COMPOSITIONS COMPRISING ASPHALTITE ADDITIVES FOR ADDITIVE MANUFACTURING

Abstract

Compositions for additive manufacturing applications are described herein, which in some embodiments provide improved printing properties. In some embodiments, the compositions include a primary build material in an amount of 10-99.9 wt.% and an asphaltite additive in an amount of up to 6 wt.%, based on the total weight of the composition. In some cases, the asphaltite additive includes a solid hydrocarbon-based mineral or a solid organic material formed primarily from hydrocarbons and found in oil-bearing deposits, such as gilsonite.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority pursuant to 35 U.S.C. § 119 to U.S. Provisional Patent Application No. 63 / 445,121, filed February 13, 2023, which is incorporated herein by reference in its entirety. [Technical Field]

[0002] The present invention relates to compositions for additive manufacturing, and in particular to compositions with improved three-dimensional (3D) printing properties. [Background technology]

[0003] Three-dimensional (3D) printers and systems use various types of materials to form various 3D objects, articles, or parts according to computer-generated files. Such materials can include build materials used to form the object itself, as opposed to sacrificial support materials that may be used to support the object during the additive manufacturing process but are subsequently removed from the final printed object. Some build materials are also known as inks, for example, when they are polymerizable liquids or other fluids that are jetted or otherwise selectively deposited to form the 3D object. In some such instances, the build material is solid at ambient temperature and converts to a liquid at elevated jetting temperatures. In other instances, the build material is liquid at ambient temperature. The build material may also be a powder or dry particulate material, as opposed to a polymerizable liquid. Such powders can be used in selective laser sintering (SLS) and similar additive manufacturing techniques. Summary of the Invention [Problem to be solved by the invention]

[0004] Build materials can include a variety of chemical species. The chemical species included in the build material can be selected according to various factors, including, but not limited to, the desired chemical and / or mechanical properties of the printed article and the operating parameters of the 3D printing device or system. Unfortunately, some build materials and resulting articles printed therefrom can have undesirable solidification behavior, flow behavior (e.g., relatively high viscosity), and / or relatively low resistance to degradation caused by ultraviolet (UV) light, and improved materials for additive manufacturing with improved solidification behavior, reduced viscosity, and / or improved resistance to UV light are needed. [Means for solving the problem]

[0005] In view of the foregoing, compositions (or build materials) for additive manufacturing applications are described herein, which, in some embodiments, have desirable solidification and / or flow behavior for additive manufacturing processes. The compositions may also provide articles formed from the compositions with improved mechanical or chemical properties, such as improved resistance to degradation caused by UV light. In some embodiments, the compositions described herein comprise a primary build material in an amount of 10 to 99.9 wt. % and an asphaltite additive in an amount up to 6 wt. %, based on the total weight of the composition. As further described herein, various asphaltite additives may be used in compositions according to the present disclosure. In some cases, for example, the asphaltite additives described herein comprise solid hydrocarbon-based minerals (e.g., gilsonite) or solid organic materials formed primarily from hydrocarbons and found in oil-bearing deposits. In some examples, the asphaltite additives described herein comprise 50 to 80 wt. % asphaltenes, 15 to 40 wt. % resins (e.g., maltenes), and up to 10 wt. % oil. Additionally, in some embodiments, the asphaltite additives described herein have a weight average molecular weight of 2000 to 4000 g / mol or 2500 to 3500 g / mol.

[0006] Furthermore, such asphaltite additives can be combined with various primary build materials, such as those used in SLS, fused deposition modeling (FDM), fused granular modeling (FGM), or other forms of additive manufacturing or 3D printing. For example, in some embodiments, the primary build material of the compositions described herein comprises a sinterable powder. Furthermore, in some such cases, the sinterable powder comprises a semi-crystalline polymer, such as polyamide (PA), polyesters (PEs), polyurethanes (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing. The sinterable powder can also comprise a thermoplastic polymer, such as acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more thereof. Such sinterable powders described herein may be particularly suitable for use in SLS.

[0007] Additionally, the compositions described herein may be used in other methods of 3D printing, not necessarily limited to SLS. In some embodiments, for example, the compositions described herein comprise, consist of, or consist essentially of a filament material. In some such cases, the asphaltite additive is dispersed within the primary build material within the filament material. In other cases, the compositions described herein comprise, consist of, or consist essentially of a pellet material. Furthermore, in some such examples, the asphaltite additive is dispersed within the primary build material within the pellet material. Alternatively, in some cases, the pellet material is formed from the primary build material, and the asphaltite additive is physically blended or mixed with the pellet material, but not necessarily dispersed within the pellet material, as may occur, for example, by melt blending.

[0008] In another aspect, methods of printing 3D articles are described herein. In some cases, such methods include providing a composition described herein and selectively solidifying a layer of the composition to form the article. In some implementations, the composition is provided in a layer-by-layer process. Furthermore, in some embodiments, selectively solidifying a layer of the composition includes sintering the layer of the composition (e.g., as in an SLS process). In other cases, selectively solidifying a layer of the composition includes depositing the layer of the composition in a molten state and then freezing or partially freezing the layer of the composition (e.g., as may occur in an FDM or FGM process). In yet other examples, selectively solidifying a layer of the composition can include melting the layer of the composition and then refreezing or partially refreezing it.

[0009] Also described in this disclosure are printed 3D articles or objects, which may be formed or primarily formed from the compositions described herein, including the asphaltite additive.

[0010] These and other embodiments are further described in the detailed description that follows. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 shows a differential scanning calorimetry (DSC) plot of one embodiment of a composition described herein compared to a comparative composition. [Figure 2] FIG. 1 shows a DSC plot of one embodiment of a composition described herein compared to a comparative composition. DETAILED DESCRIPTION OF THE INVENTION

[0012] The embodiments described herein can be more readily understood by reference to the following detailed description and examples. However, the elements, devices, and methods described herein are not limited to the specific embodiments presented in the detailed description and examples. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

[0013] Furthermore, all ranges disclosed herein should be understood to encompass any and all subranges subsumed therein. For example, a range of "1.0 to 10.0" is interpreted to include any and all subranges beginning with a minimum value greater than or equal to 1.0 and ending with a maximum value less than or equal to 10.0, such as 1.0 to 5.3, or 4.7 to 10.0, or 3.6 to 7.9.

[0014] All ranges disclosed herein are also intended to include the endpoints of the range unless expressly stated otherwise. For example, a range of "5 to 10" is generally interpreted as including the endpoints 5 and 10.

[0015] Furthermore, when the term "up to" is used in connection with an amount or quantity, it is understood that the amount is at least a detectable or non-zero amount or quantity. For example, a substance present in an amount "up to" a particular amount can be present in an amount from a detectable or non-zero amount up to and including the particular amount.

[0016] Additionally, in any disclosed embodiment, the terms "substantially," "approximately," and "about" can be substituted for "within [a percentage]" of what is specified, where the percentage can be 0.1, 1, 5, or 10 percent, unless the use of such terms in a given example indicates otherwise.

[0017] The article "a" or "an" should also be understood to refer to "at least one" unless the context of the particular use requires otherwise.

[0018] Terms such as "3D printing system," "3D printer," and "printing" generally describe various solid freeform manufacturing techniques for creating three-dimensional articles or objects by selective laser sintering (SLS), stereolithography (SLA), dynamic light projection (DLP), selective deposition, jetting, fused deposition modeling (FDM), fused granule modeling (FGM), multi-jet modeling (MJM), and other additive manufacturing techniques currently known or that may become known in the art that use build materials or inks to create three-dimensional objects.

[0019] In one aspect, compositions for use in additive manufacturing applications are described herein. The compositions can be used, for example, in SLS, FDM, and FGM printing applications. In some embodiments, the compositions described herein include a primary build material (e.g., in an amount of 10-99.9 wt. % based on the total weight of the composition) and an asphaltite additive (e.g., in an amount of up to 6 wt. % based on the total weight of the composition). Specific components of compositions according to the present disclosure are described in further detail below.

[0020] The asphaltite additives described herein, in some embodiments, can include solid hydrocarbon-based minerals, such as those known as gilsonite, uintaite, or uintaite. Such asphaltites can be obtained from the Uinta Basin in Utah, USA. Asphaltite can also be obtained from Iran. Furthermore, in some embodiments, the asphaltite additives described herein include solid organic material formed primarily from hydrocarbons and found in oil-bearing sedimentary basins (e.g., the Uinta Basin or a different basin). In some examples, the asphaltite additives described herein contain 50-80 wt. % asphaltenes, 15-40 wt. % resins (e.g., maltenes), and up to 10 wt. % oil (e.g., as identified by Fourier transform infrared spectroscopy (FTIR) and / or nuclear magnetic resonance spectroscopy (NMR)). Furthermore, in some embodiments, the asphaltite additives described herein have a weight average molecular weight of 2000-4000 g / mol or 2500-3500 g / mol.

[0021] Additionally, in some cases, the asphaltite additives described herein comprise a thermoplastic hydrocarbon resin (or resinous hydrocarbon) that (1) contains at least 30% by weight asphaltenes, based on the total weight of the asphaltite; (2) is soluble in aromatic hydrocarbon solvents (e.g., toluene, ethylbenzene, or xylene) and / or chlorinated hydrocarbon solvents (e.g., carbon tetrachloride, perchloroethylene, or 1,1,1-trichloroethane); and / or (3) has a chemical composition of 82-88% by weight carbon, 8-12% by weight hydrogen, 2.5-3.5% by weight nitrogen, up to 1% by weight sulfur, up to 2% by weight oxygen, and up to 0.5% by weight other elements, based on the total weight of the asphaltite. Additionally, in some cases, the carbon content of the asphaltite additives described herein is predominantly aliphatic (e.g., 65-70% by weight aliphatic compared to 30-35% by weight aromatic).

[0022] Additionally, in some embodiments, the asphaltite additives described herein include one, two, three, four, five, or all six of the compositional parameters or characteristics listed in Table 1 below (depending on the composition and microstructure of the asphaltite additive). [Table 1]

[0023] Furthermore, it should be understood that the "softening point" in Table 1 above can be synonymous with the "melting point" of the asphaltite, as some asphaltites have relatively sharp melting points and others melt more gently.

[0024] The asphaltite additive can be present in the compositions described herein in any amount consistent with the technical objectives of the present disclosure. In some embodiments, the asphaltite additive is present in the composition in an amount of 0.1 to 6 weight percent, based on the total weight of the composition. In other cases, the asphaltite additive is present in the composition in an amount of 0.1 to 5 weight percent, 0.1 to 4 weight percent, 0.1 to 3 weight percent, 0.1 to 2 weight percent, 0.1 to 1.5 weight percent, 0.1 to 1 weight percent, 0.5 to 6 weight percent, 0.5 to 5 weight percent, 0.5 to 4 weight percent, 0.5 to 3 weight percent, 0.5 to 2 weight percent, 0.5 to 1.5 weight percent, 0.5 to 1 weight percent, 1 to 6 weight percent, 1 to 5 weight percent, 1 to 4 weight percent, 1 to 3 weight percent, or 1 to 2 weight percent, based on the total weight of the composition. In some preferred embodiments, the asphaltite additive is present in the composition in an amount less than 3 wt.%, less than 2.5 wt.%, or less than 2 wt.%, based on the total weight of the composition.

[0025] Referring now to the primary build material of the compositions described herein, it should be understood that a variety of primary build materials can be used. Furthermore, the primary build material can be selected based at least in part on the method of additive manufacturing. Generally, the compositions described herein can be used for additive manufacturing, including sintering (e.g., SLS), adhesive fusing of particles, and / or fused deposition of materials (e.g., FDM using filaments or FGM using pellets).

[0026] Thus, in some embodiments, the primary build material of the compositions described herein comprises a sinterable powder. As will be appreciated by those skilled in the art, a "sinterable" powder can be selectively sintered or melted by the application of energy, such as provided by a laser beam or other electromagnetic radiation source. The application of energy (e.g., a selectively applied laser beam) can selectively heat powder particles, resulting in partial melting of the powder and fusing adjacent particles together. Thus, "sintering" can, in some cases, involve heating a powder to a temperature that induces viscous flow only at the adjacent boundaries of individual powder particles, while at least a portion of substantially all particles remain solid. As discussed above, such sintering can result in the fusion of particles into a sintered solid mass, the bulk density of which is increased compared to the bulk density of the powder particles before they are sintered. Such fusion can provide a solidified portion (e.g., a cross section or layer) of an article or object printed or formed by the process. Thus, an article or object formed by the layer-by-layer or "slice-like" joining of vertically successive layers that are sintered into stacked "layers" or "slices" can be described as self-densified. Such slices or layers may, for example, have a thickness of up to about 250 μm, for example in the range of 50 μm to 180 μm.

[0027] Thus, the sinterable powders of the present disclosure can have optical, thermal, and other properties suitable for use in 3D printing systems or methods that selectively fuse or sinter individual powder particles to form objects. For example, the sinterable powders can have optical (e.g., absorbance) and / or thermal (e.g., glass transition temperature, Tg; melting point, MP; or crystallization temperature, Tc) properties selected for sintering by a particular electromagnetic radiation source. In some embodiments, the sinterable powders described herein have a non-zero absorbance or absorbance peak at wavelengths used in 3D printing processes (e.g., the peak wavelength of a laser, such as a CO2 laser used in an SLS process). Furthermore, in some cases, the sinterable powders described herein have a sintering window (defined as the metastable thermodynamic region between melting and crystallization, or the difference between the MP onset and the Tc onset) of at least 10°C, as measured by differential scanning calorimetry (DSC), e.g., 10-30°C, 10-25°C, or 10-20°C. Additionally, in some examples, the sinterable powders described herein have an MP of 120-270°C, 150-250°C, 150-200°C, 150-180°C, 170-250°C, 170-220°C, 170-200°C, 190-250°C, 190-220°C, or 200-250°C.

[0028] Further, in some cases, the sinterable powders can have an average particle size and flowability suitable for use in such additive manufacturing processes. For example, in some embodiments, the sinterable powders described herein have an average particle size (D) of 60-300 μm, 60-250 μm, 60-200 μm, 60-150 μm, 60-100 μm, 80-300 μm, 80-250 μm, 80-200 μm, 80-150 μm, 80-100 μm, 100-300 μm, 100-250 μm, 100-200 μm, 150-300 μm, 150-250 μm, 150-200 μm, 200-300 μm, or 200-250 μm. 50). The sinterable powders described herein, in some implementations, have a monomodal particle size distribution (PSD), as opposed to a bimodal or other higher-order PSD. Furthermore, in some cases, the sinterable powders described herein have a normalized packing density of 20-45% or 25-40%. Furthermore, in some embodiments, the sinterable powders described herein have an average circularity (defined as the ratio of the measured area of ​​a particle to the area of ​​an equivalent circle whose diameter is the particle's longest length) of 0.4-0.6. Furthermore, in some embodiments, the sinterable powders described herein have a bulk density and / or tapped density of greater than 0.35 g / mL or greater than 0.4 g / mL, e.g., 0.35-1 g / mL or 0.4-1 g / mL, as measured according to ASTM D1895B (bulk density) or ASTM B527 (tapped density).

[0029] It is further noted that in some cases, the asphaltite additives described herein do not significantly alter the sintering window of the sinterable powders described herein. For example, in some cases, the sintering window of a composition comprising the asphaltite additive described herein has a width (in degrees Celsius) and / or one or more endpoints (in degrees Celsius) that is within 1°C, 2°C, or 5°C of another similar composition without the asphaltite additive. Furthermore, in some examples, the compositions described herein that comprise the asphaltite additive do not emit or produce smoke when heated by a laser or other heat source in an additive manufacturing process as described herein. Thus, in some embodiments, performing the methods described herein does not produce smoke observable to a human observer with average visual acuity when observing the method without the use of any equipment or visual aids other than corrective lenses, such as glasses or contact lenses.

[0030] Any sinterable powder consistent with the objectives of the present disclosure can be used. In some cases, the sinterable powder includes a semi-crystalline polymer, and in some cases, it is included as the major or majority component (by mass or weight) of the sinterable powder. Any semi-crystalline polymer consistent with the objectives of the present disclosure can be used. In some implementations, the sinterable powder of the compositions described herein includes (or includes as a major component) polyamide (PA), polyester (PEs), polyurethane (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing. When the sinterable powder includes polyamide (PA), any PA consistent with the objectives of the present disclosure can be used. For example, in some cases, the PA includes polyamide-11 (PA11), polyamide-12 (PA12), or a combination of PA11 and PA12.

[0031] In some cases, the sinterable powders described herein comprise up to 100%, up to 99%, up to 95%, or up to 90% by weight of semi-crystalline polymer, based on the total weight of the sinterable powder (rather than based on the total weight of the entire composition). In some examples, the sinterable powders comprise 50-100%, 50-99%, 50-90%, 50-80%, 50-70%, 60-100%, 60-99%, 60-90%, 70-100%, 70-99%, 70-90%, 80-100%, 80-99%, 80-95%, 85-100%, 85-99%, 85-95%, 90-100%, or 90-99% by weight of semi-crystalline polymer, based on the total weight of the sinterable powder.

[0032] Additionally, in some embodiments, the sinterable powders described herein include a thermoplastic polymer (e.g., instead of or in addition to a semi-crystalline polymer). Furthermore, the thermoplastic polymer can include any thermoplastic polymer not inconsistent with the technical objectives of the present disclosure. For example, in some cases, the thermoplastic polymer includes acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more thereof.

[0033] In some cases, the sinterable powders described herein comprise up to 100%, up to 99%, up to 95%, or up to 90% by weight of thermoplastic polymer, based on the total weight of the sinterable powder (rather than based on the total weight of the entire composition). In some examples, the sinterable powders comprise 50-100%, 50-99%, 50-90%, 50-80%, 50-70%, 60-100%, 60-99%, 60-90%, 70-100%, 70-99%, 70-90%, 80-100%, 80-99%, 80-95%, 85-100%, 85-99%, 85-95%, 90-100%, or 90-99% by weight of thermoplastic polymer, based on the total weight of the sinterable powder.

[0034] In addition to the primary or major components described above, the sinterable powders described herein may also include one or more additional components. In some embodiments, for example, the sinterable powder includes a filler. Any filler not inconsistent with the objectives of the present disclosure may be used. For example, in some cases, the filler includes glass, ceramic, or carbon fiber. In some embodiments, the filler is in the form of a sphere, plate, or fiber, and the shape of any filler is not particularly limited.

[0035] When a filler is used, it can be present in the sinterable powder in any amount consistent with the technical objectives of the present disclosure. For example, in some cases, the sinterable powders described herein include up to 30%, up to 20%, up to 15%, or up to 10% by weight of filler material, based on the total weight of the sinterable powder (not based on the total weight of the entire composition). In some examples, the sinterable powder includes 1-30%, 1-25%, 1-20%, 1-15%, 1-10%, 1-5%, 5-30%, 5-25%, 5-20%, 5-15%, or 5-10% by weight of filler material, based on the total weight of the sinterable powder.

[0036] The sinterable powders described herein may also include a flow agent. Any flow agent consistent with the technical objectives of the present disclosure may be used. For example, in some cases, the flow agent comprises a nanoparticle coating or other coating, such as a silica nanoparticle coating, on the sinterable powder or on the semi-crystalline polymer of the sinterable powder. One example of a flow agent suitable for use in some embodiments described herein is Aerosil 200.

[0037] When used, a flow agent can be present in the sinterable powder in any amount consistent with the technical objectives of the present disclosure. For example, in some cases, the sinterable powders described herein include up to 10 wt.%, up to 5 wt.%, up to 1 wt.%, or up to 0.5 wt.% of flow agent, based on the total weight of the sinterable powder (not based on the total weight of the entire composition). In some examples, the sinterable powder includes 0.01 to 10 wt.%, 0.01 to 5 wt.%, or 0.01 to 1 wt.% of flow agent, based on the total weight of the sinterable powder.

[0038] As noted above, the compositions described herein do not necessarily include a sinterable powder. In some embodiments, the compositions described herein include, consist of, or consist essentially of a filament material such as may be used in FDM applications. Furthermore, in some examples, the asphaltite additive is dispersed within a primary build material within the filament material. That is, the filament material can be formed from a blend or combination of the primary build material and the asphaltite additive. Similarly, in some implementations, the compositions described herein include, consist of, or consist essentially of a pellet material such as may be used in FGM applications. In some such embodiments, the asphaltite additive is dispersed within a primary build material within the pellet material. In other words, in some cases, the pellet material is formed from a blend or combination of the primary build material and the asphaltite additive. Alternatively, in other examples, the pellet material is formed from a primary build material, and the asphaltite additive is physically blended or mixed with the pellet material, but not necessarily dispersed within the pellet material (this dispersion can occur, for example, by melt blending).

[0039] Furthermore, it should be understood that if a sinterable powder is not or necessarily not present in a composition, the primary build material of the composition can nevertheless comprise a semi-crystalline polymer and / or a thermoplastic polymer as described above in the context of a sinterable powder. For example, in some cases, the compositions described herein comprise, consist of, or consist essentially of pellet material (or filaments), which comprises a primary build material comprising a semi-crystalline polymer (e.g., polyamide (PA), polyesters (PEs), polyurethanes (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more thereof) and / or a thermoplastic polymer (e.g., acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more thereof).

[0040] It should further be understood that the "primary" build material described herein is not necessarily present in the composition in an amount greater than 50% by weight of the total weight of the composition. Instead, the primary build material is understood to be the main or primary material that (a) is mixed with the asphaltite additive as a "base" or "carrier" for the additive to form the overall composition, and (b) remains present in the printed article or object after the additive manufacturing process is complete (e.g., compared to a sacrificial support material). However, in some preferred embodiments, the primary build material is present in the composition in an amount of at least 50% by weight, based on the total weight of the composition. In some cases, the primary build material is present in an amount of 20-99.9% by weight, 20-99% by weight, 20-98% by weight, 20-95% by weight, 20-90% by weight, 20-85% by weight, 20-80% by weight, 20-75% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, 20-40% by weight, 30-99.9% by weight, 30-9 ... Mass%, 30-98% by mass, 30-95% by mass, 30-90% by mass, 30-85% by mass, 30-80% by mass, 30-75% by mass, 30-70% by mass, 30-60% by mass, 30- 50% by mass, 30-40% by mass, 40-99.9% by mass, 40-99% by mass, 40-98% by mass, 40-95% by mass, 40-90% by mass, 40-85% by mass, 40-80% by mass. 40-75 mass%, 40-70 mass%, 40-60 mass%, 40-50 mass%, 50-99.9 mass%, 50-99 mass%, 50-98 mass%, 50-95 mass%, 50-90 mass%, 50-85 mass%, 50-80 mass%, 50-75% by mass, 50-70% by mass, 50-60% by mass, 60-99.9% by mass, 60-99% by mass, 60-98% by mass, 60-95% by mass, 60-90% by mass, 60-85% by mass, 60-80% by mass, 60-75% by mass.60-70 mass%, 70-99.9 mass%, 70-99 mass%, 70-98 mass%, 70-95 mass%, 70-90 mass%, 70-85 mass%, 70-80 mass%, 80-99.9 mass%, 80-99 mass%, 80-98 mass% %, 80-95% by weight, 80-90% by weight, 90-99.9% by weight, 90-99% by weight, 90-98% by weight, 90-95% by weight, 95-99.9% by weight, 95-99% by weight, or 95-98% by weight.

[0041] The compositions described herein can be formed or produced by any method consistent with the technical objectives of the present disclosure.For example, in some cases, the compositions described herein are formed by mixing or blending various components together, with or without heating.In some embodiments, the compositions described herein are formed by melt mixing or extrusion.

[0042] In addition to compositions for additive manufacturing, methods of additive manufacturing are also described herein. Such methods of forming or printing 3D articles, objects, or parts can include forming the 3D article from multiple layers of the compositions described herein as build materials, including layer-by-layer embodiments or processes. For example, in some examples, the methods of printing 3D articles described herein include providing a composition described herein and selectively solidifying layers of the composition to form the article. Any of the compositions described above can be used. Furthermore, the layers of the composition can be formed or provided according to a digital file or image of the article, for example, according to preselected computer-aided design (CAD) parameters.

[0043] In some embodiments, as described above, such methods can include SLS or other sintering methods. As will be understood by those skilled in the art, SLS methods can include holding a composition described herein in a container (e.g., a build bed or powder bed) and selectively applying energy to the composition in the container to solidify (or freeze or sinter) at least a portion of the layer of the composition, thereby forming a solidified (or frozen or sintered) layer that defines a cross-section of the 3D article. Additionally, methods described herein can further include raising or lowering the solidified layer of the composition to provide a new or second layer of unsolidified composition on a surface of the composition in the container, and then again selectively applying energy to the composition in the container to solidify (or freeze or sinter) at least a portion of the new or second layer of composition to form a second solidified layer that defines a second cross-section of the 3D article. Furthermore, the first and second cross sections of the 3D article can be bonded or adhered to each other in the z-direction (or a build direction corresponding to the direction of rising or falling) by applying energy to solidify (or solidify or sinter) the composition. Furthermore, selectively applying energy to the composition in the container can include applying electromagnetic radiation having sufficient energy to solidify (or solidify or sinter) the composition. In some instances, the electromagnetic radiation has an average wavelength of 300 to 1500 nm. In some instances, the solidifying (or solidifying or sintering) radiation is provided by a computer-controlled laser beam. Furthermore, in some instances, the raising or lowering of the solidified layer of composition is performed using an elevator platform disposed within the container. The methods described herein can also include flattening the new layer of composition provided by raising or lowering the elevator platform, or rolling the new layer of composition. Such flattening or rolling can be performed, in some instances, by a wiper or roller.

[0044] It should be further understood that the foregoing process can be repeated as many times as desired to provide a 3D article. For example, in some cases, the process can be repeated "n" times, where n can be up to about 100,000, up to about 50,000, up to about 10,000, up to about 5000, up to about 1000, or up to about 500. Thus, in some embodiments, methods of printing a 3D article described herein can comprise selectively applying energy to the composition in the container to solidify (or coagulate or sinter) at least a portion of the nth layer of the composition, thereby forming an nth solidified layer that defines the nth cross-section of the 3D article; raising or lowering the nth solidified layer of the composition to provide an (n+1)th layer of unsolidified composition on a surface of the composition in the container; selectively applying energy to the (n+1)th layer of the composition in the container to solidify at least a portion of the (n+1)th layer of the composition to form the (n+1)th solidified layer that defines the (n+1)th cross-section of the 3D article; raising or lowering the (n+1)th solidified layer of the composition to provide an (n+2)th layer of unsolidified composition on a surface of the composition in the container; and continuing to repeat the foregoing steps to form the 3D article. It should further be understood that one or more steps of the methods described herein, e.g., selectively applying energy to a layer of a composition, can be performed according to a digital file or image of the desired 3D article, e.g., according to pre-selected CAD parameters or other parameters in a computer-readable format.

[0045] Thus, in some embodiments, the methods of printing 3D articles described herein include providing the above-described composition and selectively solidifying layers of the composition to form the article. Further, in some cases, the composition is provided in a layer-by-layer process. In some cases, the method is SLS or other particle sintering method of additive manufacturing.

[0046] The compositions and methods described herein are not necessarily limited to selective laser sintering (SLS) or other sintering applications or uses. The present disclosure also contemplates compositions and methods for forming articles using other additive manufacturing techniques. For example, in some examples, compositions and methods for fused deposition modeling (FDM) or fused granular modeling (FGM) are also described. In such embodiments, the sinterable powders described above can be replaced with a different material, for example, a thermoplastic polymer that can be extruded, sprayed, or otherwise deposited (e.g., from filaments or pellets / granules) in a layer-by-layer manner to form a 3D article.

[0047] The compositions described above can be used in additive manufacturing material deposition methods, such as FDM or FGM, in which one or more layers of the compositions described herein are selectively deposited onto a substrate as a build material and solidified. In some cases, solidification involves rapid cooling of the composition or a phase transition (e.g., from liquid to solid) of the composition.

[0048] Thus, in some examples, the compositions (or build materials) described herein are selectively deposited in a fluid or molten state onto a substrate, such as a build pad of a 3D printing system. Selective deposition may include, for example, depositing the build material according to a digital file or image of the desired 3D article, for example, according to preselected CAD parameters or other parameters in a computer-readable format. For example, in some embodiments, a CAD file drawing (or other digital image or file) corresponding to the desired 3D article to be printed is generated and sliced ​​into a sufficient number of horizontal slices. The build material is then selectively deposited layer by layer according to the horizontal slices of the CAD file drawing (or other digital image or file) to print the desired 3D article. A "sufficient" number of horizontal slices is, for example, the number necessary for successful printing to accurately and precisely manufacture the desired 3D article.

[0049] Furthermore, in some embodiments, a preselected amount of the build material described herein is heated to an appropriate temperature and extruded or ejected from a nozzle or print head or nozzles or print heads of a suitable printer to form a layer on a print pad in a print chamber. For example, the build material can be in the form of a filament (e.g., on a spool) that is heated and extruded or ejected (e.g., as in FDM); or the build material can be in the form of pellets or granules that are heated and extruded or ejected (e.g., as in FGM). Furthermore, in some embodiments, each layer of build material is deposited according to preselected CAD or other preselected parameters based on a digital file, image, or model of the desired article. As mentioned above, in some embodiments, the composition (or build material) described herein exhibits a phase change upon deposition and / or solidifies upon deposition. Furthermore, in some cases, the temperature of the printing environment can be controlled so that the deposited portion of the build material solidifies upon contact with the receiving surface. Furthermore, in some cases, after each layer is deposited, the deposited material is planarized prior to depositing the next layer. Optionally, multiple layers can be deposited before planarization. Planarization compensates for the thickness of one or more layers by flattening the applied material and removing excess material to form a uniformly smooth, exposed, or flat, upward-facing surface on the printer's support platform. In some embodiments, planarization is performed using a wiper device, e.g., a roller, which may counter-rotate in one or more printing directions but not in one or more other printing directions. In some cases, the wiper device comprises a roller and a wiper that removes excess material from the roller. Additionally, in some cases, the wiper device is heated. Note that the consistency of the deposited build material described herein, in some embodiments, is desirably sufficient to retain its shape and not experience excessive viscous resistance from the planarization device. The layer-by-layer deposition of build material can be repeated until the 3D article is formed.

[0050] The compositions and methods described herein (e.g., SLS, FDM, or FGM methods) can, in some embodiments, form 3D articles that are resistant to degradation by UV light (due to their composition and microstructure). Furthermore, in some cases, the compositions and methods described herein can be used to provide 3D articles that also have desirable mechanical properties.

[0051] These foregoing embodiments are further illustrated in the following non-limiting examples. [Example]

[0052] Tables 2 and 3 provide formulations of compositions according to some embodiments described herein. DuraForm PA and DuraForm HST both comprise polyamide and are commercially available from 3D Systems, Inc. The amounts listed in Table 2 are weight percents based on the total weight of the composition. A dash (--) indicates that a particular component was not used. "Comparative" identifies a comparative example. [Table 2] [Table 3]

[0053] The solidification behavior of Examples 1 and 2 and Comparative Examples 1 and 2 is shown in Table 4. Additionally, Figures 1 and 2 show differential scanning calorimetry (DSC) plots for the Examples and Comparative Examples. Specifically, Figure 1 shows the DSC plots for Example 1 (light line) and Comparative Example 1 (dark line). Figure 2 shows the DSC plots for Example 2 (light line) and Comparative Example 2 (dark line). [Table 4]

[0054] Some additional non-limiting exemplary embodiments are described below.

[0055] Embodiment 1. An additive manufacturing composition comprising: a primary build material in an amount of 10 to 99.9% by weight, based on the total weight of the composition; and Asphaltite additive in an amount of up to 6% by weight, based on the total weight of the composition A composition comprising:

[0056] Embodiment 2. The composition of embodiment 1, wherein the asphaltite additive has a chemical composition of 82-88 wt.% carbon, 8-12 wt.% hydrogen, 2.5-3.5 wt.% nitrogen, up to 1 wt.% sulfur, up to 2 wt.% oxygen, and up to 0.5 wt.% other elements, based on the total weight of the asphaltite.

[0057] Embodiment 3. The composition of embodiment 1 or embodiment 2, wherein the asphaltite additive has a weight average molecular weight of 2000 to 4000 g / mol.

[0058] Embodiment 4. The composition of any of the previous embodiments, wherein the asphaltite additive has a Mohs hardness of 1.8 to 2.2.

[0059] Embodiment 5. The composition of any of the previous embodiments, wherein the asphaltite additive has a softening point of 125 to 205°C.

[0060] Embodiment 6. The composition of any of the preceding embodiments, wherein the asphaltite additive is present in the composition in an amount of 0.1 to 6 wt.%, based on the total weight of the composition.

[0061] Embodiment 7. The composition of any of the preceding embodiments, wherein the asphaltite additive is present in the composition in an amount less than 2% by weight, based on the total weight of the composition.

[0062] Embodiment 8. The composition of any of the previous embodiments, wherein the primary build material comprises a sinterable powder.

[0063] Embodiment 9. The composition of embodiment 8, wherein the sinterable powder comprises a semi-crystalline polymer.

[0064] Embodiment 10. The composition of embodiment 8, wherein the sinterable powder comprises polyamide (PA), polyesters (PEs), polyurethane (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing.

[0065] Embodiment 11. The composition of any of embodiments 8-10, wherein the sinterable powder comprises a polyamide.

[0066] Embodiment 12. The composition of embodiment 8, wherein the sinterable powder comprises a thermoplastic polymer.

[0067] Embodiment 13. The composition of embodiment 12, wherein the thermoplastic polymer comprises acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more of the foregoing.

[0068] Embodiment 14. The composition of any of embodiments 8-13, wherein the sinterable powder comprises a filler.

[0069] Embodiment 15. The composition of any of embodiments 1-7, wherein the composition comprises, consists of, or consists essentially of filamentary material.

[0070] Embodiment 16. The composition of embodiment 15, wherein the asphaltite additive is dispersed within the primary shape material within the filament material.

[0071] Embodiment 17. The composition of embodiment 15 or embodiment 16, wherein the primary build material comprises a semi-crystalline polymer.

[0072] Embodiment 18. The composition of embodiment 17, wherein the semi-crystalline polymer comprises polyamide (PA), polyesters (PEs), polyurethane (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing.

[0073] Embodiment 19. The composition of embodiment 17 or embodiment 18, wherein the semi-crystalline polymer comprises a polyamide.

[0074] Embodiment 20. The composition of embodiment 15 or embodiment 16, wherein the primary build material comprises a thermoplastic polymer.

[0075] Embodiment 21. The composition of embodiment 20, wherein the thermoplastic polymer comprises acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more of the foregoing.

[0076] Embodiment 22. The composition of any of embodiments 1-7, wherein the composition comprises, consists of, or consists essentially of pellet material.

[0077] Embodiment 23. The composition of embodiment 22, wherein the asphaltite additive is dispersed within the primary shaping material within the pellet material.

[0078] Embodiment 24. The composition of embodiment 22 or embodiment 23, wherein the primary build material comprises a semi-crystalline polymer.

[0079] Embodiment 25. The composition of embodiment 24, wherein the semi-crystalline polymer comprises polyamide (PA), polyester (PEs), polyurethane (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing.

[0080] Embodiment 26. The composition of embodiment 24 or embodiment 25, wherein the semi-crystalline polymer comprises a polyamide.

[0081] Embodiment 27. The composition of embodiment 22 or embodiment 23, wherein the primary build material comprises a thermoplastic polymer.

[0082] Embodiment 28. The composition of embodiment 27, wherein the thermoplastic polymer comprises acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more of the foregoing.

[0083] Embodiment 29. A method for printing a three-dimensional article, comprising: providing a composition according to any one of embodiments 1 to 28; and Selectively solidifying the layer of composition to form the article. A method comprising:

[0084] Embodiment 30. The method of embodiment 29, wherein the composition is provided in a layer-by-layer process.

[0085] Embodiment 31. The method of embodiment 29 or embodiment 30, wherein selectively solidifying the layer of composition comprises sintering the layer of composition.

[0086] Embodiment 32. The method of embodiment 29 or embodiment 30, wherein selectively solidifying the layer of the composition comprises depositing the layer of the composition in a molten state and then freezing or partially freezing the layer of the composition.

[0087] Embodiment 33. The method of embodiment 29 or embodiment 30, wherein selectively solidifying the layer of the composition comprises melting the layer of the composition and then refrozen or partially refrozen the layer of the composition.

[0088] Embodiment 34. A printed three-dimensional article formed from the composition of any of embodiments 1-28.

[0089] All patent documents mentioned herein are incorporated by reference in their entirety. In accomplishing various objectives of the present invention, various embodiments of the present invention have been described. It is to be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations thereof will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

Claims

1. 1. An additive manufacturing composition comprising: a primary build material in an amount of 10 to 99.9% by weight, based on the total weight of the composition; and an asphaltite additive in an amount of up to 6% by weight, based on the total weight of the composition; A composition comprising:

2. 10. The composition of claim 1, wherein the asphaltite additive has a chemical composition of 82-88 wt. % carbon, 8-12 wt. % hydrogen, 2.5-3.5 wt. % nitrogen, up to 1 wt. % sulfur, up to 2 wt. % oxygen, and up to 0.5 wt. % other elements, based on the total weight of the asphaltite.

3. 2. The composition of claim 1, wherein the asphaltite additive has a weight average molecular weight of 2000 to 4000 g / mol.

4. 10. The composition of claim 1, wherein the asphaltite additive has a Mohs hardness of 1.8 to 2.

2.

5. 2. The composition of claim 1, wherein the asphaltite additive has a softening point of 125 to 205°C.

6. 10. The composition of claim 1, wherein the asphaltite additive is present in the composition in an amount of 0.1 to 6 wt. %, based on the total weight of the composition.

7. 10. The composition of claim 1, wherein the asphaltite additive is present in the composition in an amount of less than 2 wt.%, based on the total weight of the composition.

8. The composition of claim 1 , wherein the primary build material comprises a sinterable powder.

9. The composition of claim 8, wherein the sinterable powder comprises a semi-crystalline polymer.

10. 9. The composition of claim 8, wherein the sinterable powder comprises polyamide (PA), polyester (PEs), polyurethane (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing.

11. The composition of claim 8, wherein the sinterable powder comprises a polyamide.

12. The composition of claim 8, wherein the sinterable powder comprises a thermoplastic polymer.

13. 13. The composition of claim 12, wherein the thermoplastic polymer comprises acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more of the foregoing.

14. The composition of claim 8, wherein the sinterable powder comprises a filler material.

15. 10. The composition of claim 1, wherein the composition comprises, consists of, or consists essentially of a filamentary material.

16. 16. The composition of claim 15, wherein the asphaltite additive is dispersed within the primary shape material within the filament material.

17. 16. The composition of claim 15, wherein the primary build material comprises a semi-crystalline polymer.

18. 18. The composition of claim 17, wherein the semi-crystalline polymer comprises polyamide (PA), polyester (PEs), polyurethane (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing.

19. 20. The composition of claim 17, wherein the semi-crystalline polymer comprises a polyamide.

20. The composition of claim 15, wherein the primary build material comprises a thermoplastic polymer.

21. 21. The composition of claim 20, wherein the thermoplastic polymer comprises acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more of the foregoing.

22. 10. The composition of claim 1, wherein the composition comprises, consists of, or consists essentially of pellet material.

23. 23. The composition of claim 22, wherein the asphaltite additive is dispersed within the primary shaping material within the pellet material.

24. 23. The composition of claim 22, wherein the primary build material comprises a semi-crystalline polymer.

25. 25. The composition of claim 24, wherein the semi-crystalline polymer comprises polyamide (PA), polyester (PEs), polyurethane (PU), polyethylene (PE), polypropylene (PP), poly(butylene terephthalate) (PBT), or a combination of two or more of the foregoing.

26. 25. The composition of claim 24, wherein the semi-crystalline polymer comprises a polyamide.

27. 23. The composition of claim 22, wherein the primary build material comprises a thermoplastic polymer.

28. 30. The composition of claim 27, wherein the thermoplastic polymer comprises acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), nylon, polycarbonate, or a combination, block copolymer, or melt of two or more of the foregoing.

29. 1. A method of printing a three-dimensional object, comprising: Providing the composition of claim 1; and Selectively solidifying the layer of composition to form the article. A method comprising:

30. 30. The method of claim 29, wherein the composition is applied in a layer-by-layer process.

31. 31. The method of claim 30, wherein selectively solidifying the layer of composition comprises sintering the layer of composition.

32. 31. The method of claim 30, wherein selectively solidifying the layer of composition comprises depositing the layer of composition in a molten state and then freezing or partially freezing the layer of composition.

33. 31. The method of claim 30, wherein selectively solidifying the layer of composition comprises melting the layer of composition and then refrozen or partially refrozen the layer of composition.

34. A printed three-dimensional article formed from the composition of claim 1.

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