Method for including voids in polymer filaments for FDM printing

Abstract

The invention provides a method for producing a 3D item by means of fused deposition modeling, the method comprising a 3D printing phase comprising depositing a 3D printable material layer by layer to provide a 3D item comprising the 3D printed material, wherein the 3D item comprises layers of the 3D printed material, wherein the 3D printable material comprises a thermoplastic material, wherein during at least a part of the 3D printing phase the 3D printable material further comprises porous inorganic particles embedded in the thermoplastic material, wherein the inorganic particles have a porosity in the range of 5-60% by volume, and wherein the inorganic particles (410) have an open porosity. The invention further comprises a product resulting from the above method.

Description

Technical Field

[0001] This invention relates to a method for manufacturing 3D (3D-printed) articles. The invention also relates to 3D (3D-printed) articles obtainable by this method. Furthermore, the invention relates to a lighting device comprising such a 3D (3D-printed) article. Background Technology

[0002] The use of thermoplastic polymers including particulate fillers for the fabrication of 3D objects is known in the art. For example, WO2017 / 040893 describes a powder composition comprising a plurality of thermoplastic particles characterized by a bimodal particle size distribution, and wherein the powder composition may further include particulate fillers, antioxidants, heat stabilizers, light stabilizers, UV stabilizers, UV absorbing additives, near-infrared absorbing additives, infrared absorbing additives, plasticizers, lubricants, release agents, antistatic agents, antifogging agents, antimicrobial agents, colorants, laser marking additives, surface effect additives, radiation stabilizers, flame retardants, anti-drip agents, fragrances, fibers, or combinations thereof, preferably including colorants or metallic particles. This document also describes a method for fabricating three-dimensional objects, comprising bed melting of a powder composition to form a three-dimensional object. Summary of the Invention

[0003] Over the next 10 to 20 years, digital manufacturing will increasingly transform the nature of global manufacturing. One aspect of digital manufacturing is 3D printing. Currently, many different technologies have been developed to produce a wide variety of 3D-printed objects using a variety of materials such as ceramics, metals, and polymers. 3D printing can also be used to produce molds, which can then be used to replicate objects.

[0004] For mold making purposes, polymer jetting technology has been suggested. This technology utilizes the layer-by-layer deposition of a photopolymerizable material, which cures after each deposition to form a solid structure. While this technology produces a smooth surface, photopolymerizable materials are not very stable, and they also have relatively low thermal conductivity for injection molding applications.

[0005] The most widely used additive manufacturing technology is a process known as Fused Deposition Modeling (FDM). Fused Deposition Modeling (FDM) is an additive manufacturing technology commonly used for molding, prototyping, and production applications. FDM is based on the "additive" principle of laying up materials layer by layer; plastic or metal filaments are unwound from coils and the material is supplied to produce parts. Possibly (for thermoplastics), the filament is melted and extruded before being laid up. FDM is a rapid prototyping technology. Other terms for FDM are "Fused Filament Fabrication" (FFF) or "Filament 3D Printing" (FDP), which are considered equivalent to FDM. Generally, FDM printers use thermoplastic filaments that are heated to their melting point and then extruded layer by layer (or practically filament-to-filament) to create three-dimensional objects. FDM printers are relatively fast, inexpensive, and can be used to print complex 3D objects. This type of printer is used to print a wide variety of shapes using a variety of polymers. The technology is also being further developed in the production of LED luminaires and lighting solutions.

[0006] Therefore, one aspect of the present invention is to provide an alternative 3D printing method and / or 3D (3D-printed) article, which preferably further eliminates at least partially one or more of the disadvantages described above. The object of the present invention may be to overcome or mitigate at least one of the disadvantages of the prior art or to provide a useful alternative.

[0007] Therefore, in a first aspect, the present invention provides a method for producing 3D articles (“articles” or “3D-printed articles”) by means of fused deposition modeling. In particular, the method may include a 3D printing stage comprising layer-by-layer deposition of a 3D-printable material to provide the 3D article. The 3D article comprises the 3D-printable material. Deposition may be performed, in particular, on a receiver article. The 3D article comprises, in particular, layers of the 3D-printable material. In particular, the 3D-printable material comprises a thermoplastic material. In particular, during at least a portion of the 3D printing stage, the 3D-printable material further comprises porous inorganic particles embedded in the thermoplastic material. In embodiments, the porosity of the inorganic particles is in the range of 5%-60% by volume.

[0008] The term "porosity" refers to a porous state. In other words, it refers to a state in which a material has pores (or is also referred to as an opening, cavity, or gap). In this invention, the porous material is a particulate material, and a distinction is made between two types of porosity: (i) closed porosity and (ii) open porosity. For particles with closed porosity, the pores are located inside the particle, and the pores cannot be accessed from the outside (or are not open). For particles with open porosity, at least some of the pores are located very close to the particle surface, such that the pores are open to the outside. The total amount of pore space accessible from the surface can be referred to as the accessible pore volume or accessible pore space. For particles with open porosity, the accessible pore volume is greater than zero.

[0009] The pores of a porous material can be interconnected to form an open pore morphology, or they can be non-interconnected to form a closed pore morphology.

[0010] Open porosity can be achieved in various ways during glass or ceramic formation. For example, micro-hollow spheres can be used and sintered. Sacrificial microspheres of polymers can also be used and added to a precursor. Closed porosity is obtained after the sintering step. Foaming agents can also be used to create closed-cell morphologies.

[0011] Porous glasses are typically prepared by one of the following processes: (i) separation of a metastable phase in a borosilicate glass (such as in a system of SiO2-B2O3-Na2O) followed by liquid extraction of the resulting phase; (ii) a sol-gel process; or (iii) sintering of glass powder. During these processes, open-cell morphologies can occur.

[0012] It can also be a porous material with a closed shell. In other words, a porous interior and a non-porous shell made of a solid material.

[0013] For the purposes of this invention, and as will be explained below, particles included in a thermoplastic material should have open porosity to allow controlled introduction of voids into printable materials (e.g., filaments) and / or transprintable materials. The presence of moisture on the surface of the porous particles can contribute to obtaining greater porosity in printable and / or transprintable materials.

[0014] Therefore, in a specific embodiment, the present invention provides a method for producing 3D articles by means of fused deposition modeling, the method comprising a 3D printing stage, the 3D printing stage comprising layer-by-layer deposition of a 3D-printable material to provide a 3D article comprising layers of the 3D-printable material, wherein the 3D-printable material comprises a thermoplastic material, wherein during at least a portion of the 3D printing stage, the 3D-printable material further comprises porous inorganic particles embedded in the thermoplastic material, wherein the porosity of the inorganic particles is in the range of 5%-60% by volume, and wherein the inorganic particles have open porosity.

[0015] In this way, it may be possible to use FDM to prepare porous 3D printed objects while reducing the amount of material used, thus reducing the weight of the printed object, and maintaining the structural integrity of the object. This is achieved by controlling the introduction of voids into the printed material.

[0016] Controlled introduction of voids into a printable material requires embedded particles with open porosity. When encapsulated within the printable material, a gas or liquid (such as air or nitrogen) located within the pores expands during extrusion, thus creating larger voids within the filament. The mechanical integrity of the filament is maintained as the voids remain around the embedded inorganic particles. Because the voids remain around the embedded inorganic particles, their position can be controlled by controlling the position of the inorganic particles. Since the size of the voids depends on the size of the pores, this can also be controlled by the type of inorganic particles used. This allows for a relatively simple 3D printing method but also increases the controllability of local material properties in 3D-printed articles for purposes such as reducing object weight.

[0017] Therefore, it is also desirable to provide such filaments, which can be used in particular in the methods described herein. Accordingly, in one aspect of the invention, the invention further provides 3D printable materials, particularly filaments comprising 3D printable materials, wherein the 3D printable material comprises a (body) polymer (particularly a thermoplastic material) and (embedded therein) inorganic porous particles. Such 3D printable materials (particularly such filaments) can be extruded (using a 3D printer, such as the 3D printer described in the embodiments herein).

[0018] In the embodiments, the porosity of the inorganic particles is in the range of 5%-60% by volume, particularly in the range of 10%-50% by volume, even more particularly in the range of 10%-40% by volume, such as less than 40% by volume, even more particularly equal to or less than 35% by volume. Porosity determines the amount of gas or liquid that can expand. Particles with low porosity cannot produce sufficiently large voids, and if the porosity of the particles is too high, the particles may be too weak mechanically, and they may break into small pieces. Porosity can be determined by direct methods, such as, in particular, determining the gross volume of the porous sample, and then determining the volume of the pore-free framework material (pore volume = total volume - material volume). Alternatively, porosity can be determined by optical methods, such as, in particular, determining the area of ​​the material visible under a microscope and the area of ​​the pores. For porous media with random structures, "area" porosity and "volume" porosity are substantially equal. In particular, optical methods can be applied.

[0019] Similarly, pore size can at least partially determine the amount of expandable gas or liquid, and can also at least partially determine the particle strength. In the embodiments, the inorganic particles have an average pore size in the range of 10-100 μm. Pore size can be determined by optical methods, such as, in particular, measuring the diameter of pores visible under a microscope. Alternatively, porosity can be determined, in particular, using mercury intrusion porosimetry. Alternatively, X-ray refraction can be applied, in particular.

[0020] As mentioned above, voids can remain located around the embedded porous inorganic particles, so the shape of the particles can affect the distribution of voids in the filament. The shape of the particles can also affect the ease of printing. Depending on the size, elongated particles may be more difficult to embed into printable materials. In embodiments, the inorganic particles may have a length (L1), a width (L2), and a height (L3), wherein in a specific embodiment, the aspect ratio AR1 = L1 / L2 may be in the range of 0.5 ≤ AR1 ≤ 2. Alternatively or additionally, in embodiments, the aspect ratio AR2 = L1 / L3 may be in the range of 0.5 ≤ AR2 ≤ 2. Further, in embodiments, the aspect ratio AR3 = L2 / L3 may be in the range of 0.5 ≤ AR2 ≤ 2. Further, in embodiments, the inorganic particles may have a length (L1) in the range of 10-500 μm, more particularly in the range of 30-300 μm, and most particularly in the range of 50-150 μm. Therefore, particularly in the embodiments, the inorganic particles may have a length (L1), a width (L2), and a height (L3), the length (L1) being in the range of 10-500 μm, wherein the aspect ratio AR1 = L1 / L2 is in the range of 0.5 ≤ AR1 ≤ 2, wherein the aspect ratio AR2 = L1 / L3 is in the range of 0.5 ≤ AR2 ≤ 2, and wherein the aspect ratio AR3 = L2 / L3 is in the range of 0.5 ≤ AR2 ≤ 2.

[0021] In the embodiments, the concentration of porous inorganic particles can be in the range of 5%-30% by volume, particularly in the range of 10%-30% by volume. The concentration is calculated as the total volume of the porous inorganic particles divided by the sum of the total volume of the porous inorganic particles and the volume of the thermoplastic material in which the particles are embedded, and then multiplied by 100%. If the concentration is too low, the amount of void formation may be too low. If the particle concentration is too high, the voids may coalesce, and the structure may collapse. During processing, the polymer material may not substantially enter the pores.

[0022] Many inorganic materials are suitable for use as porous inorganic particles, and metal oxide particles, in particular, appear to be advantageous. In the embodiments, porous inorganic particles include porous glass particles. Throughout this document, the term "metal oxide" may refer to MO-based systems, but also to borates, silicates, phosphates, etc.

[0023] In addition to porous inorganic particles, 3D printable materials may also include other additives and / or particles. In embodiments, stabilizers, light absorbers, dyes, reflective particles, etc., may be included. This is described in more detail below.

[0024] In embodiments, porous inorganic particles comprise core-shell particles, which include a hollow core and a porous shell. This can result in a reduction in particle mass and thus a reduction in the weight of the printed article. In embodiments where the hollow core is permeable through pores, the amount of gas or liquid that can be incorporated into the particle can be increased, and thus the volume of voids that a single particle can introduce into the printable material can be increased. In other embodiments, the hollow core may not be fluidly connected to the pores (e.g., due to an intermediate shell that defines the hollow core and supports the porous shell, although other embodiments may also be possible).

[0025] In one embodiment, the porous inorganic particles comprise core-shell particles, which include a hollow core and a bulky shell. This can result in a reduction in particle mass and thus a reduction in the weight of the printed article.

[0026] For ease of production, it is convenient for the porous inorganic particles to remain uniformly mixed during filament production, rather than rapidly accumulating on top (floating) or at the bottom (sinking) of the thermoplastic material. Therefore, in this embodiment, the densities of the particles and the thermoplastic material can be matched. In this embodiment, the porous inorganic particles have a first density n1, and the thermoplastic material has a second density n2, wherein in a specific embodiment, 0.8 ≤ n1 / n2 ≤ 1.2, and more particularly, 0.9 ≤ n1 / n2 ≤ 1.1.

[0027] In embodiments, the printable material may include multiple types of porous inorganic particles with respect to one or more of the following: (i) material, (ii) average particle size, (iii) particle size distribution, (iv) average pore size, (v) pore size distribution, and (v) aspect ratio. In this way, mechanical properties can be controlled more precisely. In one specific embodiment, one type of particle is used in a first portion of the filament and another type of particle is used in a second portion of the filament, thereby providing the possibility of localized control over the mechanical properties (e.g., density) within the printed object.

[0028] In specific embodiments, at least five layers, such as at least eight layers, such as at least ten layers, may comprise the porous particles described herein. In still other embodiments, layers having these particles and layers not having these particles may alternate with each other. In still other embodiments, sets of at least two layers having these particles and sets of at least two layers not having these particles may alternate with each other.

[0029] Before incorporating porous inorganic particles into a thermoplastic material, the pores can be filled with a gas or liquid. Since different materials have different coefficients of thermal expansion, using different filler materials can result in different pore sizes, and therefore different material densities in the printed article. In embodiments, the pores are filled with air or nitrogen; air is particularly suitable. A non-airy environment may be desired, especially for further crosslinking of the thermoplastic material. In embodiments, substantially pure gases, such as nitrogen, oxygen, or helium, or mixtures thereof, are used. In embodiments, the water content is less than or equal to 100 ppm, such as a maximum of 50 ppm, such as a maximum of 20 ppm, such as a maximum of 5 ppm in specific embodiments.

[0030] As mentioned above, the location of porous inorganic particles can determine the location where voids are formed. Therefore, controlling the particle location can be useful. For example, in a specific embodiment, a core-shell filament can be used, in which porous inorganic particles are incorporated into the core of the filament and a low concentration (e.g., no particles) is included in the shell.

[0031] Therefore, in another aspect of the invention, a core-shell filament is also provided, wherein porous inorganic particles are incorporated into the core of the filament, and a lower concentration (e.g., at least 50% lower, e.g., no porous inorganic particles) can be included in the shell. This provides a high level of control over particle placement, and thus a high level of control over void placement, and can result in better mechanical integrity of the printed article. In a specific embodiment, the porous inorganic particles have a first concentration c1 in the core and a second concentration c2 in the shell, wherein c2 / c1 ≤ 0.5, particularly wherein c2 / c1 ≤ 0.25, and even more particularly wherein c2 / c1 ≤ 0.1.

[0032] In the embodiments, the thermoplastic material itself (i.e., without considering the porous inorganic particles) may be translucent, although this is not necessarily the case. In the embodiments, the refractive index RI1 of the thermoplastic material and the refractive index RI2 of the inorganic particles may be substantially the same, such as 0.85 ≤ RI1 / RI2 ≤ 1.15. In this way, the 3D-printable material (and the 3D-printed material) may be translucent to light. In the embodiments, the porous inorganic particles may be translucent, although this is not necessarily the case. In particular, the porous inorganic particles may be translucent, although this is not necessarily the case.

[0033] Therefore, in embodiments, 3D printable materials (and 3D-printed materials) may thus include light-transmitting materials, or even be substantially light-transmitting materials.

[0034] The transmittance of a light-transmitting material to one or more wavelengths (in visible light) can be at least 80% / cm, such as at least 90% / cm, or even more particularly at least 95% / cm, such as at least 98% / cm, such as at least 99% / cm. This means that under perpendicular illumination of radiation with a selected wavelength in the visible light spectrum, for example at 1cm... 3 The cube-shaped translucent material block will have a transmittance of at least 95%.

[0035] In this document, the value of transmittance specifically refers to transmittance without considering Fresnel losses at the interface (e.g., with air). Therefore, the term "transmittance" specifically refers to internal transmittance. Internal transmittance can be determined, for example, by measuring the transmittance of two or more bodies with different widths at which the transmittance is measured. Based on this measurement, the contribution of Fresnel reflection loss can then be determined, and (therefore) the internal transmittance can be determined. Therefore, in particular, the transmittance values ​​indicated herein neglect Fresnel losses.

[0036] The term "wavelength of interest" can specifically refer to one or more wavelengths in the visible light spectrum.

[0037] The terms “light” and “radiation” are used interchangeably herein unless the context clearly indicates that the term “light” refers only to visible light. Therefore, the terms “light” and “radiation” can refer to UV radiation, visible light, and IR radiation. In specific embodiments, particularly for lighting applications, the terms “light” and “radiation” refer to visible light. In this document, the term “visible light” specifically refers to light having wavelengths selected from the range of 380-780 nm.

[0038] In the embodiments, the thermoplastic material itself (i.e., without considering porous inorganic particles) may be light reflective, although this is not necessarily the case. This can be achieved by incorporating reflective particles into the thermoplastic material and / or by using (e.g., white) colorants.

[0039] In the embodiments, the porous inorganic particles may be light-reflective, and the thermoplastic material may be light-transmitting, although this is not necessarily the case.

[0040] The reflectivity of the printed light-reflecting material to one or more wavelengths (in visible light) can be at least 80%, such as at least 90%, or even more particularly at least 95%, such as at least 98%, such as at least 99%.

[0041] As indicated above, the method includes depositing a 3D-printable material during the printing phase. In this document, the term "3D-printable material" refers to the material to be deposited or printed, and the term "3D-printed material" refers to the material obtained after deposition. These materials can be substantially the same, as 3D-printable material can specifically refer to material in a printer head or extruder at high temperatures, and 3D-printed material refers to the same material but in a later stage of deposition. The 3D-printable material is printed as a filament and thus deposited. The 3D-printable material can be provided as a filament or can be formed as a filament. Therefore, regardless of the starting material applied, filaments including 3D-printable material are provided by the printer head and 3D-printed. The term "extrudate" can be used to define 3D-printable material downstream of the printer head but not yet deposited. The latter is indicated as "3D-printed material." In fact, extrudate includes 3D-printable material because the material has not yet been deposited. After the deposition of 3D-printable material or extrudate, the material is therefore indicated as 3D-printed material. Basically, the materials are the same, because the upstream, downstream and deposited thermoplastic materials of the printer head are essentially the same.

[0042] In this document, the term "3D printable material" may also be referred to as "printable material". In embodiments, the term "polymer material" may refer to a blend of different polymers, but in embodiments, it may also refer to a single polymer type having substantially different polymer chain lengths. Therefore, the term "polymer material" or "polymer" may refer to a single type of polymer, but may also refer to multiple different polymers. The term "printable material" may refer to a single type of printable material, but may also refer to multiple different printable materials. The term "printable material" may refer to a single type of printable material, but may also refer to multiple different printable materials.

[0043] Therefore, the term "3D printable material" can also refer to a combination of two or more materials. Generally, these (polymer) materials have a glass transition temperature T0. g and / or melting temperature T m The 3D printable material is heated by the 3D printer to a temperature at least the glass transition temperature (and typically at least the melting temperature) before leaving the nozzle. Therefore, in a specific embodiment, the 3D printable material includes materials having a glass transition temperature (T0). g ) and / or melting point (T m The 3D printable material is a thermoplastic polymer, and if it is a semi-crystalline polymer with a melting temperature above its glass transition temperature, then the print head action includes heating the 3D printable material above its glass transition temperature. In another embodiment, the 3D printable material includes materials having a melting point (T0). mThe (thermoplastic) polymer, and the actions of the printer head include heating the 3D printable material to be deposited onto the receiver article to a temperature at least its melting point. Generally, glass transition temperature and melting temperature are not the same thing. Melting is a transformation that occurs in crystalline polymers. Melting occurs when polymer chains break away from their crystalline structure and become a disordered liquid. Glass transition is a transformation that occurs in amorphous polymers (i.e., polymers whose chains are not arranged in an ordered crystal but are simply scattered in any way, even if they are in a solid state). Polymers can be amorphous, essentially having a glass transition temperature but not a melting temperature; or they can be (semi-)crystalline, typically having both a glass transition temperature and a melting temperature, with the latter usually being higher than the former. Glass temperature can be determined, for example, by differential scanning calorimetry. Melting point or melting temperature can also be determined by differential scanning calorimetry.

[0044] As indicated above, the present invention therefore provides a method comprising: providing a filament of a 3D printable material; and printing the 3D printable material onto a substrate during a printing phase to provide the 3D article.

[0045] Therefore, in another aspect, the present invention provides a filament for producing 3D articles by means of fused deposition modeling. In particular, the filament may comprise a 3D printable material. Specifically, the 3D printable material comprises a component wherein the component comprises at least (i) a thermoplastic material and (ii) porous inorganic particles. In particular, in at least a portion of the filament, the 3D printable material comprises porous inorganic particles embedded in a thermoplastic material. In embodiments, the porosity of the inorganic particles is in the range of 5%-60% by volume. In particular, the concentration of the porous inorganic particles relative to the 3D printable material is in the range of 10%-30% by volume. In embodiments, the filament has a material density n. f The filament has a theoretical material density n defined by the density of its components. fc In a specific embodiment, 0.6 ≤ n f / n fc ≤l. The filaments described in this paper can be used in the methods described in this paper.

[0046] Therefore, in a specific embodiment, the present invention provides a filament for producing 3D articles by means of fused deposition modeling, the filament comprising a 3D printable material, wherein the 3D printable material comprises a component comprising at least (i) a thermoplastic material and (ii) porous inorganic particles; wherein in at least a portion of the filament, the 3D printable material comprises porous inorganic particles embedded in the thermoplastic material, wherein the porosity of the inorganic particles is in the range of 5%-60% by volume, wherein the inorganic particles (410) have open porosity, wherein the concentration of the porous inorganic particles relative to the 3D printable material is in the range of 10%-30% by volume, and wherein the filament has a material density nf The filament has a theoretical material density n defined by the density of its components. fc , where 0.6≤n f / n fc ≤1.

[0047] In this way, it may be possible to prepare porous 3D printed articles by means of FDM, starting from previously prepared filaments.

[0048] When encapsulated within a printable material, the gas or liquid (e.g., air or nitrogen) within the pores of the inorganic particles expands during heating. Therefore, the porosity of the filament can depend on the temperature used to prepare the filament. When the filament is prepared at a temperature below the printing temperature, the voids in the filament may be smaller than those in the 3D-printed article, or voids may not yet exist in the filament. In an embodiment, the filament can be prepared at a first temperature T1. Further, the 3D printing method may include 3D printing the filament, wherein the filament is heated in a printer nozzle at a second temperature T2. In an embodiment, T2 > T1. Therefore, in an embodiment, the porosity can be further increased during printing. In an embodiment, T2-T1 ≥ 5°C, especially T2-T1 ≥ 10°C, and even more especially T2-T1 ≥ 20°C. Alternatively, the filament can be prepared at the same temperature as printing or at a higher temperature, thus T1 ≥ T2. Therefore, the density n of the printed article... m It can be equal to or lower than the density n of the silk. f Therefore n m ≤n f .

[0049] In one specific embodiment, the filament comprises multiple components, including at least a thermoplastic material and porous inorganic particles, wherein the filament has a material density n. f The filament has a theoretical material density n defined by the density of its components. fc , where 0.6≤n f / n fc ≤1, especially where 0.7≤n f / n fc ≤1. Among other things, due to the voids, the density can be lower, and therefore the weight of 3D objects can be reduced.

[0050] As indicated above, in the embodiments, the porosity of the inorganic particles is in the range of 5%-60% by volume, particularly in the range of 10%-50% by volume, even more particularly in the range of 10%-40% by volume, such as less than 40% by volume, even more particularly less than 35% by volume.

[0051] As indicated above, in the embodiments, the inorganic particles have an average pore size in the range of 10-100 μm.

[0052] In the embodiments, the inorganic particles have a length (L1), a width (L2), and a height (L3), wherein the length (L1) is in the range of 1-500 μm, more particularly in the range of 5-300 μm, and most particularly in the range of 10-250 μm, wherein the aspect ratio AR1 = L1 / L2 is in the range of 0.5 ≤ AR1 ≤ 2, wherein the aspect ratio AR2 = L1 / L3 is in the range of 0.5 ≤ AR2 ≤ 2, and wherein the aspect ratio AR3 = L2 / L3 is in the range of 0.5 ≤ AR2 ≤ 2.

[0053] In the embodiments, the concentration of porous inorganic particles is in the range of 5%-30% by volume, especially in the range of 10%-30% by volume.

[0054] Many inorganic materials are suitable for use as porous inorganic particles, and metal oxide particles, in particular, appear to be advantageous. In embodiments, porous inorganic particles include porous glass particles.

[0055] In an embodiment, the porous inorganic particles include core-shell particles, which include a hollow core and a porous shell.

[0056] In an embodiment, the porous inorganic particles include core-shell particles, which include a hollow core and a blocky shell.

[0057] In embodiments, the printed material comprises various types of porous inorganic particles with respect to: material, average particle size, particle size distribution, average pore size, pore size distribution, and / or aspect ratio. In one specific embodiment, one type of particle is used for a first portion of the printed article, and another type of particle is used for a second portion of the printed article.

[0058] As mentioned above, in the embodiments, core-shell filaments are used, wherein porous inorganic particles are incorporated into the core of the filament, and a lower concentration (e.g., no particles) is included in the shell. In one specific embodiment, the porous inorganic particles have a first concentration c1 in the core and a second concentration c2 in the shell, wherein c2 / c1 ≤ 0.5, particularly wherein c2 / c1 ≤ 0.25, and even more particularly wherein c2 / c1 ≤ 0.1.

[0059] In the embodiments, the thermoplastic material itself (i.e., without considering porous inorganic particles) may be translucent, although this is not necessarily the case.

[0060] In this embodiment, the porous inorganic particles may be translucent, although this is not always the case. In particular, the porous inorganic particles may be translucent, although this is not always the case.

[0061] The transmittance of a light-transmitting material to one or more wavelengths (in visible light) can be at least 80% / cm, such as at least 90% / cm, or even more particularly at least 95% / cm, such as at least 98% / cm, such as at least 99% / cm. This means that under perpendicular illumination of radiation with a selected wavelength in the visible light spectrum, for example at 1cm... 3 The cube-shaped translucent material block will have a transmittance of at least 95%.

[0062] In the embodiments, the thermoplastic material itself (i.e., without considering porous inorganic particles) may be light reflective, although this is not necessarily the case.

[0063] In the embodiments, the porous inorganic particles may be light-reflective, although this is not necessarily the case.

[0064] The reflective material may reflect at least 80%, such as at least 90%, or even more particularly at least 95%, such as at least 98%, such as at least 99%, for one or more wavelengths (in visible light).

[0065] Materials particularly suitable as 3D printing materials can be selected from the group consisting of: metals, glass, thermoplastic polymers, silicone, etc. Specifically, 3D printing materials include (thermoplastic) polymers selected from the group consisting of: ABS (acrylonitrile butadiene styrene), nylon (or polyamide), acetate (or cellulose), PLA (polylactic acid), terephthalates (such as PET polyethylene terephthalate), acrylates (polymethyl methacrylate, plexiglass, polymethyl methacrylate PMMA), polypropylene (or polypropene), polycarbonate (PC), polystyrene (PS), PE (such as expanded high-impact polyethylene (or polyethylene), low-density (LDPE), high-density (HDPE)), PVC (polyvinyl chloride), polychloroethene, and thermoplastic elastomers such as copolyester-based elastomers, polyurethane elastomers, polyamide elastomers, polyolefin-based elastomers, styrene-based elastomers, etc. Optionally, 3D printable materials include those selected from the group consisting of: urea-formaldehyde, polyester resins, epoxy resins, melamine-formaldehyde, thermoplastic elastomers, etc. Optionally, 3D printable materials include those selected from the group consisting of polysulfones. Elastomers (especially thermoplastic elastomers) are of particular interest because they are flexible and can help obtain relatively more flexible filaments including thermally conductive materials. Thermoplastic elastomers may include one or more of the following: styrene block copolymers (TPS(TPE-s)), thermoplastic polyolefin elastomers (TPO(TPE-o)), thermoplastic vulcanizates (TPV(TPE-v or TPV)), thermoplastic polyurethanes (TPU(TPU)), thermoplastic copolyesters (TPC(TPE-E)), and thermoplastic polyamides (TPA(TPE-A)).

[0066] Suitable thermoplastic materials (such as those also mentioned in WO2017 / 040893) may include one or more of the following: polyacetals (e.g., polyoxyethylene and polyoxymethylene), poly(C) 1-6Alkyl) acrylates, polyacrylamide, polyamides (e.g., aliphatic polyamides, polyphthalamides, and polyarylamides), polyamide imides, polyanhydrides, polyarylates, polyaryl ethers (e.g., polyphenylene ether), polyaryl sulfides (e.g., polyphenylene sulfide), polyaryl sulfones (e.g., polyphenylene sulfone), polybenzothiazoles, polybenzoxazoles, polycarbonates (including polycarbonate copolymers, such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbonate-ester-siloxanes), polyesters (e.g., polycarbonates, polyethylene terephthalate, polynaphthol esters, polybutylene terephthalate, polyaryl esters), and polyester copolymers, such as polyester-ethers), polyetheretherketones, polyetherimides (including copolymers, such as polyetherimide-siloxane copolymers), polyetherketoneketones, polyetherketones, polyethersulfones, polyimides (including copolymers, such as polyimide-siloxane copolymers), poly(C) 1-6 Alkyl) methacrylates, polymethacrylamide, polynorbornene (including copolymers containing norbornene units), polyolefins (e.g., polyethylene, polypropylene, polytetrafluoroethylene and their copolymers, such as ethylene-α-olefin copolymers), polyoxadiazole, polyoxymethylene, polyphthalamide, polysilazane, polysiloxane, polystyrene (including copolymers such as acrylonitrile butadiene styrene (ABS) and methyl methacrylate-butadiene-styrene (MBS)), polysulfides, polysulfonamides, polysulfonates, polysulfones, polysulfides, polytriazines, polyureas, polyurethanes, polyvinyl alcohol, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinyl ketones, polyvinyl sulfides, polyvinylidene fluoride, etc., or combinations of at least one of the aforementioned thermoplastic polymers. Examples of polyamides may include, but are not limited to, the synthesis of linear polyamides, such as nylon-6,6; nylon-6,9; nylon-6,10; nylon-6,12; nylon-11; nylon-12 and nylon-4,6 (preferably nylon 6 and nylon 6,6), or combinations comprising at least one of the above. Polyurethanes that can be used include aliphatic polyurethanes, alicyclic polyurethanes, aromatic polyurethanes, and polycyclic polyurethanes, including those described above. Furthermore, poly(C) 1-6 Alkyl) acrylates and poly(C) 1-6 Alkyl methacrylates, such as polymers of methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, n-butyl acrylate, and ethyl acrylate. In embodiments, polyolefins may include one or more of the following: polyethylene, polypropylene, polybutene, polymethylpentene (and copolymers thereof), polynorbornene (and copolymers thereof), poly-1-butene, poly(3-methylbutene), poly(4-methylpentene), and copolymers of ethylene with propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 1-octadecene.

[0067] In specific embodiments, 3D printable materials (and 3D-printed materials) include one or more of the following: polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), semi-crystalline polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), polymethyl methacrylate (PMMA), polystyrene (PS), and styrene-acrylic copolymer (SMMA).

[0068] The term 3D printable material will be further elaborated below, but the term 3D printable material specifically refers to thermoplastic material that optionally includes additives, with the volume percentage (of the additives relative to the total volume of the thermoplastic material and the additives) being at most about 60%, and in particular, at most about 30% by volume, such as at most 20% by volume.

[0069] Therefore, in embodiments, the printable material may include two phases. The printable material may include a phase of a printable polymeric material (particularly thermoplastic materials (see also below)), which is particularly a substantially continuous phase. In this continuous phase of the thermoplastic material, polymeric additives may be present, such as one or more of the following: antioxidants, heat stabilizers, light stabilizers, ultraviolet light stabilizers, ultraviolet light absorbing additives, near-infrared light absorbing additives, infrared light absorbing additives, plasticizers, lubricants, mold release agents, antistatic agents, antifogging agents, antimicrobial agents, colorants, laser marking additives, surface effect additives, radiation stabilizers, flame retardants, and anti-drip agents. The additives may have useful properties selected from optical, electrical, thermal, and mechanical properties (see also above).

[0070] The printable material in the embodiments may include particulate material, i.e., particles embedded in a printable polymer material, which form a generally discontinuous phase. Particularly in applications for reducing the coefficient of thermal expansion, the number of particles in the total mixture is particularly no more than 60% by volume relative to the total volume of the printable material (including (anisotropically conductive) particles). For optical and surface-related effects, the number of particles in the total mixture is equal to or less than 20% by volume relative to the total volume of the printable material (including particles), such as up to 10% by volume. Therefore, 3D printable material particularly refers to a continuous phase of a substantially thermoplastic material in which other materials (such as particles) may be embedded. Similarly, 3D printable material particularly refers to a continuous phase of a substantially thermoplastic material in which other materials (such as particles) are embedded. The particles may include one or more additives as defined above. Therefore, in the embodiments, the 3D printable material may include particulate additives.

[0071] Printable material is printed onto a receiver article. Specifically, the receiver article can be a construction platform or can be included by a construction platform. The receiver article can also be heated during 3D printing. However, the receiver article can also be cooled during 3D printing.

[0072] Among other things, the phrase “printing on a receiver article” and similar phrases include printing directly on a receiver article, or printing on a coating on a receiver article, or printing on 3D-printed material previously printed on a receiver article. The term “receiver article” can refer to a printing platform, print bed, substrate, support, construction plate, or construction platform, etc. The term “substrate” may also be used instead of the term “receiver article.” Among other things, the phrase “printing on a receiver article” and similar phrases also include printing on or on a separate substrate including: a printing platform, print bed, support, construction plate, or construction platform, etc. Therefore, among other things, the phrase “printing on a substrate” and similar phrases include printing directly on a substrate, or printing on a coating on a substrate, or printing on 3D-printed material previously printed on a substrate. Hereinafter, the term substrate is also used, which can refer to a printing platform, print bed, substrate, support, construction plate, or construction platform, or a separate substrate thereon or a separate substrate included therein.

[0073] Printable material is deposited layer by layer, thereby generating a 3D-printed article (during the printing stage). The 3D-printed article may exhibit a characteristic ribbed structure (derived from deposited filaments). However, additional stages, such as a finishing stage, may be performed after the printing stage. This stage may include: removal of the printed article from the receiver article, and / or one or more post-processing actions. One or more post-processing actions may be performed before or after removal of the printed article from the receiver article. Post-processing may include one or more of, for example, polishing, coating, adding functional parts, cross-linking, etc. Post-processing may include smoothing the ribbed structure, which can produce a substantially smooth surface. Post-processing may include cross-linking of thermoplastic materials. This can result in the material having less or no thermoplastic properties.

[0074] Furthermore, the present invention relates to a software product that can be used to perform the methods described herein. Therefore, in yet another aspect, the present invention also provides a computer program product that, when functionally coupled to or running on a fused deposition modeling 3D printer or a computer included with a fused deposition modeling 3D printer, is capable of implementing the methods as described herein.

[0075] Therefore, in one aspect, the present invention provides a software product that, when run on a computer, enables the implementation of one or more embodiments of the method described herein for producing 3D articles by means of fused deposition modeling.

[0076] The methods described herein provide 3D-printed articles. Therefore, in another aspect, the present invention also provides 3D-printed articles obtainable by the methods described herein. In another aspect, a 3D-printed article obtainable by the methods described herein is provided.

[0077] In particular, the present invention provides a 3D article comprising a 3D-printed material. As indicated above, the 3D article comprises multiple layers of the 3D-printed material. Further, in particular, the 3D-printed material comprises porous inorganic particles. As indicated above, the 3D-printed material comprises a thermoplastic material. In particular, at least a portion of the 3D-printed material further comprises porous inorganic particles embedded in the thermoplastic material. In embodiments, the porosity of the inorganic particles is in the range of 5%-60% by volume. Therefore, in particular, the present invention provides, in embodiments, a 3D article comprising a 3D-printed material, wherein the 3D article comprises multiple layers of the 3D-printed material, wherein the 3D-printed material comprises a thermoplastic material, wherein at least a portion of the 3D-printed material further comprises porous inorganic particles embedded in the thermoplastic material, wherein the porosity of the inorganic particles is in the range of 5%-60% by volume, and wherein the inorganic particles (410) have open porosity.

[0078] 3D printed articles may include multiple layers (i.e., stacked layers) on top of each other. The width (thickness) and height of the layers (individually 3D printed) may, for example, be selected from the range of 100-5000 μm in the embodiments, such as the range of 200-2500 μm, where the height is generally smaller than the width. For example, the ratio of height to width may be equal to or less than 0.8, such as equal to or less than 0.6.

[0079] The layer can be a core-shell layer, or it can be composed of a single material. Within the layer, the composition can also vary, for example, when a core-shell printing process is applied, and during the printing process, the printing process changes from printing the first material (without printing the second material) to printing the second material (without printing the first material).

[0080] At least a portion of a 3D-printed article may include a coating.

[0081] The above discussion of methods has already illustrated some specific embodiments of 3D-printed articles. Below, we will discuss some more specific embodiments of 3D-printed articles in greater detail.

[0082] As indicated above, in the embodiments, the porosity of the inorganic particles is in the range of 5%-60% by volume, especially in an atmosphere of 10%-50% by volume, and even more especially in the range of 10%-40% by volume, such as less than 40% by volume, and even more especially less than 35% by volume.

[0083] As indicated above, in the embodiments, the inorganic particles have an average pore size in the range of 10-100 μm.

[0084] In the embodiments, the inorganic particles have a length (L1), a width (L2), and a height (L3), wherein the length (L1) is in the range of 1-500 μm, more particularly in the range of 5-300 μm, and most particularly in the range of 10-250 μm, wherein the aspect ratio AR1 = L1 / L2 is in the range of 0.5 ≤ AR1 ≤ 2, wherein the aspect ratio AR2 = L1 / L3 is in the range of 0.5 ≤ AR2 ≤ 2, and wherein the aspect ratio AR3 = L2 / L3 is in the range of 0.5 ≤ AR2 ≤ 2.

[0085] In the embodiments, the concentration of porous inorganic particles is in the range of 5%-30% by volume, especially in the range of 10%-30% by volume.

[0086] Many inorganic materials are suitable for use as porous inorganic particles, and metal oxide particles, in particular, appear to be advantageous. In embodiments, porous inorganic particles include porous glass particles.

[0087] In an embodiment, the porous inorganic particles include core-shell particles, which include a hollow core and a porous shell.

[0088] In an embodiment, the porous inorganic particles include core-shell particles, which include a hollow core and a blocky shell.

[0089] In embodiments, the printed material comprises various types of porous inorganic particles with respect to: material, average particle size, particle size distribution, average pore size, pore size distribution, and / or aspect ratio. In one specific embodiment, one type of particles is used for a first portion of the printed article, and another type of particles is used for a second portion of the printed article.

[0090] As mentioned above, in the embodiments, core-shell filaments are used, wherein porous inorganic particles are incorporated into the core of the filament, and a lower concentration (e.g., no particles) is included in the shell. In one specific embodiment, the porous inorganic particles have a first concentration c1 in the core and a second concentration c2 in the shell, wherein c2 / c1 ≤ 0.5, particularly wherein c2 / c1 ≤ 0.25, and even more particularly wherein c2 / c1 ≤ 0.1.

[0091] In a specific embodiment, the 3D-printed article comprises at least five layers, such as at least eight layers, such as at least ten layers, which include the porous particles described herein. In yet another embodiment, layers having these particles and layers not having these particles may alternate with each other. In still another embodiment, sets of at least two layers having these particles and sets of at least two layers not having these particles may alternate with each other.

[0092] In a specific embodiment, the cross-sectional area of ​​the 3D-printed article comprising at least two (such as at least five) layer axes Ax is greater than or equal to 5 cm². 2 Such as equal to or greater than 25cm 2 .

[0093] In the embodiments, the thermoplastic material itself (i.e., without considering porous inorganic particles) may be translucent, although this is not necessarily the case.

[0094] In this embodiment, the porous inorganic particles may be translucent, although this is not always the case. In particular, the porous inorganic particles may be translucent, although this is not always the case.

[0095] The transmittance of a light-transmitting material to one or more wavelengths (in visible light) can be at least 80% / cm, such as at least 90% / cm, or even more particularly at least 95% / cm, such as at least 98% / cm, such as at least 99% / cm. This means that under perpendicular illumination of radiation with a selected wavelength in the visible light spectrum, for example at 1cm... 3 The cube-shaped translucent material block will have a transmittance of at least 95%.

[0096] In the embodiments, the thermoplastic material itself (i.e., without considering porous inorganic particles) may be light reflective, although this is not necessarily the case.

[0097] In the embodiments, the porous inorganic particles may be light-reflective, although this is not necessarily the case.

[0098] The reflective material may reflect at least 80%, such as at least 90%, or even more particularly at least 95%, such as at least 98%, such as at least 99%, for one or more wavelengths (in visible light).

[0099] In one specific embodiment, the 3D article comprises multiple components, including at least a thermoplastic material and porous inorganic particles, wherein the printed material has a material density n. m The printed material has a theoretical material density n defined by the density of its components. mc , where 0.6≤n m / n mc≤0.95, especially where 0.7≤n m / n mc ≤0.9. Among other things, the density can be lower due to the voids, and therefore the weight of 3D objects can be reduced.

[0100] The 3D-printed articles obtained (through the methods described herein) can be functional. For example, 3D-printed articles can be lenses, collimators, reflectors, etc. The resulting 3D articles can (optionally) be used for decorative or artistic purposes. 3D-printed articles may include or be provided with functional components. These functional components can be selected from the group consisting of: optical components, electrical components, and magnetic components. The term "optical component" specifically refers to components with optical functions, such as lenses, mirrors, light-transmitting elements, filters, etc. The term "optical component" can also refer to a light source (such as an LED). The term "electrical component" can refer, for example, to integrated circuits, PCBs, batteries, drivers, but can also refer to light sources (since light sources can be considered both optical and electrical components). The term "magnetic component" can refer, for example, to magnetic connectors, coils, etc. Alternatively or additionally, functional components may include thermal components (e.g., configured to cool or heat electrical components). Thus, functional components can be configured to generate or remove heat, etc.

[0101] As indicated above, 3D-printed articles can be used for various purposes. Among other things, 3D-printed articles can be used for lighting. Therefore, in another aspect, the invention also provides a lighting device that includes a 3D article as defined herein. In one specific aspect, the invention provides a lighting system comprising: (a) a light source configured to provide (visible) light; and (b) a 3D article as defined herein, wherein the 3D article can be configured as one or more of: (i) at least a portion of a housing, (ii) at least a portion of a wall of an illumination chamber, and (iii) functional components, wherein the functional components can be selected from the group consisting of: optical components, support members, electrically insulating components, conductive components, thermally insulating components, and thermally conductive components. Therefore, in a specific embodiment, the 3D article can be configured as one or more of: (i) at least a portion of a housing of a lighting device, (ii) at least a portion of a wall of an illumination chamber, and (iii) an optical element. Because it can provide a relatively smooth surface, 3D-printed articles can be used as mirrors or lenses, etc. In embodiments, 3D articles can be configured as masks. Devices or systems may include multiple different 3D-printed articles with different functions. Returning to the 3D printing process, a specific 3D printer can be used to provide the 3D-printed articles described herein. Therefore, in another aspect, the invention also provides a fused deposition modeling 3D printer comprising (a) a print head including print nozzles; and (b) a 3D-printable material supply device configured to supply 3D-printable material to the print head, wherein the fused deposition modeling 3D printer is configured to supply the 3D-printable material as indicated above.

[0102] A printer nozzle may include a single opening. In other embodiments, a printer nozzle may be a core-shell type having two (or more) openings. The term "printer head" may also refer to multiple (different) printer heads; therefore, the term "printer nozzle" may also refer to multiple (different) printer nozzles.

[0103] A 3D printable material supply device can supply a filament comprising 3D printable material to a print head, or can supply 3D printable material in such a way that the print head creates a filament comprising 3D printable material. Therefore, in an embodiment, the present invention provides a fused deposition modeling 3D printer comprising (a) a print head including a print nozzle; and (b) a filament supply device configured to supply a filament comprising 3D printable material to the print head, wherein, as indicated above, the fused deposition modeling 3D printer is configured to supply the 3D printable material to a substrate.

[0104] In particular, the 3D printer includes a controller (or is functionally coupled to a controller) that is configured to perform the methods described herein in a control mode (or “operation mode”). The term “control system” (see above, for example) may also be used instead of the term “controller”.

[0105] The term "control" and similar terms specifically refer to at least determining the behavior of an element or regulating the operation of an element. Therefore, "control" and similar terms as used herein can, for example, refer to applying actions to an element (determining the behavior of the element or regulating the operation of the element), such as, for example, measuring, displaying, actuating, opening, shifting, changing temperature, etc. In addition, the term "control" and similar terms can additionally include monitoring. Thus, the term "control" and similar terms can include applying actions to an element, and can also include applying actions to an element and monitoring the element. Control of the element can be accomplished using a control system, which can also be referred to as a "controller." The control system and the element can therefore be functionally coupled, at least temporarily or permanently. The element can include a control system. In embodiments, the control system and the element may not be physically coupled. Control can be accomplished via wired and / or wireless control. The term "control system" can also refer to multiple different control systems that are functionally coupled, and one of these multiple different control systems may be a master control system, and one or more other control systems may be slave control systems. The control system may include a user interface, or may be functionally coupled to a user interface.

[0106] The control system can also be configured to receive and execute commands from a remote control. In embodiments, the control system can be controlled via an application (App) on the device, such as a portable device, like a smartphone or iPhone, tablet, etc. Therefore, the device is not necessarily coupled to the lighting system, but can be (temporarily) functionally coupled to it.

[0107] Therefore, in embodiments, the control system can also be configured to be controlled by an app on a remote device. In such embodiments, the control system of the lighting system can be a slave control system or controlled in a slave mode. For example, the lighting system can be identified by a code, particularly a unique code for each lighting system. The control system of the lighting system can be configured to be controlled by an external control system that accesses the lighting system based on knowledge of the (unique) code (input via a user interface with optical sensors, e.g., a QR code reader). The lighting system may also include means for communicating with other systems or devices, such as based on Bluetooth, Wi-Fi, LiFi, ZigBee, BLE, or WiMAX, or another wireless technology.

[0108] A system, apparatus, or device may perform actions in a “mode,” “operating mode,” or “mode of operation.” Similarly, in a method, actions, stages, or steps may be performed in a “mode,” “operating mode,” “mode of operation,” or “operable mode.” The term “mode” may also indicate “control mode.” This does not preclude the system, apparatus, or device from being adapted to provide another control mode or multiple other control modes. Likewise, this does not preclude the possibility of performing one or more other modes before and / or after performing a particular mode.

[0109] However, in embodiments, the control system may be available and is adapted to provide at least a control mode. If other modes are available, the selection of such modes can be performed, in particular, via a user interface, although other options (such as performing modes based on sensor signals or (time) schemes) are also possible. In embodiments, an operating mode may also refer to a system, apparatus, or device that can only operate in a single operating mode (i.e., "on," without additional tunability).

[0110] Therefore, in this embodiment, the control system can be controlled based on one or more of the following: input signals from the user interface, sensor signals (from sensors), and timers. The term "timer" can refer to a clock and / or a predetermined timing scheme.

[0111] The abbreviations “3D printer,” “FDM printer,” or “printer” can be used instead of “Fused Deposition Modeling (FDM) 3D printer.” Printer nozzles may also be indicated as “nozzle” or sometimes as “extruder nozzle.” Attached Figure Description

[0112] Embodiments of the invention will now be described by way of example only with reference to the accompanying drawings, in which corresponding reference numerals indicate corresponding parts, and in the accompanying drawings:

[0113] Figures 1a-1c schematically depict some general aspects of one embodiment of a 3D printer and 3D printed material;

[0114] Figures 2a-2b schematically depict some aspects of embodiments of porous inorganic particles;

[0115] Figures 3a-3d schematically depict some other aspects of the invention;

[0116] Figures 4a-4b schematically depict some aspects and embodiments; and

[0117] Figure 5 An application is illustrated schematically.

[0118] The diagram is not necessarily to scale. Specific Implementation

[0119] Figure 1a schematically depicts some aspects of a 3D printer. Reference numeral 500 indicates a 3D printer. Reference numeral 530 indicates a functional unit configured for 3D printing, particularly FDM 3D printing; this reference numeral may also indicate a 3D printing stage unit. Here, only a printer head for supplying 3D-printable material, such as an FDM 3D printer head, is schematically depicted. Reference numeral 501 indicates a printer head. The 3D printer of the present invention may, in particular, include multiple printer heads (see below). Reference numeral 502 indicates a printer nozzle. The 3D printer of the present invention may, in particular, include multiple printer nozzles, although other embodiments are also possible. Reference numeral 320 indicates a filament of printable 3D-printable material (such as indicated above). For clarity, not all features of the 3D printer are depicted, only those particularly relevant to the present invention are depicted (see also further below). Reference numeral 321 indicates the extrudate (of the 3D-printable material 201).

[0120] The 3D printer 500 is configured to generate a 3D article 1 by depositing a plurality of layers 322 layer by layer on a receiver article 550, wherein, in an embodiment, the receiver article 550 may be at least temporarily cooled, and each layer 322 comprises, for example, layers having a melting point T. m 3D printable material 201. 3D printable material 201 can be deposited on substrate 1550 (during the printing stage). Through deposition, 3D printable material 201 has become 3D printable material 202. 3D printable material 201 escaping from nozzle 502 is also indicated as extrudate 321. Reference numeral 401 indicates thermoplastic material.

[0121] The 3D printer 500 can be configured to heat the filament 320 material upstream of the printer nozzle 502. This can be accomplished, for example, by a device that includes one or more of an extrusion function and / or a heating function. Such a device is indicated by reference numeral 573 and is arranged upstream of the printer nozzle 502 (i.e., before the filament material leaves the printer nozzle 502). The printer head 501 may (therefore) include a liquefier or a heater. Reference numeral 201 indicates printable material. When deposited, this material is indicated as a 3D-printable material, which is indicated by reference numeral 202.

[0122] Reference numeral 572 indicates a spool or roller containing material (especially in the form of a filament), which may be indicated as filament 320. The 3D printer 500 transforms this material into an extrusion 321 downstream of the printer nozzle, which becomes a layer 322 on the receiver article or already deposited on the printed material. Generally, the diameter of the extrusion 321 downstream of the nozzle 502 is smaller than the diameter of the filament 322 upstream of the printer head 501. Therefore, the printer nozzle is sometimes (also) indicated as an extruder nozzle. Layers 322 are arranged sequentially to form a 3D article 1. Reference numeral 575 indicates a filament supply device, which, among other things, includes a spool or roller and a drive wheel indicated using reference numeral 576.

[0123] Figure label A x Indicates the longitudinal axis, wire axis, or layer axis (of the 3D printed layer).

[0124] Reference numeral C schematically depicts a control system, such as a temperature control system configured, in particular, to control the temperature of the receiver article 550. The control system C may include a heater capable of heating the receiver article 550 to a temperature of at least 50°C, but in particular, to a range up to about 350°C, such as at least 200°C.

[0125] Alternatively or additionally, in an embodiment, the receiver plate may also be movable in one or both directions in the xy plane (horizontal plane). Further, alternatively or additionally, in an embodiment, the receiver plate may also be rotatable about the (vertical) z-axis. Therefore, the control system can move the receiver plate along one or more of the x, y, and z directions.

[0126] Alternatively, the printer may have a printhead that can also rotate during printing. This type of printer has the advantage that the printed material cannot rotate during printing.

[0127] The layers are indicated by reference numeral 322 and have a layer height H and a layer width W.

[0128] Note that the 3D printable material is not necessarily provided to the printer head as filament 320. Furthermore, filament 320 can also be produced in the 3D printer 500 from a block of 3D printable material.

[0129] The reference numeral D in the attached figure indicates the diameter of the nozzle (which forces the 3D printable material 201 through the nozzle).

[0130] Figure 1b schematically depicts the printing of the 3D article 1 in construction in more detail in 3D. Here, in this schematic, the ends of the filaments 321 in a single plane are not interconnected, but this can actually be the case in the embodiment. The reference numeral H indicates the height of the layer. Layers are indicated by reference numeral 322. Here, the layers have a substantially circular cross-section. However, they can typically be flat, such as having an external shape similar to a flat elliptical tube or flat elliptical conduit (i.e., a circular rod with a diameter that is compressed to have a height smaller than the width, wherein the sides (defining the width) are (still) round).

[0131] Therefore, Figures 1a-1b schematically depict some aspects of a fused deposition modeling 3D printer 500, including (a) a first printhead 501 comprising a printer nozzle 502; (b) a filament supply device 575 configured to supply a filament 321 comprising a 3D printable material 201 to the first printhead 501; and optionally (c) a receiver article 550. In Figures 1a-1b, the first printable material or the second printable material or the first printed material or the second printed material is indicated using the generic indicator printable material 201 and printed material 202, respectively. Directly downstream of the nozzle 502, the filament 321 having the 3D printable material becomes a layer 322 having the printed material 202 when deposited.

[0132] Figure 1c schematically depicts a stack of 3D-printed layers 322, each having a layer height H and a layer width W. Note that in embodiments, the layer width and / or layer height of two or more layers 322 may be different. Reference numeral 252 in Figure 1c indicates the surface of the 3D article (schematically depicted in Figure 1c).

[0133] Referring to Figures 1a-1c, the deposited filaments of 3D printable material produce layers with a height H (and width W). These layers are deposited in a layer-by-layer manner to generate 3D article 1. Figure 1c schematically depicts a single-walled 3D article 1.

[0134] For ease of understanding, Figure 2a schematically depicts the particles and some aspects thereof. Particle 410 has a first dimension or length L1. In the example on the left, L1 is essentially the diameter of a substantially spherical particle. The right side depicts particles with non-spherical shapes (such as elongated particles 410). Here, by way of example, L1 is the particle length. L2 and L3 can be considered as width and height. Of course, particles can include combinations of particles with different shapes.

[0135] Figure 2b schematically depicts some aspects of particle 410. Some particles 410 have a longest dimension A1 and a shortest dimension A2, with the longest dimension A1 having a longest dimension length L1 and the shortest dimension A2 having a shortest dimension length L2. Figure 2b schematically depicts particle 410 in 3D, wherein particle 410 has length, height, and width, and wherein the particle is substantially elongated. Thus, the particle may have an additional (secondary or primary) axis, indicated herein as an additional dimension A3. The relative lengths L1, L2, and L3 in Figure 2b do not imply a specific aspect ratio; the figures are used to illustrate some aspects of the invention.

[0136] Note that the symbols L1, L2, and L3, as well as A1, A2, and A3, are used only to indicate axes and their lengths, and the numbers are used only to distinguish axes. Furthermore, note that the particles are not substantially elliptical or cuboid; particles can have any shape.

[0137] Figures 3a and 3b schematically depict porous inorganic particles (410) with pores 411. Figure 3b schematically depicts porous inorganic particles (410) with a hollow core (415) and a porous shell (416).

[0138] Figure 3c schematically depicts a filament 321, such as when it escapes from a printer nozzle (not shown), comprising a 3D printable material 201. The 3D printable material comprises a thermoplastic material 401 having porous inorganic particles 410 embedded therein, wherein the particles are surrounded by voids 412.

[0139] Figure 3d schematically depicts 3D article 1, showing a rib-like structure (derived from deposited filaments) with height H. This height can also be indicated as width. Here, a layer 322 with printed material 202 and height H and width W is schematically depicted. Figure 3b can be viewed as a stack of layers 322, with multiple adjacent stacks shown in Figure 1b. The 3D printed material comprises a thermoplastic material 401 with embedded porous inorganic particles 410, wherein the particles are surrounded by voids 412.

[0140] Figure 4a schematically depicts some additional aspects of the method of the present invention, in which a core-shell filament 350 can be used. The filament 350 can be used in a printer 500, for example, the printer 500 depicted in Figures 1a-1b, which has a nozzle 502 having a single opening. The geometry in the filament is indicated, in particular the width W1F of the core, the height H1F of the core, and the width (or thickness) W2F of the shell. The shell 340 comprises a thermoplastic material 401 and optionally also includes porous inorganic particles 410 (comprising thermoplastic material 401 and porous inorganic particles 410) that completely surround the core 330.

[0141] In an embodiment, the filament 320 of FIG4a can be used in the 3D printing stage to produce the 3D article 1 depicted in FIG4b.

[0142] Figure 5 An embodiment of a lamp or illuminator, indicated by reference numeral 2, is schematically depicted, comprising a light source 10 for generating light 11. The lamp may include a housing or shield or another element that may comprise or be a 3D-printed article 1. Here, a hemisphere (in a cross-sectional view) schematically indicates the housing or shield. The lamp or illuminator may be or may include an illumination device 1000 (which includes the light source 10). Thus, in a specific embodiment, the illumination device 1000 includes a 3D article 1. The 3D article 1 may be configured as one or more of the following: (i) at least a portion of the illumination device housing, (ii) at least a portion of the wall of the illumination chamber, and (iii) an optical element. Thus, in an embodiment, the 3D article may be reflective to the light source 11 and / or transmissive to the light source 11. Here, the 3D article may be, for example, a housing or shield. The housing or shield includes an article portion 400. See also above for possible embodiments of the article portion 400.

[0143] The term "multiple" refers to two or more.

[0144] The terms “substantially” or “basically” and similar terms used herein will be understood by those skilled in the art. The term “substantially” or “basically” may also include embodiments with terms such as “entire,” “complete,” “all,” etc. Therefore, in embodiments, the adjective “substantially” or “basically” may also be removed. Where applicable, the term “substantially” or “basically” may also refer to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%.

[0145] The term "comprising" also includes embodiments thereof, which are defined as "consisting of".

[0146] The term “and / or” specifically refers to one or more of the items mentioned before and after “and / or”. For example, the phrase “item 1 and / or item 2” and similar phrases may refer to one or more of item 1 and item 2. The term “comprising” may mean “consisting of” in one embodiment, but may also mean “containing at least the defined species and one or more optional other species” in another embodiment.

[0147] Furthermore, the terms first, second, third, etc., used in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequence or chronological order. It should be understood that such terms are interchangeable where appropriate, and the embodiments of the invention described herein can operate in orders other than those described or illustrated herein.

[0148] Among other things, the devices, apparatuses, or systems described herein may refer to those used during operation. It will be apparent to those skilled in the art that the invention is not limited to the methods of operation, or the devices, apparatuses, or systems in operation.

[0149] It should be noted that the embodiments mentioned above are illustrative and not limiting of the invention, and those skilled in the art will be able to devise many alternative embodiments without departing from the scope of the appended claims.

[0150] In the claims, any reference numerals placed in parentheses should not be construed as limiting the claims.

[0151] The use of the verb "comprising" and its variations does not exclude the presence of elements or steps other than those described in the claims. Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprising," "including," etc., should be interpreted in a inclusive sense, the opposite of exclusive or exhaustive; that is, in the sense of "including but not limited to."

[0152] The article "one" or "a" preceding an element does not preclude the existence of multiple such elements.

[0153] This invention can be implemented by means of hardware comprising several different elements and by means of a suitably programmed computer. In the device claims, apparatus claims, or system claims that enumerate several means, several of these means may be embodied by the same hardware. The simple fact that certain measures are recited in mutually different dependent claims does not indicate that combinations of these measures cannot be advantageously used. The invention also provides a control system that can control a device, apparatus, or system, or can perform the methods or processes described herein. Furthermore, the invention provides a computer program product that, when functionally coupled to or executed on a computer included in a device, apparatus, or system, controls one or more controllable elements of such device, apparatus, or system.

[0154] The present invention is also applicable to devices, apparatuses, or systems that include one or more of the characterizing features described in the specification and / or shown in the drawings. The present invention also relates to a method or process that includes one or more of the characterizing features described in the specification and / or shown in the drawings.

[0155] Various aspects discussed in this patent can be combined to provide additional advantages. Furthermore, those skilled in the art will understand that embodiments can be combined, and more than two embodiments can be combined. In addition, some features of the design can form the basis of one or more divisional applications.

[0156] It goes without saying that one or more of the first (printable or printable) material and the second (printable or printable) material may contain fillers, such as glass and fibers, that have no (or do) an effect on the material’s Tg or Tm.

Claims

1. A method for producing a 3D article (1) by means of fused deposition modeling, the method comprising a 3D printing stage, the 3D printing stage comprising layer-by-layer deposition of a 3D printable material (201) to provide the 3D article (1) comprising a layer (322) of the 3D printable material (202), wherein the 3D article (1) comprises a layer (322) of the 3D printable material (202), wherein the 3D printable material (201) comprises a thermoplastic material (401), wherein during at least a portion of the 3D printing stage, the 3D printable material (201) further comprises porous inorganic particles (410) embedded in the thermoplastic material (401), wherein the porosity of the porous inorganic particles (410) is in the range of 5% to 60% by volume, and wherein the porous inorganic particles (410) have open porosity to allow controlled introduction of voids in the 3D printable material.

2. The method according to claim 1, wherein the porous inorganic particles (410) have a length (L1), a width (L2), and a height (L3), the length (L1) being in the range of 1 μm to 500 μm, wherein the aspect ratio AR1 = L1 / L2 is in the range of 0.5 ≤ AR1 ≤ 2, wherein the aspect ratio AR2 = L1 / L3 is in the range of 0.5 ≤ AR2 ≤ 2, and wherein the aspect ratio AR3 = L2 / L3 is in the range of 0.5 ≤ AR3 ≤ 2.

3. The method according to claim 1 or 2, wherein the concentration of the porous inorganic particles (410) is in the range of 10% to 30% by volume relative to the 3D printable material (201).

4. The method according to claim 1 or 2, wherein the porous inorganic particles (410) comprise porous glass particles.

5. The method according to claim 1 or 2, wherein the porous inorganic particle (410) comprises a core-shell particle, the core-shell particle comprising a hollow core (415) and a porous shell.

6. The method according to claim 1 or 2, wherein the porous inorganic particles (410) have a first density n1, and the thermoplastic material (401) has a second density n2, wherein 0.8 ≤ n1 / n2 ≤ 1.

2.

7. The method according to claim 1 or 2, wherein the layer (322) comprises a core-shell layer of 3D-printed material (202), the core-shell layer comprising: (i) a core (330), the core (330) comprising a thermoplastic material (401), the core (330) further comprising porous inorganic particles (410) embedded in the thermoplastic material (401) at a concentration c1; and (ii) a shell (340), the shell (340) comprising a thermoplastic material (401), the shell (340) further comprising porous inorganic particles (410) embedded in the thermoplastic material (401) at a concentration c2; wherein the shell (340) at least partially surrounds the core (330); wherein the core (330) has a core height (H1) and a core width (W1), wherein the shell (340) has a shell width (W2); wherein the 3D printing stage comprises 3D printing the core-shell layer of the 3D printing material (202); Where c2 / c1≤0.

5.

8. The method according to claim 1 or 2, wherein the porous inorganic particles (410) have pores having an average pore size in the range of 10 μm to 100 μm, and wherein the porous inorganic particles (410) are light-transmitting, and wherein the 3D printable material (201) is light-transmitting.

9. A filament (320) for producing 3D articles (1) by means of fused deposition modeling, the filament (320) comprising a 3D printable material (201), wherein the 3D printable material (201) comprises a component, wherein the component comprises at least (i) a thermoplastic material (401) and (ii) porous inorganic particles (410); wherein in at least a portion of the filament (320), the 3D printable material (201) comprises the porous inorganic particles (410) embedded in the thermoplastic material (401), wherein the porosity of the porous inorganic particles (410) is in the range of 5% to 60% by volume, wherein the porous inorganic particles (410) have open porosity, wherein the concentration of the porous inorganic particles (410) relative to the 3D printable material (201) is in the range of 10% to 30% by volume; wherein the filament (320) has a material density n f The filament (320) has a theoretical material density n defined by the density of the components of the filament (320). fc , where 0.6≤n f / n fc ≤l.

10. A 3D article (1) comprising a 3D printed material (202), wherein the 3D article (1) comprises a plurality of layers (322) of the 3D printed material (202), wherein the 3D printed material (202) comprises a thermoplastic material (401), wherein at least a portion of the 3D printed material (202) further comprises porous inorganic particles (410) embedded in the thermoplastic material (401), wherein the porosity of the porous inorganic particles (410) is in the range of 5% to 60% by volume, and wherein the porous inorganic particles (410) have open porosity to allow controlled introduction of voids in the 3D printed material.

11. The 3D article (1) according to claim 10, wherein the porous inorganic particles (410) have a length (L1), a width (L2) and a height (L3), wherein the length (L1) is in the range of 1 μm to 500 μm, wherein the aspect ratio AR1 = L1 / L2 is in the range of 0.5 ≤ AR1 ≤ 2, wherein the aspect ratio AR2 = L1 / L3 is in the range of 0.5 ≤ AR2 ≤ 2, and wherein the aspect ratio AR3 = L2 / L3 is in the range of 0.5 ≤ AR3 ≤ 2.

12. The 3D article (1) according to any one of claims 10-11, wherein the concentration of the porous inorganic particles (410) is in the range of 10%-30% by volume relative to the 3D printed material (202).

13. The 3D article (1) according to any one of claims 10-11, wherein the porous inorganic particles (410) comprise porous glass particles.

14. The 3D article (1) according to any one of claims 10-11, wherein the 3D article (1) comprises a plurality of components, the plurality of components including at least the thermoplastic material (401) and the porous inorganic particles (410), wherein the 3D printed material (202) has a material density n m The 3D printed material (202) has a theoretical material density n defined by the density of the components of the 3D printed material (202). mc , where 0.6≤n m / n mc ≤0.

95.

15. A lighting device (1000) comprising a 3D article (1) according to any one of claims 10-14, wherein the 3D article (1) is configured as one or more of: (i) at least a portion of a housing of the lighting device, (ii) at least a portion of a wall of a lighting chamber, and (iii) an optical element.

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