Method for manufacturing beryllium articles

Abstract

A method for grain refinement of a beryllium article is disclosed. Grain refinement enables the beryllium article to have beneficial properties in terms of strength and durability. The method disclosed herein exhibits efficient grain refinement using in situ formed beryllium intermetallic compounds.

Description

[Technical Field]

[0001] Priority claims

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 397,163, filed August 11, 2022, which is incorporated by reference in its entirety herein.

[0002]

[0002] This disclosure relates to methods of manufacturing beryllium articles, and more particularly to grain refinement of beryllium articles that generates nucleating agents in situ, leading to improved strength and processing. [Background technology]

[0003] Beryllium is a metal with highly desirable properties. These properties include high stiffness (Young's modulus = 287 GPa), low density (1.85 g / cc), high modulus of elasticity (130 GPa), high specific heat (1925 J / kg·K), high thermal conductivity (216 W / m·K), and a low coefficient of linear thermal expansion (11.4 × 10 6 / °K). As such, beryllium and its composites are useful in aircraft and spacecraft structures, high performance engines and brakes, and electronic components for thermal performance and vibration damping. Beryllium and its composites are also useful in a variety of different applications, including combustion applications, hypersonic vehicles, computer components, optical systems for space and ground systems, satellite structures, solar energy collection devices, and nuclear energy growth applications.

[0004] One limitation is that casting methods are not suitable for producing beryllium products, leading to columnar solidification. Beryllium is a highly reactive metal with a high melting point, and therefore easily reacts with the mold wall material to form beryllium compounds (e.g., BeO), which become trapped in the solidified metal. Furthermore, grain sizes exceed 500 microns, typically reaching 50,000 microns. This is too large to meet strength requirements, resulting in a brittle material. Further attempts to refine the grain size through machining have not met commercial success. To overcome the beryllium production problem, beryllium powder has been used. Beryllium powder can be formed by ball milling, disc grinding, or gas atomization. The powder is consolidated into ingots and further processed into beryllium molded parts. This powder processing requires careful handling of the beryllium powder. Furthermore, powder processing results in inefficiencies due to low material utilization, increasing costs. Powder processing also has limitations in forming complex shapes.

[0005]

[0005] There remains a need to eliminate columnar solidification in order to efficiently produce reduced grain size beryllium articles. Summary of the Invention

[0006]

[0006] The present disclosure relates to a method for making beryllium articles. In one embodiment, the method is a method for efficient grain refinement of beryllium, which provides improvements in strength and durability. In one embodiment, the method disclosed herein provides efficient grain refinement using an in situ formed beryllium intermetallic compound. In one embodiment, the in situ formed intermetallic compound may be a beryllide.

[0007] In one embodiment, a method for manufacturing a beryllium article includes the steps of depositing an initial layer on a surface, the initial layer comprising beryllium and at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium; forming a plurality of particles in the initial layer comprising an intermetallic compound of beryllium and the at least one metal; and dispersing the plurality of particles to form grains having an average grain size of 1 to 40 microns. A method is provided that includes inducing nucleation of beryllium on a portion, more preferably an outer portion, of the initial layer; depositing one or more successive layers on at least a portion of the initial layer opposite the surface, the one or more successive layers comprising beryllium and at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium; and repeating the forming and nucleating steps for one or more successive layers. The initial and successive layers may be deposited in a design or pattern to form a complex article of beryllium. In one embodiment, the initial layer may comprise 0.001 to 1.0 wt. % of at least one metal, based on the total weight of the initial layer. In one embodiment, the amount of the at least one metal may be similar in each of the successive layers. Thus, the one or more successive layers may comprise 0.001 to 1.0 wt. % of at least one metal, based on the total weight of the one or more successive layers. Intermetallic compounds produced in situ by this method include beryllides, such as beryllium-titanium (Be 12 Ti, Be2Ti), Beryllium-Chromium (Be2Cr, or Be 12 Cr), iron-beryllium (FeBe5), beryllium-zirconium (Be 13 Zr, Be5Zr, Zr2Be 17 ), tantalum beryllide (TaBe2, Ta2Be 17 ,TaBe 12 or TaBe17 ), beryllium-molybdenum (Be2Mo, Be 12 Mo, Be 22 Mo), or niobium-beryllium (NbBe2, NbBe3, Nb2Be 17 , NbBe 12 ), beryllium-tungsten (Be 22 W), Beryllium-Strontium (Be 13 The metal powder may be selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium. The metal powder may be smaller in size than the beryllium. In one embodiment, the at least one metal remains unreacted prior to deposition to reduce premature formation of intermetallic compounds.

[0008] In one embodiment, a method for manufacturing a beryllium article includes depositing an initial layer on a surface, the initial layer comprising beryllium and at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium; directing energy to a portion of the initial layer to form a plurality of grains in the initial layer comprising an intermetallic compound of beryllium; cooling the initial layer; depositing one or more successive layers on at least a portion of the initial layer opposite the surface, the successive layers containing beryllium; directing energy to a portion of the one or more successive layers; and inducing beryllium nucleation in a portion, preferably the outer portions, of the plurality of grains to form grains having an average grain size of 1 to 40 microns. The initial and successive layers may be deposited in a pattern to form a complex beryllium article. In one embodiment, the method may include at least one metal in the initial layer to function as a nucleation precursor. Thus, the amount of the at least one metal decreases in successive layers. Thus, the initial layer may contain 0.01 to 10 wt. % of the at least one metal, while successive layers contain a reduced amount of the at least one metal. Intermetallic compounds produced in situ by this method include beryllides, such as beryllium-titanium (Be 12 Ti, Be2Ti), Beryllium-Chromium (Be2Cr, or Be 12 Cr), iron-beryllium (FeBe5), beryllium-zirconium (Be 13 Zr, Be5Zr, Zr2Be 17 ), tantalum beryllide (TaBe2, Ta2Be 17 ,TaBe 12 or TaBe 17 ), beryllium-molybdenum (Be2Mo, Be 12 Mo, Be 22 Mo), or niobium-beryllium (NbBe 2、 NbBe3, Nb2Be 17 , NbBe 12), beryllium-tungsten (Be 22 W), Beryllium-Strontium (Be 13 The initial layer may be formed of a metal such as Sr (Sr), or beryllium-hafnium (Be5Hf). In one embodiment, the method includes exposing the deposited initial layer to an energy source, such as an electron beam or a laser, to form a plurality of particles. The method may include providing beryllium in powder form, and preferably, the beryllium powder has a spherical shape. The method may further include providing at least one metal in powder form. The size of the at least one metal powder may be smaller than the size of the beryllium powder. In one embodiment, the at least one metal remains unreacted prior to deposition to reduce premature formation of intermetallic compounds.

[0009]

[0009] These and other non-limiting properties are described in more detail below.

[0010] The following is a brief description of the drawings, which are presented for the purpose of illustrating exemplary embodiments disclosed herein and are not presented for the purpose of limiting the invention. [Brief explanation of the drawings]

[0010] [Figure 1]

[0011] 1 is a flow chart of an exemplary method for forming a beryllium article, each layer containing beryllium and at least one metal, according to one embodiment of the present invention. [Figure 2]

[0012] 1 is a flowchart of an exemplary method for forming a beryllium article in which the initial layer contains at least one metal, according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0013] The present disclosure may be understood more readily by reference to the following detailed description of the preferred embodiments and the examples included therein. In the following specification and claims that follow, reference will be made to certain terms that shall be defined to have the following meanings.

[0012]

[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In case of conflict, the present document, including definitions, will prevail. Preferred methods and materials are described below, but methods and materials similar or equivalent to those described herein can be used to practice or test this disclosure. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are for illustrative purposes only and are not limiting.

[0013]

[0015] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0016] As used herein and in the claims, the term "comprising" can include embodiments including "consisting of" and "consisting essentially of." As used herein, terms such as "comprise," "include," "having," "has," "can," "contain," and variations thereof are intended to be open-ended transitional phrases that require the presence of the specified components / steps and permit the presence of other components / steps. However, such descriptions should also be construed as describing compositions or methods "consisting of" and "consisting essentially of" the listed components / steps, thereby permitting the presence of only the specified components / steps along with impurities that may result therefrom, and excluding other components / steps.

[0014]

[0017] All ranges disclosed herein are inclusive of the recited endpoints and are independently combinable (e.g., the range "1 micron to 40 microns" includes the 1 micron and 40 micron endpoints, and all intermediate values). The endpoints of the ranges and any values ​​disclosed herein are not limited to the exact ranges or values, but are inexact to the extent that they include values ​​close to those ranges and / or values.

[0015]

[0018] As used herein, approximation language can be used to modify any quantitative expression that can vary without resulting in a change in the underlying function to which it pertains. Thus, values ​​modified by terms such as "about" and "substantially" may not necessarily be limited to the exact value specified. The modifier "about" should also be considered to disclose a range defined by the absolute values ​​of the two endpoints. For example, the expression "about 2 to about 4" also discloses a range of "2 to 4." The term "about" may refer to plus or minus 10% of the indicated numerical value. For example, "about 10%" may indicate a range of 9% to 11%, and "about 1" may mean 0.9 to 1.1.

[0016]

[0019] In describing ranges of values ​​herein, each intervening value is expressly contemplated with the same precision. For example, for the range of 6 to 9, the values ​​7 and 8 are contemplated in addition to 6 and 9, and for the range of 6.0 to 7.0, the values ​​6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are expressly contemplated.

[0017]

[0020] As described herein, there is a method for producing a beryllium article. One advantage of the method described herein is the ability to produce articles with complex three-dimensional designs and shapes, material compositions, and desirable mechanical or structural properties. In one embodiment, the method includes forming multiple layers in which beryllium intermetallic compounds are formed in situ. The in situ formation provides a distribution of intermetallic compounds beneficial for grain refinement, reducing the need for direct intermetallic compound addition to each layer. The beryllium intermetallic compounds act as nucleating agents for grain refinement. In contrast to the various limitations, drawbacks, and disadvantages associated with known methods for producing beryllium, the method disclosed herein offers significant improvements in material composition, energy efficiency, and reduced manufacturing costs.

[0018]

[0021] The methods described herein use nucleation precursor materials to form beryllium intermetallic compounds that act as nucleating agents to reduce the size of grain growth. Preferably, the beryllium intermetallic compounds are formed in situ in at least one layer of the article. This is therefore effective in improving the strength of the article and reducing or even eliminating problems associated with many types of beryllium manufacturing methods.

[0019]

[0022] One advantage of in-situ methods for forming nucleating agents is the ability to eliminate or reduce the use of grain refiners. The methods described herein form nucleating agents in-situ and produce grain sizes in beryllium articles previously unattainable by conventional processes. Thus, grain sizes are reduced and the beryllium articles have improved properties.

[0020] material

[0023] The beryllium articles described herein are made from multiple layers, including an initial layer and one or more successive layers. In one embodiment, the initial layer includes beryllium and a nucleation precursor material. The beryllium and nucleation precursor may be deposited separately to form the initial layer or mixed together with the beryllium. In one embodiment, the beryllium is provided as precursor particles with unreacted nucleation precursor on the surface of the precursor particles. The precursor particles may have a spherical or irregular morphology.

[0021]

[0024] In one embodiment, the nucleation precursor may comprise at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium. Preferably, the metal is iron, zirconium, tantalum, titanium, molybdenum, niobium, chromium, hafnium, tungsten, or strontium. More preferably, the metal is iron, tantalum, titanium, niobium, or chromium. In some embodiments, there may be a combination of metals used as the nucleation precursor. Preferably, the nucleation precursor remains unreacted during addition and is not formed into an intermetallic compound before being deposited.

[0022]

[0025] Thus, the initial layer contains beryllium in an amount of 20 to 99.99 wt %, e.g., 60 to 99.9 wt %, 65 to 99.5 wt %, 70 to 99.5 wt %, 75 to 99 wt %, or 80 to 99 wt %, based on the total weight of the initial layer. In some embodiments, the initial layer contains beryllium in an amount of 95 wt % or more, e.g., 96 wt % or more, 97 wt % or more, 98 wt % or more, 99 wt % or more, or 99.5 wt % or more. In some embodiments, the beryllium may be a beryllium alloy, such as aluminum-beryllium or beryllium copper. A high amount of beryllium in the initial layer allows it to be formed into complex shapes. The amount of metal or nucleation precursor is relatively less than the amount of beryllium. An effective amount of metal for forming the particles is 0.001 to 1.0 wt %, for example 0.005 to 0.95 wt %, 0.01 to 0.75 wt %, 0.025 to 0.5 wt %, or 0.1 to 0.5 wt %, based on the total weight of the initial layer.

[0023]

[0026] In one embodiment, the beryllium comprises beryllium powder. Exemplary beryllium metals include S-65 grade (99.2% minimum Be content, 0.9% maximum BeO content), S-200 (98.5% minimum Be content), and 0-30 (hot isostatically pressed beryllium, 99% minimum Be content, 0.5% maximum BeO content), all available from Materion Corporation. The beryllium powder may have an aspect ratio (average length to average width) of 1:1 to 100:1, e.g., 1:1 to 50:1, 1:1 to 20:1, 1:1 to 10:1, or 1:1 to 5:1. In one embodiment, the beryllium powder may be spherical. The beryllium powder may have an average diameter (D) of 1 micron to 200 microns, e.g., 5 microns to 175 microns, 10 microns to 150 microns, 15 microns to 100 microns, 25 microns to 70 microns, or 25 microns to 50 microns. 50 ) particle size. 50, i.e., the diameter at which 50% of the particles by volume are cumulative. Powders less than 200 microns tend to form beryllium articles with highly refined grains. If necessary, the beryllium powder may be sieved to the desired size.

[0024]

[0027] In one embodiment, the beryllium powder may be in the form of particles having a core-shell structure, with the beryllium forming the core and a continuous or semi-continuous coating forming the shell. In some embodiments, the continuous or semi-continuous coating may be a nucleation precursor. The beryllium coating may be achieved by ball milling, resonance mixing, spray bonding, spray drying, laser ablation, electrical discharge machining, and atomic layer deposition. In some embodiments, the coating includes nickel in the form of pure nickel or a nickel alloy. The core may comprise 0.1% to 99.9% by weight of the beryllium particles, e.g., 50% to 99.9% by weight of the beryllium particles, or more preferably, about 92% to less than 100% by weight of the beryllium particles. In some embodiments, the coating may comprise 0.1% to 99.9% by weight of the nickel particles, e.g., 0.1% to 50% by weight of the nickel particles, or more preferably, greater than 0% to about 8% by weight. In certain embodiments, the beryllium powder comprises about 92% to less than 100% beryllium by weight and greater than 0% to about 8% nickel by weight. Generally, the coating is believed to form particles for grain refinement.

[0025]

[0028] Nucleation precursors, such as iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium, may be supplied as powders. The metal powders may be present as loose powders, pastes, or suspensions that are mixed with the beryllium. In one embodiment, the nucleation precursors remain unreacted when added to the beryllium. The metal powders may have an aspect ratio (average length to average width) of 1:1 to 100:1, e.g., 1:1 to 50:1, 1:1 to 20:1, 1:1 to 10:1, or 1:1 to 5:1. The metal powders are generally about the same size as the beryllium, although smaller metal powders may be preferred. The metal powders may have an average (D 50 ) particle size can be less than 10 microns, e.g., less than 8 microns, less than 5 microns, less than 2.5 microns, less than 2 microns, or less than 1 micron. In some embodiments, the metal powder is a nanoparticle, e.g., an average (D 50 In some embodiments, the nanoparticles may have an average diameter (D) of 10 to 1000 nanometers, e.g., 25 to 950 nanometers, 50 to 900 nanometers, 100 to 800 nanometers, or 300 to 700 nanometers. 50 Thus, the metal powder may have an average diameter (D) of 0.0001 to 10 microns, e.g., 0.0005 to 7.5 microns, 0.001 to 5 microns, 0.01 to 2.5 microns, or 0.1 to 1.5 microns. 50 ) particle size. To form grains for grain refinement, the nucleation precursor is preferably capable of crystallizing prior to the beryllium. In one embodiment, the nucleation precursor is capable of remaining crystalline above the liquidus temperature of beryllium.

[0026]

[0029] Successive layers used to form the beryllium article may contain beryllium with or without a nucleation precursor. In some embodiments, a portion of the successive layers may contain a nucleation precursor. If the successive layers do not contain a nucleation precursor, the amount of nucleation precursor in the initial layer may be 0.01 to 10 wt. %, e.g., 0.01 to 5 wt. %, or 0.01 to 1 wt. %, based on the weight of each successive layer.

[0027]

[0030] When a nucleation precursor is included in successive layers, the beryllium and the nucleation precursor may be deposited separately to form successive layers, or may be mixed together with the beryllium. In one embodiment, the nucleation precursor may include at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium. More preferably, the metal is iron, tantalum, titanium, niobium, or chromium. In some embodiments, a combination of metals may be used as a nucleation precursor. In one embodiment, the amount of beryllium and the at least one metal may be determined as needed to form a beryllium article. Thus, the amount of beryllium and the at least one metal may vary from one successive layer to another. Typically, each successive layer may include a range of 20 to 99.99 wt %, for example, 60 to 99.9 wt %, 65 to 99.5 wt %, 70 to 99.5 wt %, 75 to 99 wt %, or 80 to 99 wt %, based on the total weight of the initial layer. The amount of the at least one metal is in the range of 0.001 to 1.0 wt%, for example, 0.005 to 0.95 wt%, 0.01 to 0.75 wt%, 0.025 to 0.5 wt%, or 0.1 to 0.5 wt%. In one embodiment, the successive layers contain less nucleation precursor than the initial layer.

[0028]

[0031] In one embodiment, the successive layers may contain beryllium with little or no nucleation precursor. The amount of at least one metal may be reduced to less than 0.5 wt.%, e.g., less than 0.25 wt.%, 0.01-0.75 wt.%, 0.025-0.5 wt.%, or 0.1-0.5 wt.%. The beryllium intermetallic compound is formed using the nucleation precursor of the initial layer to control the grain size of the successive layers.

[0029] method

[0032] A combination of initial and subsequent layers can be used to form a beryllium article. In one embodiment, the method preferably deposits the initial layer at a relatively fast rate. In one embodiment, the initial layer is deposited uniformly. The beryllium and nucleation precursor may be supplied separately or uniformly mixed together. When mixed together, the uniform distribution of the nucleation precursor may contribute to the formation of particles suitable for controlling grain refinement. Additionally, optional binder, diluent, or solvent materials may be present, which can be added separately from or along with the beryllium. In some embodiments, the initial layer may be deposited on a surface, such as a substrate, platform, or base plate. In one embodiment, the initial layer is deposited on a build box. Preferably, the powder is transferred to the build box while minimizing powder loss or contamination of surrounding areas. The build box is comprised of a surface, such as a build platform and sidewalls. The build platform is generally a flat or planar surface on which the initial and subsequent layers are deposited. The build platform may move along a vertical z-axis based on signals provided by a computer-operated controller. The sidewalls cooperate with the build platform to form a "box" to contain the deposited powder. Generally, the sidewalls remain in a fixed position while the build platform moves downward to allow the next layer of powder to be deposited.

[0030] initial layer

[0033] The initial layer may be deposited on the build surface in a predetermined pattern. In some embodiments, the preset pattern is determined based on layers in a computer-aided design (CAD) model. Any suitable technique for depositing the initial layer is suitable for this method, including, for example, spreading, coating, brushing, rolling, spraying, or dispensing. In one embodiment, one or more deposition heads are used and move in a horizontal xy plane. A controller may be used to move the one or more deposition heads as specified in the design. The horizontal xy plane is the plane defined by the x-axis and the y-axis, where the x-axis, y-axis, and z-axis are orthogonal to one another. In some embodiments, the deposition is performed under an inert gas atmosphere.

[0031]

[0034] In one embodiment, the initial layer is deposited uniformly. The initial layer may have a thickness of 20 to 200 microns, e.g., 25 to 150 microns, 25 to 110 microns, 30 to 100 microns, 35 to 75 microns, or 40 to 60 microns. In some embodiments, the initial layer may be formed by compressing the deposited material using any compaction method. It may be desirable to compress the powder using a mechanical compactor, such as a doctor blade, double roller, or electrostatic force, to provide a thin layer.

[0032]

[0035] Following deposition of the initial layer, an energy source may be directed at at least a portion of the initial layer. The energy source may generate localized or focused energy to heat at least a portion of the initial layer. In one embodiment, the energy source may be sufficient to initiate a reaction between the nucleation precursor and beryllium to form a beryllium intermetallic compound. The beryllium intermetallic compound particles are nucleating agents for reducing the size of beryllium grain growth. The energy source may be an electron beam or a laser beam, and may be 10 3 W / mm 2 ~10 7 W / mm 2 , e.g., 10 4 W / mm 2 ~107 W / mm 2 , or 10 5 W / mm 2 ~10 6 W / mm 2 It has a power density of 10 7 W / mm 2 Operation of the energy source at a power less than 1000 W is sufficient to initiate an in situ reaction to produce the nucleating agent. Additionally, some of the beryllium may be sintered into the nucleating agent. In one embodiment, the effective diameter of the energy source may be 10 to 200 microns, e.g., 25 to 150 microns, or 35 to 100 microns. The scanning speed of the energy source may be 10 mm / s to 2000 m / s, e.g., 50 to 1500 m / s, or 100 to 1000 m / s. The raster width of the energy source may be 50 to 500 microns, e.g., 75 to 450 microns, 75 to 400 microns, or 100 to 350 microns. In one embodiment, the layer thickness may be 20 microns to 200 microns, e.g., 25 microns to 175 microns, or 50 microns to 150 microns. In one embodiment, the energy source and / or another source heats the initial layer to a temperature between 20°C and 800°C, such as between 30°C and 600°C, between 40°C and 500°C, or between 100°C and 400°C.

[0033]

[0036] If no preheating is used, the initial layer may be deposited at room temperature (20-25°C). In some embodiments, the deposited initial layer may be preheated in the build box to a temperature of at least 100°C, e.g., at least 120°C, or 150°C, at least 200°C, at least 400°C, at least 450°C, or at least 500°C.

[0034]

[0037] Carrying out the method under reduced pressure or vacuum allows for quality control of the layer and beryllium article material, although in some embodiments the method may be carried out at atmospheric pressure.

[0035]

[0038] In one embodiment, after the reaction is initiated, cooling forms a plurality of particles comprising beryllium intermetallic compounds. Cooling the initial layer allows for the formation of particles by seeding of the intermetallic compounds. The minimum cooling rate may be greater than 10°C / min, such as greater than 15°C / min, or greater than 20°C / min. In some embodiments, to achieve rapid solidification, the cooling rate may be greater than 1000°C / min, such as greater than 10,000°C / min. In one embodiment, having a sufficient cooling rate allows for improved grain refinement. Depending on the type and amount of nucleation precursor, various intermetallic compounds may be formed. In one embodiment, the beryllium intermetallic compound is a beryllide, such as beryllium-titanium (Be 12 Ti, Be2Ti), Beryllium-Chromium (Be2Cr, or Be 12 Cr), iron-beryllium (FeBe5), beryllium-zirconium (Be 13 Zr, Be5Zr, Zr2Be 17 ), tantalum beryllide (TaBe2, Ta2Be 17 ,TaBe 12 or TaBe 17 ), beryllium-molybdenum (Be2Mo, Be 12 Mo, Be 22 Mo), or niobium-beryllium (NbBe2, NbBe3, Nb2Be 17 , NbBe 12 ), beryllium-tungsten (Be 22 W), Beryllium-Strontium (Be 13 The intermetallic compounds may be selected from the group consisting of Sr, beryllium hafnium (Be5Hf), and beryllium hafnium (Be5Hf). As the particles are formed, the nucleation energy of beryllium is reduced, resulting in grain refinement. Therefore, beryllium nucleation may be induced in a portion of the intermetallic compound particles, resulting in the formation of grains with a small average grain size. In one embodiment, nucleation may be induced in the outer portion or surface region of the intermetallic compound particles. In one embodiment, the average grain size may be 1 to 40 microns, e.g., 5 to 25 microns, 5 to 15 microns, or 10 to 15 microns.

[0036] Continuous layer

[0039] After allowing sufficient time for particle formation and nucleation, one or more successive layers can be deposited in a predetermined pattern on at least a portion of the initial layer opposite the build surface, thereby continuing the construction of the beryllium article. Successive layers can be deposited at room temperature or preheated similarly to the initial layer. Similarly, an energy source is directed at at least a portion of the successive layer, followed by particle formation, and during cooling, beryllium nucleation is induced on a portion of the particle. In one embodiment, beryllium nucleation can be induced on the outer portion or surface of the particle. In one embodiment, the energy source is controlled within the same operating parameters as the initial layer. Depending on the article, the pattern of each successive layer can vary. In some embodiments, a successive layer can be deposited on at least a portion of the preceding or initial layer. In some embodiments, the surface or build plate can be lowered by the thickness of the next successive layer. The thickness of successive layers may vary, and in one embodiment, successive layers may have a thickness of 20 to 200 microns, e.g., 25 to 150 microns, 25 to 110 microns, 30 to 100 microns, 35 to 75 microns, or 40 to 60 microns. In some embodiments, each successive layer may have a similar thickness, or the thickness may be matched to the beryllium article.

[0037]

[0040] In one embodiment, the successive layers further comprise at least one metal, and the method may include forming a nucleating agent in situ in each successive layer, thus refining the grain size in each layer. In another embodiment, the at least one metal is provided in an initial layer, and the grain size is refined as the initial layer and successive layers are heated and cooled.

[0038]

[0041] The process can continue with repeated deposition, heating, and cooling until the desired beryllium article is formed. In one embodiment, the beryllium article may be formed from one or more successive layers, for example, at least five successive layers, at least ten successive layers, or at least twenty successive layers. In some articles, hundreds of layers may be used, and thus the number of layers is not limited.

[0039]

[0042] The direction of the microstructure is not limited to the build direction of successive layers, and the microstructure of the beryllium article may contain multiple dendritic layers with different angles to the primary growth direction relative to one another, resulting in a crack-free beryllium article.

[0040]

[0043] In some embodiments, the method further includes curing the multiple layers before sintering the preform. The beryllium article may be annealed for 6 to 12 hours, e.g., 8 to 10 hours. The annealed article may be finished, e.g., by polishing or plating. The surface roughness of the article may be reduced, e.g., by bead blasting or barrel finishing. In some embodiments, the fabricated beryllium article may have loose or unfused particles in one or more layers. Unfused particles can be removed by blowing or vacuuming, as needed.

[0041]

[0044] FIG. 1 is a flowchart of an exemplary method 100 for manufacturing a beryllium article. In step 110, an initial layer is deposited on a surface. The initial layer may include beryllium 112 and at least one metal 114 selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium. The beryllium 112 and the metal 114 may be deposited together or separately. In step 120, an intermetallic compound is formed. The intermetallic compound may be a beryllide and is formed by exposing the deposited initial layer to an energy source. In step 130, nucleation of beryllium is induced. Nucleation may be induced in a portion of the particle, such as the intermetallic compound. In one embodiment, nucleation may be induced in an outer portion or surface of the particle. Although not shown, a cooling step may occur after step 130. In step 140, a successive layer is deposited on the initial layer. The successive layer may include beryllium 142 and at least one metal 144 selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium. In step 150, an intermetallic compound is formed in the successive layer. The intermetallic compound may be beryllide and is formed by exposing the deposited initial layer to an energy source. In step 160, nucleation of beryllium is induced in the successive layer. Nucleation may be induced in a portion of the particle, for example, the intermetallic compound. In one embodiment, nucleation may be induced in an outer portion or surface of the particle. The method may continue by repeating steps 140 through 160 to build successive layers as desired to form a beryllium article.

[0042]

[0045] FIG. 2 is a flowchart of an exemplary method 200 for manufacturing a beryllium article. In step 210, an initial layer is deposited on a surface. The initial layer may include beryllium 212 and at least one metal 214 selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium. The beryllium 212 and metal 214 may be deposited together or separately. In step 220, an intermetallic compound is formed. The intermetallic compound may be a beryllide and is formed by exposing the deposited initial layer to an energy source. In step 230, the initial layer is cooled. In step 240, a successive layer is deposited on the initial layer. The successive layer may include beryllium 242. In one embodiment, the successive layer preferably does not contain a metal because the intermetallic compound was previously formed in step 220. In step 250, nucleation of beryllium is induced in the successive layer. Nucleation may be induced in a portion of the particle, e.g., an intermetallic compound. In one embodiment, nucleation may be induced in an outer portion or surface of the particle. In this manner, steps 240 and 250 may be repeated to continue building successive layers as desired to form the beryllium article.

[0043]

[0046] The present disclosure has been described with reference to exemplary embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the foregoing detailed description. It is intended that the present disclosure be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims

1. 1. A method of manufacturing a beryllium article, comprising: depositing an initial layer on the surface, said initial layer comprising beryllium and at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium; forming a plurality of particles in the initial layer comprising an intermetallic compound of beryllium and the at least one metal; inducing nucleation of beryllium on a portion of the plurality of grains to form grains having an average grain size of 1 to 40 microns; depositing one or more successive layers on at least a portion of the initial layer opposite the surface, the one or more successive layers comprising beryllium and at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium; repeating the forming and nucleating steps for the one or more successive layers; A method comprising:

2. The method of claim 1, wherein the initial layer comprises 0.001 to 1.0 wt. % of the at least one metal, based on the total weight of the initial layer.

3. 3. The method of claim 1, wherein the one or more continuous layers comprise 0.001 to 1.0 wt. % of the at least one metal, based on the total weight of the one or more continuous layers.

4. The method of claim 1 , wherein the intermetallic compound of beryllium comprises beryllide.

5. The method of claim 1 , wherein the step of forming a plurality of particles is performed by exposing the deposited initial layer to an energy source.

6. 6. The method of any one of claims 1 to 5, including providing a supply of powdered beryllium.

7. 7. The method of any one of claims 1 to 6, comprising providing a supply of the at least one selected metal in powder form.

8. 8. The method of any one of claims 1 to 7, wherein the average grain size is from 5 to 25 microns.

9. 1. A method of manufacturing a beryllium article, comprising: depositing an initial layer on the surface, said initial layer comprising beryllium and at least one metal selected from the group consisting of iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium; directing energy to a portion of the initial layer to form a plurality of grains comprising an intermetallic compound of beryllium in the initial layer; cooling the initial layer; depositing one or more successive layers on at least a portion of the initial layer opposite the surface, the successive layers containing beryllium; directing energy to a portion of the one or more continuous layers; inducing nucleation of beryllium on a portion of the plurality of grains to form grains having an average grain size of 1 to 40 microns; A method comprising:

10. 10. The method of claim 9, wherein the initial layer comprises 0.01 to 10% by weight of the at least one metal.

11. 11. The method of claim 9 or 10, wherein the beryllium intermetallic compound comprises beryllide.

12. 12. The method of claim 9, wherein the step of forming a plurality of particles is performed by exposing the deposited initial layer to an energy source.

13. 13. A method according to any one of claims 9 to 12, including providing a supply of beryllium in powder form.

14. 14. The method of any one of claims 9 to 13, comprising providing a supply of the at least one selected metal in powder form.

15. 15. The method of any one of claims 9 to 14, wherein the average grain size is from 5 to 25 microns.

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