Method for producing beryllium product

Abstract

The invention discloses a grain refinement method for beryllium products. The grain refinement enables the beryllium product to have excellent properties in terms of strength and durability. The methods disclosed herein provide efficient grain refinement using intermetallic compounds of beryllium formed in situ.

Description

Priority declaration

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

[0002] The present disclosure relates to a method of producing beryllium articles. In particular, grain refinement of beryllium articles generates nucleating agents in situ to provide improved strength and processing. Background Art

[0003] Beryllium is a metal with very desirable properties. These include high stiffness (Young's modulus = 287 GPa), low density (1.85 g / cc), high elastic modulus (130 GPa), high specific heat (1925 J / kg·K), high thermal conductivity (216 W / m·K), and low linear thermal expansion coefficient (11.4×10 6 / °K). Therefore, beryllium and its composites can be used in aviation and aerospace structures, high-performance engines and brakes, and in electronic components due to thermal properties and vibration damping. Beryllium and its composites can also be used in several different applications, including combustion applications, hypersonic vehicles, computer components, optics for space-based and land-based systems, satellite structures, solar collectors, and nuclear energy growth applications.

[0004] One limitation is that casting methods are not suitable for making beryllium products and result in columnar solidification. Beryllium is a highly reactive metal with a high melting point, making it easy to react with the mold wall material to form beryllium compounds (BeO, etc.) trapped in the solidified metal. In addition, the grain size is greater than 500 microns, and is often much higher, up to 50,000 microns. This is too large to meet strength requirements and results in brittle materials. Further attempts to refine the grains by mechanical processing have not yet achieved commercial success. In order to overcome the beryllium production problem, beryllium powder has been used. Beryllium powder can be formed by ball milling, disc milling or gas atomization processes. The powder is consolidated into an ingot, which can be further processed into a molded component of beryllium. This powder process requires careful handling of the beryllium powder. In addition, the powder process has a low material utilization rate, which leads to low efficiency and increased costs. The powder process is also limited in forming complex shapes.

[0005] There remains a need to eliminate columnar solidification in order to produce beryllium articles having reduced grain size in an efficient manner. Summary of the invention

[0006] The present disclosure relates to methods of making beryllium articles. In one embodiment, the method is used to grain refine beryllium in an efficient manner to achieve improvements in strength and durability. In one embodiment, the method disclosed herein provides efficient grain refinement using an in-situ formed intermetallic compound of beryllium. In one embodiment, the in-situ formed intermetallic compound can be a beryllium.

[0007] In one embodiment, a method for producing a beryllium article is provided, comprising 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 comprising an intermetallic compound of beryllium and the at least one metal in the initial layer; inducing beryllium nucleation on a portion, more preferably an outer portion, of the plurality of particles 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; and repeating the forming and nucleation steps for the one or more successive layers. The initial layer 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 weight percent of the 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 the at least one metal, based on the total weight of the one or more successive layers. The intermetallic compound generated in situ by the method may be a beryllium compound, such as beryllium titanium (Be 12 Ti, Be2Ti), beryllium chromium (Be2Cr or Be 12 Cr), beryllium iron (FeBe5), beryllium zirconium (Be 13 Zr, Be5Zr, Zr2Be 17 ), Tantalum Beryllium (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 13Sr), beryllium hafnium (Be5Hf). In one embodiment, the method exposes the deposited initial layer to an energy source, such as an electron beam or a laser, to form the plurality of particles. The method may include supplying beryllium in powder form, and the beryllium powder may preferably have a spherical shape. In addition, the method may include supplying iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, or strontium in powder form. The size of the metal powder may be smaller than that of beryllium. In one embodiment, the at least one metal remains unreacted prior to deposition to reduce early formation of intermetallic compounds.

[0008] In one embodiment, a method for producing a beryllium article is provided, comprising 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 particles of an intermetallic compound comprising 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 to the surface, wherein the successive layers contain beryllium; directing energy to a portion of the one or more successive layers; and inducing beryllium nucleation on a portion, more preferably an outer portion, of the plurality of particles to form grains having an average grain size of 1 to 40 microns. The initial layer and successive layers may be deposited in a pattern to form a complex article of beryllium. In one embodiment, the method may include the at least one metal acting as a nucleating agent precursor in the initial layer. Thus, the amount of the at least one metal is reduced in the successive layers. Thus, the initial layer may comprise 0.01 to 10 wt % of the at least one metal, while the successive layers comprise a reduced amount of the at least one metal. The intermetallic compound generated in situ by the method may be a beryllium compound, such as beryllium titanium (Be 12 Ti, Be2Ti), beryllium chromium (Be2Cr or Be 12 Cr), beryllium iron (FeBe5), beryllium zirconium (Be 13 Zr, Be5Zr, Zr2Be 17 ), Tantalum Beryllium (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 13In one embodiment, the method exposes the deposited initial layer to an energy source, such as an electron beam or a laser, to form the plurality of particles. The method may include supplying the beryllium in powder form, and the beryllium powder preferably has a spherical shape. In addition, the method may include supplying the at least one metal in powder form. The size of the powder of the at least one metal may be smaller than the powder form of beryllium. In one embodiment, the at least one metal remains unreacted prior to deposition to reduce early formation of intermetallic compounds.

[0009] These and other non-limiting features of the present disclosure are more particularly described below. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0012] Figure 2 is a flow chart of an exemplary method of forming a beryllium article according to one embodiment of the present invention, wherein the initial layer contains the at least one metal. DETAILED DESCRIPTION

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

[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as are generally understood by those of ordinary skill in the art. In the event of a conflict, this document (including definitions) shall prevail. Preferred methods and materials are described below, although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present disclosure. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety. The materials, methods, and examples disclosed herein are exemplary only and are not intended to be limiting.

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

[0016] The term "comprising" as used in the specification and claims may include the embodiments of "consisting of" and "consisting essentially of." As used herein, the terms "comprising," "including," "having," "may," "containing," and variations thereof are intended to be open transition phrases that require the presence of specified ingredients / steps and allow for the presence of other ingredients / steps. However, such descriptions should be interpreted as also describing compositions or methods as "consisting of" and "consisting essentially of" the listed ingredients / steps, which only allow for the presence of the specified ingredients / steps, and any impurities that may result therefrom, and exclude other ingredients / steps.

[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 endpoints 1 micron and 40 microns, and all intermediate values). The endpoints of the ranges and any values ​​disclosed herein are not limited to the exact ranges or values; they are imprecise enough to include values ​​approximating these ranges and / or values.

[0018] As used herein, approximations can be used to modify any quantitative representation that can vary without causing a change in the basic function to which it relates. Therefore, values ​​modified by terms such as "approximately" and "substantially" may not be limited to the specified exact value in some cases. The modifier "approximately" should also be considered to disclose a range defined by the absolute values ​​of the two endpoints. For example, the phrase "about 2 to about 4" also discloses a range of "2 to 4". The term "approximately" can refer to plus or minus 10% of the numerical value shown. For example, "about 10%" can refer to a range of 9% to 11%, and "about 1" can refer to 0.9-1.1.

[0019] For the enumeration of numerical ranges herein, each intermediate number with the same precision is explicitly considered. For example, for the range of 6-9, in addition to 6 and 9, the numbers 7 and 8 are also considered, and for the range of 6.0-7.0, the numbers 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9 and 7.0 are explicitly considered.

[0020] As described herein, a method for producing beryllium products is provided. An advantage of the methods described herein is the ability to produce products having complex three-dimensional designs and shapes, material compositions, and desirable mechanical or structural properties. In one embodiment, the method includes forming a plurality of layers, wherein intermetallic compounds of beryllium are formed in situ. In situ formation provides a distribution of intermetallic compounds, which is beneficial to grain refinement and reduces the need to add intermetallic compounds directly to each layer. Intermetallic compounds of beryllium act as nucleating agents for grain refinement. Compared to the various limitations, shortcomings, and disadvantages associated with known beryllium manufacturing methods, the methods disclosed herein provide significant improvements in material composition, energy efficiency, and reduced manufacturing costs.

[0021] The method described herein uses a nucleating agent precursor material to form an intermetallic compound of beryllium, which acts as a nucleating agent to reduce the grain growth size. Preferably, the intermetallic compound of beryllium is formed in situ in at least one layer of the article. Therefore, this effectively improves the strength of the article and reduces or even eliminates the problems associated with many types of beryllium manufacturing methods.

[0022] One advantage of the in-situ method for forming nucleating agents is that grain refiners can be eliminated or reduced. The method described herein forms in-situ nucleating agents to produce grain sizes in beryllium products that were previously unattainable by existing methods. As a result, the beryllium products have improved properties as the grain size is reduced. Material

[0023] The beryllium articles described herein are made of a plurality of layers including an initial layer and one or more successive layers. In one embodiment, the initial layer comprises beryllium and a nucleating agent precursor material. The beryllium and the nucleating agent precursor can be deposited separately to form the initial layer, or can be blended with the beryllium. In one embodiment, the beryllium is provided as a precursor particle having an unreacted nucleating agent precursor on the surface of the precursor particle. The precursor particle can have a spherical or irregular morphology.

[0024] In one embodiment, the nucleating agent precursor may comprise at least one metal selected from 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 and strontium. More preferably, the metal is iron, tantalum, titanium, niobium or chromium. In some embodiments, there may be a combination of metals used as nucleating agent precursors. Preferably, the nucleating agent precursor remains unreacted when added and no intermetallic compounds are formed prior to deposition.

[0025] Thus, based on the total weight of the initial layer, the initial layer comprises beryllium in an amount of 20 to 99.99 wt %, such as 60 to 99.9 wt %, 65 to 99.5 wt %, 70 to 99.5 wt %, 75 to 99 wt %, or 80 to 99 wt %. In some embodiments, the initial layer comprises beryllium in an amount greater than or equal to 95 wt %, such as greater than or equal to 96 wt %, greater than or equal to 97 wt %, greater than or equal to 98 wt %, greater than or equal to 99 wt %, or greater than or equal to 99.5 wt %. In some embodiments, the beryllium can be a beryllium alloy, such as aluminum-beryllium or copper-beryllium. A large amount of beryllium in the initial layer can be formed into complex shapes. The amount of metal or nucleating agent precursor is relatively less than beryllium. An effective amount of metal for forming the particles is 0.001 to 1.0 wt %, such as 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.

[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), S-200 grade (98.5% minimum Be content), 0-30 (hot isostatic pressed beryllium, minimum 99% Be content, 0.5% maximum BeO), and are all available from Materion Corporation. The beryllium powder may have an aspect ratio (ratio of average length to average width) of 1:1 to 100:1, such as 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 (D) of 1 micron to 200 microns, such as 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. The particle size is D 50 , or the diameter at which a cumulative percentage of particles of 50% by volume is reached. Powders less than 200 microns exhibit an increased tendency to form beryllium products with reduced grain refinement. When necessary, the beryllium powder can be screened to achieve the desired size.

[0027] In one embodiment, beryllium powder can be in the form of particles with a core-shell structure, wherein beryllium constitutes the core and a continuous or semi-continuous coating constitutes the shell. In some embodiments, the continuous or semi-continuous coating can be a nucleating agent precursor. The coating of beryllium can be achieved by ball milling, resonance mixing, spray bonding, spray drying, laser ablation, electrospark machining and atomic layer deposition. In some embodiments, the coating includes nickel, in the form of pure nickel or a nickel alloy. The core can be 0.1 wt % to 99.9 wt % of beryllium particles, such as 50 wt % to 99.9 wt % of beryllium particles, or more preferably about 92 wt % to less than 100 wt % of beryllium particles. In some embodiments, the coating can be 0.1 wt % to 99.9 wt % of nickel particles, such as 0.1 wt % to 50 wt % of nickel particles, or more preferably greater than 0 wt % to about 8 wt %. In a particular embodiment, the beryllium powder includes about 92 wt % to less than 100 wt % of beryllium and greater than 0 wt % to about 8 wt % of nickel. Generally, the coating is considered to constitute the particles used for grain refinement.

[0028] Nucleating agent precursors, such as iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten and strontium, may also be supplied as powders. The metal powders may be present as loose powders, pastes or suspensions that may be blended with the beryllium. In one embodiment, the nucleating agent precursor remains unreacted when added to the beryllium. The metal powder may have an aspect ratio (ratio of average length to average width) of 1:1 to 100:1, such as 1:1 to 50:1, 1:1 to 20:1, 1:1 to 10:1 or 1:1 to 5:1. The metal powder is generally about the same size as the beryllium, although smaller metal powders may be preferred. The metal powder may have an average (D) of less than 10 microns, such as less than 8 microns, less than 5 microns, less than 2.5 microns, less than 2 microns or less than 1 micron. 50 ) particle size. In some embodiments, the metal powder may have an average (D 50 ), such as less than 1 micron. In some embodiments, the nanoparticles may have an average (D) of 10 to 1000 nanometers, such as 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 (D) of 0.0001 to 10 microns, such as 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. In order to form particles for grain refinement, it is preferred that the nucleating agent precursor is able to crystallize before beryllium. In one embodiment, the nucleating agent precursor can be kept crystallized at a temperature above the liquidus temperature of beryllium.

[0029] The successive layers used to form the beryllium article may contain beryllium with or without the presence of a nucleating agent precursor. In some embodiments, a portion of the successive layers may contain a nucleating agent precursor. When the successive layers do not contain a nucleating agent precursor, the amount of the nucleating agent precursor in the initial layer may be 0.01 to 10 weight percent, such as 0.01 to 5 weight percent or 0.01 to 1 weight percent, based on the weight of each successive layer.

[0030] When the nucleating agent precursor is included in the successive layers, beryllium and the nucleating agent precursor can be deposited separately to form the successive layers, or can be blended with beryllium. In one embodiment, the nucleating agent precursor may include at least one metal selected from 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, there may be a combination of metals used as nucleating agent precursors. In one embodiment, the amount of beryllium and the at least one metal can be determined as needed to form a beryllium product. Therefore, the amount of beryllium and the at least one metal can vary in each successive layer. Typically, based on the total weight of the initial layer, each successive layer may include 20 to 99.99% by weight, such as 60 to 99.9% by weight, 65 to 99.5% by weight, 70 to 99.5% by weight, 75 to 99% by weight, or 80 to 99% by weight. The at least one metal is present in an amount of 0.001 to 1.0 wt%, such as 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, successive layers contain less nucleating agent precursor than the initial layer.

[0031] In one embodiment, the successive layers may contain beryllium and little to no nucleating agent precursor. The amount of the at least one metal is reduced and may be less than 0.5 wt %, such as less than 0.25 wt %, 0.01 to 0.75 wt %, 0.025 to 0.5 wt %, or 0.1 to 0.5 wt %. Intermetallic compounds of beryllium are formed using nucleating agent precursors from the initial layer to control grain size in the successive layers. method

[0032] Using a combination of an initial layer and successive layers, a beryllium product can be formed. In one embodiment, the method preferably deposits the initial layer at a relatively high rate. In one embodiment, the initial layer is uniformly deposited. Beryllium and nucleating agent precursors can be supplied separately or uniformly blended together. When blended together, the uniform distribution of nucleating agent precursors can help form particles suitable for controlling grain refinement. In addition, there may be optional adhesives, diluents or solvent materials that can be separated or added together with beryllium. In some embodiments, the initial layer can be deposited on a surface such as a substrate, a platform or a base plate. In one embodiment, the initial layer is deposited in a build box. Preferably, the powder is transferred to the build box with minimal powder loss or contamination of the surrounding area. The build box comprises a surface, such as a build platform, and a side wall. The build platform is typically a plane or flat surface on which the initial layer and successive layers are deposited. The build platform can be moved along the vertical z-axis based on a signal provided by a computer-operated controller. The side wall cooperates with the build platform to form a "box" containing deposited powder. Typically, the side wall remains in a fixed position and the build platform moves downward to allow the next powder layer to be deposited. Initial layer

[0033] The initial layer can be deposited on the build surface with a predetermined pattern. In some embodiments, the layer based on the computer-aided design (CAD) model determines the preset pattern. Any suitable technology for depositing the initial layer is applicable to the method, including spreading, coating, brushing, roller coating, spraying or dispensing. In one embodiment, one or more deposition heads are used and moved in the horizontal xy plane. A controller can be used to move the one or more deposition heads specified by the design. The horizontal xy plane is a plane defined by an x-axis and a y-axis, wherein the x-axis, the y-axis and the z-axis are orthogonal to each other. In some embodiments, the deposition is carried out under an inert gas atmosphere.

[0034] In one embodiment, the initial layer can be deposited in a uniform manner. The initial layer can have a thickness of 20 to 200 microns, such as 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 can be formed by compacting the deposited material with an optional compaction method. It may be necessary to use a mechanical compactor such as a scraper or double rolling or electrostatic force to compact the powder to provide a thin layer.

[0035] After depositing the initial layer, an energy source may be directed to 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 nucleating agent precursor and the beryllium to form an intermetallic compound of beryllium. The particles of the intermetallic compound of beryllium are nucleating agents for reducing the grain growth size of the beryllium. The energy source may be a 10 3 W / mm 2 Up to 10 7 W / mm 2 , for example 10 4 W / mm 2 Up to 10 7 W / mm 2 , or 10 5 W / mm 2 Up to 10 6 W / mm 2 The power density of the electron beam or laser beam is less than 10 7 W / mm 2The power of the energy source is sufficient to initiate an in-situ reaction to produce a nucleating agent. In addition, a portion of the beryllium may be sintered to the nucleating agent. In one embodiment, the effective diameter of the energy source may be 10 to 200 microns, such as 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, such as 50 to 1500 m / s or 100 to 1000 m / s. The grating width of the energy source may be 50 to 500 microns, such as 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, such as 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 of 20°C to 800°C, such as 30°C to 600°C, 40°C to 500°C, or 100°C to 400°C.

[0036] Unless preheating is used, the initial layer can be deposited at room temperature (20 to 25° C.). In some embodiments, the deposited initial material can be preheated in the build box to a temperature of at least 100° C., such as at least 120° C., or 150° C., at least 200° C., at least 400° C., at least 450° C., or at least 500° C.

[0037] Operating the process under reduced atmospheric conditions or vacuum can provide quality control for the layer and beryllium article material. Nevertheless, in some embodiments, the process can be operated at atmospheric pressure.

[0038] In one embodiment, after the reaction begins, the plurality of particles comprising an intermetallic compound of beryllium are formed upon cooling. Cooling of the initial layer enables the formation of particles by intermetallic seeding. 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, the cooling rate may be greater than 1000°C / min, such as greater than 10,000°C / min, to achieve rapid solidification. In one embodiment, having a sufficient cooling rate may achieve improvements in grain refinement. Depending on the type and amount of the nucleating agent precursor, various intermetallic compounds may be formed. In one embodiment, the intermetallic compound of beryllium is a beryllium compound, such as beryllium titanium (Be 12 Ti, Be2Ti), beryllium chromium (Be2Cr or Be 12 Cr), beryllium iron (FeBe5), beryllium zirconium (Be 13 Zr, Be5Zr, Zr2Be 17 ), Tantalum Beryllium (TaBe2, Ta2Be 17 、TaBe 12 or TaBe 17 ), beryllium molybdenum (Be2Mo, Be 12 Mo, Be22 Mo) or niobium beryllium (NbBe2, NbBe3, Nb2Be 17 、NbBe 12 ), beryllium tungsten (Be 22 W), beryllium strontium (Be 13 Sr), beryllium hafnium (Be5Hf). Once the particles are formed, the nucleation energy of beryllium is reduced to achieve grain refinement. Therefore, beryllium nucleation can be induced on a portion of the intermetallic particles to form grains with a small average size. In one embodiment, nucleation can be induced on the outer portion or surface area of ​​the intermetallic particles. In one embodiment, the average grain size can be 1 to 40 microns, such as 5 to 25 microns, 5 to 15 microns, or 10 to 15 microns. Successive layers

[0039] After leaving enough time for particles to form and nucleate, one or more successive layers can be deposited in a predetermined pattern on at least a portion of the initial layer opposite to the build surface. This continues to build the beryllium product. The successive layers can be deposited at room temperature, or can be preheated similar to the initial layer. In a similar manner, an energy source is directed to at least a portion of the successive layers, and then particles are formed during cooling and beryllium nucleation is induced on a portion of the particles. In one embodiment, beryllium nucleation can be induced on the outer portion or surface of the particles. In one embodiment, the energy source is controlled within operating parameters similar to the initial layer. Depending on the product, the pattern of each successive layer can be different. In some embodiments, the successive layers can be deposited on at least a portion of the previous layer or the initial layer. In some embodiments, the surface or build plate can be lowered by the thickness of the next successive layer. The thickness of the successive layers may vary, and in one embodiment, the successive layers may have a thickness of 20 to 200 microns, such as 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 adapted to the beryllium article.

[0040] In one embodiment, the successive layers further comprise the at least one metal, and the method may involve forming a nucleating agent in situ in each successive layer. Thus, the grain size is refined in each layer. In other embodiments, the at least one metal is provided in the initial layer, and the grain size is refined when the initial layer and the successive layers are heated and cooled.

[0041] The method can continue to repeat deposition, heating and cooling until the desired beryllium product is formed. In one embodiment, the beryllium product can be formed from one or more sequential layers, such as at least 5 sequential layers, at least 10 sequential layers, or at least 20 sequential layers. For some products, hundreds of layers can be used, so the number of layers is not limited.

[0042] The orientation of the microstructure is not limited to the direction of build-up of successive layers. The microstructure of the beryllium article may contain multiple dendrite layers having different primary growth direction angles relative to each other. This provides a crack-free beryllium article.

[0043] In some embodiments, the method further includes solidifying the multiple layers before sintering the preform. The beryllium product can be annealed for 6 to 12 hours, for example, 8 to 10 hours. The annealed product can be finished, for example, by polishing or electroplating. The surface roughness of the product can be reduced, for example, by sandblasting or drum cleaning. In some embodiments, the beryllium product produced may have scattered or unfused particles in one or more layers. Unfused particles can be removed by blowing or vacuuming as needed.

[0044] Figure 1 1 is a flow chart of an exemplary method 100 for producing 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 iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten and strontium. Beryllium 112 and metal 114 may be deposited together or separately. In step 120, an intermetallic compound is formed. The intermetallic compound may be a beryllium compound and is formed by exposing the deposited initial layer to an energy source. In step 130, beryllium nucleation is induced. Nucleation may be induced on a portion of the particles, such as the intermetallic compound. In one embodiment, nucleation is induced on an outer portion or surface of the particle. Although not shown, there may be a cooling step after step 130. In step 140, successive layers are deposited on the initial layer. The successive layers may include beryllium 142 and at least one metal 144 selected from 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 layers. The intermetallic compound may be a beryllium compound and is formed by exposing the deposited initial layer to an energy source. In step 160, beryllium nucleation is induced in the successive layers. Nucleation may be induced on a portion of the particle, such as the intermetallic compound. In one embodiment, nucleation is induced on an outer portion or surface of the particle. The method may continue to repeat steps 140 to 160 to build up successive layers as needed to form a beryllium article.

[0045] Figure 22 is a flow chart of an exemplary method 200 for producing 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 iron, zirconium, tantalum, titanium, yttrium, molybdenum, niobium, chromium, nickel, cobalt, hafnium, tungsten, and strontium. 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 beryllium compound 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 subsequent layer is deposited on the initial layer. The subsequent layer may include beryllium 242. In one embodiment, it is preferred that the subsequent layer does not contain any metal because the intermetallic compound is previously formed in step 220. In step 250, beryllium nucleation is induced in the subsequent layer. Nucleation may be induced on a portion of the particle, such as the intermetallic compound. In one embodiment, nucleation is induced on an outer portion or surface of the particle. The method may continue to repeat steps 240 and 250 to build up successive layers as desired to form the beryllium article.

[0046] The present disclosure has been described with reference to exemplary embodiments. Obviously, after reading and understanding the foregoing detailed description, others will think of modifications and variations. The present disclosure is intended to be interpreted as including all such modifications and variations as long as they fall within the scope of the appended claims or their equivalents.

Claims

1. A method for producing a beryllium product, comprising: depositing an initial layer on the 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 comprising an intermetallic compound of beryllium and the at least one metal in the initial layer; inducing beryllium nucleation on a portion of the plurality of particles 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; and The forming and nucleating steps are repeated for the one or more successive layers. 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. The method according to claim 1 or 2, wherein the one or more successive layers comprise 0.001 to 1.0 wt. % of the at least one metal, based on the total weight of the one or more successive layers.

4. The method according to any one of claims 1 to 3, wherein the intermetallic compound of beryllium comprises beryllium.

5. The method of any one of claims 1 to 4, wherein the plurality of particles are formed by exposing the deposited initial layer to an energy source.

6. A method according to any one of claims 1 to 5, comprising providing the supply of beryllium in powder form.

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

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

9. A method for producing a beryllium product, comprising: depositing an initial layer on the 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 initiation layer to form a plurality of particles of an intermetallic compound comprising beryllium in the initiation layer; cooling the initial layer; depositing one or more successive layers on at least a portion of the initial layer opposite the surface, wherein the successive layers contain beryllium; directing energy to a portion of the one or more successive layers; and Beryllium nucleation is induced on a portion of the plurality of particles to form grains having an average grain size of 1 to 40 microns.

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

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

12. The method of any one of claims 9-11, wherein the plurality of particles are formed by exposing the deposited initial layer to an energy source.

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

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

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

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