 micrometers). mieras, from approximately 100 mieras to approximately 400 mieras),and / or a D90 of approximately 1 mi to approximately 700 mi (for example, from approximately 1 mi to approximately 600 mi, from approximately 1 mi to approximately 500 mi, from approximately 1 mi to approximately 400 mi, from approximately 1 mi to approximately 300 mi, from approximately 1 mi to approximately 200 mi, from approximately 1 mi to approximately 200 mi, from approximately 1 mi to approximately 100 mi, from approximately 5 mi to approximately 700 mi, from approximately 10 mi to approximately 700 mi, from approximately 20 mi to approximately 700 mi, from approximately 40 mi to approximately 700 mi, from approximately 50 mi to approximately 700, ZQQ L Ln / ίZΖΠZ / Β / YΙΛΙ mieras, from approximately 75 mieras to approximately 700 mieras, from approximately 100 mieras to approximately 700 mieras). Titanium-zirconium alloy powder can have a BET surface area of ​​approximately 0.1 m2 / ga to approximately 20 m2 / ga or higher, such as approximately 0.5 m2 / ga to approximately 20 m2 / g, approximately 1 m2 / ga to approximately 20 m2 / g, approximately 3 m2 / ga to approximately 20 m2 / g, approximately 5 m2 / ga to approximately 20 m2 / g, approximately 0.1 m2 / ga to approximately 15 m2 / g, approximately 0.1 m2 / ga to approximately 10 m2 / g, approximately 0.1 m2 / ga to approximately 5 m2 / g, or approximately 0.3 m2 / ga to approximately 2 m2 / g. As an additional example, a Ti-Zr alloy powder may have a BET of 5 m2 / go less with an average particle size of approximately 400 nm to 600 nm, or 500 nm to 600 nm. Alternatively, titanium-zirconium alloy powder can be considered an oxide-free metallic powder (excluding any oxide layer that may be present). In other words, Ti-Zr powder does not contain an oxide as part of the alloy itself, as an option. The Ti-Zr alloy powder of the present invention can have a fractal dimension of approximately 1.9 to approximately 3, such as approximately 2 to approximately 3, or approximately 2.0 to 2.95, or approximately 2.2 to 2.8, or approximately 2 to approximately 2.2. The fractal dimension can be calculated, for example, using the Hausdorff method or the Minkowski-Bouligand method, or it can be determined using the modified box-counting method and the numerical calibration curves provided by Wozniak et al. in the Journal of Aerosol Science, ISSN: 0021-8502, Vol: 47, Page: 12-26) (incorporated by reference in its entirety herein). The Ti-Zr alloy powders of the present invention may have one or more of the following parameters, wherein any combination of these parameters may be present in the Ti-Zr alloy powders. Average Particle Size: from 500 nm to 2 microns Mesh Size (US): -400 to -40 Scott density: from approximately 6 g / in3 to approximately 30 (e.g., 6 g / in3 to 13 g / in3). 7QQ L LO / LZnZ / E / YILI The Ti-Zr alloy powders of the present invention, as stated above, may have a purity (with respect to Ti-Zr) of at least 99% by weight, such as at least 99.5% by weight, at least 99.9% by weight, at least 99.99% by weight, at least 99.995% by weight and the like, wherein the weight percent refers to the alloy powder by weight (and excludes any oxide layer or other layer that may be present). The Ti-Zr alloy powders of the present invention may be porous or have porosity. The Ti-Zr alloy powders of the present invention may be agglomerated or non-agglomerated. If agglomerated, the agglomerate sizes may range from approximately 10 to approximately 500,000 primary particles. As an option, the Ti-Zr alloy powders can be doped with one or more dopants, such as nitrogen, phosphorus, carbon, boron, and / or hydrogen, or any combination thereof. The amount of dopant present in the Ti-Zr alloy powders of the present invention can be any suitable amount, such as from approximately 10 ppm to 1,000 ppm, approximately 50 ppm to 1,000 ppm, approximately 100 ppm to 1,000 ppm, approximately 200 ppm to 1,000 ppm, approximately 350 ppm to 1,000 ppm, or more. The dopants can be present as a solid solution or as compounds with the metallic elements or other dopants, including oxygen. The Ti-Zr alloy powder of the present invention can be formed into a sintered granule and used to form an anode and ultimately be present as part of a capacitor. The capacitor or anode within the capacitor can be wet or dry. In the present invention, the sintered granule may comprise, essentially consist of, or include the Ti-Zr alloy powders of the present invention, wherein the Ti-Zr alloy powder is pressed and sintered. For example, the Ti-Zr alloy powder may be pressed into any size or shape, for example, a cylindrical shape, a square shape, or another geometric shape, and preferably a shape suitable for the purposes of an anode. The TiZr powder of the present invention may be pressed, for example, to form a green body, and this pressing may occur at a pressing density of approximately 1.2 to approximately 3.0 g / cm³. The sintering to form the sintered granule may occur at a temperature of approximately 400°C to approximately 1200°C. The sintering times may be any time suitable for forming a ZQQ L LO / LZnZ / E / YILI synthesized granule, for example, for a time of approximately 1 minute to 60 minutes or more. As an option, the sintered granule may further comprise a conductive wire embedded at least partially within the sintered granule. This conductive wire may be a metallic conductor wire, such as one made of a Ti-Zr alloy material, or titanium itself, or zirconium itself, or tantalum, or niobium, or another electrically conductive material, such as aluminum and the like. As indicated, the present invention further relates to a capacitor anode comprising at least one sintered granule of the present invention. As indicated, the granule can have any shape or dimension. The capacitor anode of the present invention can have a capacitance of at least 1,000 pFV / g. For example, the capacitance can be at least 5,000 pFV / g, at least 10,000 pFV / g, for example, from approximately 1,000 pFV / g to approximately 50,000 pFV / g, from approximately 10,000 pFV / g to approximately 100,000 pFV / g, from approximately 50,000 pFV / g to approximately 150,000 pFV / g, or from approximately 1,000 pFV / g to approximately 260,000 pFV / g and higher. The capacitor anode of the present invention may have a DC leakage of less than 15 nA / pFV, such as less than 10 nA / pFV, or less than 5 nA / pFV, such as from approximately 0.1 nA / pFV to 5 nA / pFV, or from 0.1 nA / pFV to 10 nA / pFV. With the present invention, the sintered granule or capacitor anode, when anodized, forms an anodic oxide film on the anode surface. With the present invention, this anodic film comprises, essentially consists of, or comprises one or more oxides. The one or more oxides may or may not be amorphous, or may be only amorphous. With the present invention, the oxide crystals may, optionally, be significantly reduced, be nonexistent, or be at such a negligible level that they do not affect the overall performance of the capacitor anode. For example, the oxide crystals, if present, would be less than 5% by volume, or less than 1% by volume depending on the total volume of the anodic film. The anodic film may be, include, or form part of a passivation layer, or it may be considered a passivation layer. The thickness of this film may be from approximately 5 nm to approximately 600 nm, or from approximately 20 nm to approximately 600 nm thick, or more. The anode of the present invention can have a cumulative porosity of approximately 0.1 ml / ga, approximately 0.6 ml / g, such as approximately 0.1 ml / ga, approximately 0.5 ml / ga, or approximately 0.2 ml / ga. ZQQ L LO / LZnZ / E / YILI 0.4 ml / g. The present invention further relates to a method for forming a capacitor anode comprising the Ti-Zr alloy powder of the present invention. The method includes forming the Ti-Zr alloy powder into the shape of an anode and sintering it at a suitable sintering temperature, such as from approximately 400°C to approximately 1200°C for a time, for example, from approximately 1 minute to approximately 30 minutes or more. Then, as an option, the anodization of the sintered material can occur, for example, at an anodizing voltage of approximately 10 volts to approximately 200 volts or from approximately 10 volts to approximately 75 volts or more at a forming temperature of approximately 10°C to approximately 80°C. Other forming voltages and / or other forming temperatures may be used.The anode can then be tempered, for example, at a temperature of approximately 300 °C to approximately 350 °C for a period of approximately 10 minutes to approximately 60 minutes or more. Alternatively, the anode can be manganized, for example, at a temperature of 220 °C to approximately 280 °C or other temperatures. When forming the anode, the Ti-Zr alloy powder can be mixed with at least one binder and / or at least one lubricant to form the pressed anode. Therefore, the pressed anode may comprise, essentially consist of, or consist of a pressed Ti-Zr alloy powder of the present invention with at least one binder and / or at least one lubricant. To form the Ti-Zr alloy powders of the present invention, a flame-forming process is preferably used, for example, one similar to the processes described in U.S. Patent Nos. 7,442,227 and 5,498,446, incorporated herein by reference in their entirety. More specifically, an alkali metal feed, preferably a sodium feed, is injected into a flame reactor, and separate feeds of a titanium-containing halide and a zirconium-containing halide are introduced into the flame reactor. The Ti-containing halide can be TiCu, and the Zr-containing halide can be ZrCl4. These three feeds are then introduced (for example, injected) into the flame reactor. The titanium halide and zirconium halide feeds can be combined before entering the flame reactor or introduced separately.The introduction of the feeds can generally be carried out in an inert gas environment, such as argon. In the flame reactor, various feeds can be used as an option. The feeds can be converted into steam or fed to the reactor as steam. Titanium and zirconium halides react with the alkali metal to form Ti-Zr alloy powders, which are typically in the presence of a halide, such as sodium chloride. As shown, for example, in Figure 3, the primary particles nucleate and grow, eventually forming aggregates of these particles. These aggregates can be encapsulated within a salt, such as sodium chloride, and eventually solidify, encapsulating the Ti-Zr alloy powders within the salt. Excess sodium is then removed using various techniques, and the salt-coated Ti-Zr alloy particles are generally collected using a particle collection system or filters, which may be under an inert gas or other non-reactive environment.Alternatively, further heat treatment can be performed in an inert gas or vacuum environment, which can increase the primary particle size. Finally, the sodium chloride can be removed (e.g., by washing, dissolving, or sublimation), and the Ti-Zr alloy powder is recovered. Figure 2 shows a preferred method of introducing the reagents into the flame reactor. As can be seen in Figure 2, flow straighteners can be used to maintain the feeds in a suitable direction and alignment, and preferably, the reagents are enveloped in an inert environment, as shown in Figure 2. The XRDs of example Ti-Zr alloys of the present invention are shown in Figures 4A and 4B and compared with pure zirconium. The present invention will be further clarified by the following examples, which are intended to be exemplary of the present invention. EXAMPLES Example 1 A salt-encapsulated alloy powder with a Ti to Zr mass ratio of 27:63 was manufactured by flame synthesis as described in U.S. Patent No. 7,442,227 and as shown in Figure 2. Vaporized titanium chloride and zirconium chloride (halides) were introduced with argon into a reactor through a central tube at a TiCl4 to ZrCl4 mass ratio of 0.67. A concentric Ar flow was placed between the halides and the excess vaporized sodium flow. As described in U.S. Patent No. 7,442,227, the sodium chloride byproduct acted as a condensable vapor to inhibit the sintering behavior of the particles. This salt-encapsulated metal powder was collected and washed with deionized water to remove the sodium chloride coating. Dilute nitric acid was used to aid particle sedimentation.This washing process introduced a thin oxide passivation layer onto the particle surface, which was retained while the particles were vacuum dried. The resulting zirconium-titanium alloy was then pressed to a density of 2.0 g / cm³ and sintered for 30 minutes under vacuum at 500 °C. Anodizing was performed at 25 °C using a voltage of 30 V for 18 hours with a 0.1 M ammonium pentaborate electrolytic solution. For the resulting anode, the leakage current was determined after 2 minutes of applying a 21 V DC voltage to a 10 wt% phosphoric acid solution. The capacitance was also determined at a frequency of 100 Hz in the same phosphoric acid solution with a 2 V bias. The capacitance was 260 mFV / g with a leakage current of 7 nA / CV. Example 2 A salt-encapsulated alloy powder having a Ti to Zr mass ratio of 27:63 was fabricated by the flame synthesis process and washed as in Example 1, then pressed and sintered for 30 minutes at 500 °C as in Example 1. Anodizing was performed at 25 °C using a voltage of 10 V for 12 hours with a 0.1 M ammonium pentaborate electrolytic solution. For the resulting anode, the leakage current was determined after 2 minutes of applying a 7 V DC voltage to a 10 wt% phosphoric acid solution. The capacitance was also determined at a frequency of 100 Hz in the same phosphoric acid solution with a 2 V bias. The capacitance was 140 mFV / g with a leakage current of 120 nA / CV. Example 3 A salt-encapsulated alloy powder with a Ti to Zr mass ratio of 15:85 was prepared by flame synthesis with 2.5 wt% nitrogen doping, as in Example 1, except for the reagent quantities and the nitrogen doping. The nitrogen doping was achieved by introducing a small amount of nitrogen into the argon flow between the halides and concentric with the sodium vapor flow. It was determined that all the nitrogen had reacted with the powder. The resulting powder was washed as in Example 1, then pressed to 1.7 g / cm³ and sintered for 30 minutes at 550 °C under vacuum. The XRD of this alloy is shown in Figures 4A and 4B. Anodizing was performed at 25 °C using a voltage of 30 V for 6 hours. ZQQ L LO / LZnZ / E / YILI with a 0.1 M electrolytic solution of ammonium pentaborate. For the resulting anode, the leakage current was determined after 2 minutes of applying a 21 V DC voltage to a 10 wt% phosphoric acid solution. The capacitance was also determined at a frequency of 100 Hz in the same phosphoric acid solution with a 2 V bias. The capacitance was 200 mFV / g with a leakage of 340 nA / CV. Example 4 A salt-encapsulated alloy powder with a Ti to Zr mass ratio of 27:63 was prepared by flame synthesis as in Example 1, and the product was divided into six batches. A dilute solution of nitric acid, hydrogen peroxide, sulfuric acid, phosphoric acid, ammonium pentaborate, or sodium acetate was used to remove sodium chloride from the surface of the alloy powder. The resulting powders were then pressed and sintered for 30 minutes at 500 °C as in Example 1. Anodizing was carried out at 25 °C using a voltage of 30 V for 24 hours with a 0.1 M ammonium pentaborate electrolytic solution. For the resulting anodes, the leakage current was determined after 2 minutes of applying a 7 V DC voltage in a 10 wt% phosphoric acid solution. The capacitance was also determined at a frequency of 100 Hz in the same phosphoric acid solution with a 2 V bias. The difference in average anode capacitance was not found to be statistically significant once a broken anode was excluded, but the leakage results are summarized in the following table: ZQQ L LO / LZnZ / E / YILI Leakage Solution (nA / CV, standardized to anodes washed in HNO3 solution) Nitric acid (0.1 M) 1.0 Hydrogen peroxide (3% wt) 1.4 Sulfuric acid (1.0 M) 0.46 Phosphoric acid (0.1 M) 0.22 Ammonium pentaborate (0.1 M) 0.81 Sodium acetate (0.1 M) 0.34 The powder was found to have significant phosphorus doping after being treated with an initial phosphoric acid wash, followed by additional washing with DI water and nitric acid, and then drying. The present invention includes the following aspects / embodiments / features in any order and / or in any combination: 1. The present invention relates to a titanium-zirconium (Ti-Zr) alloy powder comprising an atomic ratio of Ti and Zr of 10:90 to 90:10, and having an average primary particle size of 550 nm to 2 microns. 2. The titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder further comprises a Ti-Zr oxide layer on said titanium-zirconium alloy powder. 3. The titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said Ti-Zr oxide layer further comprises phosphorus. 4. The titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said Ti-Zr oxide layer further comprises phosphorus at a level of approximately 50 ppm to approximately 5,000 ppm. 5. The titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said Ti-Zr oxide layer further comprises phosphorus at a level of approximately 200 ppm to approximately 5,000 ppm. 6. The titanium-zirconium alloy powder according to any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder further comprises a Ti-Zr oxide layer on said titanium-zirconium alloy powder and said Ti-Zr oxide layer has a thickness of approximately 5 nm to approximately 20 nm. 7. The titanium-zirconium alloy powder in accordance with any above or following embodiment / feature / aspect, wherein said titanium-zirconium alloy powder further comprises a Ti-Zr oxide layer that completely encapsulates said titanium-zirconium alloy powder. 8. Titanium-zirconium alloy powder in accordance with any above or following embodiment / feature / aspect, wherein said titanium-zirconium alloy powder consists of particles comprising a homogeneous single-phase solid solution of Ti and Zr. 9. Titanium-zirconium alloy powder in accordance with any foregoing or following embodiment / feature / aspect, wherein said titanium- 7QQ L Ln / Lznz / E / YILI zirconium has less than 50 ppm of carbon. 10. Titanium-zirconium alloy powder conforming to any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy has less than 500 ppm of individual grains of titanium or zirconium or both. 11. Titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder has a D10 and D90 that is within 35% of D50. 12. Titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder has a D10 and D90 that is within 25% of D50. 13. The titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder has a D10 of approximately 0.3 miers to approximately 10 miers, a D50 of approximately 0.5 miers to approximately 400 miers, and a D90 of approximately 1 mier to approximately 700 miers. 14. Titanium-zirconium alloy powder in accordance with any above or following embodiment / feature / aspect, wherein said titanium-zirconium alloy powder has an oxygen content of approximately 0.1% by weight to approximately 5% by weight. 15. Titanium-zirconium alloy powder in accordance with any above or following embodiment / feature / aspect, wherein said titanium-zirconium alloy powder has a nitrogen content of approximately 0.01% by weight to approximately 20% by weight. 16. The titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder has a BET surface area of ​​approximately 0.1 m2 / ga or approximately 20 m2 / g. 17. Titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder, excluding any oxide layer present, is a non-metallic oxide powder. 18. Titanium-zirconium alloy powder in accordance with any above or below embodiment / feature / aspect, wherein said titanium-zirconium alloy powder is a binary Ti-Zr alloy powder. 19. Titanium-zirconium alloy powder in accordance with any ZQQ L LO / ίZРZ / Β / YΙΛΙ realization / feature / aspect prior or following, wherein said titanium-zirconium alloy has less than 500 ppm of elements other than Ti, Zr, O, N, H and P. 20. Titanium-zirconium alloy powder in accordance with any above or following embodiment / feature / aspect, wherein said titanium-zirconium alloy has less than 100 ppm of elements other than Ti, Zr, O and P. 21. A sintered granule comprising titanium zirconium alloy powder in accordance with any above or below embodiment / feature / aspect that is shaped into a granule and is sintered. 22. A condenser anode comprising said titanium-zirconium alloy powder in accordance with any above or following embodiment / feature / aspect, which is pressed and sintered. 23. An electrolytic capacitor comprising the capacitor anode in accordance with any above or following embodiment / feature / aspect. 24. A method for forming a condenser anode comprising the Ti-Zr alloy in accordance with any above or following embodiment / feature / aspect, said method comprising forming said Ti-Zr alloy into the shape of an anode and sintering at a temperature of approximately 400 °C to approximately 1200 °C for a time of at least 1 minute; anodize between approximately 16 and approximately 200 volts; temper said anode to a temperature of approximately 300 to approximately 350 °C for a time of approximately 10 minutes to approximately 60 minutes; and manganize said anode. The present invention may include any combination of these various features or embodiments, as set forth in sentences and / or paragraphs. Any combination of the features described herein is considered part of the present invention, and no limitation is intended with respect to the combinable features. Applicants specifically incorporate the full content of all references cited in this disclosure. Furthermore, when an amount, concentration, or other value or parameter is provided as a range, preferred range, or list of upper preferred and lower preferred values, this should be understood as a specific description of all ranges formed from any pair of any upper range limit or preferred value and any lower range limit. ZQQ L LO / LZnZ / E / YILI or preferred value, regardless of whether the intervals are described separately. When a range of numerical values ​​is indicated in the present invention, unless otherwise stated, the range is intended to include its endpoints and all whole numbers and fractions within the range. The scope of the invention is not intended to be limited to the specific values ​​indicated in defining a range. Other embodiments of the present invention will become evident to those skilled in the art from consideration of this specification and the practice of the invention described herein. This specification and its examples are intended to be considered as examples only, with the true scope and spirit of the invention indicated by the following claims and their equivalents.

Claims

1. A titanium-zirconium (Ti-Zr) alloy powder comprising a Ti and Zr atomic ratio of 10:90 to 90:10 and having an average primary particle size of 550 nm to 2 microns.

2. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder further comprises a Ti-Zr oxide layer on said titanium-zirconium alloy powder.

3. The titanium-zirconium alloy powder according to claim 2, wherein said Ti-Zr oxide layer further comprises phosphorus.

4. The titanium-zirconium alloy powder according to claim 2, wherein said Ti-Zr oxide layer further comprises phosphorus at a level of approximately 50 ppm to approximately 5,000 ppm.

5. The titanium-zirconium alloy powder according to claim 2, wherein said Ti-Zr oxide layer further comprises phosphorus at a level of approximately 200 ppm to approximately 5,000 ppm.

6. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder further comprises a Ti-Zr oxide layer on said titanium-zirconium alloy powder and said Ti-Zr oxide layer has a thickness of approximately 5 nm to approximately 20 nm.

7. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder further comprises a Ti-Zr oxide layer that completely encapsulates said titanium-zirconium alloy powder.

8. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder consists of particles comprising a homogeneous single-phase solid solution of Ti and Zr.

9. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy has less than 50 ppm of carbon.

10. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy has less than 500 ppm of individual grains of titanium or zirconium or both.

11. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder has a D10 and D90 that is within 35% of D50. ZQQ L LO / LZnZ / E / YILI 12. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder has a D10 and D90 that is within 25% of D50.

13. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder has a D10 of approximately 0.3 micrometers to approximately 10 micrometers, a D50 of approximately 0.5 micrometers to approximately 400 micrometers, and a D90 of approximately 1 micrometer to approximately 700 micrometers.

14. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder has an oxygen content of approximately 0.1% by weight to approximately 5% by weight.

15. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder has a nitrogen content of approximately 0.01% by weight to approximately 20% by weight.

16. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder has a BET surface area of ​​approximately 0.1 m2 / ga or approximately 20 m2 / g.

17. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder, excluding any oxide layer present, is a non-metallic oxide powder.

18. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy powder is a binary Ti-Zr alloy powder.

19. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy has less than 500 ppm of elements other than Ti, Zr, O, N, H and P.

20. The titanium-zirconium alloy powder according to claim 1, wherein said titanium-zirconium alloy has less than 100 ppm of elements other than Ti, Zr, O and P.

21. A sintered granule comprising the titanium zirconium alloy powder according to claim 1, which is shaped into a granule and is sintered.

22. A capacitor anode comprising said titanium-zirconium alloy powder according to claim 1, which is pressed and sintered. ZQQ L LO / LZnZ / E / YILI 23. An electrolytic capacitor comprising the capacitor anode according to claim 22.

24. A method for forming a capacitor anode comprising the Ti-Zr alloy according to claim 1, said method comprising: forming said Ti-Zr alloy into the shape of an anode and sintering at a temperature of approximately 400 °C to approximately 1200 °C for a time of at least 1 minute; anodizing between approximately 16 and approximately 200 volts; quenching said anode at a temperature of approximately 300 to approximately 350 °C for a time of approximately 10 minutes to approximately 60 minutes; and manganizing said anode.