Manufacture of a workpiece having a nanostructured phase from a functionalized powder raw material

Abstract

Nanoengineered materials for powder metallurgy and workpieces made using the materials are provided. The present invention provides a nano-engineered coating for metal, polymer, and / or ceramic powder metallurgy feedstock powders for producing workpieces with superior performance and / or functional benefits, including a first phase powder having a partial or complete nano-engineered coating and / or a second phase adhered to the interface of its constituent materials. The present invention also provides a method for producing injection molding and additive manufacturing feedstock powders that include the coating and additional respective functional benefits.

Description

Technical Field

[0001] The present technology generally relates to the field of powder metallurgy (PM). In particular, the present technology relates to powders used as raw materials for injection molding (IM), additive manufacturing (AM), and other powder-based fabrication systems, which have a nanotechnology partial or complete coating and / or a second phase adhered to the interface of their constituent materials. More particularly, the present technology relates to nanotechnology coatings for metal, polymer, and ceramic IM and AM feedstock powders for manufacturing workpieces having excellent performance and / or functional advantages, and to methods of manufacturing IM and AM feedstock powders including such coatings and their respective additional functional advantages.

Background Art

[0002] The incorporation of particles sized from millimeters down to nanometers is ubiquitous in end-use products. These particles are typically synthesized as powders from vapor, liquid, or solid precursors and are produced on an industrial scale in many substance state conversion processes such as gas, subcritical liquid, supercritical fluid, solid, or plasma. Many synthesis processes have been used and optimized for decades if not centuries. However, these process optimization steps are typically done within each individual process, and how the particles are used, processed, or further improved by the next step in the value chain is done with little, if any, consideration. A significant proportion of the particles used in all industries can be enhanced by improvement or post-treatment processes that change the surface properties without adversely affecting the bulk material. The improvement processes can result in an interdiffusion layer that is a homogeneous region incorporating materials, functions, structures, or other physical or chemical properties derived from individual shells, layers, coatings, or other coatings in the thickness range from sub-nanometers to hundreds of micrometers, or both the bulk and surface compositions. Alternative processing steps can result in a second phase attached to the first particle. The coating, or more generally the second phase, can contain from 0.0001 mass% (typically measured in ppm) up to 50 mass%, and, if desired, third, fourth, etc. phases (hereinafter referred to as the second phase, which is understood to include the incorporation of additional sub-phases) can be incorporated to achieve functional benefits in the end-use mixture or product. In the absence of a coating or second phase, adjacent particles may undergo fusion, sintering, aging, or other similar processes when subjected to certain post-treatments, and the coating is sometimes designed to function as a barrier to suppress, delay, prevent, or otherwise reduce the tendency for such processes to occur. Sometimes the second phase is designed to enhance or modify processes designed to cause the particles to fuse, sinter, or age either during a common welding or joining process or, preferentially, during post-treatment.Alternatively, the post-treatment process can be used to remove the original surface by physical or chemical etching, reaction, conversion, or other removal processes. In most cases, if one post-treatment process can enhance the value of a particular product, multiple post-treatment processes can be expected to synergistically enhance performance, whether by similar processes involving different materials, similar materials applied using different processes, or different materials applied using different processes. The field of metallurgy and, more generally, the field of composite matrix formation are rich in examples of the advantages of post-treatment processing, often examples of the importance of post-treatment processing, particularly in the formation of high-strength steels and metal alloys.

Summary of the Invention

Problems to be Solved by the Invention

[0003] For example, a manufacturer of particles useful as raw materials for an AM system may optimize a high-yield process for a product having a specific particle size or particle size distribution, enabling the manufacturer to sell one product to many customers at a high yield. However, when the powder is deployed in highly fragmented markets such as batteries, pigments, catalysts, additives, AM raw materials, etc., and can be sold, for example, as dry powder, slurry, suspension or granular solid, there is a growing need for customers to better manage the size, type, format, composition and improvement technologies used in order to enable the customer's product to be better optimized and meet end-use specifications. As an example, conductive carbon products can be deployed in batteries, capacitors or fuel cells, each of which can be further segmented by the use or type of product, each of which may benefit from different sizes, surface areas and functional coatings, and it is rare for material manufacturers to visualize the impact of the manufacturer's process optimization efforts on the customer's end-use performance or understand the complexity of that impact. Separately, from an AM perspective, there are many types of metal alloys that can be used to manufacture metal workpieces using AM tools, but the specific size, shape, function and mechanical properties can vary greatly depending on the alloy and the type of product being manufactured, thereby potentially limiting their commercialization separately. Ultimately, there is a value proposition that metal workpieces manufactured using an additive manufacturing process can achieve the same mechanical properties as metal parts forged, injection molded, cast, or machined by other methods without any of the drawbacks associated with these conventional methods.

Means for Solving the Problems

[0004] One aspect of many embodiments of the present invention relates to a workpiece including a first phase and a second phase, wherein the first phase powder has a nanotechnology partial or complete coating and / or a second phase adhered to the interface of its constituent materials. Some embodiments described herein provide nanotechnology coatings for PM feedstock powders of metals, polymers or ceramics for producing workpieces having excellent performance and / or functional advantages, as well as methods for producing IM and AM feedstock powders including these coatings and their respective additional functional advantages.

[0005] In at least one embodiment, a workpiece includes a first phase including at least one of metal, metal alloy, ceramic, glass and polymer, and a second phase including at least one of metal, metal alloy, ceramic, glass and polymer, wherein the second phase is chemically or physically adhered to the surface of the first phase before fabrication of the workpiece. In at least one embodiment, the first phase is derived from a powdered feedstock configured for use in an additive manufacturing, 3D printing, binder jet printing, laser melting, plasma sintering, injection molding, extrusion-based, cold spray, or subtractive manufacturing process.

[0006] In at least one embodiment, the first phase has a characteristic grain size of about 500 μm or less. In at least one embodiment, the first phase has a characteristic grain size of 10 nm to 100 μm. In at least one embodiment, the first phase has a characteristic grain size of 100 nm to 10 μm. In at least one embodiment, the first phase has a characteristic grain size of about 1 μm or less.

[0007] In at least one embodiment, the first phase or the second phase is uniformly distributed throughout the workpiece.

[0008] In at least one embodiment, the workpiece includes a plurality of volume elements. In at least one embodiment, one or more physical or mechanical properties of any two distinct volume elements of the same size of the workpiece have a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece. In at least one embodiment, one or more chemical or electrical properties of any two distinct volume elements of the same size of the workpiece have a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece. In at least one embodiment, the chemical composition of any two distinct volume elements of the same size of the workpiece has a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece.

[0009] In at least one embodiment, the material of the second phase is in the form of a coating that covers at least 70% of the outer surface area of the powder of the first phase before fabrication of the workpiece. In at least one embodiment, the coating is applied using one or more of sol-gel, microemulsion, physical vapor, chemical vapor, atomic layer, pyrolysis, chemical decomposition, or supercritical fluid deposition processes. In at least one embodiment, the material of the second phase: i) remains adjacent to the grains of the material of the first phase, ii) remains dispersed with the grains of the material of the first phase, or iii) maintains an interface with the grains of the material of the first phase.

[0010] In at least one embodiment, the first phase includes titanium, aluminum, boron, chlorine, iron, chromium, cobalt, magnesium, molybdenum, tungsten, nickel, tin, tantalum, vanadium, yttrium, carbon, zinc, silicon, or zirconium. In at least one embodiment, the grains of the material of the first phase are separated by a uniform distance in the range of 0.1 nm to 100 nm.

[0011] In at least one embodiment, the workpiece is manufactured using one or more of additive manufacturing, 3D printing, binder jet printing, laser melting, plasma sintering, injection molding, extrusion-based, cold spray, or subtractive manufacturing processes.

[0012] In at least one embodiment, the second phase comprises an oxide, nitride, carbide, boride, halide, or aluminide. In at least one embodiment, the second phase comprises one or more additional subphases.

[0013] In at least one embodiment, the composition of the second phase in the workpiece is different from the composition of the second phase of the starting raw material powder prior to fabrication of the workpiece. In at least one embodiment, the composition of the second phase is formed during fabrication of the workpiece.

[0014] In at least one embodiment, the workpiece is configured for use (i) in nuclear applications, (ii) as an anode, anode fluid, cathode, cathode fluid, electrolyte, current collector, stack member, electrode assembly, separator, membrane, or as a pack member of an electrochemical cell, (iii) in a battery containing a liquid electrolyte, a battery containing a solid electrolyte, a capacitor, an electrolytic cell, a fuel cell containing a liquid electrolyte, or a fuel cell containing a solid electrolyte, (iv) as a structural or reinforcement member, (v) as an exterior or shielding member of a stationary or mobile device, (vi) as a weight reduction means for mobile or portable applications.

[0015] In one embodiment, the workpiece of the present technology includes a first phase including one or more of titanium metal, titanium alloy, aluminum metal, or aluminum alloy, and the second phase may include one or more of a metal oxide or a metal nitride.

[0016] In one embodiment, the workpiece of the present technology includes a first phase including a stainless steel alloy, and the second phase may include one or more of a metal oxide or a metal nitride.

[0017] In one embodiment, the workpiece of the present technology includes a first phase containing one or more of chromium metal, chromium alloy, cobalt metal or cobalt alloy, and the second phase may contain one or more of metal oxide or metal nitride.

[0018] In one embodiment, the workpiece of the present technology includes a first phase containing one or more of ferrous metal, ferrous alloy or ferrite material, and the second phase may contain one or more of metal, metal oxide or metal nitride.

[0019] In one embodiment, the workpiece of the present technology includes a first phase containing magnesium or magnesium alloy, and the second phase may contain one or more of metal oxide or metal nitride.

Brief Description of the Drawings

[0020] The details of one or more embodiments are described in the accompanying drawings and the following specification. Other features, aspects and advantages of the disclosure will become apparent from the specification, drawings and claims. In the drawings, like reference numerals are used throughout the various figures to indicate like components.

[0021] [Figure 1] FIG. 1A is an embodiment of a particle having a geometrically simple first phase and a second phase in the form of a geometrically simple and uniform coating. FIG. 1B is an embodiment of a particle having a geometrically complex first phase and a second phase in the form of a geometrically simple and uniform coating. FIG. 1C is an embodiment of a particle having a geometrically simple first phase and a second phase in the form of a geometrically complex discontinuous or particulate-based coating (however, the coating is uniform in thickness over the entire external surface area). FIG. 1D is an embodiment of a particle having a geometrically complex first phase and a second phase in the form of a geometrically complex discontinuous or particulate-based coating (however, the coating is not uniform in thickness over the external surface area).

[0022] [Figure 2] Figure 2 is an exploded view of a local and regional micro-structure, showing a simplified schematic diagram of the workpiece of the present technology.

[0023] [Figure 3] Figure 3 shows an exploded view of the local micro-structure of the workpiece of an embodiment of the present technology, emphasizing the uniform distribution of the first and second phases.

[0024] [Figure 4] Figure 4A shows a geometrically simplified schematic diagram of the local micro-structure of the workpiece of an embodiment of the present technology when the first and second phases have similar compounding amounts. Figure 4B shows a geometrically simplified schematic diagram of the local micro-structure of the workpiece of an embodiment of the present technology when the compounding ratio of the first and second phases is high. Figure 4C shows a geometrically simplified schematic diagram of the local micro-structure of the workpiece of an embodiment of the present technology when the compounding ratio of the first and second phases is very high. Figure 4D shows an alternative schematic diagram of the local micro-structure of the workpiece of an embodiment of the present technology when the compounding ratio of the first and second phases is very high and the second phase is distributed throughout the workpiece.

[0025] [Figure 5] Figure 5A shows a cross-sectional image of the non-uniform micro-structure of a conventional workpiece without nano-engineering powder raw materials. Figure 5B shows a cross-sectional image of the uniform micro-structure of the workpiece of the present technology containing nano-engineering raw materials.

[0026] [Figure 6] Figure 6 shows photographic images of a series of samples of annealed Ti-64 powder with various coating thicknesses of metal oxides applied to the surface of the powder raw material, indicating oxidation resistance (retained gray) or lack of oxidation resistance (dark brown).

[0027] Some or all of the figures may be recognized as schematic depictions for illustrative purposes. It should be clearly understood that the figures are provided to illustrate one or more embodiments and are not used to limit the scope or meaning of the claims. Descriptions of specific heights, lengths, widths, relative dimensions, etc. are intended to serve only as examples and are not intended to limit the scope of the technology.

Best Mode for Carrying Out the Invention

[0028] Various embodiments are described below. It should be noted that no particular embodiment is intended as an exhaustive description or as a limitation to a broader aspect discussed herein. One aspect described in relation to a particular embodiment is not necessarily limited to that embodiment and can be implemented in any other embodiment.

[0029] Features may be described herein as part of the same or separate aspects or embodiments of the technology for purposes of clarity and concise description. Those skilled in the art will recognize that the scope of the technology can include embodiments having all or some combination of the features described herein as part of the same or separate embodiments.

[0030] Various techniques and mechanisms of the technology may sometimes be described in the singular for clarity. However, it should be noted that some embodiments include multiple iterations of the technique or multiple exemplifications of the mechanism, unless otherwise stated. The following description sets forth numerous specific details to provide a complete understanding of the technology. Some or all of these specific details may not be present in particular exemplary embodiments of the technology. In other instances, well-known process operations are not described in detail so as not to unnecessarily obscure the technology.

[0031] The following terms are used throughout and are defined as follows.

[0032] As used in this specification and the appended claims, the singular forms of articles and elements such as "a", "an", and "the" in the context of describing singular items (particularly in the context of the following claims) are to be construed as including both the singular and the plural, unless otherwise indicated in this specification or clearly contradicted by the context. The recitation of a range of values in this specification is intended only to serve as a shorthand method of referring individually to each separate value within the range, and each separate value is incorporated into this specification as if it were individually recited herein. All methods described in this specification can be performed in any suitable order, unless otherwise indicated in this specification or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "such as") provided in this specification is intended only to clarify the embodiments and is not intended to limit the claims unless otherwise stated. Words in the specification should not be construed as indicating any non-claimed element as essential.

[0033] The embodiments exemplified in this specification can be appropriately implemented without any element or limitation not specifically disclosed in this specification. Thus, for example, terms such as "comprising", "including", "containing", etc. shall be read expansively and without limitation. Further, the terms and expressions used in this specification are used as terms of explanation rather than limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the features shown and described or a part thereof, but it is recognized that various changes are possible within the scope of the technology described in the claims. Further, the phrase "consisting essentially of" shall be understood to include those specifically described elements and those additional elements that do not materially affect the basic and novel features of the technology described in the claims. The phrase "consisting of" excludes any element not specifically described. The expression "comprising" means "including but not limited to". Thus, other substances, additives, carriers or steps not mentioned may be present. Unless otherwise specified, "a" or "an" means one or more.

[0034] Unless otherwise indicated, all numbers expressing quantities of characteristics, parameters, conditions, etc. used in the specification and claims shall be understood to be modified in all cases by the term "about". Thus, unless otherwise indicated, the numerical parameters shown in the following specification and the appended claims are approximate values. Any numerical parameter should be interpreted in light of the reported number of significant figures and by applying ordinary rounding techniques. The term "about", when used before a numerical designation including a range (e.g., temperature, time, amount and concentration), indicates an approximate value that may vary by (+) or (-) 10%, 5% or 1%.

[0035] As will be understood by those skilled in the art, for all purposes, and particularly from the perspective of providing a written description, the scope disclosed in this specification includes all possible sub-ranges and combinations of those sub-ranges. It can be readily recognized that any of the listed ranges can be sufficiently described and are capable of being divided, for example, into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed in this specification can be readily divided, such as into lower thirds, middle thirds, and upper thirds. Also, as will be understood by those skilled in the art, all words such as "below", "at least", "greater than", "less than", etc. include the recited numbers and refer to ranges that can be divided into sub-ranges as discussed above. Finally, as will be understood by those skilled in the art, ranges include each individual component.

[0036] In this specification, injection molding (IM) and additive manufacturing (AM) are, for simplicity, referred to together as AM.

[0037] The various embodiments of the present technology described in this specification relate to the use of a nanostructured coating process that will add a homogeneous distribution of nano-sized grains on the powder used for a more performant additive manufactured workpiece and / or will result in a homogeneous distribution of nano-sized grains in the finished part after AM is applied.

[0038] In one aspect, a nanoengineering coating for metal, polymer, and ceramic injection M and AM feedstock powders for manufacturing workpieces having excellent performance and / or functional advantages, and a method for manufacturing IM and AM feedstock powders including these coatings and their respective additional functional advantages are disclosed.

[0039] For various reasons, each sector or industry has determined that the incorporation of coated particles into end-use products provides added value in product performance sufficient to justify the costs associated with each coating process. Deposition techniques are sometimes used to deposit coatings. Examples of deposition techniques can include molecular layering (ML), chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular layer deposition (MLD), vapor phase epitaxy (VPE), atomic layer chemical vapor deposition (ALCVD), ion implantation, or similar techniques. In each of these, the coating is formed by exposing a powder to a reactive precursor, which reacts either in the vapor phase (e.g., in the case of CVD) or at the surface of the powder particles (as in the case of ALD and MLD). These processes can be enhanced by the incorporation of plasma, pulsed or non-pulsed lasers, RF energy, and electric arc or similar discharge techniques. Sometimes, liquid phase techniques are used to synthesize and / or deposit coatings. Examples of liquid phase techniques include, but are not limited to, sol-gel, co-precipitation, self-assembly, alternate lamination, or other techniques. Liquid phase techniques share at least one common point when manufacturing powders. That is, greater efficiency can be obtained by utilizing gas-solid unit operations due to the energy concentration and costs of mixing, separating, and drying substances synthesized or coated using liquid phase techniques. Additionally, typical AM feedstock powders need to maintain a high degree of particle size uniformity and are typically sold in a state as monodisperse as possible to help with the uniformity of the printing process. Dry powders that undergo liquid phase processing may suffer from changes in particle size distribution, aggregation during separation / drying, or other drawbacks of liquid phase processes that bind to inferior workpieces. Another advantage of utilizing gas-solid unit operations is the ability to continuously perform solid state reaction techniques (e.g., annealing, sintering, or other heat treatments in various controlled gas environments) in conjunction with the synthesis or coating step. In one aspect, provided herein are manufacturing systems and strategies that can fully control all aspects of the manufacture of the desired substance in one comprehensive scheme, resulting in the highest performance workpieces at the lowest possible cost.

[0040] Currently, when workpieces or delicate parts are manufactured using conventional fabrication processes as small orders, significant cost increases occur due to the custom nature of these types of manufacturing processes. AM, also known as 3D printing, can provide a mechanism for manufacturing short-run, custom parts on a just-in-time or on-demand basis (reducing cost barriers). However, differences in mechanical or structural properties (especially at high strain rates) cause parts derived from today's AM to exhibit properties that do not meet those of their higher-cost, conventional (delicate) equivalents. One embodiment of this disclosure relates to a cost reduction strategy for workpiece manufacturing that uses a low-cost, high-productivity atomic layer deposition (ALD) nanostructure coating process to precisely tailor the grain size and structure of a finished workpiece in order to accurately match the mechanical properties of AM-derived parts to those of currently procured parts.

[0041] In one aspect, a workpiece is disclosed that includes a first phase and a second phase. In some embodiments, the second phase may be included as a coating over the first phase. In certain embodiments, the material of the second phase is in the form of a coating that covers at least 70% of the external surface area of the powder of the first phase prior to fabrication of the workpiece. This includes coatings that cover about 75%, 80%, 85%, 90%, or 95% of the external surface area of the powder of the first phase prior to fabrication of the workpiece.

[0042] The first phase may include one or more of metals, metal alloys, ceramics, glasses, and polymers. The second phase may include one or more of metals, metal alloys, ceramics, glasses, and polymers. In some embodiments, the second phase is chemically or physically adhered to the surface of the first phase prior to fabrication of the workpiece. In at least one embodiment, the first phase is derived from a powdered feedstock configured for use in an additive manufacturing, 3D printing, binder jet printing, laser melting, plasma sintering, injection molding, extrusion-based, cold spray, or subtractive manufacturing process.

[0043] The characteristic grain size of the first phase may depend on various factors such as the desired workpiece characteristics and the specific end use. In an exemplary embodiment, the first phase may have a characteristic grain size of about 1000 μm or less. In at least one embodiment, the first phase has a characteristic grain size of about 5 nm to about 500 μm, about 10 nm to about 100 μm, about 1 nm to about 50 μm, or about 5 μm to about 20 μm, and may include ranges between any two of these values or ranges less than any one of these values, of about 500 μm or less. In at least one embodiment, the first phase has a characteristic grain size of 10 nm to 100 μm. In at least one embodiment, the first phase has a characteristic grain size of 100 nm to 10 μm. In at least one embodiment, the first phase has a characteristic grain size of about 1 μm or less.

[0044] The workpiece of the present technology may include a plurality of volume elements. In some embodiments, one or more physical or mechanical properties of any two distinct volume elements of the same size of the workpiece have a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece. In other embodiments, one or more chemical or electrical properties of any two distinct volume elements of the same size of the workpiece have a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece. In still other embodiments, the chemical composition of any two distinct volume elements of the same size of the workpiece has a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece.

[0045] Suitable materials for the first phase are described herein. In at least one embodiment, the first phase includes titanium, aluminum, boron, chlorine, iron, chromium, cobalt, magnesium, molybdenum, tungsten, nickel, tin, tantalum, vanadium, yttrium, carbon, zinc, silicon, or zirconium. In at least one embodiment, the grains of the material of the first phase are separated by a uniform distance in the range of 0.1 nm to 100 nm, including from about 1 nm to about 50 μm, from about 10 nm to about 25 μm, or from about 1 μm to about 10 μm, and ranges between any two of these values, or ranges less than any one of these values.

[0046] Suitable materials for the second phase are described herein. In at least one embodiment, the second phase includes oxides, nitrides, carbides, borides, halides, or aluminides. In some embodiments, the second phase includes one or more additional sub-phases. In some embodiments, the composition of the second phase in the workpiece is different from the composition of the second phase of the starting raw material powder before fabrication of the workpiece. In some embodiments, the composition of the second phase is formed during the fabrication of the workpiece.

[0047] A method suitable for applying or depositing a material of a second phase onto a material of a first phase is described herein. In some embodiments, the second phase or coating is applied using one or more of sol-gel, microemulsion, physical vapor, chemical vapor, atomic layer, pyrolysis, chemical decomposition, or supercritical fluid deposition processes. In at least one embodiment, the material of the second phase remains adjacent to the grains of the material of the first phase, remains dispersed with the grains of the material of the first phase, or maintains an interface with the grains of the material of the first phase.

[0048] A method suitable for manufacturing a workpiece of the present technology is described herein. In some embodiments, the workpiece is manufactured using one or more of additive manufacturing, 3D printing, binder jet printing, laser melting, plasma sintering, injection molding, extrusion-based, cold spray, or subtractive manufacturing processes.

[0049] In some embodiments, the second phase is designed to improve a joining, welding, or bonding process for forming a solid workpiece that includes metals or metal alloys that are typically non-weldable or non-bondable and metals or metal alloys that are difficult to weld or bond. As described in ISO standard 581-1980, which states that "a metal material is considered easy to weld within the established limits for a given process and for a given purpose when the welding provides the integrity of the metal by the corresponding technical process such that the welded parts meet the technical requirements for their own quality as well as the technical requirements for their influence on the structure they form." The term "weldability" is often defined qualitatively rather than quantitatively. In one aspect, the present technology provides a second phase that improves weldability and achieves the technical requirements and quality of a finished workpiece manufactured using any of the processes described herein.

[0050] In other embodiments, the nanoengineering powder-based raw materials are designed to enable sintering or bonding of ceramics that are typically difficult to sinter and glassy materials that are difficult to bond. It can be inferred that the sintering temperature of the ceramic is about two-thirds of the melting temperature of the ceramic material. Ceramics with very high melting temperatures (e.g., carbide materials, among which tungsten carbide and silicon carbide are typical examples) are difficult to sinter or bond with other similar or dissimilar materials. In another aspect, the present technology provides a second phase that improves sinterability and achieves the technical requirements and quality of the finished workpieces manufactured using any of the processes described herein. A uniform coating of a specific second phase (or a combination of additional phases provided previously), also known as a sintering aid, will maximize the degree of sintering with the lowest net energy input to achieve the same functional performance without the presence of the specific second phase. Second phases derived from fine particles are commonly used as sintering aids, but the prior art does not teach that a specific coating of a uniform nanoscale material on the surface of the material to be sintered, especially when assembled into a workpiece using one of the processes described herein, can achieve specific functional advantages for net shape forming, grain size / structure, and / or mechanical properties. For example, 3D printed ceramics would be difficult to manufacture using the standard fine particle-based second phase approach for sintering aids used in the prior art. The uniform distribution and homogeneity of the aforementioned second phase would not be consistent from particle to particle or from layer to layer for workpieces constructed by a powder-based additive manufacturing process. The technology described herein aims to overcome the insurmountable difficulties and property limitations of workpieces additive manufactured in the prior art by incorporating a very uniform second phase on top of the first fine particle phase such that the uniformity of each layer is identical to other layers in the Z-direction across the entire workpiece. The uniform and homogeneous distribution of the aforementioned second phase (or second phases) will minimize the net energy required for both assembling each workpiece into its finished state and post-processing each workpiece into its finished state.Energy savings are typically over 10%, often over 25%, sometimes over 50%, and in some cases and for some materials over 60%. This dramatically reduces the net cost of manufacturing additively manufactured ceramics of equivalent quality to those made using alternative and / or more conventional manufacturing processes.

[0051] In some embodiments, the nanoengineered feedstocks are designed to enable the fusion, polymerization, or bonding of polymer materials (as the first or second phase) with poor bonding characteristics. The term "rheological weldability" has been developed as an attempt to quantify the criteria for successfully welding or bonding polymer materials to an interface. The mechanics of the interface of the constituent materials containing the molten polymer material and their respective surface tensions play a role similar to the activation energy of the polymer material. Incorporation of a second phase of the polymer with a lower activation energy or lower viscosity under desired welding conditions will improve the overall bondability or rheological weldability of the polymer material. In some cases, the second phase includes a glass, ceramic, or metallic material that can create one or more additional functional advantages for the fabricated part having the first phase containing the polymer material. In one aspect, the technology provides a method for facilitating the synthesis of a polymer workpiece composed of a block copolymer, which is either a) producing a bulk block copolymer by a conventional injection molding, casting, or extrusion process in which two separate polymer materials (including a block copolymer material) are simultaneously administered to a fabrication system, or b) constructing in an alternating lamination system by alternately performing a step of providing a layer containing a first polymer material and a step of providing a layer containing a second polymer material (wherein the first and second materials represent the final block copolymer material). This latter approach will be most useful when benefiting from the fact that the layer thicknesses effectively corresponding to the molecular weights of each individual polymer are large compared to the molecular scale, or when it is desired that the ratio of the first phase to the second phase approaches 1.

[0052] For manufacturing purposes, it is often desirable to use a lower-cost polymer material to constitute most of the polymer system and utilize a small amount of a second phase to create block copolymers that serve as means to maintain high adhesion between localized interfaces. The invention described herein does not require a very uniform cross-linking of polymer chains uniformly over a significant portion of the polymer workpiece to achieve appropriate mechanical properties. Instead, it benefits from the formation of a homogeneous block copolymer interface that, when a smaller portion of the polymer workpiece is uniformly distributed throughout the finished workpiece, unexpectedly imparts sufficient mechanical strength to enable bonding or welding. Further, by adding a second phase that includes a ceramic, glass, or metallic substance, the mechanical strength can be further improved, or other electrical, thermal, optical, or chemical advantages can be added to the finished workpiece without sacrificing other beneficial properties of the workpiece fabricated without said ceramic, glass, or metallic substance. Characteristic examples include the incorporation of layers of thermally conductive ceramics such as aluminum nitride or boron nitride, or the incorporation of a second phase that includes a highly thermally conductive metal such as copper or aluminum. The ability to adjust the degree of wetting of the interface by using a specific coating material, with or without an adhesive or bonding promoter as useful, has been shown to significantly increase the thermal conductivity of a workpiece having a first phase that includes a lightweight polymer. A homogeneous distribution of the second phase applied as raw material particles as a coating, which would all be in direct contact when administered in a layer-by-layer manufacturing system, enables an increase in target properties or performance at a formulation amount below the bulk workpiece's percolation threshold by a local formulation that exceeds the percolation threshold in the immediate vicinity of the second phase. This 2D or 3D network of the second phase provides unexpected advantages to the additive manufactured workpiece, and one skilled in the art can recognize that this example of a polymer material as the first phase is merely illustrative and extends to all features and conditions for which a percolation threshold is required to observe a change in bulk properties. In some embodiments, the workpiece, first phase, or second phase of the present technology is uniformly distributed throughout the workpiece.

[0053] Figure 1 shows four general embodiments of materials (selected from more available embodiments) formed in the first and second phases of the workpiece of the present technology. The shape of the powdery raw material 101 can be described as "geometrically simple" and can have a sphericity greater than 80%, 85%, 90% or 95% in the case of a spheroid. Those skilled in the art of AM understand the value of using spherical powdery raw materials that may have been intentionally spheroidized. However, the workpiece of the present technology is not limited to geometrically simple powder types (such as those shown in FIGS. 1A and 1C), and also includes powders having angular, rough, serrated, or other irregular descriptive terms or features (such as those shown in FIGS. 1B and 1D). The second phase of the workpiece of the present technology may be derived from the second-phase material 201 shown as a continuous uniform coating in FIGS. 1A and 1B, a discontinuous uniform coating in FIG. 1C, and a discontinuous non-uniform coating in FIG. 1D. The second-phase material 201 may be derived from the incorporation of second-phase material particles added or adhered to the powdery raw material 101. For simplicity, FIG. 1 shows only the second phase, but in some embodiments, the second phase further includes a third phase, a fourth phase, or one or more additional phases generally described as one or more sub-phases, which may, among other things, be in the form of coatings, particles, layers, lamellae, scales or shells, all of which form part of the complex second phase of the manufactured workpiece of the present technology.

[0054] FIG. 2 shows a workpiece 10, which is an example of a workpiece of the present technology. The workpiece 10 includes many sub-elements depicted here as region volume elements 20, each of which also includes sub-elements depicted as microstructural elements 30. In one aspect, the present technology enables maximizing the dispersion and / or homogeneous distribution of a second phase within a first phase in a fabricated workpiece, and the uniformity of the application of the material of the second phase onto the powdered raw material of the first phase is maintained throughout the workpiece fabrication process. Although an idealized embodiment is shown in FIG. 2, it has been observed that two arbitrary region volume elements of a workpiece fabricated using uniform process conditions result in mostly uniform sub-features and microstructural elements. One skilled in the art will understand that uniform process conditions may not be experienced at the ends of a workpiece or other regions where non-steady state process conditions are experienced. Mostly uniform is intended to represent fluctuations of at most 20%, usually less than 15%, often less than 10%, sometimes less than 5%, and in some cases less than 3% throughout an equivalent volume element. Further, this typically also applies to similarly sized cross-sectional slices derived from two separate identically sized volume elements processed using the same conditions. The uniformity of the application of the material of the second phase onto the powdered raw material of the first phase is a major factor in determining the homogeneity of the phase distribution in the finished workpiece of the present technology.

[0055] Figure 3 shows a microstructural section 40 which is a further breakdown view of the microstructural element 30 (the volumetric element 20 of the present technology and the element of the workpiece 10), showing a highly simplified version of the phase separation along one dimension. The microstructural section 40 includes a first phase 102 derived from the powdered raw material 101 and a second phase 202 derived from the material 201 of the second phase. In this depiction, the second phase 202 is separated from the material 102 of the first phase, and the material 102 of the first phase includes a first grain size 103. The first grain size 103 may be the same as the particle size of the powdered raw material 101, or one fraction of it, or a multiple of it, but ultimately depends on the process parameters used to fabricate the workpiece 10. Further, the presence of the material 201 of the second phase (and its related composition, dimensions, etc.) may also directly affect the dimension of the first grain size 103. In other words, a workpiece 10 derived from a powdered raw material 101 without the presence of a minimum critical amount of the material 201 of the second phase will result in a different (larger) first grain size 103 compared to a workpiece 10 derived from a powdered raw material 101 having a minimum critical amount of the material 201 of the second phase. The first grain size 103 is shown as a single measurement point for simplicity, but those skilled in the art will recognize that the numerical interpretation of the grain size may be the average or median of the size distribution. Similarly, Figure 3 also shows a simplified depiction of the grain boundary 203, which may have a characteristic length scale that further provides separation between the first grains. Since it is difficult to clearly and permanently maintain or fix the second phase between each individual grain, the schematic diagram of 203 is intended to represent the overall phenomenon developed by the uniform application of the material 201 of the second phase onto the powdered raw material 101. Similarly, the composition and important parameters of the second phase are probabilistic and distributive in nature and may be more widely spread across the void space between the powdered raw materials 101 before the fabrication of the workpiece 10, and in particular, may depend on the blending ratio, the raw material particle size, and the geometric simplicity of the powdered raw material 101.Ultimately, since it is difficult to apply the overall fabrication parameters to each individual microstructural section 40, it was unexpected that the overall uniformity of the effect of the second-phase material 201 would generally result in uniform results with respect to the electrical, physical, mechanical, chemical, and compositional properties of the workpiece 10 of the present technology. This is especially the case when the second-phase material 201 is applied to the powder feedstock 101 on the angstrom or nanometer length scale (typically a length scale of less than 30 nanometers), which is not yet predicted by the use of modern powder metallurgy theory.

[0056] Figure 4 shows an alternative embodiment of the microstructural section 40 that includes the first-phase material 102 and the second phase 202. Figure 4A shows a rare example where the blending ratio of 102 and 202 is similar and conducive to phase separation. Nevertheless, this type of separation is typically only experienced in an AM or layer-by-layer fabrication process as opposed to a bulk IM or other conventional PM process. For such a pattern to be formed in such a cross-section in such a one-dimensional direction during the AM process, the interactions between the fabrication processes as well as the interactions between the powder feedstock 101 and the second-phase material 201 must be correct. Such a one-dimensional cross-sectional microstructure is achievable when the powder feedstock 101 is more susceptible to melting during the fabrication process than the second-phase material 201 and when there is a surface energy difference between the two materials and phases that is conducive to phase separation.

[0057] Figure 4B shows a more general example of the microstructure section 40, even though it is still idealized as a geometrically simple repeating unit (the ellipsoid of revolution may replace the square shown in Figure 4B). Such a two-dimensional patterning and / or repeating unit of such a cross-sectional area (corresponding to a 3D repeating unit of volume elements). Again, the simplified first grain size 103 is shown here, but the invention is not intended to be limited to such an idealized exactly identical grain size, but rather represents an average or median grain size distribution. Figure 4C shows a schematic diagram of a microstructure section 40 similar to that shown in Figure 4B, but the difference in the two reaches is based on the starting ratio of the powdered raw material 101 to the material 201 of the second phase (i.e., the decrease in the line thickness corresponds to an increase in the ratio of 101:201 in the workpiece).

[0058] Figure 4D shows different types of microstructure section 40 layouts, one of which can be such that the first phase can be connected together across the second phase (the second phase no longer takes the form of a coating or shell, but rather takes the form of a distribution of discrete second-phase material, or vice versa one of which can be such that the second phase is uniformly distributed throughout the workpiece 10. In practice, when the material 201 of the second phase is applied in the form of a surface coating on the powdered raw material 101 by a homogeneous distribution of the second phase 202, it has been observed that there is a minimal difference between the idealized schematic diagram of Figure 4C and that of Figure 4D. This can be explained, in particular, when the material 201 of the second phase has a length scale of less than 30 nanometers. If the material 201 of the second phase starts as discrete particles adhering to the surface of the powdered raw material 101, it is difficult to produce a microstructure section 40 as shown in Figure 4D due to i) the relatively broad particle size distribution characteristic of a powder having an average particle diameter of 30 nanometers (such powders are typically agglomerated chains of particles), and ii) the inability to produce a well-mixed sample having such a small particle size. The schematic diagrams shown in Figures 4C and 4D are the results expected based on the use of exemplary embodiments of the present technology.

[0059] Figure 5A shows a cross-sectional micrograph cut from a workpiece made from 316L stainless steel powder stock without the second phase material 201. Based on the highlighted regions identified as 301 and 302, the bright and dark regions show a very non-uniform area. Instead, Figure 5B shows a cross-sectional micrograph cut from a workpiece made from 316L stainless steel powder stock with the second phase material (aluminum oxide as a representative material that produced an unexpectedly positive result at such thickness) 201 applied in the form of a coating less than 30 nanometers. Again, regions 301 and 302 are highlighted (using the same size scale, cross-sectioning method, and fabrication parameters as the Figure 5A workpiece) and show a very uniform area across distinct volume elements and regions.

[0060] Figure 6 shows photographic images of uncoated and coated powdered titanium alloy (Ti-64) feedstock powder (101). The sample labeled "B" shows a bare substrate with no second phase material coating applied, and the sample labeled "A" shows an aluminum oxide-based second phase material coating (201) applied using atomic layer deposition technology ("A-1" = 1 nm, "A-3" = 3 nm). Table 1 describes the conditions for each sample. Sample "B-0-0" is a purely gray powder and turned dark brown when annealed at 450°C for 20 hours (sample "B-0-20") due to the formation of a thermally grown oxide layer. Sample "A-1-20" was coated with a 1 nm coating of aluminum oxide and annealed under the same conditions. This very thin coating was not sufficient to prevent oxidation and also reverted to dark brown. However, when a 3 nm alumina layer was applied, a purely gray powder resulted when annealed at 450°C for the same 20 hours (sample "A-3-20"). Sample "A-3-120" (annealed at 450°C for 120 hours) is shown to have a slightly darker gray coloration, which is a sign that a small amount of oxidation occurred during the longer annealing time.

Table 1

[0061] Common powder alloys used for 3D printing of metals include, among others, stainless steel, maraging steel, other steels, cobalt chrome, inconel, aluminum alloys, and titanium (and alloys). Powder bed fusion bonding, directed energy deposition, and binder jetting are the main methods used to build up components layer by layer. Laser powder bed fusion bonding is the most mature and well-studied metal printing technology, representing approximately 90% of the metal AM market. All powder bed fusion bonding processes (e.g., selective laser melting or SLM) involve the spreading of powder material over the previous layer. An important attribute of the SLM process includes high resolution and the ability to achieve high density without post-processing, which can be easily customized to build any moderately sized part from a 3D drawing generated in a CAD program. A second software program divides the drawing into several "slices" of a pre-determined thickness. The powder is first placed in the build chamber and smoothed by a rake. Subsequently, a high-power laser beam scans the powder bed in the required pattern to build the desired cross-section. Next, the platform is lowered by the pre-determined layer thickness, and the process continues until the part is complete. The dry powder rheology of AM feedstock materials plays a major role in both the AM process and the uniformity and quality of the finished part. Near-complete density is achieved by SLM. However, due to the high heat input, it can result in loss of alloying elements, residual stress, and thermal distortion, which need to be addressed by process parameter control and feedstock powder alloy adjustment. Ultimately, there are over 200 process variables that can affect the final microstructure in laser powder bed additive manufacturing. Of these, approximately four variables (laser power, speed, hatch spacing, and layer thickness) have the greatest impact on the core properties and printability of AM workpieces. ALD processes, materials, and dosages can unexpectedly rather dramatically change the properties of AM workpieces, and the adjustment of an optimized ALD-compatible AM process using optimized AM feedstock powders is linked to the ability to build metal, ceramic, and polymer workpieces with substantially improved properties.In the case of AM processes for metals, it has been shown that the finished workpieces can have mechanical properties that match or exceed those of their wrought counterparts under a wide range of service conditions. In some cases, the use of ALD-compatible AM feedstock powders can reduce or eliminate the need for post-processing required for AM workpieces manufactured using feedstock powders without ALD nanostructured coatings.

[0062] Smaller grains mean more grain boundaries, and thus an increase in small grain boundaries results in the Hall-Petch effect:

Eq.

[0063] One commonality among vapor-phase processing systems for manufacturing or encapsulating powders is that the chemical reactant precursors need to be volatile or able to evaporate in other ways. Considerable efforts have been made over the past several decades to increase the number and types of evaporable precursors that can be made available in such systems. Potential evaporable precursors include aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, diethylaluminum ethoxide, dimethylaluminum isopropoxide, tris(ethylmethylamide)aluminum, tris(dimethylamide)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamide)aluminum, tris(ethylmethylamide)aluminum, trimethylantimony(III), triethylantimony(III), triphenylantimony(III), tris(dimethylamide)antimony(III), trimethylarsine, triphenylarsine, triphenylarsine oxide, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)barium hydrate, barium nitrate, bis(pentamethylcyclopentadienyl)barium tetrahydrofuran, bis(triisopropylcyclopentadienyl)barium tetrahydrofuran, bis(acetato-O)triphenylbismuth(V), triphenylbismuth, tris(2-methoxyphenyl)bismuthine, diborane, trimethylboron, triethylboron, triisopropyl borate, triphenylborane, tris(pentafluorophenyl)borane, cadmium acetylacetonate, calcium bis(2,2,6,6-tetramethyl-3,5-heptanedionate), carbon tetrabromide, carbon tetrachloride, cerium(III) trifluoroacetylacetonate, tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium(IV), tris(cyclopentadienyl)cerium(III), tris(isopropylcyclopentadienyl)cerium(III), tris(1,2,3,4-tetramethyl-2,(4-Cyclopentadienyl)cerium(III), bis(cyclopentadienyl)chromium(II), bis(pentamethylcyclopentadienyl)chromium(II), chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), chromium(II) chloride, chromium(III) chloride, chromium(II) carbonyl, chromium(III) carbonyl, cyclopentadienyl(II)chromium carbonyl, bis(cyclopentadienyl)cobalt(II), bis(ethylcyclopentadienyl)cobalt(II), bis(pentamethylcyclopentadienyl)cobalt(II), tris(N,N′-diisopropylacetamido)cobalt(II), dicarbonyl(cyclopentadienyl)cobalt(III), cyclopentadienylcobalt(II) carbonyl, copper bis(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), (N,N′-diisopropylacetomido)copper(II), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)dysprosium(III), tris(isopropylcyclopentadienyl)dysprosium(III), erbium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(butylcyclopentadienyl)erbium(III), tris(N,N-bis(trimethylsilyl)amide)europium(III), tris(tetramethylcyclopentadienyl)europium(III), nitrogen trifluoride, tris(N,N-bis(trimethylsilyl)amide gadolinium(III), tris(cyclopentadienyl)gadolinium(III), tris(tetramethylcyclopentadienyl)gadolinium(III), gallium tribromide, gallium trichloride, triethylgallium, triisopropylgallium, trimethylgallium, tris(dimethylamide)gallium, tri-tert-butylgallium, digermanium, germanium, tetramethylgermanium, germanium(IV) fluoride, germanium(IV) chloride, hexaethyldigermanium(IV), hexaphenyldigermanium(IV), tributylgermanium hydride, triphenylgermanium hydride, dimethyl(acetylacetonato)gold(III), dimethyl(trifluoroacetylacetonato)gold(III), hafnium(IV) chloride, hafnium(IV) tert-butoxide, tetrakis(diethylamide)hafnium(IV), tetrakis(dimethylamide)hafnium(IV), tetrakis(ethylmethylamide)hafnium(IV), bis(tert-butylcyclopentadienyl)dimethylhafnium(IV), bis(methyl-n-cyclopentadienyl)dimethylhafnium, bis(trimethylsilyl)amide hafnium(IV) chloride, dimethylbis(cyclopentadienyl)hafnium(IV), hafnium isopropoxide, tris(N,N-bis(trimethylsilyl)amide)holmium(III), indium trichloride, indium(I) iodide, indium acetylacetonate, triethylindium, tris(dimethylamide)indium, tris(diethylamide)indium, tris(cyclopentadienyl)indium, 1,5-cyclooctadiene(acetylacetonato)iridium(I), 1,5-cyclooctadiene(hexafluoroacetylacetonato)iridium(I), 1-ethylcyclopentadienyl-1,3-cyclohexadieneiridium(I), (methylcyclopentadienyl)(1,5-cyclooctadiene)iridium(I), bis(N,N′-di-tert-butylacetamidinato)iron(II), bis(pentamethylcyclopentadienyl)iron(II), ferrocene, 1,1′-diethylferrocene, iron pentacarbonyl, iron(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(N,N′-di-tert-butylacetamidinate)lanthanum(III), lanthanum(III) isopropoxide, tris(N,N-bis(trimethylsilyl)amide)lanthanum(III), tris(cyclopentadienyl)lanthanum(III), tris(tetramethylcyclopentadienyl)lanthanum(III), tetraethyllead, tetramethyllead, tetraphenyllead, lithium tert-butoxide, lithium trimethylsilylamide, lithium(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(N,N-diisopropylacetamidinate)lutetium(III), lutetium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)magnesium(II), bis(pentamethylcyclopentadienyl)magnesium(II), bis(pentaethylcyclopentadienyl)magnesium(II), bis(cyclopentadienyl)manganese(II), bis(N,N-diisopropylpentylamidinate)manganese(II), bis(ethylcyclopentadienyl)manganese(II), bis(pentamethylcyclopentadienyl)manganese(II), bis(isopropylcyclopentadienyl)manganese(II), cyclopentadienyltricarbonylmanganese, manganese carbonyl, methylcyclopentadienylmanganesetricarbonyl, manganese tris(2,2,6,6-tetramethyl-3,5-heptanedionate), hexacarbonylmolybdenum, molybdenum(V) chloride, molybdenum(VI) fluoride, bis(cyclopentadienyl)molybdenum(IV) dichloride, cyclopentadienylmolybdenum(II) tricarbonyl, propylcyclopentadienylmolybdenum(I) tricarbonyl, tris(N,N-bis(trimethylsilyl)amide)neodymium(III), bis(methylcyclopentadienyl)nickel(II), allyl(cyclopentadienyl)nickel(II), bis(cyclopentadienyl)nickel(II), bis(ethylcyclopentadienyl)nickel(II), bis(triphenylphosphine)nickel(II) dichloride, nickel(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)niobium(IV) dichloride, niobium(V) chloride, niobium(V) isopropoxide, niobium(V) ethoxide, N,N-dimethylhydrazine, ammonia, hydrazine, ammonium fluoride, azidotrimethylsilane, triosmium dodecacarbonyl, allyl(cyclopentadienyl)palladium(II), palladium(II) hexafluoroacetylacetonate, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II), phosphine, tert-butylphosphine, tris(trimethylsilyl)phosphine, phosphorus oxychloride, triethyl phosphate, trimethyl phosphate, methylcyclopentadienyl(trimethyl)platinum(IV), chloroplatinic acid, praseodymium(III) hexafluoroacetylacetonate hydrate, dirhenium decacarbonyl, acetylacetonato(1,5-cyclooctadiene)rhodium(I), bis(ethylcyclopentadienyl)ruthenium(II), bis(cyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium(II), tolylruthenium decacarbonyl, tris(N,N-bis(trimethylsilyl)amide)samarium(III), tris(tetramethylcyclopentadienyl)samarium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)scandium(III), dimethyl selenide, diethyl selenide, 2,4,6,8-tetramethylcyclotetrasiloxane, dimethoxydimethylsilane, disilane, methylsilane, octamethylcyclotetrasiloxane, silane, tris(isopropoxy)silanol, tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, (3-aminopropyl)triethoxysilane, N-sec-butyl(trimethylsilyl)amine, chloropentamethyldisilane, hexamethyldisilazane, silicon(IV) chloride, silicon(IV) bromide, pentamethyldisilane, tetraethylsilane, N,N′,N″-tri-tert-butylsilanetriamine, (2,2,6,6-tetramethyl-3,5-heptanedionato)silver(I), triethoxyphosphine(trifluoroacetylacetonate)silver(I), silver(I) triethylphosphine(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), trimethylphosphine(hexafluoroacetylacetonato)silver(I), vinyltriethylsilane(hexafluoroacetylacetonato)silver(I), strontium tetramethylheptanedionate, pentakis(dimethylamide)tantalum(V), tantalum(V) chloride, tantalum(V) ethoxide, tantalum(V) fluoride, tris(ethylmethylamide)(tert-butylimide)tantalum(V), tris(diethylamide)(tert-butylimide)tantalum(V), tellurium tetrabromide, tellurium tetrachloride, terbium(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(cyclopentadienyl)terbium(III), tris(tetramethylcyclopentadienyl)terbium(III), thallium(I) ethoxide, thallium(I) hexafluoroacetylacetonate, cyclopentadienylthallium, 2,2,6,6-tetramethyl-3,5-heptanedionatothallium(I), tris(N,N-bis(trimethylsilyl)amide)thulium(III), tris(cyclopentadienyl)thulium(III), tin(IV) chloride, tetramethyltin, tin(II) acetylacetonate, tin(IV) tert-b, Toxid, tin(II) hexafluoroacetylacetonate, bis(N,N′-diisopropylacetamidinato)tin(II), N,N-di-tert-butyl-2,3-diamidobutane tin(II), tetrakis(dimethylamino)tin(IV), bis(diethylamido)bis(dimethylamido)titanium(IV), tetrakis(diethylamido)titanium(IV), tetrakis(dimethylamido)titanium(IV), tetrakis(ethylmethylamido)titanium(IV), titanium(IV) bromide, titanium(IV) chloride, titanium(IV) fluoride, titanium(IV) tert-butoxide, titanium(IV) isopropoxide, titanium(IV) ethoxide, titanium(IV) methoxide, titanium(IV) isopropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate), dichlorotitanium(IV) oxide, bis(tert-butylimide)bis(dimethylamido)tungsten(VI), tungsten hexacarbonyl, tungsten(VI) chloride, tungsten(VI) fluoride, triaminotungsten(IV) tricarbonyl, cyclopentadienyltungsten(II) tricarbonyl hydride, bis(isopropylcyclopentadienyl)tungsten(IV) dihydride, bis(cyclopentadienyl)tungsten(IV) dihydride, bis(cyclopentadienyl)tungsten(IV) dichloride, bis(butylcyclopentadienyl)tungsten(IV) diiodide, bis(cyclopentadienyl)vanadium(II), vanadium(V) oxychloride, vanadium(V) oxytris(isopropoxide), tris(N,N-bis(trimethylsilyl)amide)ytterbium(III), tris(cyclopentadienyl)ytterbium(III), tris(N,N-bis(trimethylsilyl)amide)yttrium(III), yttrium(III) tris(tert-butoxide), yttrium(III) triisopropoxide, yttrium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(butylcyclopentadienyl)yttrium(III), tris(cyclopentadienyl)yttrium(III), yttrium 2-methoxyethoxide, diethylzinc, dimethylzinc, diphenylzinc, bis(2,2,6,6-tetramethyl-3,Compounds selected from the group consisting of zinc(II) 5-heptanedionate, bis(pentafluorophenyl)zinc, zirconium(IV) dibutoxide (bis-2,4-pentanedionate), zirconium(IV) 2-ethylhexanoate, zirconium(IV) tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)zirconium(IV) dihydride, bis(methyl-n-cyclopentadienyl)methoxymethyldizirconium, tetrakis(diethylamide)zirconium(IV), dimethylbis(pentamethylcyclopentadienyl)zirconium(IV), tetrakis(dimethylamide)zirconium(IV), tetrakis(ethylmethylamide)zirconium(IV), zirconium(IV) bromide, zirconium(IV) chloride, zirconium(IV) tert-butoxide, and any two or more mixtures thereof can be mentioned. Precursors for the synthesis of powders and particles and sometimes precursors for their encapsulation often include metal salts and metal hydroxides and are administered as dry powders, liquid or gaseous raw materials, or dissolved in a suitable solvent by syringe, nozzle, spray device, evaporator, sonicator or other sub-components known to those skilled in the art. The metal salts may be in the form of halides, sulfates, nitrates, oxalates, phosphates or other inorganic or organic compounds of Ac, Ag, Al, Am, As, At, Au, B, Ba, Be, Bh, Bi, Bk, Br, C, Ca, Cd, Ce, Cf, Cm, Cn, Co, Cr, Cs, Cu, Db, Ds, Dy, Er, Es, Eu, Fe, Fl, Fm, Fr, Ga, Gd, Ge, H, Hf, Hg, Ho, Hs, In, K, La, Li, Lr, Lu, Lv, Me, Md, Mg, Mn, Mo, Mt, N, Na, Nb, Nd, Nh, Ni, No, Np, O, Og, Os, P, Pa, Pb, Pd, Pm, Po, Pr, Pt, Pu, Ra, Rb, Re, Rf, Rg, Rh, Ru, S, Sb, Sc, Se, Sg, Si, Sm, Sn, Sr, Ta, Tb, Tc, Te, Th, Ti, Tl, Tm, Ts, EG, V, W, Y, Yb, Zn, Zr, or combinations thereof.,

[0064] In the manner of processing AM raw materials, additional advantages have been demonstrated. Flowability, compression uniformity, and cohesive powder distribution can affect the quality of AM parts and are typically overcome by using higher laser intensities or post - processing steps to reduce porosity and trapped gases. ALD is arranged to reduce the agglomeration of metal powders and, in some cases, enables powders as small as 1 - 5 microns in diameter to "flow like water". The selection of the ALD coating material (e.g., boron nitride) can impart solid lubricity to the metal raw material powder, which results in better compression and will essentially lead to higher - density layers in one or more steps of the AM process. A second value proposition is that ALD - based solid lubricant coatings enable the use of coarser irregular (i.e., non - spheroidized) raw materials that can be obtained at a substantially lower cost than the spherical monodisperse metal powders required today. In some embodiments, the AM powder raw material is coated with a second - phase material that enhances lubricity, and the build density of the workpiece can be increased by 15 - 25% without additional post - processing, or conversely, the net energy consumption of the post - processing process performed on the finished workpiece can be reduced by 20 - 30%.

[0065] Additional features of this technology relate to the ability to impart resistance to air and moisture in order to handle titanium and other pyrophoric or environmentally sensitive powders more safely. Although much research has been done on the oxidation of titanium and its alloys, little attention has been paid to the expected role of the oxidation products as a tribological treatment. Various base metals, pyrophoric metal nanoparticles, and environmentally sensitive powders such as sulfides have been coated with ALD coatings to provide safety and handling advantages in air or high humidity conditions. Oxygen in solution, along with α-Ti, significantly strengthens the material. The excellent corrosion resistance of titanium under normal conditions is mainly due to the formation of a very stable, highly adherent and protective titanium dioxide film on the surface. The conventional approach is to perform a simple thermal oxidation process in which the original oxide film becomes thicker and more robust with time and / or temperature, thus providing additional protection against corrosion. When titanium and titanium alloys are heated in air at temperatures between 450 and 800 °C for 2 to 10 minutes, a protective oxide film exceeding 1 micron can be formed. However, the oxide coatings produced by this method tend to be quite brittle and thus can be easily damaged by mechanical shock, leaving the problem that the wear resistance is hardly improved. Therefore, it was unexpected to find that extremely thin films (<20 - 30 nanometers) remained mechanically adhered to the surface of Ti or Ti alloy powders and could have a beneficial effect on the handling of the powders in air and the tribological and mechanical properties (e.g., wear resistance and ductility) of the material and the finished workpieces containing the material. Furthermore, TGA test data of Ni nanopowders coated with a 5 nm thick aluminum oxide ALD coating showed that the oxidation onset temperature of the pristine powder was 300 °C, whereas the ALD-coated material did not begin to oxidize until above 700 °C. The second advantage of ALD coatings is that they can produce AM metal powders that are safe to handle and process without the additional cost of a high flow of inert gas during the printing process.Specifically, the second phase containing oxides, nitrides, carbides and halides can be applied to the first powder (e.g., titanium nitride and boron nitride), and more specifically, can be deposited on metal and metal alloy feedstock powders containing titanium, aluminum, nickel, tungsten, cobalt, chromium, iron, vanadium, yttrium, manganese or combinations thereof, enabling the AM process to be carried out safely without a significant amount of inert gas flow that is required to prevent a potentially dangerous and exothermic natural oxide formation process.

[0066] Furthermore, it was unexpectedly found that the ALD thickness, weight loading, crystallinity, grain structure, and application sequence of one or more compounds or materials comprising the second phase are important with a reasonable selection of said second phase. ALD is a relatively simple technique in that the self-limiting nature of the "brick and mortar" chemistry prevents overbuild, and deposition onto the surface is further suppressed by the specific surface area of the substrate material. Typical growth rates are on the order of 0.3 - 2 angstroms per ALD cycle, depending on the chemistry of the coating, and this level of precise control is important for optimizing grain size, structure, and quantity. The stabilizing ALD coating should be thick enough to impart robustness and stability, and the second phase should be appropriately low but thin enough to maintain a particular thickness and / or weight percent. Furthermore, the ideal encapsulation material should be "stable" under AM process conditions (or alternatively, designed for controlled degradation in the AM process when there are metallurgical advantages), and have the appropriate chemical composition to positively affect the properties of the finished part. ALD can achieve these criteria and is now the only technique that can be cost-effectively integrated into the AM part supply chain with high productivity manufacturing systems as described by King et al. in U.S. Patent Application Publication No. 201 / 10236575, the contents of which and all of the contents of its cited references are hereby incorporated by reference in their entirety. For example, stainless steel parts derived from initial AM feedstock powder were measured to have specific yield strength, tensile strength, hardness, and ductility. Applying a nanotechnology boron nitride coating to the AM feedstock powder and forming exact copy parts may be able to adjust the yield strength and tensile strength by 10%, often 50%, sometimes 100%, and in some cases 500%, thereby creating robust parts with one or more enhanced functional advantages.Additional phases and compounds were used to demonstrate that further control of ductility and hardness is achievable with properly designed aggregated second phases, and could also affect (sometimes upwards but in some cases downwards) the thickness, dosage, or other properties already adjusted from the physical or chemical constitution of the second phase. In one aspect, the technology allows for the production of very complex compositions and second phases homogeneously distributed throughout the manufactured parts with optimal functional properties, with the simplicity that a second phase can be premixed onto the raw powder before incorporation into the part by powder metallurgy (or similar particulate raw material fabrication processes).

[0067] One or more specific elements selected from the group consisting of Ac, Ag, Al, Am, As, At, Au, B, Ba, Be, Bh, Bi, Bk, Br, C, Ca, Cd, Ce, Cf, Cm, Cn, Co, Cr, Cs, Cu, Db, Ds, Dy, Er, Es, Eu, Fe, Fl, Fm, Fr, Ga, Gd, Ge, H, Hf, Hg, Ho, Hs, In, K, La, Li, Lr, Lu, Lv, Me, Md, Mg, Mn, Mo, Mt, N, Na, Nb, Nd, Nh, Ni, No, Np, O, Og, Os, P, Pa, Pb, Pd, Pm, Po, Pr, Pt, Pu, Ra, Rb, Re, Rf, Rg, Rh, Ru, S, Sb, Sc, Se, Sg, Si, Sm, Sn, Sr, Ta, Tb, Tc, Te, Th, Ti, Tl, Tm, Ts, U, V, W, Y, Yb, Zn, Zr or combinations thereof, when incorporated into a second phase of nanotechnology, have unique advantages that can be imparted onto the finished part. The advantages may result in the form of reduced processing energy, or the number of steps of the fabrication process itself, or one or more post-treatments required as compared to what is required in the absence of one or more second phases of nanotechnology. The advantages may also result in the form of obtaining preferential physical or mechanical properties of the parts fabricated when all other process variables are held constant. The advantages may also result in the form of durability and longer service life of the fabricated parts when the fabricated parts are used in their end use. One or more of these or other value propositions can be revealed or otherwise developed by the application of the techniques as described herein.The first phase includes at least one of solid metal, metal alloy, ceramic, glass and polymer, and substantial advantages are measured when the second phase includes one or more of (i) metal oxides, (ii) metal halides, (iii) metal oxyhalides, (iv) metal phosphates, (v) metal sulfates, (vi) non-metal oxides, (vii) cancrinite structures, (viii) NaSICON structures, (ix) perovskite structures, (x) spinel structures, (xi) polymetallic ion structures, (xii) metal organic structures or complexes, (xiii) polymetallic organic structures or complexes, (xiv) structures with periodic properties, (xv) randomly distributed functional groups, (xvi) periodically distributed functional groups in a 2D or 3D periodic arrangement, (xvii) metal nitrides, (xviii) metal oxynitrides, (xix) metal carbides, (xx) metal oxycarbides, (xxi) non-metal organic structures or complexes, and (xxii) non-metal inorganic structures or complexes.

[0068] For example, certain combinations of the foregoing can be used to fabricate structures used in the design of reactors that can someday enable fusion energy as a clean and reliable energy source. To create a highly tailored oxide coating on ferrite-based oxide dispersion strengthened (ODS) particles, a second phase of nanotechnology containing metal oxides can be combined with a first phase of iron-based or ferrite-based metals or metal alloys, which will improve the oxide dispersion in the final sintered composite material. The improved homogeneity and uniformity enable improvements in material properties such as fracture toughness, but also additional benefits such as neutron absorption as an example of an application-specific functional benefit that can be demonstrated, as well as additional benefits of anisotropic behavior resulting from an extrusion process that may be applicable to multiple fields or applications. The construction materials required to contain a sustained fusion reaction will be subjected to very harsh conditions. The development of improved radiation-resistant, corrosion-resistant, and heat-resistant alloys will be of great benefit for fusion and the next-generation fission reactor systems of accurate information. Furthermore, replacing the mechanical alloying method with other methods that incorporate a second phase of nanotechnology including ALD coatings or a homogeneous distribution of materials or compounds will result in a significant improvement in the composition and properties of the alloy while reducing production costs. Existing ODS materials have exceptional high-temperature creep strength and exhibit excellent irradiation damage control. Examples of current ODS alloy manufacturing methods include milling the metal phase with nanopowders of additional oxide phases, typically commercially available TiO2 or Y2O3 nanoparticles. The milled mixture is then sintered by extrusion or hot isostatic pressing. In this application, a completely homogeneous dispersion of the oxide phase within the metal matrix (and preferably a homogeneous distribution of the components of the entire second phase) protects against neutron degradation. This phenomenon enables the alloy to maintain appropriate mechanical properties for much longer than conventional alloys that have received a large amount of radiation damage. Maximizing the uniformity of the dispersion of the second phase also leads to better performance by reducing the migration distance of defects within the bulk material. Fusion reactors will create higher neutron radiation levels and will require materials that can continue to be used for long periods under dose levels as high as 200 dpa.Existing manufacturing methods are severely limited by: i) the amount of oxide they can add to the alloy; ii) how well the oxide can be dispersed before the grain size and oxygen / nitrogen uptake become detrimental to the material properties; iii) how much the second phase can be nano-processed; and iv) how uniformly and homogeneously the dispersion can be maintained over parts of various sizes manufactured using a series of techniques that use particles as raw materials.

[0069] For applications or processes incorporating nanoparticles or other second phases using milling or high-energy mixing processes, impurity uptake at ppm levels or higher cannot be overcome for several reasons and is detrimental. First, as the milling time increases, the uptake of impurities into the matrix increases. These impurities can be contaminants from the milling media and parts, the addition of oxygen, carbon dioxide, and nitrogen in the air environment, or other constituents from an alternative environment. The addition of increased oxygen as a contaminant is detrimental to some material properties of the alloy, while the addition of a second oxide phase improves the overall mechanical strength of the material. As the targeted oxide content in the second phase preferentially increases, the mixing and / or milling time must be increased to distribute the oxide homogeneously. Thus, in the milling procedures currently practiced in the art, the practical limits of oxide addition and improvement are offset by the additional oxygen uptake during the extended milling process.

[0070] A second limitation caused by milling is a change in crystallite size. When a material is milled, a large amount of mechanical work is applied to the material. This work not only decreases the particle size but also changes the crystallite size and structure, which can be further exacerbated by contamination of a few ppm from the milling media itself. This reduces the amount of process control that manufacturers can perform on both the raw materials and the fabricated parts. Furthermore, this effect may require significant heat treatment and recrystallization post-processing, which adds minimal cost, adds an unnecessary risk of precipitation and / or coalescence of oxide phases at grain boundaries, and as a result, may reduce homogeneity. The last drawback of using a mechanical milling process to disperse oxide particles is the inherent size limitation. Typical commercially available oxide powders used for milling in the range of 20 - 50 nanometers are not designed or otherwise processed for the general fields or applications described herein. Particles of these sizes are not only expensive, but they are difficult to handle correctly and safely and difficult to physically intermix with the first particle phase. Milling can further reduce the particle size of the oxide, but as discussed previously, there is a limit to the time milling can be performed. This leaves oxide particles that are typically found to be in the 10 - 20 nanometer size range. When the material is extruded, these particles transform into elongated defects oriented in a direction parallel to the extrusion direction, and when cast or molded, they distribute randomly (i.e., non-uniformly) into discrete phases that exceed the optimal grain size that can be achieved through the practice of the present invention. Ultimately, this leads to significant material anisotropy that limits the use of these materials.

[0071] Many of the described drawbacks can be removed by omitting or significantly modifying the grinding processes described in the art as currently used in the production of ODS steels. By incorporating highly controllable oxide coating processes of nanotechnology, existing alloy properties can be improved, and the creation of new alloys will lead to enhanced material properties that can meet the stringent conditions required for fusion reactor materials and enable many other applications of nanocomposite materials. The discussion of ODS steels is intended to serve as an exemplary application of the technology described herein and is not intended to limit the applicability or scope to other first phases (non-“steel” materials) or second phases (non-“oxide” materials). Such examples would include nitride dispersion strengthened materials; first phases of aluminum or titanium alloys; halide, phosphate and / or borate strengthened metals, alloys or glasses; ceramic strengthened polymers; polymer-derived ceramics incorporated onto metals, ceramics or glasses, etc. The ability to nano-process a homogeneous second phase, which may include a specific composition, dosage or sequence of materials, processes or steps, can provide direct functional benefits to the first phase of any material, thereby enabling the production of nanocomposite materials with performance so high that it can be measured when fabricated into workpieces using any number of manufacturing processes that utilize powder-based raw materials. In particular, AM feedstock materials containing a second phase of nanotechnology produced using a specific ALD process will produce fully homogeneous finished parts that exhibit more useful properties than workpieces produced without a second phase of nanotechnology.

[0072] The workpieces of the present technology may be very suitable for use in various applications, and it will likely be more suitable for use than comparative workpieces that do not utilize the nanotechnology raw materials of the present technology at least. Related applications that should not be considered to be limiting in any way include: i) structural or containment members for nuclear applications, ii) as anodes, anode liquids, cathodes, cathode liquids, electrolytes, current collectors, stack members, electrode assemblies, separators, membranes, or as pack members of an electrochemical cell including one or more of a battery, capacitor, electrolytic cell, liquid-based fuel cell, or solid oxide fuel cell, iii) those configured for general use as structural members, for example, in construction or other building projects, iv) those configured to be used as exterior or shielding members (physical, chemical, or electrical shielding / protection) of movable or stationary devices for military and civilian purposes, or v) those configured to be used as lightweight means for fixed or mobile / portable applications.

[0073] An important feature of the ability to add a nanostructured phase into AM-derived parts fabricated in a layer-by-layer stacking manner in the Z direction is that it can minimize or eliminate the anisotropy typically inherent in such manufacturing methods. The enhanced bonding and improved interparticle welding characteristics of the present invention not only improve the bulk mechanical (and other) properties of the finished workpiece, but it has also been discovered that since each layer applied in the build direction contains multiple sublayers of the nanostructured phase, the finished part tends to have increasingly lower anisotropy, particularly in the Z direction. The manufactured workpieces containing the particles of the present invention can be built with a higher aspect ratio without adversely affecting the properties and can be built higher and faster based on including a highly functional second phase.

[0074] To facilitate the aforementioned improvement in anisotropy, another advantage of the functionalized powder with enhanced fluidity is that it allows for the use of thicker powder layers without sacrificing the quality or yield of the built or finished workpiece, which leads to a more rapid process for manufacturing individual parts.

[0075] In some embodiments, the composition and amount of the material of the second phase (e.g., thickness in the case of a coating) are selected to maximize the uniformity of the interaction between the laser beam and the powder particles. Practically, the standardization of absorption, reflection, and scattering has also made it possible to use a wider particle size distribution and more irregular particles without sacrificing the quality or yield of the constructed or finished workpiece.

[0076] Similar to any industrially oriented process development, ways to increase the speed of the AM manufacturing process or reduce the number of steps that can be decreased would be valuable to the industry. Thus, unexpectedly, simply by i) enabling an increase in stripe width, ii) enabling an increase in the hatching space between adjacent scan tracks, and / or iii) reducing the overlap required for adjacent stripes with a uniform coating without adversely affecting the mechanical properties of the manufactured workpiece, it has been observed that the overall productivity can be significantly improved and the cost can be significantly reduced. In some embodiments, such an improvement in productivity can be achieved by incorporating a beneficial second-phase material to reduce the overall cost while enhancing the end-use performance.

[0077] In at least one embodiment, it has been shown that defects (e.g., micropores, microcracks, etc.) in the manufactured workpiece can be reduced by optimizing keyhole beam welding interactions, gas distribution or enhanced removal during processing, controlled or other uniform interlayer shrinkage, etc. In particular, in embodiments containing ALD-compatible metal or metal alloy powders, the creep strength, ductility, toughness (especially impact toughness), and fatigue life have been significantly improved. Post-treatment using the hot isostatic pressing method (HIP) can be performed at reduced pressure, temperature, or time as the degree of separation due to a more homogeneous microstructure and less residual stress in the constructed part.

[0078] Often, powder blends are manufactured before being fed into the AM process and may be described as a first and second phase within the powder based on formulation considerations. However, the intended functionalized powder is a first particle having a second particle adhered to most of its outer surface. There are many challenges associated with creating this type of system. The first is that the van der Waals forces must be sufficient to allow the particles of the second phase to adhere to the surface of the first powder feedstock material, and that the particles of the second phase will be small and the particles of the first phase will be large. Second, it is often a challenge that cannot be overcome to de-aggregate the particles of the second phase such that they form only as uniform a layer as possible of adhering particles when re-aggregating to the particles of the first phase. A concurrent challenge is to have a second-phase particle feedstock with a size distribution that is narrow enough and ideally monodisperse while maintaining a size small enough to allow the van der Waals forces to dominate. This is far from impossible, but for example instead of applying ceramic reinforcing nanopowders onto metal or metal alloy matrix powders, ALD can be used here, thereby enabling the creation of composite powders for AM. Surface coatings remove the need to limit the set of materials and classes available to those that can be obtained in powder form while overcoming the constraints described herein. Hybrid approaches are also interesting in that they can enjoy the advantages of both approaches, which is to create a second material phase that includes multiple sub-phases, one of which may be a powder substrate that can be blended, and one of which may be induced using an ALD coating to promote a more robust adhesion of the adhered particle phase. Such composite powders can be achieved using the present technology. In some embodiments, powders of boron nitride or silicon nitride are physically blended with a metal alloy feedstock powder, and then the material is loaded into an ALD reactor to apply a ceramic overcoat to the composite powder. In a particular embodiment, AM feedstock powders of aluminum and titanium are separately blended with silicon nitride powder and an aluminum oxide ALD coating is applied thereon. Each set of powders was printed onto a dogbone-type workpiece.When characterizing each chemical composition, in addition to a first phase of either aluminum or titanium, it has been revealed that a second phase of each type of workpiece contains a "SiAlON" material, i.e., silicon aluminum oxynitride. Such materials are known to impart strength and mechanical property advantages to the finished workpiece. In one aspect, the present technology provides the ability to rationally design the first and second phases to maximize the quality of the finished workpiece while minimizing manufacturing time and cost.

[0079] In another aspect, the present technology provides the ability to design a second-phase coating that improves the health, safety, and environmental issues of conventional metal powders through improved handling and increases the storage life of the metal powders through improved corrosion resistance. Furthermore, some materials are difficult to recycle after the execution of the PM process, which is outside the scope of the finished workpiece as unused material. This example is the powder contained within the powder bed of an AM printing tool. Excess material can be recycled to some extent, but raw material powders with an ALD corrosion-resistant coating can be recycled two to three times the number of times of raw material powders without a surface coating. Ultimately, the ability to enhance the recyclability or reusability of the powdered raw material after being processed by the AM cycle will reduce the total cost per manufactured workpiece.

[0080] In some embodiments, the present technology can enable the use of smaller powder raw material particle sizes or the strategic use of a bimodal distribution of powder raw material particle sizes for a second-phase material that provides enhanced lubricity while overcoming the tendency to oxidize. For example, AM raw material powders typically have an average particle diameter in the range of 40 - 50 microns. It has been observed that smaller first particles of the same substrate material with a second material phase in the form of a coating can be incorporated into the larger first-phase particles to fill voids. Such means of adjusting the packing of the gaps have been shown to improve the mechanical properties of the finished workpiece.

[0081] In one aspect, the present technology provides a reduction in the vaporization of the material of the first phase in the presence of excessive energy. This provides an opportunity to manufacture high-value products that are difficult, costly, or cumbersome to manufacture today, such as solid-state batteries, catalyst surfaces and catalytic converters with optimized shapes, and advanced motor designs that can be optimized for use with high-temperature stabilized permanent magnets. Further, the workpiece of the present invention can be manufactured from an unconventional first particle feedstock having a second phase of nanostructure that enables the use of such materials. For example, exotic metals such as precious metals, platinum group metals, refractory metals, low evaporation temperature metals can now be incorporated into additively manufactured workpieces, and either the first phase or the second phase (or multiple second phases) can include the material depending on the shape, function, and application of the workpiece. One such application is the fabrication of workpieces for particle accelerator components, and the exotic metal powder can be configured for use in a binder jetting, direct metal laser sintering, or bound metal deposition 3D printer by incorporating a specific second phase. Generally, many components used in applications considered to be niche or for which essentially low-volume production is required due to limited demand may benefit from being manufactured from exotic metals for various physical and engineering reasons. One example is the use of niobium for superconducting RF cavities and ancillary components. By additively manufacturing these workpieces, complex shapes can be fabricated easily and quickly, but many of the exotic materials are not yet printable. Binder jetting and bound metal deposition printers offer a relatively low cost of entry into metal 3D printing and use standard metal injection molding (MIM) powder as the feedstock. Direct metal laser sintering (DMLS) printers are more costly and utilize special uniform particle size powders as their feedstock. In one aspect, the present technology provides the development and realization of exotic metal powders (such as niobium) that can be made suitable for printing in any of the aforementioned processes, enabling more exotic materials to be an option for the manufacture of complex components such as those used in accelerators.

[0082] Similarly, detectors for particle physics require sophisticated performance and need to be composed of materials that can withstand severe conditions such as cryogenic temperatures, high pressures, or high-radiation environments. Workpieces related to this field, such as sensors and detectors, often feature large areas or volumes. Therefore, higher localized uniformity of powder melting within each additive manufacturing layer and more homogeneous bonding of successive layers enable more homogeneous mechanical properties to be demonstrated in the X, Y, and Z directions, allowing for greater uniformity between larger workpieces. This enhanced uniformity between workpieces then provides opportunities to manufacture increasingly large parts (e.g., blades for wind turbines or large objects with complex and precise shapes) using additive manufacturing techniques. The enhanced uniformity in all directions has also been demonstrated to reduce (to less than 25 microns) the surface roughness of the fabricated workpieces at positions that are several millimeters, often several centimeters, sometimes several decimeters, and in some cases several meters apart from each other. This enhanced uniformity also minimizes residual stresses in the fabricated parts and results in a measurable reduction in the thermal stress, fatigue, and warping of the finished parts. The present invention includes the following embodiments. [1] A workpiece comprising a first phase including at least one of metal, metal alloy, ceramic, glass, and polymer, and a second phase including at least one of metal, metal alloy, ceramic, glass, and polymer, wherein the first phase is derived from a powdered material configured for use in an additive manufacturing process such as laminated object manufacturing, 3D printing, binder jet printing, laser melting, plasma sintering, and injection molding, extrusion-based, cold spray, or subtractive manufacturing process, and the second phase is chemically or physically adhered to the surface of the first phase before the production of the workpiece. [2] The workpiece according to [1], wherein the first phase has a characteristic grain size of about 500 μm or less. [3] The workpiece according to [1], wherein the first phase has a characteristic grain size of 10 nm to 100 μm. [4] The workpiece according to [1], wherein the first phase has a characteristic grain size of 100 nm to 10 μm. [5] The workpiece according to [1], wherein the first phase has a characteristic grain size of about 1 μm or less. [6] The workpiece according to [1], wherein the first phase or the second phase is uniformly distributed throughout the workpiece. [7] The workpiece according to [1], wherein the workpiece includes a plurality of volume elements, and one or more physical or mechanical properties of any two separate volume elements of the same size of the workpiece have a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece. [8] The workpiece according to [1], wherein the workpiece includes a plurality of volume elements, and one or more chemical or electrical properties of any two separate volume elements of the same size of the workpiece have a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece. [9] The workpiece according to [1], wherein the workpiece includes a plurality of volume elements, and the chemical composition of any two separate volume elements of the same size of the workpiece has a deviation of 10% or less, and the cube root of each volume element is 3 times or less the median grain size of the first phase of the workpiece.

[10] The workpiece according to [1], wherein the material of the second phase is in the form of a coating covering at least 70% of the external surface area of the powder of the first phase before the production of the workpiece.

[11] The work piece according to

[10] , wherein the coating is applied using one or more of sol-gel, microemulsion, physical vapor, chemical vapor, atomic layer, pyrolysis, chemical decomposition, or supercritical fluid deposition processes.

[12] The work piece according to [2], wherein the material of the second phase remains adjacent to the grains of the material of the first phase, ii) remains dispersed with the grains of the material of the first phase, or iii) maintains an interface with the grains of the material of the first phase.

[13] The work piece according to

[12] , wherein the grains of the material of the first phase are separated by a uniform distance in the range of 0.1 nm to 100 nm.

[14] The work piece according to [1], wherein the work piece is manufactured using one or more of additive manufacturing, 3D printing, binder jet printing, laser melting, plasma sintering, and injection molding, extrusion-based, cold spray, or subtractive manufacturing processes.

[15] The work piece according to [1], wherein the first phase comprises titanium, aluminum, boron, chlorine, iron, chromium, cobalt, magnesium, molybdenum, tungsten, nickel, tin, tantalum, vanadium, yttrium, carbon, zinc, silicon, or zirconium.

[16] The work piece according to [1], wherein the second phase comprises oxides, nitrides, carbides, borides, halides, or aluminides.

[17] The work piece according to [1], wherein the second phase comprises one or more additional sub-phases.

[18] The work piece according to [1], wherein the composition of the second phase in the work piece is different from the composition of the second phase of the starting raw material powder before fabrication of the work piece.

[19] The work piece according to

[18] , wherein the composition of the second phase is formed during the fabrication of the work piece.

[20] i. For nuclear applications, ii. In anodes, anode liquids, cathodes, cathode liquids, electrolytes, current collectors, stack members, electrode assemblies, separators, membranes, or as a pack member of an electrochemical cell, iii. In batteries containing liquid electrolytes, batteries containing solid electrolytes, capacitors, electrolytic cells, fuel cells containing liquid electrolytes, or fuel cells containing solid electrolytes, iv. As a structural or reinforcing member, v. As an exterior or shielding member of a fixed or mobile device, vi. As a weight reduction means for mobile or portable applications The work piece according to [1], configured for use.

Claims

1. A workpiece comprising a first phase containing at least one of titanium metal and titanium alloys and a second phase containing a ceramic, The first phase is derived from a powdery raw material configured for use in a laminated manufacturing, 3D printing, binder jet printing, or direct metal laser sintering process, The second phase is derived from a coating layer with a thickness of 5 nm or less chemically adhered to the surface of the powdery raw material by atomic layer deposition before the production of the workpiece, A workpiece in which the grains of the first phase are separated from each other by a uniform distance in the range of 0.1 nm to 100 nm, 0.5 nm to 20 nm, 1 nm to 15 nm, or 2 nm to 5 nm by the second phase.

2. The workpiece according to claim 1, wherein the first phase contains a titanium alloy and the second phase contains a metal oxide.

3. The workpiece according to claim 1 or 2, wherein the powdery raw material consists of a core containing the first phase and a coating consisting of the second phase.

4. The workpiece according to claim 2 or 3, made by laminating particles consisting of a core of a titanium alloy and a coating consisting of aluminum oxide with a thickness of 3 to 5 nm.

5. The workpiece according to any one of claims 1 to 3, manufactured using laminated manufacturing.

6. A method of making a workpiece according to any one of claims 1 to 5, including laminated manufacturing of a powdery raw material in the absence of a flow of inert gas.

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