DE102015118441A1 - Composite materials and processes for the laser production and repair of metals - Google Patents

Abstract

Composite materials (2, 8) disclosed herein include a metal alloy (4, 10) and a flux composition (6, 12). The metal alloy may be a superalloy, and a volume ratio of the flux composition to the metal alloy may be in the range of about 30:70 to about 70:30. The composite materials may be in the form of particles (2) comprising a core (6) surrounded by a metallic layer (4), the core comprising the flux composition and the metallic layer comprising the metal alloy. The composites may also be in the form of fused materials (8) wherein the metal alloy (10) and flux composition (12) are randomly distributed and randomly oriented. Also disclosed are processes comprising melting composites to form metal deposits (32).

Description

The present application is a continuation-in-part of US Application No. 13 / 755,098 (Attorney Docket No. 2012P28301 US), filed January 31, 2013 and published May 30, 2013, as US-A document 2013/0136868 A1, which is a continuation-in-part of US Pat Application No. 13 / 005,656 (Attorney Docket No. 2010P13119US), filed January 13, 2011 and published July 19, 2012 as US Patent 2012/0181255 A1, the entire contents of which are hereby incorporated by reference.

FIELD OF THE INVENTION

The present application relates generally to materials technology, and more particularly to composites and methods useful in the manufacture and repair of metallic materials, including superalloys.

BACKGROUND OF THE INVENTION

Laser powder deposition (or laser deposition welding with powdered filler) is a process in which a thin layer of metallic powder is melted with an energy beam, forming a metal deposit. Because of their potential use in the manufacture and repair of complex objects formed of various metallic materials and alloys, this approach to metalworking has recently attracted interest. For example, Selective Laser Melting (SLM) is a powder bed process in which a thin layer of metal powder is deposited on a substrate, whereupon the powder surface is scanned with a powerful laser beam that generates heat that melts the powder particles and forming a melt which solidifies into a metal deposition layer, is rasterized. After deposition of the layer can then be added to another layer of powder, which is melted again by means of the laser. In this way, successive layers can be sequentially deposited to produce three-dimensional objects in a process known as LAM (Laser Additive Manufacturing). Although SLM is generally limited to flat work surfaces, laser micro-deposition welding is a 3D-enabled process in which a small, thin layer is created by using a laser beam to melt a flow of powder that is propelled toward the surface by a gas jet made of material deposited on a surface.

Although various forms of laser powder deposition offer high potential for the fabrication and repair of complex objects, they are limited by certain disadvantages often associated with the use of metallic powders. One drawback relates to the reactivity of metallic powders with components in air, such as with oxygen and nitrogen. Reactive metals, such as iron, aluminum and titanium, may react with air to form impurities containing metal oxides as well as metal nitrides - the rate of such unwanted reactions generally increasing with increasing surface area of the metallic powder. Metallic powders also tend to readily adsorb moisture which, in addition, can react to form metal oxides and also result in unwanted porosity in metallic objects formed using laser powder deposition. For high strength steels, moisture also serves as a source of hydrogen, which is known to result in late cracking.

These problems with air and moisture can be particularly problematic for high temperature materials that require more rigorous process conditions to affect reader powder deposition. Superalloys, for example, are recognized to be the most difficult to machine with lasers because of their relatively high melting points, relatively low ductility, and susceptibility to weld set cracking and strain age cracking. These mechanical defects can be caused or exacerbated by the presence of air and / or water in laser processing.

As used herein, the term "superalloy" is used as is commonly used in the art, ie, an alloy having high corrosion and oxidation resistance exhibiting excellent mechanical and creep resistance at high temperatures. Superalloys usually have a high nickel or cobalt content. Examples of superalloys include alloys sold under the trademarks and trade names Hastelloy, Inconel alloys (e.g., IN 100, IN 700, IN 713, IN 738, IN 792, IN 939), Rene alloys (e.g. B. Rene N5, Rene 41, Rene 80, Rene 108, Rene 142, Rene 220), Haynes alloys (282), Mar M, CM 247, CM 247 LC, C263, 718, X-750, ECY 768, 282, X45, PWA 1480, PWA 1483, PWA 1484, CMSX single crystal alloys (eg CMSX-4, CMSX-8, CMSX-10), GTD 111, GTD 222, MGA 1400, MGA 2400, PSM 116, Mar -M-200, Udimet 600, Udimet 500 and Titanium Aluminide. The terms "metal", "metallic material", "alloy" and "metal alloy" are used herein in general Sense used to describe pure metals, semi-pure metals and metal alloys.

To mitigate the deleterious effects of air, the melt resulting from laser powder deposition is often shielded by the application of an inert gas such as argon and helium. However, such shielding does not remove any preexisting oxides that tend to form on the exterior of metal powders during manufacture, storage, and handling. As a result, such oxide-coated metal fillers often need to be reduced during melt processing to avoid porosity and other defects in the resulting metallic deposit. Aftertreatment processes, such as hot isostatic pressing (HIP), are also often used to collapse pores (voids), inclusions and tears to enhance the properties of laser deposited metals. To prevent moisture adsorption, metal powder fillers are often stored in preheated funnels. Such protective and post-treatment measures are particularly important in highly reactive metal-containing metallic powders (eg superalloys) and fine powders with large surface areas.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be explained in the following description with reference to the drawings, in which:

1 a sectional view of a composite particle containing a metallic outer layer surrounding an inner flux-containing core.

2 shows a laminated glass particle containing a metal alloy and a flux composition.

3A - 3C show composite materials with different shapes.

4 shows a method of processing a previously arranged composite material to form a metal deposit.

5 shows a method of forming a metal deposit by passing a composite material into an energy beam.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have recognized that there is a need to discover alternative materials and methods for remedying the deleterious effects air and moisture can have on laser powder deposition of metals. With ideal materials and processes, it would be possible to fabricate metal materials with laser powder deposition of metal in various contexts (eg, metal component fabrication and repair, bulk fabrication) that contain less impurities and defects due to exposure to air and moisture while avoiding them that one must rely on currently used protective techniques, such as the use of preheated powder funnels, inert gases and / or vacuum conditions, reducing agents and hot isostatic pressing (HIP) as aftertreatment. Ideal materials and processes would also be compatible with the laser processing of superalloys or superalloy precursors to form superalloys.

It is suggested that the problems associated with air and moisture can be alleviated by using novel composite materials containing a metal and a flux composition. Such composites are expected to be effective in reducing moisture content and avoiding unwanted reactions with air because the metal material and flux composition in solid, particulate forms, which are less susceptible to moisture adsorption compared to conventional metallic filler powders, are relatively stable (inert) under atmospheric conditions ) are intimately connected. Composite materials described herein may provide additional protection against air and moisture which can not be achieved by means of separate powders of metal and flux (as powdered mixtures or various polymer layers) since the composite materials contain a physical or chemical barrier to adsorption (and permeation). withstands atmospheric substances.

1 shows an embodiment of a composite material 2 in the form of coated particles containing a flux-containing core 6 include that of a metallic layer 4 surrounded (coated) is. In this non-limiting illustration, the metallic layer acts 4 as a physical barrier that resists adsorption and permeation through atmospheric materials such as oxygen, nitrogen and moisture. In some embodiments, the metallic layer 4 also contain at least one metal (such as nickel) that is chemically resistant to atmospheric materials, including oxygen and nitrogen.

The metallic layer 4 can be a pure metal like nickel, a metal alloy like a superalloy, or combinations of different ones Contain metals and alloys. Superalloys can be mixtures of parent metals (eg, Ni, Fe, and Co) along with other metals, semimetals, and nonmetals such as chromium, molybdenum, tungsten, tantalum, aluminum, titanium, zirconium, niobium, rhenium, yttrium, vanadium, carbon, boron, and hafnium included, just to name a few. Examples of superalloys are alloys marketed under the trademarks and trade names Hastelloy, Inconel alloys (e.g., IN 100, IN 700, IN 713, IN 738, IN 792, IN 939), Rene alloys (e.g. Rene N5, Rene 41, Rene 80, Rene 108, Rene 142, Rene 220), Haynes alloys (282), Mar M, CM 247, CM 247 LC, C263, 718, X-750, ECY 768, 282, X45, PWA 1480, PWA 1483, PWA 1484, CMSX single crystal alloys (eg CMSX-4, CMSX-8, CMSX-10), GTD 111, GTD 222, MGA 1400, MGA 2400, PSM 116, Mar-M -200, Udimet 600, Udimet 500 and titanium aluminide.

The metallic layer 4 may have a metal content that is consistent with the composition of a metallic deposit to be formed by melt processing, or it may contain a single metal or a subset of metals contained in the metallic deposit. Thus, as will be explained in more detail below, laser powder deposition can be accomplished using the composite material 2 from 1 be used to form a melt, the one with the metallic layer 4 identical metal composition, or to form a melt whose metal compound is supplemented by at least one additional metal filler or metal-containing flux material.

The metallic layer 4 may be formed from a single metal layer having a homogeneous composition, or may be formed from a single metal layer of graded composition. In some embodiments, the metallic layer 4 from 1 For example, be graded such that the outer surface has a higher proportion of nickel than the inner surface of the metallic layer 4 contains - giving greater protection against reactive metals (for example, Al, Ti and Fe) in the metallic layer 4 are included. When melting, the metallic components of a metallic layer 4 graded composition, so that a resulting metal deposit is a homogeneous composition having a desired alloy content. The metallic layer 4 may also be formed of more than one metal layer having the same or different metallic compositions. For example, in some embodiments, the composite material includes 2 from 1 a flux-containing core 6 which is surrounded (coated) by a superalloy interlayer surrounded (coated) by an outer layer of nickel.

As will be explained in more detail below, the flux-containing core comprises 6 a flux composition that provides at least one protective function in melt processing the composite material 2 provides. Flux compositions may contain one or more inorganic compounds, such as metal oxide, metal halide, metal oxometalate, metal carbonate, or mixtures thereof, and may also contain one or more organic compounds, such as a high molecular weight hydrocarbon, a carbohydrate, a natural or synthetic oil organic reducing agent, a carboxylic acid or polybasic acid, a carboxylic acid salt or derivative, an amine, an alcohol, a natural or synthetic resin or mixtures of such compounds, to name but a few.

In some embodiments, the composite material may be 2 also include an additional outer protective layer (not shown) containing an inorganic protective material comprising the metallic layer 4 surrounds (coated). Such inorganic protective materials may include metal oxides such as aluminum oxide (AL ₂ O ₃ ) and silica (SiO ₂ ), which may be the metallic layer 4 during storage and may also act as a protective flux material during laser processing. Most useful is when the inorganic outer protective layer is introduced as a smooth (for example glass-like) coating on the particles, so that the surfaces are not hygroscopic.

It is expected that composite materials, such as composite material 2 from 1 , physical and chemical defects in the corresponding melt-processed materials reduce, since the metal layer 4 may contain chemically resistant metals, such as nickel, which are inert to atmospheric reactants, and may also be surface treated to resist the adsorption of atmospheric moisture.

Metal coated composite materials such as the embodiment of FIG 1 , can be prepared by various different methods, depending on the desired composition, size and geometry. Such processes include hydrometallurgical processing, physical and chemical vapor deposition, electroless deposition, and gas phase coating.

In some non-limiting processes, a flux-containing particulate may be initially prepared by agglomerating individual particles containing a flux composition by means of organic or inorganic binders, and by grinding the resulting agglomeration to form a flux-binder mixture, which is then cured to form flux-containing particles. The flux-containing particles may then be screened to a desired particle size, size range, or geometry needed for a particular application. On the order of flux-containing particles, a metal composition is deposited thereon to form coated composite materials such as the composite material 2 from 1 train.

For example, the flux-containing particles can be coated with nickel by means of hydrometallurgical processing, whereupon, at elevated temperature and elevated pressure, by reduction with hydrogen, a dissolved nickel complex precipitates on the flux-containing particles. After the nickel precipitates on the flux-containing particles, the resulting metal-coated composite particles may be washed and dried. Additional metal plating and / or alloying may also occur to produce multilayer or graded coatings or to modify the composition of the metallic layer by processes such as chemical vapor deposition (CVD).

Physical Vapor Deposition (PVD) can also be used to form metal-coated composites such as the composite material 2 from 1 be used. In such processes, a metallic material is vaporized and transported in the form of a vapor through a vacuum or gaseous low pressure environment (or plasma) to size-ordered flux-containing particles where the metallic material condenses. PVD processes can be used to deposit films of metal elements or alloys. For example, PVD may be used to coat flux-containing particles suspended in a fluidized bed by a fluidizing gas. The PVD may be out of alignment or direction, allowing metal coated composites to be provided with defined and repeatable coatings. Directed vapor deposition (DVD) may also be used in combination with electron beam based evaporation techniques (or ion beam based sputtering techniques) to improve the yield and / or quality of melt-bonderized metal coated composites , PVD can be used to produce single-layer metallic coatings as well as multi-layer coatings and coatings of graded composition.

Electroless plating can also be used with metal coated composite materials such as the composite material 2 from 1 to create. For example, a electroless plating solution containing a metal ion (such as a nickel ion) and a soluble reducing agent (such as a hypophosphorate salt) can be mixed with flux-containing particles to form a metallic layer covering the flux-containing particles. Gas phase coating may also be used by preparing a mixture of flux-containing particles in a flowable medium that is converted to an aerosol containing droplets of the flux-containing particles suspended in a carrier gas. Optionally, the liquid contained in the aerosol may be removed and the resulting gas-dispersed particles may optionally be dried by heating. The resulting flux-containing gas phase particles may then be coated, for example, by physical vapor deposition (PVD) or chemical vapor deposition (CVD) with a reactive gas containing a metal such as nickel or a metal alloy.

Metal coated composite materials such as the composite particle 2 from 1 can be produced in various sizes, for example in the range of about 1 to about 1000 microns in average diameter. In some embodiments, the sizes range from about 5 to about 500 μm, or from about 20 to about 100 μm, in average diameter. Optimal size ranges may vary depending on the application, for example requiring ultrafine particulate to fill narrow cracks, finer but not ultrafine particulate for gas assisted feeds, and coarser particulate acceptable for processing pre-arranged or gravity fed powder. Such composites are formed such that a flux to metal volume ratio is in the range of about 10:90 to about 90:10. In some embodiments, the flux to metal volume ratio ranges from about 30:70 to about 70:30 or from about 40:60 to about 60:40. In other embodiments, the flux to metal volume ratio ranges from about 45:55 to about 55:45 or is about 50:50.

2 shows a further embodiment of a composite material 8th in the form of fused particles containing a metal alloy 10 and a flux composition 12 contain, wherein the metal alloy 10 and the flux composition 12 in a fused composite grid 13 randomly distributed and randomly oriented. In this non-limiting illustration, the fused structure of the composite material acts 8th as a physical or chemical barrier which resists adsorption and permeation of atmospheric materials such as oxygen, nitrogen and moisture. For example, the fused structure may be in the form of flux / metalglass particles as a conglomerate having high resistance to moisture adsorption and low reactivity with atmospheric reactants - as opposed to merely agglomerated flux / metal materials, which often have high potencies due to their relatively large surface area and porosity Moisture adsorption and air reactivity tend.

The metal or the alloy 10 in the fused composite material 8th from 2 may be a pure metal such as nickel or metal alloys such as nickel, iron and cobalt based superalloys, possibly containing other metals, semimetals and nonmetals as described above. The metallic part of the composite material 8th may be in the form of equivalent metallic particles having the same composition, uniformly distributed throughout the fused particles, or may be in the form of non-equivalent metallic particles having different compositions. In an example of subsequent embodiments, the fused composite material may 8th contain non-equivalent metallic particles having different compositions which, when melted and mixed together into a melt, can form a superalloy metal deposit.

As will be explained in more detail below, the flux composition includes 12 a flux material during the melt processing of the composite material 8th provides at least one protective function. Flux compositions may contain one or more inorganic compounds, such as metal oxide, metal halide, metal oxometalate, metal carbonate, or mixtures thereof, and may also contain one or more organic compounds, such as a high molecular weight hydrocarbon, a carbohydrate, a natural or synthetic oil organic reducing agent, a carboxylic acid or polybasic acid, a carboxylic acid salt or derivative, an amine, an alcohol, a natural or synthetic resin or mixtures of such compounds, to name but a few.

It is expected that fused composite materials, such as the composite material 8th from 2 reduce physical and chemical defects in the respective melt-processed materials because the fused structure is in the form of a glass-like composite lattice which is highly resistant to both moisture adsorption and reactivity with atmospheric species such as oxygen and nitrogen.

Fused composite materials, such as the embodiment of 2 , can be made using, for example, a high temperature furnace by dry blending the metal alloy 10 with the flux composition 12 and fusing or melting the resulting conglomerate mixture to a liquid state. The resulting molten glass is then cooled and allowed to solidify into a molten conglomerate glass mold, which can then be crushed and ground into various particle sizes and shapes.

Fused composite materials, such as the composite particle 8th from 2 , can be made in various sizes, for example in the range of about 1 to about 1000 microns in average diameter. In some embodiments, the sizes range from about 5 to about 500 μm, or from about 20 to about 100 μm, in average diameter. Such composites are formed such that a flux to metal volume ratio is in the range of about 10:90 to about 90:10. In some embodiments, the flux to metal volume ratio ranges from about 30:70 to about 70:30 or from about 40:60 to about 60:40. In other embodiments, the flux to metal volume ratio ranges from about 45:55 to about 55:45 or is about 50:50.

Both metal-coated and fused composite particles 2 . 8th can be made in various different shapes and geometries. The non-limiting examples in 3A - 3C show three different particle shapes that may be suitable for laser powder deposits in the present disclosure. 3A shows a spherical composite particle 18 Useful for example for powder feed processing and fluidized bed processing. 3B shows a rod-like composite particle 20 Useful, for example, for weaving into threads and fabrics for the production of preforms, which can be arranged in advance on a substrate or fed to the point of processing. 3C shows a flake-shaped composite particle 21 Useful, for example, when a bed of material having a high void-to-volume ratio is desired in order to prevent the Introducing a reactive gas to reach the particulate surface.

The coated and fused composite materials described above and incorporated in US Pat 1 and 2 can be used in a variety of processes involving melting and solidification to form metal deposits and components. Such applications include powder-applied (or directional) laser cladding, pre-arranged laser cladding, selective laser melting (SLM), selective laser sintering (SLS), laser micro-deposition welding, fluidized bed laser processing, and powder core wire-fed processing, to name but a few. In these and other applications, particles of the coated or fused composite material described above may be used as substituents for conventional metal fillers and / or flux materials, or may be used in conjunction with conventional metal fillers and / or flux materials. Such processes can be applied to the fabrication and repair of metallic components (using, for example, additive manufacturing techniques) and also used in bulk fabrication, as explained below.

4 FIG. 12 shows an embodiment with pre-deposited powder laser deposition welding using either the metal-coated composite particles. FIG 2 or the fused composite particles 8th which are described and shown above. In this non-limiting example, a composite powder layer becomes 26 in advance on a surface of a metal or non-metal substrate 24 arranged, whereupon an energy beam 28 (For example, a laser beam) over the surface of the powder layer 26 is moved, the powder layer 26 under formation of a melt 30 melts. The melt generally consists of a molten metal layer covered by a molten flux layer and sometimes by a gaseous protective coating 36 is superimposed, which is generated by reactions of the energy beam with flux. The melt 30 , which contains both the metal alloy and the flux composition of the composite particles, is then allowed to cool and allowed to solidify to form a metal deposit 32 form, generally by a slag layer 34 is covered.

The term "energy beam" is used herein in a general sense to describe a relatively narrow, propagating stream of particles or energy packets. An energy ray 28 As used in the present disclosure, it may include a light beam, a laser beam, a particle beam, a charged particle beam, a molecular beam, etc. that transfers kinetic (heat) energy to the material upon contact with material.

In some embodiments, the energy beam is 28 a diode laser beam having a generally rectangular cross-sectional shape, although other known types of energy jets may be used, such as electron beam, plasma jet, one or more circular laser beams, a scanning laser beam (one-dimensional, two-dimensional or three-dimensional scanning), an integrated laser beam, a pulsed laser beam (as opposed to continuous wave laser beam), etc. The rectangular shape may be particularly advantageous for embodiments having a relatively large area to be melted. In some embodiments, the intensity and shape of the energy beam 28 by using laser scanning (raster) optics precisely to form a melt 30 controlled with a precisely defined size, shape and depth.

The depth of the melt 30 can by changing the energy intensity, the focus and / or the frequency of the energy beam 28 to be controlled. Suitable laser sources may include, for example, low power lasers (eg, 503 nm and 1.06 μm Nd: YAG lasers) and higher power lasers (eg, 1.06 μm ytterbium fiber, 5.4 μm CO laser, and 10.6 μm CO ₂ lasers) - depending on the amount of laser energy intensity needed to obtain a desired depth of melt. Other processing parameters such as the raster (motion) rate or the pulsation rate (ie for a pulsed laser beam) can also be adjusted to the depth of the resulting melt 30 increase or decrease.

If the substrate 24 is a metallic substrate, the metal deposition can 32 in the form of a metallic cladding layer that matches the surface of the metal substrate 24 connected is. As explained above, the energy beam parameters can be changed to the depth of the melt 30 to control. In embodiments with a sheath of an underlying metal substrate 24 For example, the energy beam parameters may also be adjusted to melt an upper layer of the metal substrate to ensure that the resulting metal deposit 32 firmly connected to the underlying metal substrate.

In other embodiments for bulk fabrication of metals or repair of hollow components, the substrate 24 in the form of a volatile carrier material. "Volatile" means removable after formation of the cladding layer, for example by direct (physical) removal, mechanical Processes, drainage, fluid washing, chemical leaching and / or by any other known process in which the volatile carrier material 24 can be removed from his position. Examples of volatile carrier materials include powders (for example, metal, glass, ceramic, fiber), solid objects (for example, metal, glass, ceramics, composite, plastic, resinous structures, graphite, dry ice), wool-like materials (for example, steel wool , Alumina wool, zirconia wool) and foamed materials (for example, polymer foams, high temperature spray foams), to name but a few. Any material or structure that is capable of providing a carrying function, and then after formation of the metal deposit 32 can be removed as a volatile carrier material 24 serve. 5 Figure 4 shows another embodiment for powder-directed laser cladding (for example laser micro-deposition welding) using either the metal-coated composite particles 2 or the fused composite particles 8th which are described and shown above. In this non-limiting example, a current becomes 38 a composite material dispersed within a jet gas through at least one nozzle 42A into an energy beam 28 directed so that in the stream 38 contained composite particles to form a melt 30 that is on a surface of a metal or non-metal substrate 24 is to be melted. In embodiments with laser microplate welding, for example, the laser beam 28 and the nozzle 42A simultaneously over the surface of the substrate 24 moves, leaving the resulting melt 30 cools and solidifies to a metal sheath layer 32 generally generated by a slag layer 34 is covered. At least one more stream 40 containing another composite material, filler material, flux composition or additive may also be provided by means of at least one additional nozzle 42B in the energy beam 28 be directed.

In some embodiments, the adhesion of the composite particles to the surface of the substrate 24 be increased by initially in contact with composite particles with an adhesive substance such as water, alcohol, varnish or binder. Such pre-wetting of the composite powder with an adhesive-like substance can also improve the adhesion between layers when forming a plurality of adjacent metal film deposits.

As explained and described above, the composites contain 2 . 8th both a metal content 4 . 10 as well as a flux composition 6 . 12 which provides at least one protective function during melt processing. The flux composition 6 . 12 and the resulting slag layer 34 can provide a number of useful functions that enhance the chemical and / or mechanical properties of deposited metals formed by melt processing of the composite materials described herein.

First, the flux composition and the resulting slag layer 34 work so that both the area of the melt 30 as well as the frozen (but still hot) melt processed layer 32 shielded from the atmosphere. The slag floats to the surface to separate the molten or hot metal from the atmosphere, and the flux composition may be formulated to produce at least one shielding agent that produces at least one shielding gas upon exposure to laser photons or heating. In some embodiments, shielding gases can become a gaseous envelope 36 that melt 30 covered, coalesced, as in 4 and 5 shown. Shielding agents include metal carbonates such as calcium carbonate (CaCO ₃ ), aluminum carbonate (Al ₂ (CO ₃ ) ₃ ), dawsonite (NaAl (CO ₃ ) (OH) ₂ ), dolomite (CaMg (CO ₃ ) ₂ ), magnesium carbonate (MgCO ₃ ). , Manganese carbonate (MnCO ₃ ), cobalt carbonate (CoCO ₃ ), nickel carbonate (NiCO ₃ ), lanthanum carbonate (La ₂ (CO ₃ ) ₃ ) and other agents known to form protective and / or reducing gases (eg CO, CO ₂ , H ₂ ). The presence of the slag layer 34 and the optional protective gas 36 may avoid or minimize the need to perform melt processing in the presence of inert gases (such as helium and argon) or in a sealed chamber (eg vacuum chamber or inert gas chamber) or by using other specialized equipment to exclude air.

Second, the slag layer 34 act as an insulating layer, which allows the resulting melt-processed layer 32 cooling slowly and evenly, thereby reducing residual stresses that may contribute to post-weld cracking, reheat or stretch aging cracking, and secondary reaction zone formation. Such slag overlay above and next to the deposited metal layer 32 can the heat conduction to the substrate 24 further improving, which in some embodiments, directional solidification to form elongate (uniaxial) grains 33 in the melt-processed layer 32 can promote (see 4 ).

Third, the slag layer 34 for shaping and carrying the melt 30 to keep them close to a desired height / width ratio (for example, a 1/3 height / width ratio). This shape control and Supporting function further reduces freezing stresses that otherwise affect the melt-processed layer 32 can be transmitted. Together with the shape and the supporting function, the slag layer can 34 also be prepared from a flux composition formulated to increase the surface smoothness of the melt processed layer 34 improved. Improved surface smoothness may be useful in some embodiments where the melt processed layer 32 is a superalloy layer, which is then coated with a diffusion coating, such as a platinum aluminide coating. In these embodiments, the improved surface smoothness can reduce the formation of adverse secondary reaction zones (SRZs) that can compromise the physical and chemical properties of diffusion-coated superalloy components.

Fourth, the flux composition and slag layer 34 provide a cleaning effect for removing trace impurities that contribute to inferior properties. Such cleaning can oxidize the melt 30 include. Such flux compositions may also be formulated to contain at least one scavenger which can remove unwanted impurities from the melt. Scavengers include metal oxides and fluorides such as calcium oxide (CaO), calcium fluoride (CaF ₂ ), iron oxide (FeO), magnesium oxide (MgO), manganese oxides (MnO, MnO ₂ ), niobium oxides (NbO, NbO ₂ , Nb ₂ O ₅ ) , Titanium Oxide (TiO ₂ ), Zirconium Oxide (ZrO ₂ ) and other agents known to produce harmful elements such as sulfur and phosphorus and elements known to produce low melting point eutectics to form low density byproducts expected to be present they in a resulting slag layer 34 "Swim", react.

Fifth, the flux composition and the slag layer 34 increase the amount of heat energy that is the surface of the substrate 24 is supplied. This increase in heat absorption may occur due to the composition and / or form of the flux composition. In terms of composition, the flux may be formulated to contain at least one compound, the laser energy at the wavelength of a laser energy beam, which is the energy beam 28 is used, can absorb. Increasing the proportion of the laser absorbing compound causes a corresponding increase in the amount of laser energy acting on the substrate surface (as heat). This increase in heat absorption may be relieved by allowing the use of smaller laser sources and / or low power laser sources that may be capable of being relatively flatter 30 which may be useful in, for example, laser micro-deposition welding, provide greater versatility. In some cases, the laser absorbing compound could also be an exothermic compound that decomposes upon laser irradiation to release additional heat. An example of such an exothermic composite particulate would be particles having a CO ₂ -producing core (including, for example, a carbonate) surrounded by aluminum and ultimately coated with nickel. Nickel-coated aluminum powder is actually proposed as fuel for propulsion on Mars, where CO ₂ is present to a large extent and provides for such an exothermic reaction.

The shape of the composite material 2 . 8th and the resulting layer 26 may also affect laser absorption by changing layer thickness and / or particle size. In such cases, the absorption of laser heating generally increases with increasing thickness of the layer 26 (please refer 4 ). An increase in the thickness of the composite material layer 26 Also increases the thickness of a resulting molten slag overlay, which can further enhance the absorption of laser energy. The thickness of the powder layer 26 (please refer 4 ) in methods of the present disclosure typically ranges from about 1 mm to about 15 mm. In some cases, the thickness is in the range of about 3 mm to about 12 mm, while in other cases the thickness is in the range of about 5 mm to about 10 mm.

Reduce the average particle size of the composite materials 2 . 8th also causes an increase in laser energy absorption (probably due to increased photon scattering in the bed of fine particles and increased photon absorption by interaction with increased total particulate surface area). In terms of particle size, in some embodiments of the present disclosure, composites range in average particle size from about 1 to 1000 microns in diameter, or from about 5 to 500 microns, or from about 20 to 100 microns, while the average particle size of commercially available fluxes is general in the range of about 0.5 mm to about 2 mm (500 to 2000 μm) in diameter (or approximate dimension if not rounded).

In addition, the flux composition may be formulated to compensate for loss of volatilized or reacted elements during processing or active elements to the melt processed layer 32 contributed, otherwise not in the metal alloy 4 . 10 are included. Such vectoring materials include titanium, zircon, Boron and aluminum containing compounds and materials such as titanium alloys (Ti), titanium oxide (TiO ₂ ), titanite (CaTiSiO ₅ ), aluminum alloys (Al), aluminum carbonate (Al ₂ (CO ₃ ) ₃ ), dawsonite (NaAl (CO ₃ ) (OH) ₂ ), borate minerals (eg, kernite, borax, uxlex, colemanite), nickel titanium alloys (eg, nitinol), niobium oxides (NbO, NbO ₂ , Nb ₂ O ₅ ), and other metal-containing compounds and materials used to supplement molten alloys with elements. Certain oxometallates, as described below, may also be useful as vectoring agents.

Flux compositions contained in composite materials of the present disclosure may contain one or more inorganic compounds selected from metal oxides, metal halides, metal oxometallates, and metal carbonates. Such compounds may be as (i) translucent agents; (ii) viscosity / fluidity improver; (iii) shielding materials; (iv) scavenger; and / or (v) vectoring substances work.

Suitable metal oxides include compounds such as Li ₂ O, BeO, B ₂ O ₃ , B ₆ O, MgO, Al ₂ O ₃ , SiO ₂ , CaO, Sc ₂ O ₃ , TiO, TiO ₂ , Ti ₂ O ₃ , VO, V ₂ O ₃ , V ₂ O ₄ , V ₂ O ₅ , Cr ₂ O ₃ , CrO ₃ , MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO, CO ₃ O ₄ , NiO, Ni ₂ O ₃ , Cu ₂ O, CuO, ZnO, Ga ₂ O ₃ , GeO ₂ , As ₂ O ₃ , Rb ₂ O, SrO, Y ₂ O ₃ , ZrO ₂ , NiO , NiO ₂ , Ni ₂ O ₅ , MoO ₃ , MoO ₂ , RuO ₂ , Rh ₂ O ₃ , RhO ₂ , PdO, Ag ₂ O, CdO, In ₂ O ₃ , SnO, SnO ₂ , Sb ₂ O ₃ , TeO ₂ , TeO ₃ , Cs ₂ O, BaO, HfO ₂ , Ta ₂ O ₅ , WO ₂ , WO ₃ , ReO ₃ , Re ₂ O ₇ , PtO ₂ , Au ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ and mixtures thereof, to name but a few.

Suitable metal halides include compounds such as LiF, LiCl, LiBr, LiI, Li ₂ NiBr ₄ , Li ₂ CuCl ₄ , LiAsF ₆ , LiPF ₆ , LiAlCl ₄ , LiGaCl ₄ , Li ₂ PdCl ₄ , NaF, NaCl, NaBr, Na ₃ AlF ₆ , NaSbF ₆ , NaAsF ₆ , NaAuBr ₄ , NaAlCl ₄ , Na ₂ PdCl ₄ , Na ₂ PtCl ₄ , MgF ₂ , MgCl ₂ , MgBr ₂ , AlF ₃ , KCl, KF, KBr, K ₂ RuCl ₅ , K ₂ IrCl ₆ , K ₂ PtCl ₆ , K ₂ PtCl ₆ , K ₂ ReCl ₆ , K ₃ RhCl ₆ , KSbF ₆ , KAsF ₆ , K ₂ NiF ₆ , K ₂ TiF ₆ , K ₂ ZrF ₆ , K ₂ PtI ₆ , KAuBr ₄ , K ₂ PdBT ₄ , K ₂ PdCl ₄ , CaF ₂ , CaF, CaBr ₂ , CaCl ₂ , CaI ₂ , ScBr ₃ , ScCl ₃ , ScF ₃ , SCl ₃ , TiF ₃ , VCl ₂ , VCl ₃ , CrCl ₃ , CrBr ₃ , CrCl ₂ , CrF ₂ , MnCl ₂ , MnBr ₂ , MnF ₂ , MnF ₃ , MnI ₂ , FeBr ₂ , FeBr ₃ , FeCl ₂ , FeCl ₃ , FeI ₂ , CoBr ₂ , CoCl ₂ , CoF ₃ , CoF ₂ , CoI ₂ , NiBr ₂ , NiCl ₂ , NiF ₂ , NiI ₂ , CuBr, CuBr ₂ , CuCl, CuCl ₂ , CuF ₂ , CuI, ZnF ₂ , ZnBT ₂ , ZnCl ₂ , ZnI ₂ , GaBr ₃ , Ga ₂ Cl ₄ , GaCl ₃ , GaF ₃ , GaI ₃ , GaBr ₂ , GeBr ₂ , GeI ₂ , GeI ₄ , RbBr, RbCl, RbF, RbI, SrBr ₂ , SrCl ₂ , SrF ₂ , SrI ₂ , YCl ₃ , YF ₃ , YI ₃ , YBr ₃ , ZrBr ₄ , ZrCl ₄ , ZrI ₂ , YBr, ZrBr ₄ , ZrCl ₄ , ZrF ₄ , ZrI ₄ , NbCl ₅ , NbF ₅ , MoCl ₃ , MoCl ₅ , RuI ₃ , RhCl ₃ , PdBr ₂ , PdCl ₂ , PdI ₂ , AgCl, AgF, AgF ₂ , AgSbF ₆ , AgI, CdBr ₂ , CdCl ₂ , CdI ₂ , InBr, InBr ₃ , InCl, InCl ₂ , InCl ₃ , InF ₃ , InI, InI ₃ , SnBr ₂ , SnCl ₂ , SnI ₂ , SnI ₄ , SnCl ₃ , SbF ₃ , SbI ₃ , CsBr, CsCl, CsF, CsI, BaCl ₂ , BaF ₂ , BaI ₂ , BaCoF ₄ , BaNiF ₄ , HfCl ₄ , HfF ₄ , TaCl ₅ , TaF ₅ , WCl ₄ , WCl ₆ , ReCl ₃ , ReCl ₅ , IrCl ₃ , PtBr ₂ , PtCl ₂ , AuBr ₃ , AuCl, AuCl ₃ , AuI, KAuCl ₄ , LaBr ₃ , LaCl ₃ , LaF ₃ , LaI ₃ , CeBr ₃ , CeCl ₃ , CeF ₃ , CeF ₄ , CeI ₃ and mixtures thereof, to name but a few.

Suitable oxometalates include compounds such as LiIO ₃ , Li ₆ O ₂ , Li ₂ SiO ₃ , LiClO ₄ , Na ₂ B ₄ O ₇ , NaBO ₃ , Na ₂ SiO ₃ , NaVO ₃ , Na ₂ MoO ₄ , Na ₂ SeO ₄ , Na ₂ SeO ₃ , Na ₂ TeO ₃ , K ₂ SiO ₃ , K ₂ CrO ₄ , K ₂ Cr ₂ O ₇ , CaSiO ₃ , BaMnO ₄ and mixtures thereof, to name but a few.

Suitable metal carbonates include compounds such as Li ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , MgCO ₃ , K ₂ CO ₃ , CaCO ₃ , CT ₂ (CO ₃ ) ₃ , MnCO ₃ , CoCO ₃ , NiCO ₃ , CuCO ₃ , Rb ₂ CO ₃ , SrCO ₃ , Y ₂ (CO ₃ ) ₃ , Ag ₂ CO ₃ , CdCO ₃ , In ₂ (CO ₃ ) ₃ , Sb ₂ (CO ₃ ) ₃ , C ₂ CO ₃ , BaCO ₃ , La ₂ (CO ₃ ) ₃ , Ce ₂ (CO ₃ ) ₃ , NaAl (CO ₃ ) (OH) _2, and mixtures thereof, to name but a few.

Translucent agents include metal oxides, metal salts and metal silicates such as alumina (Al ₂ O ₃ ), silica gel (SiO ₂ ), zirconium oxide (ZrO ₂ ), sodium silicate (Na ₂ SiO ₃ ), potassium silicate (K ₂ SiO ₃ ), and other compounds. which are capable of optically transmitting laser energy (for example as generated by Nd: YAG, CO ₂ and Yt fiber lasers).

Viscosity / fluidity improvers include metal fluorides such as calcium fluoride (CaF ₂ ), cryolite (Na ₃ AlF ₆ ) and other agents known to improve viscosity and fluidity (e.g., reduced viscosity with CaO, MgO, Na ₂ O, K ₂ O and increasing viscosity with Al ₂ O ₃ and TiO ₂ ) in welding applications.

Shielding agents include metal carbonates such as calcium carbonate (CaCO ₃ ), aluminum carbonate (Al ₂ (CO ₃ ) ₃ ), dawsonite (NaAl (CO ₃ ) (OH) ₂ ), dolomite (CaMg (CO ₃ ) ₂ ), magnesium carbonate (MgCO ₃ ). , Manganese carbonate (MnCO ₃ ), cobalt carbonate (CoCO ₃ ), nickel carbonate (NiCO ₃ ), lanthanum carbonate (La ₂ (CO ₃ ) ₃ ) and other agents known to be protective and / or reducing gases (e.g., CO, CO ₂ , H ₂ ) form.

Scavengers include metal oxides and fluorides such as calcium oxide (CaO), calcium fluoride (CaF ₂ ), iron oxide (FeO), magnesium oxide (MgO), manganese oxides (MnO, MnO ₂ ), niobium oxides (NbO, NbO ₂ , Nb ₂ O ₅ ), Titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), and other agents known to produce low-density byproducts that are expected to result in a resulting slag layer 34 "Swim", react with harmful elements such as sulfur and phosphorus.

Vectoring materials include titanium, zirconium, boron and aluminum-containing compounds and materials such as titanium alloys (Ti), titanium oxide (TiO ₂ ), titanite (CaTiSiO ₅ ), aluminum alloys (Al), aluminum carbonate (Al ₂ (CO ₃ ) ₃ ), Dawsonit (NaAl (CO ₃ ) (CH) ₂ ), borate minerals (eg, kernite, borax, uxlex, colemanite), nickel titanium alloys (eg, nitinol), niobium oxides (NbO, NbO ₂ , Nb ₂ O ₅ ), and others Metal-containing compounds and materials used to supplement molten alloys with elements.

In some embodiments, the flux composition may also contain certain organic fluxes. Examples of organic compounds having liquefaction characteristics include high molecular weight hydrocarbons (e.g., beeswax, paraffin), carbohydrates (e.g., cellulose), natural and synthetic oils (e.g., palm oil), organic reducing agents (e.g. Coal, coke), carboxylic acids and dicarboxylic acids (e.g., abietic acid, isopimaric acid, neoabietic acid, dehydroabietic acid, rosin), carboxylic acid salts (e.g., rosin salts), carboxylic acid derivatives (e.g., dehydroabietylamine), amines (e.g. Triethanolamine), alcohols (eg, high polyglycols, glycerols), natural and synthetic resins (eg, polyol esters of fatty acids), mixtures of such compounds, and other organic compounds.

In some embodiments, flux compositions include:
5-60% by weight of metal oxide (s);
10-70% by weight of metal fluoride (s);
5-40% by weight of metal silicate (s); and
0-40% by weight of metal carbonate (s),
based on a total weight of the flux composition.

In some embodiments, flux compositions include:
5-40 wt.% Al ₂ O ₃ , SiO ₂ , and / or ZrO ₂ ;
10-50% by weight of metal fluoride (s);
5-40% by weight of metal silicate (s);
0-40% by weight of metal carbonate (s); and
15-30% by weight of other metal oxide (s),
based on a total weight of the flux composition.

In some embodiments, flux compositions include:
5-60 wt.% Al ₂ O ₃ , SiO ₂ , Na ₂ SiO ₃ and / or K ₂ SiO ₃ ;
10-50% by weight of CaF ₂ , Na ₃ AlF ₆ , Na ₂ O and / or K ₂ O;
1-30 wt.% CaCO ₃ , Al ₂ (CO ₃ ) ₃ , NaAl (CO ₃ ) (OH) ₂ , CaMg (CO ₃ ) ₂ , MgCO ₃ , MnCO ₃ , CoCO ₃ , NiCO ₃ and / or La ₂ (CO ₃ ) ₃ ;
15-30% by weight of CaO, MgO, MnO, ZrO ₂ and / or TiO ₂ ; and
0-5 wt .-% of a Ti metal, an Al metal and / or CaTiSiO ₅ ,
based on a total weight of the flux composition.

In some embodiments, the flux compositions include:
5-40 wt.% Al ₂ O ₃ ;
10-50% by weight of CaF ₂ ;
5-30% by weight of SiO ₂ ;
1-30% by weight of CaCO ₃ , MgCO ₃ and / or MnCO ₃ ;
15-30% by weight of CaO, MgO, MnO, ZTO ₂ and / or TiO ₂ ; and
0-5% by weight of Ti, Al, CaTiSiO ₅ , Al ₂ (CO ₃ ) ₃ and / or NaAl (CO ₃ ) (OH) ₂ ,
based on a total weight of the flux composition.

In some embodiments, the flux composition contains at least two compounds selected from a metal oxide, a metal halide, an oxometalate, and a metal carbonate. In other embodiments, the flux composition contains at least three of a metal oxide, a metal halide, an oxometalate, and a metal carbonate. In yet other embodiments, the flux composition may include a metal oxide, a metal halide, an oxometalate, and a metal carbonate.

The viscosity of the molten slag can be increased by the presence of at least one high melting point metal oxide which can act as a thickening agent. Thus, in some embodiments, the flux composition is formulated to include at least one high melting point metal oxide. Examples of high melting point metal oxides include metal oxides having a melting point above 2000 ° C - such as Sc ₂ O ₃ , Cr ₂ O ₃ , Y ₂ O ₃ , ZrO ₂ , HfO ₂ , La ₂ O ₃ , Ce ₂ O ₃ , Al ₂ O ₃ and CeO ₂ .

In some embodiments, the flux compositions of the present disclosure include zirconia (ZrO ₂ ) and at least one metal silicate, metal fluoride, metal carbonate, metal oxide (other than zirconia) or mixtures thereof. In such cases, the content of zirconia is often higher than about 7.5% by weight and often less than about 25% by weight. In other cases, the content of zirconia is more than over 10% by weight and less than 20% by weight. In still other cases, the content of zirconia is greater than about 3.5% by weight and less than about 15% by weight. In still other cases, the content of zirconia is between about 8% by weight and about 12% by weight.

In some embodiments, the flux compositions of the present disclosure include a metal carbide and at least one metal oxide, metal silicate, metal fluoride, metal carbonate, or mixtures thereof. In such cases, the content of metal carbide is less than about 10% by weight. In other cases, the salary is of the metal carbide is equal to or greater than about 0.001% by weight and less than about 5% by weight. In still other cases, the content of the metal carbide is greater than about 0.01 weight percent and less than about 2 weight percent. In still other cases, the content of the metal carbide is between about 0.001% and about 3% by weight.

In some embodiments, the flux compositions of the present disclosure include at least two metal carbonates and at least one metal oxide, metal silicate, metal fluoride, or mixtures thereof. For example, in some instances, the flux compositions include calcium carbonate (for phosphorus control) and magnesium carbonate and / or manganese carbonate (for sulfur control). In other cases, the flux compositions include calcium carbonate, magnesium carbonate and manganese carbonate. Some flux compositions comprise a ternary mixture of calcium carbonate, magnesium carbonate and manganese carbonate such that a proportion of the ternary mixture is equal to or less than 30% by weight relative to a total weight of the flux material. A combination of such carbonates (binary or ternary) is beneficial with the most effective rinsing multiple accompanying elements.

All weight percentages mentioned above are based on a total flux content of 100%.

Commercially available fluxes may also be used to form composite materials of the present disclosure. Examples include flux materials sold under the names Lincolnweld P2007, Bohler Soudokay NiCrW-412, ESAB OK 10.16 and 10.90, Special Metals NT100, Oerlikon OP76, Bavaria WP 380, Sandvik 50SW, 59S or SAS1, and Avesta 805. Prior to use, such commercially available fluxes may be milled to a smaller particle size range.

Embodiments:

• A composite material comprising a metal alloy and a flux composition, wherein a volume ratio of the flux composition to the metal alloy is in the range of about 30:70 to about 70:30.
• 2. Composite material according to embodiment 1, wherein the metal alloy is a superalloy.
• 3. The composite material of embodiment 1, wherein the flux composition comprises a metal oxide and at least one selected from the group consisting of a metal halide, a metal oxometalate and a metal carbonate.
• 4. The composite material of embodiment 1, wherein the flux composition comprises: a metal oxide selected from the group consisting of Li ₂ O, BeO, B ₂ O ₃ , B ₆ O, MgO, Al ₂ O ₃ , SiO ₂ , CaO, Sc ₂ O ₃ , TiO, TiO ₂ , Ti ₂ O ₃ , VO, V ₂ O ₃ , V ₂ O ₄ , V ₂ O ₅ , Cr ₂ O ₃ , CrO ₃ , MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO, CO ₃ O ₄ , NiO, Ni ₂ O ₃ , Cu ₂ O, CuO, ZnO, Ga ₂ O ₃ , GeO ₂ , As ₂ O ₃ , Rb ₂ O, SrO, Y ₂ O ₃ , ZrO ₂ , NiO, NiO ₂ , Ni ₂ O ₅ , MoO ₃ , MoO ₂ , RuO ₂ , Rh ₂ O ₃ , RhO ₂ , PdO, Ag ₂ O, CdO, In ₂ O ₃ , SnO, SnO ₂ , Sb ₂ O ₃ , TeO ₂ , TeO ₃ , Cs ₂ O, BaO, HfO ₂ , Ta ₂ O ₅ , WO ₂ , WO ₃ , ReO ₃ , Re ₂ O ₇ , PtO ₂ , Au ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and mixtures thereof; and at least one of: (i) a metal halide selected from the group consisting of LiF, LiCl, LiBr, LiI, Li ₂ NiBr ₄ , Li ₂ CuCl ₄ , LiAsF ₆ , LiPF ₆ , LiAlCl ₄ , LiGaCl ₄ , Li ₂ PdCl ₄ , NaF, NaCl, NaBr, Na ₃ AlF ₆ , NaSbF ₆ , NaAsF ₆ , NaAuBr ₄ , NaAlCl ₄ , Na ₂ PdCl ₄ , Na ₂ PtCl ₄ , MgF ₂ , MgCl ₂ , MgBr ₂ , AlF ₃ , KCl, KF, KBr, K ₂ RuCl ₅ , K ₂ IrCl ₆ , K ₂ PtCl ₆ , K ₂ PtCl ₆ , K ₂ ReCl ₆ , K ₃ RhCl ₆ , KSbF ₆ , KAsF ₆ , K ₂ NiF ₆ , K ₂ TiF ₆ , K ₂ ZrF ₆ , K ₂ PtI ₆ , KAuBr ₄ , K ₂ PdBT ₄ , K ₂ PdCl ₄ , CaF ₂ , CaF, CaBr ₂ , CaCl ₂ , CaI ₂ , ScBr ₃ , ScCl ₃ , ScF ₃ , SCl ₃ , TiF ₃ , VCl ₂ , VCl ₃ , CrCl ₃ , CrBr ₃ , CrCl ₂ , CrF ₂ , MnCl ₂ , MnBr ₂ , MnF ₂ , MnF ₃ , MnI ₂ , FeBr ₂ , FeBr ₃ , FeCl ₂ , FeCl ₃ , FeI ₂ , CoBr ₂ , CoCl ₂ , CoF ₃ , CoF ₂ , CoI ₂ , NiBr ₂ , NiCl ₂ , NiF ₂ , NiI ₂ , CuBr, CuBr ₂ , CuCl, CuCl ₂ , CuF ₂ , CuI, ZnF ₂ , ZnBT ₂ , ZnCl ₂ , ZnI ₂ , GaBr ₃ , Ga ₂ Cl ₄ , GaCl ₃ , GaF ₃ , GaI ₃ , GaBr ₂ , GeBr ₂ , GeI ₂ , GeI ₄ , RbBr, RbCl, RbF, RbI, S rBr ₂ , SrCl ₂ , SrF ₂ , SrI ₂ , YCl ₃ , YF ₃ , YI ₃ , YBr ₃ , ZrBr ₄ , ZrCl ₄ , ZrI ₂ , YBr, ZrBr ₄ , ZrCl ₄ , ZrF ₄ , ZrI ₄ , NbCl ₅ , NbF ₅ , MoCl ₃ , MoCl ₅ , RuI ₃ , RhCl ₃ , PdBr ₂ , PdCl ₂ , PdI ₂ , AgCl, AgF, AgF ₂ , AgSbF ₆ , AgI, CdBr ₂ , CdCl ₂ , CdI ₂ , InBr, InBr ₃ , InCl, InCl ₂ , InCl ₃ , InF ₃ , InI, InI ₃ , SnBr ₂ , SnCl ₂ , SnI ₂ , SnI ₄ , SnCl ₃ , SbF ₃ , SbI ₃ , CsBr, CsCl, CsF, CsI, BaCl ₂ , BaF ₂ , BaI ₂ , BaCoF ₄ , BaNiF ₄ , HfCl ₄ , HfF ₄ , TaCl ₅ , TaF ₅ , WCl ₄ , WCl ₆ , ReCl ₃ , ReCl ₅ , IrCl ₃ , PtBr ₂ , PtCl ₂ , AuBr ₃ , AuCl, AuCl ₃ , AuI, KAuCl ₄ , LaBr ₃ , LaCl ₃ , LaF ₃ , LaI ₃ , CeBr ₃ , CeCl ₃ , CeF ₃ , CeF ₄ , CeI ₃ and mixtures thereof; (ii) an oxometalate selected from the group consisting of LiIO ₃ , Li ₆ O ₂ , Li ₂ SiO ₃ , LiClO ₄ , Na ₂ B ₄ O ₇ , NaBO ₃ , Na ₂ SiO ₃ , NaVO ₃ , Na ₂ MoO ₄ , Na ₂ SeO ₄ , Na ₂ SeO ₃ , Na ₂ TeO ₃ , K ₂ SiO ₃ , K ₂ CrO ₄ , K ₂ Cr ₂ O ₇ , CaSiO ₃ , BaMnO ₄ and mixtures thereof; and (iii) a metal carbonate selected from the group consisting of Li ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , MgCO ₃ , K ₂ CO ₃ , CaCO ₃ , CT ₂ (CO ₃ ) ₃ , MnCO ₃ , CoCO ₃ , NiCO ₃ , CuCO ₃ , Rb ₂ CO ₃ , SrCO ₃ , Y ₂ (CO ₃ ) ₃ , Ag ₂ CO ₃ , CdCO ₃ , In ₂ (CO ₃ ) ₃ , Sb ₂ (CO ₃ ) ₃ , C ₂ CO ₃ , BaCO ₃ , La ₂ (CO ₃ ) ₃ , Ce ₂ (CO ₃ ) ₃ , NaAl (CO ₃ ) (OH) _2, and mixtures thereof.
• 5. Composite material according to embodiment 1, in the form of particles comprising a core, the surrounded by a metallic layer, wherein: the core comprises the flux composition; and the metallic layer comprises the metal alloy.
• 6. The composite material of Embodiment 5, wherein the metallic layer satisfies at least one condition selected from the group consisting of: (i) the metallic layer is a layer of graded composition, (ii) the metallic layer is in the form of several equivalent metallic layers comprising the metal alloy, (iii) the metallic layer is in the form of several different metallic layers containing different metallic compositions, and (iv) the metallic layer is coated by at least one protective layer comprising an inorganic protective material.
• 7. A composite material according to embodiment 1, in the form of a fused material comprising the metal alloy and the flux composition, wherein the metal alloy and the flux composition are randomly distributed within the fused material and randomly oriented.
• A composite material comprising a superalloy and a flux composition.
• 9. The composite material of embodiment 8, wherein a volume ratio of the flux composition to the superalloy ranges from about 30:70 to about 70:30.
• A composite material according to embodiment 8, in the form of particles comprising a core surrounded by a metallic layer, wherein: the core comprises the flux composition; and the metallic layer comprises the superalloy.
• 11. The composite material of embodiment 10, wherein the metallic layer meets at least one condition selected from the group consisting of: (i) the metallic layer is a layer of graded composition, (ii) the metallic layer is in the form of several equivalent metallic layers comprising the metal alloy, (iii) the metallic layer is in the form of several different metallic layers containing different metallic compositions, and (iv) the metallic layer is coated by at least one protective layer comprising an inorganic protective material.
• 12. The composite material of embodiment 8, in the form of a fused material comprising the superalloy and the flux composition, wherein the superalloy and flux composition are randomly distributed within the fused material and randomly oriented.
• 13. A composite material comprising a metal alloy and a flux composition comprising a metal oxide and at least one selected from the group consisting of a metal halide, a metal oxometalate and a metal carbonate.
• 14. The composite material of embodiment 13, wherein a volume ratio of the flux composition to the metal alloy is in the range of about 30:70 to about 70:30.
• A composite material according to embodiment 13, in the form of particles comprising a core surrounded by a metallic layer, wherein: the core comprises the flux composition; and the metallic layer comprises the metal alloy.
• 16. The composite material of embodiment 15, wherein the metallic layer meets at least one condition selected from the group consisting of: (i) the metallic layer is a layer of graded composition, (ii) the metallic layer is in the form of several equivalent metallic layers comprising the metal alloy, (iii) the metallic layer is in the form of several different metallic layers containing different metallic compositions, and (iv) the metallic layer is coated by at least one protective layer comprising an inorganic protective material.
• 17. A composite material according to embodiment 13, in the form of a fused material comprising the metal alloy and the flux composition, wherein the metal alloy and the flux composition within the fused material are randomly distributed and randomly oriented.
• 18. A process comprising melting the composite material of Embodiment 1 and allowing a resulting molten material to cool to form a metal deposit.
• 19. A process comprising melting the composite material of Embodiment 8 and allowing a resulting molten material to cool to form a metal deposit.
• 20. A process comprising melting the composite material of Embodiment 13 and allowing a resulting molten material to cool to form a metal deposit. While various embodiments of the present invention have been shown and described herein, it is apparent that such embodiments have been provided by way of example only. Various variations, changes and substitutions may be made without departing from the present invention. Accordingly, it is intended that the invention be limited only by the spirit and scope of the appended claims.

Claims (10)

A composite material comprising a metal alloy and a flux composition, wherein a volume ratio of the flux composition to the metal alloy is in the range of about 30:70 to about 70:30. The composite of claim 1, wherein the metal alloy is a superalloy. The composite of claim 1, wherein the flux composition comprises a metal oxide and at least one selected from the group consisting of a metal halide, a metal oxometalate and a metal carbonate. The composite of claim 1, wherein the flux composition comprises: a metal oxide selected from the group consisting of Li ₂ O, BeO, B ₂ O ₃ , B ₆ O, MgO, Al ₂ O ₃ , SiO ₂ , CaO, Sc ₂ O ₃ , TiO, TiO ₂ , Ti ₂ O ₃ , VO, V ₂ O ₃ , V ₂ O ₄ , V ₂ O ₅ , Cr ₂ O ₃ , CrO ₃ , MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO, CO ₃ O ₄ , NiO, Ni ₂ O ₃ , Cu ₂ O, CuO, ZnO, Ga ₂ O ₃ , GeO ₂ , As ₂ O ₃ , Rb ₂ O, SrO, Y ₂ O ₃ , ZrO ₂ , NiO, NiO ₂ , Ni ₂ O ₅ , MoO ₃ , MoO ₂ , RuO ₂ , Rh ₂ O ₃ , RhO ₂ , PdO, Ag ₂ O, CdO, In ₂ O ₃ , SnO, SnO ₂ , Sb ₂ O ₃ , TeO ₂ , TeO ₃ , Cs ₂ O, BaO, HfO ₂ , Ta ₂ O ₅ , WO ₂ , WO ₃ , ReO ₃ , Re ₂ O ₇ , PtO ₂ , Au ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and mixtures thereof; and at least one of: (i) a metal halide selected from the group consisting of LiF, LiCl, LiBr, LiI, Li ₂ NiBr ₄ , Li ₂ CuCl ₄ , LiAsF ₆ , LiPF ₆ , LiAlCl ₄ , LiGaCl ₄ , Li ₂ PdCl ₄ , NaF, NaCl, NaBr, Na ₃ AlF ₆ , NaSbF ₆ , NaAsF ₆ , NaAuBr ₄ , NaAlCl ₄ , Na ₂ PdCl ₄ , Na ₂ PtCl ₄ , MgF ₂ , MgCl ₂ , MgBr ₂ , AlF ₃ , KCl, KF, KBr, K ₂ RuCl ₅ , K ₂ IrCl ₆ , K ₂ PtCl ₆ , K ₂ PtCl ₆ , K ₂ ReCl ₆ , K ₃ RhCl ₆ , KSbF ₆ , KAsF ₆ , K ₂ NiF ₆ , K ₂ TiF ₆ , K ₂ ZrF ₆ , K ₂ PtI ₆ , KAuBr ₄ , K ₂ PdBT ₄ , K ₂ PdCl ₄ , CaF ₂ , CaF, CaBr ₂ , CaCl ₂ , CaI ₂ , ScBr ₃ , ScCl ₃ , ScF ₃ , SCl ₃ , TiF ₃ , VCl ₂ , VCl ₃ , CrCl ₃ , CrBr ₃ , CrCl ₂ , CrF ₂ , MnCl ₂ , MnBr ₂ , MnF ₂ , MnF ₃ , MnI ₂ , FeBr ₂ , FeBr ₃ , FeCl ₂ , FeCl ₃ , FeI ₂ , CoBr ₂ , CoCl ₂ , CoF ₃ , CoF ₂ , CoI ₂ , NiBr ₂ , NiCl ₂ , NiF ₂ , NiI ₂ , CuBr, CuBr ₂ , CuCl, CuCl ₂ , CuF ₂ , CuI, ZnF ₂ , ZnBT ₂ , ZnCl ₂ , ZnI ₂ , GaBr ₃ , Ga ₂ Cl ₄ , GaCl ₃ , GaF ₃ , GaI ₃ , GaBr ₂ , GeBr ₂ , GeI ₂ , GeI ₄ , RbBr, RbCl, RbF, RbI, S rBr ₂ , SrCl ₂ , SrF ₂ , SrI ₂ , YCl ₃ , YF ₃ , YI ₃ , YBr ₃ , ZrBr ₄ , ZrCl ₄ , ZrI ₂ , YBr, ZrBr ₄ , ZrCl ₄ , ZrF ₄ , ZrI ₄ , NbCl ₅ , NbF ₅ , MoCl ₃ , MoCl ₅ , RuI ₃ , RhCl ₃ , PdBr ₂ , PdCl ₂ , PdI ₂ , AgCl, AgF, AgF ₂ , AgSbF ₆ , AgI, CdBr ₂ , CdCl ₂ , CdI ₂ , InBr, InBr ₃ , InCl, InCl ₂ , InCl ₃ , InF ₃ , InI, InI ₃ , SnBr ₂ , SnCl ₂ , SnI ₂ , SnI ₄ , SnCl ₃ , SbF ₃ , SbI ₃ , CsBr, CsCl, CsF, CsI, BaCl ₂ , BaF ₂ , BaI ₂ , BaCoF ₄ , BaNiF ₄ , HfCl ₄ , HfF ₄ , TaCl ₅ , TaF ₅ , WCl ₄ , WCl ₆ , ReCl ₃ , ReCl ₅ , IrCl ₃ , PtBr ₂ , PtCl ₂ , AuBr ₃ , AuCl, AuCl ₃ , AuI, KAuCl ₄ , LaBr ₃ , LaCl ₃ , LaF ₃ , LaI ₃ , CeBr ₃ , CeCl ₃ , CeF ₃ , CeF ₄ , CeI ₃ and mixtures thereof; (ii) an oxometalate selected from the group consisting of LiIO ₃ , Li ₆ O ₂ , Li ₂ SiO ₃ , LiClO ₄ , Na ₂ B ₄ O ₇ , NaBO ₃ , Na ₂ SiO ₃ , NaVO ₃ , Na ₂ MoO ₄ , Na ₂ SeO ₄ , Na ₂ SeO ₃ , Na ₂ TeO ₃ , K ₂ SiO ₃ , K ₂ CrO ₄ , K ₂ Cr ₂ O ₇ , CaSiO ₃ , BaMnO ₄ and mixtures thereof; and (iii) a metal carbonate selected from the group consisting of Li ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , MgCO ₃ , K ₂ CO ₃ , CaCO ₃ , CT ₂ (CO ₃ ) ₃ , MnCO ₃ , CoCO ₃ , NiCO ₃ , CuCO ₃ , Rb ₂ CO ₃ , SrCO ₃ , Y ₂ (CO ₃ ) ₃ , Ag ₂ CO ₃ , CdCO ₃ , In ₂ (CO ₃ ) ₃ , Sb ₂ (CO ₃ ) ₃ , C ₂ CO ₃ , BaCO ₃ , La ₂ (CO ₃ ) ₃ , Ce ₂ (CO ₃ ) ₃ , NaAl (CO ₃ ) (OH) _2, and mixtures thereof. The composite of claim 1, in the form of particles comprising a core surrounded by a metallic layer, wherein: the core comprises the flux composition; and the metallic layer comprises the metal alloy. The composite material of claim 5, wherein the metallic layer meets at least one condition selected from the group consisting of: (i) the metallic layer is a layer of graded composition, (ii) the metallic layer is in the form of several equivalent metallic layers comprising the metal alloy, (iii) the metallic layer is in the form of several different metallic layers containing different metallic compositions, and (iv) the metallic layer is coated by at least one protective layer comprising an inorganic protective material. The composite of claim 1, in the form of a fused material comprising the metal alloy and the flux composition, wherein the metal alloy and the flux composition are randomly distributed within the fused material and randomly oriented. A composite material comprising a superalloy and a flux composition. A composite material comprising a metal alloy and a flux composition comprising a metal oxide and at least one selected from the group consisting of a metal oxide Metal halide, a metal oxometalate and a metal carbonate. A process comprising melting the composite material of claim 1 or 8 or 9 and allowing a resulting molten material to cool to form a metal deposit.

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