WO2023237494A1 - Functional filaments for 3d printing - Google Patents

Functional filaments for 3d printing Download PDF

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Publication number
WO2023237494A1
WO2023237494A1 PCT/EP2023/064997 EP2023064997W WO2023237494A1 WO 2023237494 A1 WO2023237494 A1 WO 2023237494A1 EP 2023064997 W EP2023064997 W EP 2023064997W WO 2023237494 A1 WO2023237494 A1 WO 2023237494A1
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WO
WIPO (PCT)
Prior art keywords
core
shell
sheet
shells
filament
Prior art date
Application number
PCT/EP2023/064997
Other languages
French (fr)
Inventor
Rifat Ata Mustafa Hikmet
Ties Van Bommel
Original Assignee
Signify Holding B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Signify Holding B.V. filed Critical Signify Holding B.V.
Publication of WO2023237494A1 publication Critical patent/WO2023237494A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents

Definitions

  • the invention relates to a method for manufacturing a 3D (printed) item.
  • the invention also relates to the 3D (printed) item obtainable with such method.
  • the invention also relates to a filament for use in the method for manufacturing the 3D (printed) item as well as a method for producing such filament. Further, the invention relates to a lighting device including such 3D (printed) item.
  • 3D printable material comprising filaments with multiple shells is known in the arts.
  • WO2018199959A1 describes 3D printing filaments having core and shell thermoplastic extrudates.
  • Each of the core and shell extrudates have glass transition temperatures, the glass transition temperature of the core being greater than or equal to the glass transition temperature of the shell.
  • the ratio of the viscosity of the core thermoplastic extrudate at printing temperature, over the viscosity of the shell thermoplastic extrudate at printing temperature is greater than 1, up to 20.
  • FDM Fused Deposition Modeling
  • FDM Fused deposition modeling
  • FDM is an additive manufacturing technology commonly used for modeling, prototyping, and production applications. FDM works on an "additive" principle by laying down material in layers; a plastic filament or metal wire is unwound from a coil and supplies material to produce a part. Possibly, (for thermoplastics for example) the filament is melted and extruded before being laid down. FDM is a rapid prototyping technology. Other terms for FDM are “fused filament fabrication” (FFF) or “filament 3D printing” (FDP), which are considered to be equivalent to FDM.
  • FFF fused filament fabrication
  • FDP filament 3D printing
  • the present invention may have as object to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.
  • a 3D printable filament comprising multiple shells may be provided that may then be used to create a 3D printed item.
  • the inner shell may have properties that would be desired in the 3D printed item, e.g. optical features. This may allow for the production of 3D printed items that have the desired properties that would not be obtainable with conventional fused deposition modeling 3D printing purely based on thermoplastic materials, optionally with fillers.
  • the proposed method may still retain all of the original benefits provided by fused deposition modeling 3D printing, being relatively fast, low cost, and able to produce complicated 3D printed items, while adding to the controllability of the material properties.
  • the 3D printable material may comprise a core-shell structure. More especially, the 3D printable material may comprise a core-shell filament.
  • the core-shell filament comprises a core.
  • the core may comprise a core thermoplastic material. Possible characteristics and compositions of such thermoplastic material will be further described below.
  • the core may essentially consist of thermoplastic material.
  • the core may also comprise thermoplastic material with a filler (see further also below).
  • the term “core thermoplastic material” may especially refer to thermoplastic material comprised by the core.
  • the core of the filament is enclosed by the two or more shells, providing over the substantial part of its length a core-(shell) n cross-section, wherein n is at least 2.
  • the filament may e.g. have a length (“filament length”) of at least about 50 cm, such as at least about 1 m. In embodiments, the length may be up to e.g. 50 m, such as up to about 20 m, like in embodiments up to about 15 m. However, other dimensions may also be possible.
  • the filament may have the core-shell structure, with multiple shells enclosing the core (i.e. a core-(shell) n cross-section).
  • the at least two or more shells may comprise an inner shell.
  • the inner shell may comprise a sheet-like material.
  • the sheet-like material may at least partly cover the core, as also described above in relation to a first shell covering the core.
  • inner shell and similar terms, may refer to any shell between the core and the outer shell (see also below).
  • the inner shell comprising the sheet-like material is not necessarily the shell that is in contact with the core.
  • the outer shell thermoplastic material may be transparent for (visible) light.
  • the outer shell thermoplastic may be translucent for (visible) light.
  • the outer shell thermoplastic material may be selected based on desired properties for the 3D printing stage, e.g. flexibility. Further, the outer shell thermoplastic material may be selected based on desired properties for the 3D printed item, e.g. transparent for (visible) light.
  • the outer shell thermoplastic material may be adhesive to the surface of 3D printed layers during the 3D printing process, especially when the thermoplastic material of the layers is substantially the same.
  • the outer shell thermoplastic material may cover different layers and adhere to each other within the 3D item.
  • the other shell may facilitate that layers adhere to one another during the 3D printing stage. This may especially apply to commonly used 3D printing thermoplastic polymer materials (see elsewhere).
  • the core material and the material of the one or more outer shells may especially be thermoplastic materials that may be 3D printed using e.g. FDM printing.
  • the inner shell may comprise another material, and may in embodiments especially substantially not comprise a thermoplastic material that may be 3D printed using e.g. FDM printing (see further also below).
  • the core material and the outer shell material(s) may be individually selected from thermoplastic polymers, or may individually be selected from materials comprise a thermoplastic polymer.
  • the thermoplastic polymer may be selected from the group consisting of ABS (acrylonitrile butadiene styrene), Nylon (or polyamide), Acetate (or cellulose), PLA (poly lactic acid), terephthalate (such as PET polyethylene terephthalate), Acrylic (polymethylacrylate, Perspex, polymethylmethacrylate, PMMA), Polypropylene (or polypropene), Polycarbonate (PC), Polystyrene (PS), PE (such as expanded- high impact- Polythene (or poly ethene), Low density (LDPE) High density (HDPE)), PVC (polyvinyl chloride) Polychloroethene, such as thermoplastic elastomer based on copolyester elastomers, polyurethane elastomers, polyamide elastomers polyolefine based elastomers, styrene based elastomers, etc..
  • the 3D printable material may comprise a 3D printable material selected from the group consisting of Urea formaldehyde, Polyester resin, Epoxy resin, Melamine formaldehyde, thermoplastic elastomer, etc...
  • the 3D printable material may comprise a 3D printable material selected from the group consisting of a polysulfone.
  • Elastomers, especially thermoplastic elastomers, may especially be interesting as they are flexible and may help obtaining relatively more flexible filaments comprising the thermally conductive material.
  • thermoplastic elastomer may comprise one or more of styrenic 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)).
  • TPS styrenic block copolymers
  • TPO thermoplastic polyolefin elastomers
  • TPV thermoplastic vulcanizates
  • TPU thermoplastic polyurethanes
  • TPU-E thermoplastic copolyesters
  • TPE-A thermoplastic polyamides
  • Suitable thermoplastic materials may include one or more of polyacetals (e.g., polyoxyethylene and polyoxymethylene), poly(Ci-6 alkyl)acrylates, polyacrylamides, polyamides, (e.g., aliphatic polyamides, polyphthalamides, and polyaramides), polyamideimides, polyanhydrides, polyarylates, polyarylene ethers (e.g., polyphenylene ethers), polyarylene sulfides (e.g., polyphenylene sulfides), poly aryl sulfones (e.g., polyphenylene sulfones), polybenzothiazoles, polybenzoxazoles, polycarbonates (including polycarbonate copolymers such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbonate-ester-siloxanes), polyesters (e.g., polycarbonates, polyethylene terephthalates, poly(Ci-6 alkyl)acrylates, poly
  • a polyolefine may include one or more of polyethylene, polypropylene, polybutylene, polymethylpentene (and co-polymers thereof), polynorbornene (and co-polymers thereof), poly 1 -butene, poly (3 -methylbutene), poly(4-m ethylpentene) and copolymers of ethylene with propylene, 1 -butene, 1 -hexene, 1 -octene, 1 -decene, 4-methyl-l -pentene and 1- octadecene.
  • the 3D printable material may comprise one or more of polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), and semi-crystalline polytethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), poly(methyl methacrylate) (PMMA), polystyrene (PS), and styrene acrylic copolymers (SMMA).
  • PC polycarbonate
  • PE polyethylene
  • HDPE high-density polyethylene
  • PP polypropylene
  • POM polyoxymethylene
  • PEN polyethylene naphthalate
  • SAN polystyrene-acrylonitrile resin
  • PSU polysulfone
  • PPS polyphenylene sulfide
  • the composition of the material of the outer shell(s) may differ from the composition of the material of the inner shell. In other embodiments, however, the composition of the material of the core may be similar, or the same, as the material of the outer shell. In embodiments wherein there are two or more outer shells, the compositions of the respective materials of at least two of the two or more outer shells may differ. They may differ in one or more of thermoplastic material, thermoplastic material composition, filler material, weight percentage of filler materials, etc. Especially, in embodiments wherein there are two or more outer shells, the compositions of the respective materials of at least two of the two or more outer shells may differ in type of thermoplastic material.
  • the inner shell may comprise a sheet-like material.
  • the sheet-like material may be a monolithic body circumferentially enclosing the core.
  • the sheet-like material may be a foil, such as a thin metal foil, circumferentially enclosing the core.
  • the sheet-like material may be a multi-layer reflective polymer foil circumferentially enclosing the core.
  • the sheet-like material may comprise a metal material.
  • the sheet-like material may comprise one or more of a flexible metal sheet or a flexible sheet with a metal coating.
  • the metal material may be an aluminum sheet or coating.
  • the metal sheet or coating may be silver.
  • Other solutions may also be possible, like stainless steel, other metals, or (their) metal alloys.
  • the metal sheet or coating may comprise a top layer that may be converted into an oxide of the metal. Such oxide layer may be provided via an anodizing process.
  • the metal sheet or coating may comprise anodized metal.
  • methods may be selected from anodization, electro-chemical oxidation, thermal oxidation, or chemical treatment of the metal material.
  • the metal material may provide the sheet-like material with desired features for the printing process, e.g. flexibility.
  • the metal material may provide the sheet-like material with desired features for the 3D printed item, e.g. reflectivity of visible light.
  • the sheet-like material may comprise a metal coating.
  • the metal coating on the sheet-like material may have a thickness selected from the range of 50 nm -100 nm.
  • the thickness of the sheet-like material may be selected from the range of 10 pm - 1 mm, such as 10 pm - 0.5 mm, like in embodiments 50 pm - 0.2 mm.
  • the small thickness may allow configuring the material around the core and/or may provide bendable filaments.
  • the core (of the filament) may be defined by a core diameter (de).
  • the core diameter is the diameter of the core in embodiments wherein the core has an essentially circular cross-section, which may generally be the case, and may be a circular equivalent diameter in embodiments wherein the core has no circular equivalent diameter.
  • the sheet-like material may be defined by a sheet-like material thickness ds.
  • the outer shell may be defined by an outer shell thickness (do).
  • the thickness of the at least two or more shells may especially not exceed the core diameter, which may provide most of the structural support to the core-shell filament.
  • ds may be lower than do.
  • the sheet-like material may be thinner than the outer shell, which may provide adhesion between adjacent core-shell filaments.
  • the dimensions, especially thicknesses, of the core and/or outer shells may be changed, whereas the thickness of the sheet-like material may essentially stay the same.
  • the sheet-like material may comprise at least one dimension that is substantially larger than a circular equivalent diameter of the core.
  • the circular equivalent diameter of the core, indicated by de, and a dimension of the sheet-like material, like sheet-like material length Ls or sheet-like material width Ws may comply with one or more of the following relations: (i) Ls>5*dc, more especially Ls>10*dc, such as Ls>20*dc, like in embodiments 10*dc ⁇ LS ⁇ LF, and (ii) Ws>5*dc, more especially Ws>10*dc, such as Ws>20*dc, like in embodiments 10*dc ⁇ WS ⁇ LF.
  • LF is the filament length.
  • Especially one dimension of the sheet-like material may comply with one of the above-indicated relations, such as 10*dc ⁇ LS ⁇ LF.
  • the outer shell thermoplastic material may also have dimensions such as the outer shell thermoplastic material length Lo or outer shell thermoplastic material width Wo, respectively. These dimensions may comply with one or more of the following relations: (i) Ls>Lo, more especially Ls>5*Lo, and (ii) Ws>Lo, more especially Ws>Lo.
  • the filament itself may also have a width Fw which is essentially Fw>(dc+Ws+Wo).
  • the equivalent circular diameter (or ECD) (or “circular equivalent diameter”) of an (irregularly shaped) two-dimensional shape is the diameter of a circle of equivalent area.
  • ECD equivalent circular diameter
  • the equivalent circular diameter of a square with side a is 2*a*SQRT(l/7t).
  • the diameter is the same as the equivalent circular diameter.
  • the sheet-like material may in embodiments prevent a fluid from getting into contact with the core thermoplastic material.
  • the sheet-like material may prevent gases and liquids at ambient temperature and pressure from getting into contact with the core thermoplastic material. This may prevent damage from (long-term) contact exposure with such gases and liquids.
  • the term “damage” may in embodiments refer to degradation.
  • the sheet-like material may at least partly enclose the core by being spirally wrapped around the core material.
  • the sheet-like material may be wrapped around the core by being cut into segments, each segment being subsequently wrapped around a corresponding segment of core material.
  • the sheet-like material may be configured spirally wrapped around the core.
  • the core may be funneled through the sheet-like material.
  • the sheet-like material may be deposited on the core material by a core-shell nozzle.
  • the sheet-like material may have a width selected from the range of 7t*dc-5*7t*dc. This would allow 1-5 wrapping the sheet-like material around the core (material). Note however that other dimensions may also be possible.
  • the core may comprise a core material
  • the inner shell comprises an inner shell material
  • the outer shell comprises an outer shell material
  • one or more further shells may be available, in addition to the inner shell and the outer shell.
  • there may be at least two different materials as the material of the inner shell may differ from the material of the core and/or of the outer shell.
  • the different materials may differ in one or more of optical properties, mechanical properties, and other material properties.
  • Other material properties may include e.g. one or more of thermal conductivity, electrical conductivity, adhesiveness, etc.
  • the mechanical properties may refer to one or more of flexibility, tensile strength, surface roughness, etc.
  • the invention is herein (though not exclusively) explained in relation to optical properties of the sheet-like materials, but the invention is not limited to such embodiments.
  • the sheet-like material may have one or more optical features. Especially, in embodiments the sheet-like material may provide the 3D printed item with one or more desired optical features. In such embodiments, the other one or more shells may facilitate transmission of light so that the light may reach the sheet-like material and provided the desired optical feature(s). Therefore, in such embodiments, the other one or more shells may be transmissive for visible light.
  • a first material and a second material may differ in optical properties.
  • the optical properties may be selected from the group of (a) absorption of light having a first wavelength, (b) diffuse reflection for light having the first wavelength, (c) specular reflection for light having the first wavelength, (d) transmission of light having the first wavelength, and (e) conversion of light having the first wavelength.
  • two materials of two or more parts having essentially the same absorption, but one part able to convert part of the absorbed light having the first wavelength and the other part not able to convert lead to materials that appear different to the human eye (or optical sensor), and thus have different optical properties.
  • the same may e.g. apply to materials of two or more parts having essentially the same transmission value, but one part having a low transparency due to the absorption of the light and the other part having a relatively low transparency due to scattering, may lead to materials that appear different to the human eye (or optical sensor), and thus have different optical properties.
  • Other examples may also be possible. This may apply to any two materials of two or more parts having essentially the same optical feature, but one part having a different interaction with the light reaching the material than the other part, thus having different optical properties.
  • the optical properties may be selected from the group (a) having a white color, (b) being black, (c) having metallic appearance, and (d) being light transparent.
  • the optical properties may be selected from the group (a) light reflectivity and (b) light transmissivity.
  • first material of the k materials having a first optical property may be a first material of the k materials having a first optical property and a second material of the k materials having a second optical different from the first optical property.
  • One of the optical properties may be >60% absorption (especially >70% absorption, more especially >75% absorption, most especially >80% absorption) of light having the first wavelength, wherein a conversion of the absorbed light (having the first wavelength) is ⁇ 10% (especially the conversion of the absorbed light is ⁇ 6%, more especially the conversion of the absorbed light is ⁇ 3%, most especially the conversion of the absorbed light is ⁇ 1%) of the absorbed light having the first wavelength.
  • the light is absorbed without substantial conversion, like in the case of pigments.
  • the absorption of the light having the first wavelength may be determined under perpendicular radiation of the material (or 3D printed material) with the light having the first wavelength.
  • One of the optical properties may be >60% reflection (especially >70% reflection, more especially >75% reflection, most especially >80% reflection) of light having the first wavelength.
  • absorption of the light having the first wavelength may especially be less than 40% (especially less than 30%, more especially less than 25%, most especially less than 20%).
  • the reflection of the light having the first wavelength may be determined under perpendicular radiation of the material (or 3D printed material) with the light having the first wavelength.
  • One of the optical properties may be absorption and conversion of light having the first wavelength into second light having a spectral power distribution different from the absorbed light, wherein the conversion is at least 20% of the absorbed light having the first wavelength (especially at least 30%, more especially at least 35%, most especially at least 40%, more especially at least 50%, like e.g. at least 60%, yet even more especially at least 70%).
  • the conversion of the light having the first wavelength may be determined under perpendicular radiation of the material with the light having the first wavelength. More especially, the absorption of light having the first wavelength is at least 30%, even more especially at least 50%, such as yet even more especially at least 60%.
  • the absorption of the light having the first wavelength may be determined under perpendicular radiation of the material with the light having the first wavelength. Further, in embodiments, is at least 30% of the absorbed light having the first wavelength, like at least 50%, even more especially at least 60%.
  • one or more materials of one or more parts comprised by either the filament, the layers, or the 3D item may have a high reflection and one or more other materials of one or more (other) parts (comprised by either the filament, the layers, or the 3D item, respectively) may have a low reflection.
  • a filament may have different parts along the filament which have different optical properties, such as different reflective properties.
  • the different layers when different layers are being produced during the 3D printing stage, the different layers may have different optical properties, such as different reflective properties.
  • a single layer may comprise two or more parts having different optical properties, respectively, such as different reflective properties.
  • the 3D printed item may comprise different parts which have different optical properties, such as different reflective properties.
  • one or more parts may have a high reflection and one or more other parts may have a low reflection.
  • one or more materials of one or more parts may have a high absorption and one or more other materials of one or more (other) parts may have a low absorption.
  • one or more parts may have a high absorption and one or more other parts may have a low absorption.
  • one or more materials of one or more parts may have a high transmission and one or more other materials of one or more (other) parts may have a low transmission.
  • one or more parts may have a high transmission and one or more other parts may have a low transmission.
  • a difference between high and low may be a ratio of at least 1.25, like at least 1.5, such as at least 2, of the ratio of optical property for the two different materials. For instance, this may be a ratio of high reflection, absorption, transmission, conversion, and low reflection, absorption, transmission, conversion, respectively. Likewise, such ratio may apply also in embodiments where the difference in material properties would refer to mechanical properties, and other material properties.
  • the term “light having the first wavelength”, and similar terms, may especially refer to light having a wavelength in the visible.
  • the term “first wavelength” may also refer to a plurality of different wavelengths.
  • light having the first wavelength may refer to essentially monochromatic light, but may also refer to ambient light or artificial white light.
  • terms like “absorption”, “conversion”, “transmission”, or “reflection” may especially refer to absorption, conversion, transmission, or reflection of light having one or more wavelengths in the visible (especially selected from the wavelength range of 380-780 nm).
  • the terms “absorption”, “conversion”, “transmission”, or “reflection” also the terms “light absorption”, “light conversion”, “light transmission”, or “light reflection”, respectively, may be applied.
  • the phrase “having a wavelength”, and similar phrases may specially indicate that the light has spectral power at such wavelength.
  • White light may thus have a plurality of wavelengths in the wavelength range of 380-780 nm.
  • a second material encloses a first material
  • the second material is transmissive for visible light having the first wavelength, such as for white light.
  • the transmission of visible light through the second material may in embodiments be at least 60% (one way), such as at least 80%, like even at least about 85%, such as at least about 90%.
  • a second part may at least partially enclose a first part, like a core-shell arrangement of a core comprising the first material and a shell comprising the second material.
  • a light transmissive material may be translucent or transparent.
  • the optical features of the sheet-like material may include being reflective for visible light, absorptive for visible light, transmissive for visible light, and/or luminescent upon receiving visible light.
  • the sheet-like material may be reflective for visible light.
  • the sheet-like material may especially be reflective to at least one color of visible light.
  • the optical features of the sheet-like material may provide desired optical effects to the 3D printed item.
  • the 3D printed item may be reflective to light of at least one color of visible light, hence when it receives light it may reflect it in other directions.
  • range light or “orange emission” especially relate to light having a wavelength in the range of about 590-620 nm.
  • red light or “red emission” especially relate to light having a wavelength in the range of about 620-780 nm.
  • pink light or “pink emission” refers to light having a blue and a red component.
  • cyan may refer to one or more wavelengths selected from the range of about 490-520 nm.
  • amber may refer to one or more wavelengths selected from the range of about 585-605 nm, such as about 590-600 nm.
  • Tc may be a glass-liquid transition temperature in embodiments where the core thermoplastic material is a core amorphous polymer material and Tc may yet be a melting temperature in embodiments where the core thermoplastic material is a core semicrystalline thermoplastic material.
  • the outer shell thermoplastic material may have an outer shell thermoplastic material transition temperature To. To may be a glass-liquid transition temperature in embodiments where the outer shell thermoplastic material is an amorphous shell thermoplastic material and To may yet be a melting temperature in embodiments where the outer shell thermoplastic material is an outer shell semicrystalline thermoplastic material. Further, in embodiments, To may especially be smaller than Tc. However, in other embodiments, To may yet be equal or higher than Tc.
  • the temperature of the nozzle may be higher than the outer shell thermoplastic material transition temperature and/or lower than the core thermoplastic material transition temperature. Therefore, in embodiments the 3D printing stage may comprise heating a printer nozzle to a nozzle temperature TN, wherein TO ⁇ TN. Note that the material transition temperatures are not necessarily different and the material transition temperature of the outer shell is not necessarily lower than of the core.
  • the two or more shells may further comprise one or more adhesive shells.
  • a first adhesive inner shell may comprise a first adhesive inner material.
  • the first adhesive inner material may adhere the core and the sheet-like material.
  • the first adhesive inner shell may at least partly cover the cover, as described above for a first shell covering the core.
  • a first adhesive inner shell may be used to improve the internal structure of the core-shell filament.
  • a second adhesive inner shell may comprise a second adhesive inner material.
  • the second adhesive inner material may adhere the sheet-like material and a shell surrounding the sheet-like material.
  • the second adhesive inner material may adhere the sheet-like material and the outer shell.
  • the second adhesive inner shell may at least partly cover the sheet-like material, as described above for a second shell covering a first shell.
  • a second adhesive outer shell may be used to improve the internal structure of the core-shell filament.
  • the method may comprise depositing during a printing stage 3D printable material.
  • the terms “fused deposition modeling (FDM) 3D printer” shortly the terms “3D printer”, “FDM printer” or “printer” may be used.
  • the printer nozzle may also be indicated as “nozzle” or sometimes as “extruder nozzle”.
  • the term “3D printable material” refers to the material to be deposited or printed
  • the term “3D printed material” refers to the material that is obtained after deposition. These materials may be essentially the same, as the 3D printable material may especially refer to the material in a printer head or extruder at elevated temperature and the 3D printed material refers to the same material, but in a later stage when deposited.
  • the 3D printable material may be printed as a filament and deposited as such.
  • the 3D printable material may be provided as filament or may be formed into a filament.
  • a filament comprising 3D printable material may be provided by the printer head and 3D printed.
  • the term “extrudate” may be used to define the 3D printable material downstream of the printer head, but not yet deposited. The latter may be indicated as “3D printed material”.
  • the extrudate may be considered to comprises 3D printable material, as the material is not yet deposited.
  • the material may thus be indicated as 3D printed material.
  • the materials may be the same material, as the thermoplastic material upstream of the printer head, downstream of the printer head, and when deposited, may essentially be the same material(s).
  • the present method comprises producing a 3D item by means of fused deposition modelling, wherein the 3D printing stages uses 3D printable filament to provide the 3D printed item.
  • 3D printable material may also be indicated as “printable material”.
  • polymeric material may in embodiments refer to a blend of different polymers, but may in embodiments also refer to essentially a single polymer type with different polymer chain lengths.
  • polymeric material or polymer may refer to a single type of polymers but may also refer to a plurality of different polymers.
  • printable material may refer to a single type of printable material but may also refer to a plurality of different printable materials.
  • printed material may refer to a single type of printed material but may also refer to a plurality of different printed materials.
  • Polymers can be amorphous, essentially having a glass transition temperature and not a melting temperature or can be (semi) crystalline, in general having both a glass transition temperature and a melting temperature, with in general the latter being larger than the former.
  • the glass temperature may e.g. be determined with differential scanning calorimetry.
  • the melting point or melting temperature can also be determined with differential scanning calorimetry.
  • the invention provides a fused deposition modeling 3D printer, comprising (a) a printer head comprising a printer nozzle, and (b) a filament providing device configured to provide a filament comprising 3D printable material to the printer head, wherein the fused deposition modeling 3D printer is configured to provide said 3D printable material to a substrate.
  • the phrase “printing on a substrate” and similar phrases include amongst others directly printing on the substrate, or printing on a coating on the substrate or printing on 3D printed material earlier printed on the substrate.
  • substrate is used, which may refer to a printing platform, a print bed, a substrate, a support, a build plate, or a building platform, etc., or a separate substrate thereon or comprised thereby.
  • the invention provides a method for producing a 3D item by means of fused deposition modeling.
  • Layer by layer printable material may be deposited, by which the 3D printed item may be generated (during the 3D printing stage).
  • the 3D printed item may show a characteristic ribbed structures (originating from the deposited filaments).
  • a further stage is executed, such as a finalization stage.
  • This stage may include removing the printed item from the receiver item and/or one or more post processing actions.
  • One or more post processing actions may be executed before removing the printed item from the receiver item and/or one more post processing actions may be executed after removing the printed item from the receiver item.
  • Post processing may include e.g. one or more of polishing, coating, adding a functional component, etc...
  • Post-processing may include smoothening the ribbed structures, which may lead to an essentially smooth surface.
  • the invention relates to a software product that can be used to execute the method described herein. Therefore, in yet a further aspect the invention also provides a computer program product, when running on a computer which is functionally coupled to or comprised by a fused deposition modeling 3D printer, is capable of bringing about the method as described herein.
  • the invention provides a software product, which, when running on a computer is capable of bringing about (one or more embodiments of) the method (for producing a 3D item by means of fused deposition modelling) as described herein.
  • the printable material in embodiments may comprise particulate material, i.e. particles embedded in the printable polymeric material, which particles form a substantially discontinuous phase.
  • the number of particles in the total mixture may especially not be larger than 60 vol.%, relative to the total volume of the printable material (including the (anisotropically conductive) particles) especially in applications for reducing thermal expansion coefficient.
  • For optical and surface related effect number of particles in the total mixture is equal to or less than 20 vol.%, such as up to 10 vol.%, relative to the total volume of the printable material (including the particles).
  • the 3D printable material may especially refer to a continuous phase of essentially thermoplastic material, wherein other materials, such as particles, may be embedded.
  • the 3D printed material especially refers to a continuous phase of essentially thermoplastic material, wherein other materials, such as particles, are embedded.
  • the particles may comprise one or more additives as defined above.
  • the 3D printable materials may comprise particulate additives.
  • the present invention describes a 3D printing method which may be based on a specific filament.
  • This filament may comprise a core and two or more shells, of which an inner shell comprises the sheet-like material.
  • This filament can be introduced in a 3D printer, and can be 3D printed, to provide a 3D printed item.
  • Such filament is herein also indicated as secondary filament or core-shell-shell filament (as will be further elucidated below).
  • such filament is introduced in a 3D printed with a core-shell nozzle, allowing 3D printing a 3D printed item wherein the extrudate comprises a core-shell extrudate, with the core being based on the core-shell filament (herein also indicated as primary filament, as will be further elucidated below), and with the (outer) shell based on other 3D printable material.
  • the 3D printed items obtained thereby, are herein also included.
  • a 3D printing method may also be used to first 3D print a secondary filament which may then be used for 3D printing a 3D printed item.
  • a core-shell filament comprising one or more shells, but not yet comprising one or more further shells, including the herein described outer shell, may be introduced into a 3D printer with a coreshell nozzle, with the primary filament being provided to the core, and 3D printable material to the shell of the core-shell nozzle.
  • Such primary filament, as well as the method for producing the core-shell-shell filament (secondary filament) from the primary filament, as well as the thus obtained core-shell filament are also part of the invention.
  • the invention provides a primary filament for producing a 3D item by means of fused deposition modelling.
  • the filament may comprise 3D printable material.
  • the 3D printable material may comprise a primary core-shell filament which may comprise a core and one or more shells at least partly enclosing the core.
  • the core may comprise a core thermoplastic material.
  • the one or more shells may comprise an inner shell, which may comprise a sheet-like material at least partly enclosing the core.
  • Such primary filament may be used in a core-shell printing process, wherein via the shell of the core-shell nozzle, an outer shell may be provided.
  • the invention provides a second filament for producing a 3D item by means of fused deposition modelling according to the primary core-shell filament as described above.
  • the 3D printable material may comprise a core-shell-shell filament comprising a core and two or more shells at least partly enclosing the core.
  • the two or more shells may comprise an outer shell which may comprise outer shell thermoplastic material (and an inner shell, which may comprise a sheet-like material at least partly enclosing the core).
  • the 3D printable material may comprises a core- shell-shell filament (or secondary filament) comprising (i) the primary core-shell filament and (ii) an outer shell, comprising outer shell thermoplastic material, wherein the outer shell at least partly encloses the inner shell.
  • a core- shell-shell filament or secondary filament
  • Such secondary filament may be used as filament for producing a 3D item by means of fused deposition modelling.
  • the present invention provides a method for producing a core-shell -shell filament.
  • the method may comprise feeding a primary core-shell filament to a nozzle core of a core-shell nozzle of a fused deposition modeling 3D printer.
  • the method may further comprise feeding outer shell thermoplastic material to a nozzle shell of the core shell of the fused deposition modeling 3D printer.
  • the method may comprise 3D printing the core-shell-shell filament.
  • the primary core-shell filament may comprise a core and one or more shells.
  • the one or more shells may at least partly enclose the core.
  • the core may comprise a core thermoplastic material.
  • An inner shell of the one or more shells may comprise the sheet-like material.
  • the sheet-like material may at least partly enclose the core.
  • a core-shell-shell filament may be provided comprising a core and at least two or more shells as described above.
  • the method described as such may in embodiments comprise a core-[shell] n printer.
  • the primary core-shell filament may have already been produced by the core-[shell] n printer, before being fed through the core nozzle of the core-[shell] n printer.
  • additional shells up to the number of n may be added on to the core-shell filament.
  • n may be at least 1, like 1 or 2.
  • the sheet-like material may comprise multiple layers. Especially, in embodiments the sheet-like material may comprise a sheet layer and a coating layer.
  • the sheet-like material may comprise a flexible white sheet.
  • the sheet-like material may be a flexible sheet with a white coating.
  • the sheet-like material may comprise a flexible sheet with a white reflective coating.
  • the layers in the sheet-like material may be composed of different materials.
  • the sheet-like material may comprise a flexible metal sheet layer.
  • the sheet-like material may also be a flexible sheet with a metal coating or the sheet-like material may be a flexible sheet with a white reflective coating.
  • the core-shell filament may have a low permeability.
  • the coreshell filament may be partly impermeable to a fluid.
  • such fluid may include gases and liquids at ambient temperature and pressure.
  • the two or more shells comprised by the core-shell filament may further comprise one or more adhesive shells.
  • a first adhesive inner shell may comprise a first adhesive inner material.
  • the first adhesive inner material may adhere the core and the sheet-like material.
  • the first adhesive inner shell may at least partly cover the cover, as described above for a first shell covering the core.
  • a first adhesive inner shell may be used to improve the internal structure of the core-shell filament.
  • a second adhesive inner shell comprised by the coreshell filament may comprise a second adhesive inner material.
  • the second adhesive inner material may adhere the sheet-like material and a shell surrounding the sheet-like material.
  • the second adhesive inner material may adhere the sheet-like material and the outer shell.
  • the second adhesive inner shell may at least partly cover the sheet-like material, as described above for a second shell covering a first shell.
  • a second adhesive outer shell may be used to improve the internal structure of the core-shell filament.
  • the core may be defined by a core diameter (de).
  • the sheet-like material may be defined by a sheet-like material thickness ds.
  • the outer shell may be defined by an outer shell thickness (do).
  • the thickness of the at least two or more shells will preferably not exceed the core diameter, which may provide most of the structural support to the core-shell filament.
  • ds may be higher than do.
  • the sheet-like material may be thicker than the outer shell, which provides adhesion between adjacent core-shell filaments.
  • the herein described method provides 3D printed items.
  • the invention also provides in a further aspect a 3D printed item obtainable with the herein described method.
  • a 3D printed item obtainable with the herein described method is provided.
  • the invention provides a 3D item comprising 3D printed material.
  • the 3D item may comprise one or more layers of 3D printed material. At least part of the one of the layers may comprise a core-shell layer.
  • the core-shell layer may comprise a core and two or more shells.
  • the two or more shells may at least partially enclose the core.
  • the core may comprise a core thermoplastic material.
  • An inner shell of the two or more shells may comprise the sheet-like material.
  • the sheet-like material may at least partially enclose the core.
  • Layers may be core-shell layers or may consist of a single material. Within a layer, there may also be a change in composition, for instance when a core-shell printing process was applied and during the printing process it was changed from printing a first material (and not printing a second material) to printing a second material (and not printing the first material). At least part of the 3D printed item may include a coating.
  • the 3D printed item may in embodiments have optical features.
  • the optical features of the 3D printed item may include being reflective for visible light, absorptive for visible light, transmissive for visible light, and/or luminescent upon receiving visible light.
  • the 3D printed item may be reflective for visible light.
  • the 3D printed item may especially be reflective to at least one color of visible light.
  • the 3D printed item may be reflective to light of at least one color of visible light, hence when it receives light it may reflect it in other directions.
  • a second adhesive inner shell comprised by the 3D printed item may comprise a second adhesive inner material.
  • the second adhesive inner material may adhere the sheet-like material and a shell surrounding the sheet-like material.
  • the second adhesive inner material may adhere the sheet-like material and the outer shell.
  • the second adhesive inner shell may at least partly cover the sheet-like material, as described above for a second shell covering a first shell.
  • a second adhesive outer shell may be used to improve the internal structure of the core-shell filament.
  • the 3D printed sheet-like material may be defined by a sheet-like material thickness ds’.
  • the thickness of the sheet-like material may essentially be the same in the filament as well as in the 3D printed layer(s).
  • the 3D printed outer shell may be defined by an outer shell thickness (do ).
  • the thickness of the at least two or more shells may in embodiments not exceed the core diameter, which may provide most of the structural support to the core-shell filament.
  • ds’ may be lower than do’.
  • the sheet-like material may be thinner than the outer shell, which provides adhesion between adjacent core-shell filaments.
  • the 3D printed material may comprise one or more of polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), and semicrystalline polytethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), poly(methyl methacrylate) (PMMA), polystyrene (PS), and styrene acrylic copolymers (SMMA).
  • PC polycarbonate
  • PE polyethylene
  • HDPE high-density polyethylene
  • PP polypropylene
  • POM polyoxymethylene
  • PEN polyethylene naphthalate
  • SAN polystyrene-acrylonitrile resin
  • PSU polysulfone
  • PPS polyphenylene sulfide
  • the (with the herein described method) obtained 3D printed item may be functional per se.
  • the 3D printed item may be a lens, a collimator, a reflector, etc...
  • the thus obtained 3D item may (alternatively) be used for decorative or artistic purposes.
  • the 3D printed item may include or be provided with a functional component.
  • the functional component may especially be selected from the group consisting of an optical component, an electrical component, and a magnetic component.
  • optical component especially refers to a component having an optical functionality, such as a lens, a mirror, a light transmissive element, an optical filter, etc...
  • the term optical component may also refer to a light source (like a LED).
  • electrical component may e.g.
  • the term magnetic component may e.g. refer to a magnetic connector, a coil, etc.
  • the functional component may comprise a thermal component (e.g. configured to cool or to heat an electrical component).
  • the functional component may be configured to generate heat or to scavenge heat, etc...
  • the 3D item may be configured as one or more of (i) at least part of a lighting device housing, (ii) at least part of a wall of a lighting chamber, and (iii) an optical element.
  • the 3D printed item may be used as mirror or lens, etc...
  • the 3D item may be configured as shade.
  • a device or system may comprise a plurality of different 3D printed items, having different functionalities.
  • the invention also provides a fused deposition modeling 3D printer, comprising (a) a printer head comprising a printer nozzle, and (b) a 3D printable material providing device configured to provide 3D printable material to the printer head, wherein the fused deposition modeling 3D printer is configured to provide said 3D printable material.
  • the element may comprise the control system.
  • the control system and element may not be physically coupled. Control can be done via wired and/or wireless control.
  • the term “control system” may also refer to a plurality of different control systems, which especially are functionally coupled, and of which e.g. one control system may be a master control system and one or more others may be slave control systems.
  • a control system may comprise or may be functionally coupled to a user interface.
  • the control system may also be configured to receive and execute instructions form a remote control.
  • the control system may be controlled via an App on a device, such as a portable device, like a Smartphone or I-phone, a tablet, etc..
  • the device is thus not necessarily coupled to the lighting system, but may be (temporarily) functionally coupled to the lighting system.
  • control system may (also) be configured to be controlled by an App on a remote device.
  • the control system of the lighting system may be a slave control system or control in a slave mode.
  • the lighting system may be identifiable with a code, especially a unique code for the respective lighting system.
  • the control system of the lighting system may be configured to be controlled by an external control system which has access to the lighting system on the basis of knowledge (input by a user interface of with an optical sensor (e.g. QR code reader) of the (unique) code.
  • the lighting system may also comprise means for communicating with other systems or devices, such as on the basis of Bluetooth, WIFI, LiFi, ZigBee, BLE or WiMAX, or another wireless technology.
  • the system, or apparatus, or device may execute an action in a “mode” or “operation mode” or “mode of operation”. Likewise, in a method an action or stage, or step may be executed in a “mode” or “operation mode” or “mode of operation” or “operational mode”.
  • mode may also be indicated as “controlling mode”. This does not exclude that the system, or apparatus, or device may also be adapted for providing another controlling mode, or a plurality of other controlling modes. Likewise, this may not exclude that before executing the mode and/or after executing the mode one or more other modes may be executed.
  • a control system may be available, that is adapted to provide at least the controlling mode.
  • the choice of such modes may especially be executed via a user interface, though other options, like executing a mode in dependence of a sensor signal or a (time) scheme, may also be possible.
  • the operation mode may in embodiments also refer to a system, or apparatus, or device, that can only operate in a single operation mode (i.e. “on”, without further tunability).
  • control system may control in dependence of one or more of an input signal of a user interface, a sensor signal (of a sensor), and a timer.
  • timer may refer to a clock and/or a predetermined time scheme.
  • Figs. 1A-1C schematically depict some general aspects of the 3D printer and of an embodiment of 3D printed material
  • Figs. 2A-2D schematically depict some aspects of the method and/or of an embodiment of 3D printed material, and/or of an item;
  • Figs. 3 A-C schematically depict some aspects of the 3D printable filament.
  • Fig. 4 schematically depicts the 3D printing stages that can be used to provide 3D printable filament and 3D printed item.
  • Fig. 5 schematically depicts an application.
  • pellets may be used as 3D printable material. Both can be extruded via the printer nozzle.
  • the 3D printer 500 is configured to generate a 3D item 1 by layer-wise depositing on a receiver item 550, which may in embodiments at least temporarily be cooled, a plurality of layers 322 wherein each layers 322 comprises 3D printable material 201, such as having a melting point T m .
  • the 3D printable material 201 may be deposited on a substrate 1550 (during the printing stage). By deposition, the 3D printable material 201 has become 3D printed material 202. 3D printable material 201 escaping from the nozzle 502 is also indicated as extrudate 321.
  • Reference 401 indicates thermoplastic material.
  • the 3D printer 500 may be configured to heat the filament 320 material upstream of the printer nozzle 502. This may e.g. be done with a device comprising one or more of an extrusion and/or heating function. Such device is indicated with reference 573, and is arranged upstream from the printer nozzle 502 (i.e. in time before the filament material leaves the printer nozzle 502).
  • the printer head 501 may (thus) include a liquefier or heater.
  • Reference 201 indicates printable material. When deposited, this material is indicated as (3D) printed material, which is indicated with reference 202.
  • Reference 572 indicates a spool or roller with material, especially in the form of a wire, which may be indicated as filament 320.
  • the 3D printer 500 transforms this in an extrudate 321 downstream of the printer nozzle which becomes a layer 322 on the receiver item or on already deposited printed material.
  • the diameter of the extrudate 321 downstream of the nozzle 502 is reduced relative to the diameter of the filament 320 upstream of the printer head 501.
  • the printer nozzle is sometimes (also) indicated as extruder nozzle.
  • Reference 575 indicates the filament providing device, which here amongst others include the spool or roller and the driver wheels, indicated with reference 576.
  • Reference Ax indicates a longitudinal axis or filament axis.
  • the receiver plate may also be moveable in one or two directions in the x-y plane (horizontal plane). Further, alternatively or additionally, in embodiments the receiver plate may also be rotatable about z axis (vertical). Hence, the control system may move the receiver plate in one or more of the x-direction, y- direction, and z-direction.
  • the printer can have a head can also rotate during printing.
  • Such a printer has an advantage that the printed material cannot rotate during printing.
  • Reference H indicates the height of a layer.
  • Layers are indicated with reference 322.
  • the layers have an essentially circular cross-section. Often, however, they may be flattened, such as having an outer shape resembling a flat oval tube or flat oval duct (i.e. a circular shaped bar having a diameter that is compressed to have a smaller height than width, wherein the sides (defining the width) are (still) rounded).
  • Fig. lb schematically depict some aspects of a fused deposition modeling 3D printer 500 (or part thereof), comprising a first printer head 501 comprising a printer nozzle 502, and optionally a receiver item (not depicted), which can be used to which can be used to provide a layer of 3D printed material 202.
  • Such fused deposition modeling 3D printer 500 may further comprise a 3D printable material providing device, configured to provide the 3D printable material 201 to the first printer head.
  • Fig. 1c very schematically depicts a single-walled 3D item 1.
  • Fig. 2A schematically depicts a method for producing a 3D item 1 by means of fused deposition modelling. The method comprises a 3D printing stage, wherein the 3D printing stage comprises layer-wise depositing 3D printable material 201 to provide the 3D item 1 comprising layers 322 of 3D printed material 202.
  • the 3D printable material 201 comprises a core-shell filament 320.
  • the core-shell filament 320 comprises a core 330 and two or more shells 340 at least partly enclosing the core.
  • the core 330 comprises a core thermoplastic material 331.
  • An inner shell 350 of the two or more shells 340 comprises a sheet-like material 351 at least partly enclosing the core 330.
  • An outer shell 360 of the two or more shells 340 comprises outer shell thermoplastic material 361.
  • Fig. 2A further schematically depicts an embodiment wherein the core-shell filament 320 of 3D printable material 201 is fed through the nozzle 502 of a 3D printer 500.
  • the sheet-like material 351 is one or more of (i) reflective for visible light, (ii) absorbs visible light, (iii) transmissive for visible light, (iv) luminescent upon receiving visible light; and wherein the other one or more shells (340) are transmissive for visible light.
  • the 3D printing stage comprises heating a 3D nozzle 502 of a 3D printer 500 to a nozzle temperature TN.
  • the outer shell thermoplastic material 361 has an outer shell thermoplastic material transition temperature To.
  • To is a glass-liquid transition temperature of the amorphous shell thermoplastic material or a melting temperature of the outer shell semicrystalline thermoplastic material 361.
  • TO ⁇ TN is a glass-liquid transition temperature of the amorphous shell thermoplastic material or a melting temperature of the outer shell semicrystalline thermoplastic material 361.
  • the 3D printable material 201 and the 3D printed material 202 comprise one or more of polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), and semi-crystalline polytethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), poly(methyl methacrylate) (PMMA), polystyrene (PS), and styrene acrylic copolymers (SMMA).
  • PC polycarbonate
  • PE polyethylene
  • HDPE high-density polyethylene
  • PP polypropylene
  • POM polyoxymethylene
  • PEN polyethylene naphthalate
  • SAN styrene-acrylonitrile resin
  • PSU polysulfone
  • PPS
  • Fig. 2B schematically depicts how a filament 320 (or primary filament 1320) (for producing a 3D item by means of fused deposition modelling) may be provided.
  • the filament 320 comprises printable material 201.
  • the 3D printable material comprises a primary core-shell filament 1320 of 3D printable material 201.
  • the primary core-shell filament 1320 comprises a core 1330 and one or more shells 1340 at least partly enclosing the core 1330; here by way of example a single shell 1340 is depicted.
  • the core 1330 comprises a core thermoplastic material 1331.
  • An inner shell 1350 of the one or more shells 1340 comprises a sheet-like material 1351 at least partly enclosing the core 1330.
  • 2B further schematically depicts an embodiment wherein the primary core-shell filament 1320 is fed through the nozzle 502 of a 3D printer 500, wherein the core material is with sheet material wrapped around it is fed through a single nozzle 502, a to obtain 3D printable material 201 comprising the primary core-shell filament 1320.
  • the primary core-shell filament 1320 may comprise an inner shell 1350 which is effectively an outer shell of the primary core-shell filament 1320, but which will be an inner shell in the core-shell-shell filament 2320 (see Fig. 2a).
  • Fig. 2C schematically depicts (also) a method for providing the filament 1320.
  • the method comprises feeding a primary core-shell filament 320 to a nozzle core 503 of a core-shell nozzle 502 of a fused deposition modeling 3D printer 500.
  • the method further comprises feeding sheet-like material 1351 to a nozzle shell 504 of the core-shell nozzle 502 of the fused deposition modeling 3D printer 500.
  • the method comprises 3D printing the core-shell-shell filament 1320.
  • the primary filament 1320 comprises a core 1330 and one or more shells 1340 at least partly enclosing the core 1330.
  • the core 1330 comprises a core thermoplastic material 1331.
  • An inner shell 1350 of the one or more shells 1340 comprises a sheet-like material 1351 at least partly enclosing the core 1330.
  • Fig. 2D schematically depicts a filament 320 for producing a 3D item (here effectively a layer 322 is depicted).
  • the 3D printable material comprises a core-shell-shell filament 2320 comprising two or more shells 2340 at least partly enclosing the core 1330.
  • An outer shell 2360 of the one or more shells 2340 comprises outer shell thermoplastic material 2361.
  • a primary filament 1320 is provided to the nozzle core 503 of the core-shell nozzle 502, and 3D printable material for yet another shell, the outer shell, is provided to the nozzle shell 504 of the core-shell nozzle 502.
  • the secondary filament 2320 is effectively formed which is deposited to become 3D printed layer 322.
  • Fig. 3 A-3B schematically depict a method to provide a 3D item 1 by means of fused deposition modelling.
  • the method comprises a 3D printing stage.
  • the 3D printing stage comprises layer-wise depositing 3D printable material 201 to provide the 3D item 1 comprising layers 322 of 3D printed material 202.
  • the 3D printable material 201 comprises a core-shell filament 320.
  • the core-shell filament comprises a core 330 and two or more shells 340 at least partly enclosing the core 330.
  • the core 330 comprises a core thermoplastic material 1330.
  • An inner shell 341 of the two or more shells 340 comprises a sheet-like material 1341 at least partly enclosing the core 330.
  • An outer shell 342 of the two or more shells 340 comprises outer shell thermoplastic material 1342.
  • the sheet-like material 1341 is reflective for light having a wavelength in the visible wavelength range.
  • the other one or more shells 340 are transmissive for visible light.
  • the sheet-like material 1341 comprises one or more of a flexible metal sheet, a flexible sheet with a metal coating, and a flexible white sheet.
  • the sheet-like material 1341 has a lower permeability for a fluid than the other one or more shells 340.
  • the core 330 has a core diameter de.
  • the sheet-like material 1341 has a sheet-like material thickness ds.
  • the outer shell 342 has an outer shell thickness do. In embodiments, do/dc ⁇ 0.5 and ds/dc ⁇ 0.5.
  • Fig. 3B depicts embodiments of filaments 320 wherein the two or more shells 340 comprise an inner shell 350 and an outer shell 360.
  • the core 330 has a core diameter de.
  • the inner shell 350 has a sheet-like material width Ws and a sheetlike material length Ls.
  • the outer shell 360 has an outer shell thermoplastic material width Wo and an outer shell thermoplastic material length Lo.
  • the filament has a filament width WF and a filament length LF.
  • Fig. 3C depicts embodiments wherein the layers 322 of 3D printed material 202 comprising the core 330, sheet-like material 350 and outer shell thermoplastic material 360.
  • Each of the layers 322 in the 3D printed item 1 can be defined by a core thickness De’, a sheet-like material thickness Ds’, and an outer shell thickness Do’.
  • Fig. 5 schematically depicts an embodiment of a lamp or luminaire, indicated with reference 2, which comprises a light source 10 for generating light 11.
  • the lamp may comprise a housing or shade or another element, which may comprise or be the 3D printed item 1.
  • the half sphere in cross-sectional view) schematically indicates a housing or shade.
  • the lamp or luminaire may be or may comprise a lighting device 1000 (which comprises the light source 10).
  • the lighting device 1000 comprises the 3D item 1.
  • the 3D item 1 may be configured as one or more of (i) at least part of a lighting device housing, (ii) at least part of a wall of a lighting chamber, and (iii) an optical element.
  • the 3D item may in embodiments be reflective for light source light 11 and/or transmissive for light source light 11.
  • the 3D item may e.g. be a housing or shade.
  • the housing or shade comprises the item part 400.
  • the item part 400 see also above.
  • the invention may be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer.
  • a device claim, or an apparatus claim, or a system claim enumerating several means, several of these means may be embodied by one and the same item of hardware.
  • the mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
  • the invention also provides a control system that may control the device, apparatus, or system, or that may execute the herein described method or process. Yet further, the invention also provides a computer program product, when running on a computer which is functionally coupled to or comprised by the device, apparatus, or system, controls one or more controllable elements of such device, apparatus, or system.
  • the invention may especially provide a filament for 3D printing, especially for FDM printing.
  • the invention provides a method for producing such filament.
  • the invention also provides a 3D printed item, which may be based on such filament.
  • the invention also provides a method for producing such 3D printed item on the basis of such filament.

Abstract

A method for producing a 3D item (1) by means of fused deposition modelling, the method comprising a 3D printing stage, wherein the 3D printing stage comprises: layer-wise depositing 3D printable material (201) to provide the 3D item (1) comprising layers (322) of 3D printed material (202), wherein the 3D printable material (201) comprises a core-shell filament (320), comprising a core (330) and two or more shells (340) at least partly enclosing the core (330), wherein the core (330) comprises a core thermoplastic material (331), wherein an inner shell (350) of the two or more shells (340) comprises a sheet-like material (351) at least partly enclosing the core (330), and wherein an outer shell (360) of the two or more shells (340) comprises outer shell thermoplastic material (361) at least partly enclosing the inner shell (350).

Description

Functional filaments for 3D printing
FIELD OF THE INVENTION
The invention relates to a method for manufacturing a 3D (printed) item. The invention also relates to the 3D (printed) item obtainable with such method. The invention also relates to a filament for use in the method for manufacturing the 3D (printed) item as well as a method for producing such filament. Further, the invention relates to a lighting device including such 3D (printed) item.
BACKGROUND OF THE INVENTION
3D printable material comprising filaments with multiple shells is known in the arts. WO2018199959A1, for instance, describes 3D printing filaments having core and shell thermoplastic extrudates. Each of the core and shell extrudates have glass transition temperatures, the glass transition temperature of the core being greater than or equal to the glass transition temperature of the shell. The ratio of the viscosity of the core thermoplastic extrudate at printing temperature, over the viscosity of the shell thermoplastic extrudate at printing temperature, is greater than 1, up to 20. The core and shell thermoplastic extrudates are miscible, or compatible with each other, or each comprise a polymer selected from the group consisting of polycarbonates, polyurethanes, polyesters, acrylonitrile butadiene styrene, styrene acrylonitrile, polyalkyl methacrylate, polystyrene, polysulfone, polylactic acid, polyetherimide, and polyimides.
SUMMARY OF THE INVENTION
Within the next 10-20 years, digital fabrication will increasingly transform the nature of global manufacturing. One of the aspects of digital fabrication is 3D printing. Currently, many different techniques have been developed in order to produce various 3D printed objects using various materials such as ceramics, metals, and polymers. 3D printing can also be used in producing molds which can then be used for replicating objects.
For the purpose of making molds, the use of polyjet technique has been suggested. This technique makes use of layer by layer deposition of photo-polymerisable material which is cured after each deposition to form a solid structure. While this technique produces smooth surfaces the photo curable materials are not very stable, and they also have relatively low thermal conductivity to be useful for injection molding applications.
The most widely used additive manufacturing technology is the process known as Fused Deposition Modeling (FDM). Fused deposition modeling (FDM) is an additive manufacturing technology commonly used for modeling, prototyping, and production applications. FDM works on an "additive" principle by laying down material in layers; a plastic filament or metal wire is unwound from a coil and supplies material to produce a part. Possibly, (for thermoplastics for example) the filament is melted and extruded before being laid down. FDM is a rapid prototyping technology. Other terms for FDM are “fused filament fabrication” (FFF) or “filament 3D printing” (FDP), which are considered to be equivalent to FDM. In general, FDM printers use a thermoplastic filament, which is heated to its melting point and then extruded, layer by layer, (or in fact filament after filament) to create a three-dimensional object. FDM printers are relatively fast, low cost and can be used for printing complicated 3D objects. Such printers are used in printing various shapes using various polymers. The technique is also being further developed in the production of LED luminaires and lighting solutions.
3D items composed of multi-layered stacks with various materials and functionality can be produced by FDM printing of different filaments in different layers. However, this may require relatively complex FDM printing processes. Using a single filament for FDM printing would be simpler to produce such 3D items, but it is difficult or expensive to obtain a single filament that can be used to produce multi-layered stacks with various functionalities using FDM printing.
Hence, it is an aspect of the invention to provide an alternative 3D printing method and/or 3D (printed) item which preferably further at least partly obviate(s) one or more of above-described drawbacks. The present invention may have as object to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.
Hence, in a first aspect the invention provides a method for producing a 3D item means of fused deposition modelling. The method may comprise a 3D printing stage. The 3D printing stage may comprise layer-wise depositing 3D printable material to provide the 3D item. The 3D item may comprise one or more layers of 3D printed material, especially a plurality of layers of 3D printed material. In embodiments, the 3D printable material may comprise a core-shell filament. Especially, the core-shell filament may comprise a core and two or more shells at least partly enclosing the core. The core may comprise a core thermoplastic material. Further, an inner shell of the two or more shells may comprise a sheet-like material at least partly enclosing the core. An outer shell of the two or more shells may comprise outer shell thermoplastic material. Further, the outer shell thermoplastic material may at least partly enclose the inner shell. Therefore, in embodiments the invention provides a method for producing a 3D item by means of fused deposition modelling, the method comprising a 3D printing stage, wherein the 3D printing stage comprises: layer-wise depositing 3D printable material to provide the 3D item comprising layers of 3D printed material, wherein the 3D printable material comprises a core-shell filament, comprising a core and two or more shells at least partly enclosing the core, wherein the core comprises a core thermoplastic material, wherein an inner shell of the two or more shells comprises a sheet-like material at least partly enclosing the core, and wherein an outer shell of the two or more shells comprises outer shell thermoplastic material at least partly enclosing the inner shell.
With the present method, a 3D printable filament comprising multiple shells may be provided that may then be used to create a 3D printed item. The inner shell may have properties that would be desired in the 3D printed item, e.g. optical features. This may allow for the production of 3D printed items that have the desired properties that would not be obtainable with conventional fused deposition modeling 3D printing purely based on thermoplastic materials, optionally with fillers. The proposed method may still retain all of the original benefits provided by fused deposition modeling 3D printing, being relatively fast, low cost, and able to produce complicated 3D printed items, while adding to the controllability of the material properties.
As indicated above, the invention provides a method for producing a 3D item by means of fused deposition modelling, wherein the method especially comprises a 3D printing stage. General embodiments in relation to 3D printing are also provided below.
Herein, especially the 3D printing stage comprises layer-wise depositing 3D printable material to provide the 3D item comprising one or more layers of 3D printed material, especially a plurality of layers of 3D printed material. The 3D item is further described below.
Especially, the 3D printable material (and 3D printed material) may comprise a core-shell structure. More especially, the 3D printable material may comprise a core-shell filament. In embodiments, the core-shell filament comprises a core. The core may comprise a core thermoplastic material. Possible characteristics and compositions of such thermoplastic material will be further described below. Especially, the core may essentially consist of thermoplastic material. However, the core may also comprise thermoplastic material with a filler (see further also below). The term “core thermoplastic material” may especially refer to thermoplastic material comprised by the core.
Hence, the core thermoplastic material may define a base material of the 3D printable material. The core thermoplastic material may be selected based on desired properties for the 3D printing process, e.g. flexibility. Further, the core thermoplastic may be selected based on desired properties for the 3D printed item, e.g. durability. Hence, the core thermoplastic material may be adjusted based on the specifics required for the 3D printing process and 3D item.
The core-shell filament may further comprise two or more shells. The two or more shells may at least partly enclose the core. Especially, in embodiments the two or more shells may fully enclose the core. More especially, the two or more shells may circumferentially enclose the core. Herein, the phrase “the outer shell at least partly encloses the inner shell”, and similar phrases, may refer to the outer shell being in contact (or “direct contact”) with the inner shell or may refer to an outer shell at least partly enclosing the inner shell but with one or more intermediate shells.
Note that the filament does not necessarily have a perfect circular crosssection. Hence, the term “circumferentially” herein is not limited to a circular surrounding, but may in embodiments e.g. also refer to an oval surrounding. Hence, the core may be enclosed by the at least two or more shells, providing a 3D printable filament with the core thermoplastic material enclosed within at least two or more shells.
Therefore, the core-shell filament may comprise a core with a first shell enclosing the core over at least part of its length and a second shell enclosing the first shell over at least part of its length. Further, in specific embodiments the first shell may enclose the core over 360°. Hence, unless indicated otherwise, it is herein assumed that the shell(s) enclose(s) the core over 360°. Hence, the term “enclose”, and similar terms, may in embodiments especially refer to circumferentially enclose. Especially, though not necessarily, the second shell encloses the first shell over the same length as the first shell encloses the core.
Therefore, in general over a substantial part of its length, the core of the filament is enclosed by the two or more shells, providing over the substantial part of its length a core-(shell)n cross-section, wherein n is at least 2. The filament may e.g. have a length (“filament length”) of at least about 50 cm, such as at least about 1 m. In embodiments, the length may be up to e.g. 50 m, such as up to about 20 m, like in embodiments up to about 15 m. However, other dimensions may also be possible. Over at least 80% of its length, more especially at least 90%, such as 100% of its length, the filament may have the core-shell structure, with multiple shells enclosing the core (i.e. a core-(shell)n cross-section).
The shells may provide additional features to the core-shell filament (and the 3D printed item). Especially, the shells may be selected based on desired properties for the 3D printing process, e.g. adhesive properties. Alternatively or additionally, the shells may be selected based on desired properties for the 3D printed item, e.g. optic features. Hence, the shells may be adjusted based on the specifics required for the 3D printing process and 3D item.
In embodiments, the at least two or more shells may comprise an inner shell. The inner shell may comprise a sheet-like material. The sheet-like material may at least partly cover the core, as also described above in relation to a first shell covering the core. The term “inner shell”, and similar terms, may refer to any shell between the core and the outer shell (see also below). Hence, the inner shell comprising the sheet-like material is not necessarily the shell that is in contact with the core.
The term “sheet-like material” may in embodiments especially refer to a material that is provided as sheet. Hence, the sheet like material may in embodiments be a monolithic body. Further, the sheet-like material may be relatively thin, and may in embodiments especially be thinner than a smallest cross-sectional dimension of the core (such as a diameter, or a width or height). Further, the term the term “sheet-like material” may refer to a material that is available as a sheet and then configured around the core (material) when assembling the filament (see also below). See further also below for embodiments.
The at least two or more shells may comprise an outer shell. The term “outer shell” especially refers to a shell most remote from the core. Hence, there may be one or more shells between the core and the outer shell. The outer shell may at least partly cover the inner shell, as also described above in relation to a second shell covering a first shell. The outer shell may comprise an outer shell thermoplastic material. The term “outer shell thermoplastic material” may especially refer to thermoplastic material comprised by the outer shell. The outer shell thermoplastic material may be comprised of any thermoplastic materials as described herein. The outer shell thermoplastic material may at least partly enclose the inner shell. In embodiments, the outer shell thermoplastic material may be transmissive for (visible) light, especially in such embodiments where the sheet-like material has optical features. Especially, the outer shell thermoplastic material may be transparent for (visible) light. In yet other embodiments, the outer shell thermoplastic may be translucent for (visible) light. The outer shell thermoplastic material may be selected based on desired properties for the 3D printing stage, e.g. flexibility. Further, the outer shell thermoplastic material may be selected based on desired properties for the 3D printed item, e.g. transparent for (visible) light.
Especially, the outer shell thermoplastic material may be adhesive to the surface of 3D printed layers during the 3D printing process, especially when the thermoplastic material of the layers is substantially the same. Especially, the outer shell thermoplastic material may cover different layers and adhere to each other within the 3D item. Hence, the other shell may facilitate that layers adhere to one another during the 3D printing stage. This may especially apply to commonly used 3D printing thermoplastic polymer materials (see elsewhere).
Hence, the core material and the material of the one or more outer shells may especially be thermoplastic materials that may be 3D printed using e.g. FDM printing. The inner shell, however, may comprise another material, and may in embodiments especially substantially not comprise a thermoplastic material that may be 3D printed using e.g. FDM printing (see further also below). Hence, the core material and the outer shell material(s) may be individually selected from thermoplastic polymers, or may individually be selected from materials comprise a thermoplastic polymer.
The thermoplastic polymer may be selected from the group consisting of ABS (acrylonitrile butadiene styrene), Nylon (or polyamide), Acetate (or cellulose), PLA (poly lactic acid), terephthalate (such as PET polyethylene terephthalate), Acrylic (polymethylacrylate, Perspex, polymethylmethacrylate, PMMA), Polypropylene (or polypropene), Polycarbonate (PC), Polystyrene (PS), PE (such as expanded- high impact- Polythene (or poly ethene), Low density (LDPE) High density (HDPE)), PVC (polyvinyl chloride) Polychloroethene, such as thermoplastic elastomer based on copolyester elastomers, polyurethane elastomers, polyamide elastomers polyolefine based elastomers, styrene based elastomers, etc.. Optionally, the 3D printable material may comprise a 3D printable material selected from the group consisting of Urea formaldehyde, Polyester resin, Epoxy resin, Melamine formaldehyde, thermoplastic elastomer, etc... Optionally, the 3D printable material may comprise a 3D printable material selected from the group consisting of a polysulfone. Elastomers, especially thermoplastic elastomers, may especially be interesting as they are flexible and may help obtaining relatively more flexible filaments comprising the thermally conductive material. A thermoplastic elastomer may comprise one or more of styrenic 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)).
Suitable thermoplastic materials, such as also mentioned in W02017/040893, may include one or more of polyacetals (e.g., polyoxyethylene and polyoxymethylene), poly(Ci-6 alkyl)acrylates, polyacrylamides, polyamides, (e.g., aliphatic polyamides, polyphthalamides, and polyaramides), polyamideimides, polyanhydrides, polyarylates, polyarylene ethers (e.g., polyphenylene ethers), polyarylene sulfides (e.g., polyphenylene sulfides), poly aryl sulfones (e.g., polyphenylene sulfones), polybenzothiazoles, polybenzoxazoles, polycarbonates (including polycarbonate copolymers such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbonate-ester-siloxanes), polyesters (e.g., polycarbonates, polyethylene terephthalates, polyethylene naphtholates, polybutylene terephthalates, polyarylates), and polyester copolymers such as polyester-ethers), polyetheretherketones, polyetherimides (including copolymers such as polyetherimidesiloxane copolymers), polyetherketoneketones, polyetherketones, polyethersulfones, polyimides (including copolymers such as polyimide- siloxane copolymers), poly(Ci-6 alkyl)methacrylates, polymethacrylamides, polynorbornenes (including copolymers containing norbornenyl units), polyolefins (e.g., polyethylenes, polypropylenes, polytetrafluoroethylenes, and their copolymers, for example ethylene- alpha- olefin copolymers), polyoxadiazoles, polyoxymethylenes, polyphthalides, polysilazanes, polysiloxanes, polystyrenes (including copolymers such as acrylonitrile-butadiene-styrene (ABS) and methyl methacrylate-butadiene-styrene (MBS)), poly sulfides, poly sulfonamides, polysulfonates, polysulfones, polythioesters, polytriazines, polyureas, polyurethanes, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinyl ketones, polyvinyl thioethers, polyvinylidene fluorides, or the like, or a combination comprising at least one of the foregoing thermoplastic polymers. Embodiments of polyamides may include, but are not limited to, synthetic linear polyamides, e.g., 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 a combination comprising at least one of the foregoing. Polyurethanes that can be used include aliphatic, cycloaliphatic, aromatic, and polycyclic polyurethanes, including those described above. Also useful are poly(Ci-6 alkyl)acrylates and poly(Ci-6 alkyl)methacrylates, which include, for instance, polymers of methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, n-butyl acrylate, and ethyl acrylate, etc. In embodiments, a polyolefine may include one or more of polyethylene, polypropylene, polybutylene, polymethylpentene (and co-polymers thereof), polynorbornene (and co-polymers thereof), poly 1 -butene, poly (3 -methylbutene), poly(4-m ethylpentene) and copolymers of ethylene with propylene, 1 -butene, 1 -hexene, 1 -octene, 1 -decene, 4-methyl-l -pentene and 1- octadecene.
In specific embodiments, the 3D printable material (and the 3D printed material) may comprise one or more of polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), and semi-crystalline polytethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), poly(methyl methacrylate) (PMMA), polystyrene (PS), and styrene acrylic copolymers (SMMA).
Especially, in embodiments the composition of the material of the outer shell(s) may differ from the composition of the material of the inner shell. In other embodiments, however, the composition of the material of the core may be similar, or the same, as the material of the outer shell. In embodiments wherein there are two or more outer shells, the compositions of the respective materials of at least two of the two or more outer shells may differ. They may differ in one or more of thermoplastic material, thermoplastic material composition, filler material, weight percentage of filler materials, etc. Especially, in embodiments wherein there are two or more outer shells, the compositions of the respective materials of at least two of the two or more outer shells may differ in type of thermoplastic material.
Here below, some further embodiments are described.
A indicated above, the inner shell may comprise a sheet-like material. In embodiments, the sheet-like material may be a monolithic body circumferentially enclosing the core. The sheet-like material may be a foil, such as a thin metal foil, circumferentially enclosing the core. The sheet-like material may be a multi-layer reflective polymer foil circumferentially enclosing the core.
In embodiments, the sheet-like material may comprise a metal material. Especially, the sheet-like material may comprise one or more of a flexible metal sheet or a flexible sheet with a metal coating. For instance, in embodiments the metal material may be an aluminum sheet or coating. Instead of (or in addition to) aluminum, the metal sheet or coating may be silver. Other solutions may also be possible, like stainless steel, other metals, or (their) metal alloys. In further embodiments, the metal sheet or coating may comprise a top layer that may be converted into an oxide of the metal. Such oxide layer may be provided via an anodizing process. Hence, in embodiments the metal sheet or coating may comprise anodized metal. However, other ways to provide an oxidized layer may also be possible. For instance, methods may be selected from anodization, electro-chemical oxidation, thermal oxidation, or chemical treatment of the metal material.
Hence, the metal material may provide the sheet-like material with desired features for the printing process, e.g. flexibility. Alternatively or additionally, the metal material may provide the sheet-like material with desired features for the 3D printed item, e.g. reflectivity of visible light.
The sheet-like material may comprise a metal coating. The metal coating on the sheet-like material may have a thickness selected from the range of 50 nm -100 nm.
The thickness of the sheet-like material may be selected from the range of 10 pm - 1 mm, such as 10 pm - 0.5 mm, like in embodiments 50 pm - 0.2 mm. The small thickness may allow configuring the material around the core and/or may provide bendable filaments.
In embodiments, the core (of the filament) may be defined by a core diameter (de). The core diameter is the diameter of the core in embodiments wherein the core has an essentially circular cross-section, which may generally be the case, and may be a circular equivalent diameter in embodiments wherein the core has no circular equivalent diameter.
Further, the sheet-like material may be defined by a sheet-like material thickness ds. Yet further, the outer shell may be defined by an outer shell thickness (do). Especially, in embodiments do/dc < 0.5 and/or ds/dc < 0.5. Hence, the thickness of the at least two or more shells may especially not exceed the core diameter, which may provide most of the structural support to the core-shell filament. Yet more especially, ds may be lower than do. Hence, the sheet-like material may be thinner than the outer shell, which may provide adhesion between adjacent core-shell filaments.
Note that during 3D printing, the dimensions, especially thicknesses, of the core and/or outer shells may be changed, whereas the thickness of the sheet-like material may essentially stay the same.
The sheet-like material may comprise at least one dimension that is substantially larger than a circular equivalent diameter of the core. For instance, the circular equivalent diameter of the core, indicated by de, and a dimension of the sheet-like material, like sheet-like material length Ls or sheet-like material width Ws, may comply with one or more of the following relations: (i) Ls>5*dc, more especially Ls>10*dc, such as Ls>20*dc, like in embodiments 10*dc <LS<LF, and (ii) Ws>5*dc, more especially Ws>10*dc, such as Ws>20*dc, like in embodiments 10*dc <WS<LF. Herein, LF is the filament length.
Especially one dimension of the sheet-like material may comply with one of the above-indicated relations, such as 10*dc <LS<LF. The outer shell thermoplastic material may also have dimensions such as the outer shell thermoplastic material length Lo or outer shell thermoplastic material width Wo, respectively. These dimensions may comply with one or more of the following relations: (i) Ls>Lo, more especially Ls>5*Lo, and (ii) Ws>Lo, more especially Ws>Lo. The filament itself may also have a width Fw which is essentially Fw>(dc+Ws+Wo).
The equivalent circular diameter (or ECD) (or “circular equivalent diameter”) of an (irregularly shaped) two-dimensional shape is the diameter of a circle of equivalent area. For instance, the equivalent circular diameter of a square with side a is 2*a*SQRT(l/7t). For a circle, the diameter is the same as the equivalent circular diameter. Would a circle in an xy-plane with a diameter D be distorted to any other shape (in the xy-plane), without changing the area size, than the equivalent circular diameter of that shape would be D.
Hence, the sheet-like material may in embodiments prevent a fluid from getting into contact with the core thermoplastic material. Especially, the sheet-like material may prevent gases and liquids at ambient temperature and pressure from getting into contact with the core thermoplastic material. This may prevent damage from (long-term) contact exposure with such gases and liquids. The term “damage” may in embodiments refer to degradation.
In embodiments, the sheet-like material may at least partly enclose the core by being spirally wrapped around the core material. In further embodiments, the sheet-like material may be wrapped around the core by being cut into segments, each segment being subsequently wrapped around a corresponding segment of core material. Hence, in embodiments the sheet-like material may be configured spirally wrapped around the core. In embodiments, the core may be funneled through the sheet-like material. In further embodiments, the sheet-like material may be deposited on the core material by a core-shell nozzle. In specific embodiments, the sheet-like material may have a width selected from the range of 7t*dc-5*7t*dc. This would allow 1-5 wrapping the sheet-like material around the core (material). Note however that other dimensions may also be possible. The core may comprise a core material, the inner shell comprises an inner shell material and the outer shell comprises an outer shell material. Optionally, one or more further shells may be available, in addition to the inner shell and the outer shell. Hence, there may be at least two different materials, as the material of the inner shell may differ from the material of the core and/or of the outer shell. Hence, in embodiments, there may be k different materials, wherein k is at least 2. The different materials may differ in one or more of optical properties, mechanical properties, and other material properties. Other material properties may include e.g. one or more of thermal conductivity, electrical conductivity, adhesiveness, etc. The mechanical properties may refer to one or more of flexibility, tensile strength, surface roughness, etc. Especially, the invention is herein (though not exclusively) explained in relation to optical properties of the sheet-like materials, but the invention is not limited to such embodiments.
In embodiments, the sheet-like material may have one or more optical features. Especially, in embodiments the sheet-like material may provide the 3D printed item with one or more desired optical features. In such embodiments, the other one or more shells may facilitate transmission of light so that the light may reach the sheet-like material and provided the desired optical feature(s). Therefore, in such embodiments, the other one or more shells may be transmissive for visible light.
As indicated above, a first material and a second material may differ in optical properties. In specific embodiments, the optical properties may be selected from the group of (a) absorption of light having a first wavelength, (b) diffuse reflection for light having the first wavelength, (c) specular reflection for light having the first wavelength, (d) transmission of light having the first wavelength, and (e) conversion of light having the first wavelength.
When different materials have different optical properties, this may especially indicate that they appear different to the human eye (or optical sensor) under identical observation conditions. For instance, two parts comprising the same materials, but appear different only due to a different arrangement of the parts, by which e.g. reflective properties differ to the human eye, may not be considered to have different optical properties, as e.g. under perpendicular observation, the parts may appear to have identical properties.
However, two materials of two or more parts having essentially the same absorption, but one part able to convert part of the absorbed light having the first wavelength and the other part not able to convert, lead to materials that appear different to the human eye (or optical sensor), and thus have different optical properties. The same may e.g. apply to materials of two or more parts having essentially the same transmission value, but one part having a low transparency due to the absorption of the light and the other part having a relatively low transparency due to scattering, may lead to materials that appear different to the human eye (or optical sensor), and thus have different optical properties. Other examples may also be possible. This may apply to any two materials of two or more parts having essentially the same optical feature, but one part having a different interaction with the light reaching the material than the other part, thus having different optical properties.
In specific embodiments the optical properties may be selected from the group (a) having a white color, (b) being black, (c) having metallic appearance, and (d) being light transparent. Alternatively or additionally, in specific embodiments the optical properties may be selected from the group (a) light reflectivity and (b) light transmissivity. Instead of the term “metallic appearance”, and similar terms, also the term “metallic color”, and similar terms, may be applied.
Hence, especially there may be a first material of the k materials having a first optical property and a second material of the k materials having a second optical different from the first optical property.
One of the optical properties may be >60% absorption (especially >70% absorption, more especially >75% absorption, most especially >80% absorption) of light having the first wavelength, wherein a conversion of the absorbed light (having the first wavelength) is <10% (especially the conversion of the absorbed light is <6%, more especially the conversion of the absorbed light is <3%, most especially the conversion of the absorbed light is <1%) of the absorbed light having the first wavelength. Hence, the light is absorbed without substantial conversion, like in the case of pigments. Especially, the absorption of the light having the first wavelength may be determined under perpendicular radiation of the material (or 3D printed material) with the light having the first wavelength.
One of the optical properties may be >60% reflection (especially >70% reflection, more especially >75% reflection, most especially >80% reflection) of light having the first wavelength. Hence, absorption of the light having the first wavelength may especially be less than 40% (especially less than 30%, more especially less than 25%, most especially less than 20%). Especially, the reflection of the light having the first wavelength may be determined under perpendicular radiation of the material (or 3D printed material) with the light having the first wavelength.
One of the optical properties may be >60% transmission of light having the first wavelength (especially >70% transmission, more especially >75% transmission, most especially >80% transmission). Hence, absorption and reflection may be less than 40% (especially less than 30%, more especially less than 25%, most especially less than 20%). Especially, the transmission of the light having the first wavelength may be determined under perpendicular radiation of the material (or 3D printed material) with the light having the first wavelength.
One of the optical properties may be absorption and conversion of light having the first wavelength into second light having a spectral power distribution different from the absorbed light, wherein the conversion is at least 20% of the absorbed light having the first wavelength (especially at least 30%, more especially at least 35%, most especially at least 40%, more especially at least 50%, like e.g. at least 60%, yet even more especially at least 70%). Especially, the conversion of the light having the first wavelength may be determined under perpendicular radiation of the material with the light having the first wavelength. More especially, the absorption of light having the first wavelength is at least 30%, even more especially at least 50%, such as yet even more especially at least 60%. As indicated above, especially the absorption of the light having the first wavelength may be determined under perpendicular radiation of the material with the light having the first wavelength. Further, in embodiments, is at least 30% of the absorbed light having the first wavelength, like at least 50%, even more especially at least 60%.
Hence, in embodiments one or more materials of one or more parts comprised by either the filament, the layers, or the 3D item may have a high reflection and one or more other materials of one or more (other) parts (comprised by either the filament, the layers, or the 3D item, respectively) may have a low reflection. Essentially, a filament may have different parts along the filament which have different optical properties, such as different reflective properties. In certain embodiments, when different layers are being produced during the 3D printing stage, the different layers may have different optical properties, such as different reflective properties. Alternatively or additionally, in certain embodiments, a single layer may comprise two or more parts having different optical properties, respectively, such as different reflective properties. In specific embodiments, the 3D printed item may comprise different parts which have different optical properties, such as different reflective properties. Hence, one or more parts may have a high reflection and one or more other parts may have a low reflection.
Hence, in embodiments one or more materials of one or more parts may have a high absorption and one or more other materials of one or more (other) parts may have a low absorption. Hence, one or more parts may have a high absorption and one or more other parts may have a low absorption. In embodiments one or more materials of one or more parts may have a high transmission and one or more other materials of one or more (other) parts may have a low transmission. Hence, one or more parts may have a high transmission and one or more other parts may have a low transmission.
In embodiments one or more materials of one or more parts may have a high conversion and one or more other materials of one or more (other) parts may have a low conversion. Hence, one or more parts may have a high conversion and one or more other parts may have a low conversion.
In embodiments, a difference between high and low (in relation to the optical properties) may be a ratio of at least 1.25, like at least 1.5, such as at least 2, of the ratio of optical property for the two different materials. For instance, this may be a ratio of high reflection, absorption, transmission, conversion, and low reflection, absorption, transmission, conversion, respectively. Likewise, such ratio may apply also in embodiments where the difference in material properties would refer to mechanical properties, and other material properties.
When two or more different optical properties are selected, these may in embodiments be individually selected from the group of high reflection, low reflection, high absorption, low absorption, high transmission, low transmission, high conversion, and low conversion. In other embodiments, two or more different optical properties are selected, these may in embodiments be individually selected from the group of high reflection, low reflection, high absorption, low absorption, high transmission but scattering, low transmission and scattering, high transmission and highly transparent, low transmission (and low transparency but essentially not due to scattering), high conversion, and low conversion.
Hence, in an example a first part may have a high absorption and a second part may have a low absorption. However, in another example a first part may have a high absorption and a second part may have a high transmission. In yet another example, a first part has a high conversion and a second part has a high transmission. In yet another example, a first part may have a low transmission (but is transparent) and a second part has a low transmission (but is scattering). Other examples may also be possible.
The term “light having the first wavelength”, and similar terms, may especially refer to light having a wavelength in the visible. The term “first wavelength” may also refer to a plurality of different wavelengths. For instance, light having the first wavelength may refer to essentially monochromatic light, but may also refer to ambient light or artificial white light. Hence, terms like “absorption”, “conversion”, “transmission”, or “reflection” may especially refer to absorption, conversion, transmission, or reflection of light having one or more wavelengths in the visible (especially selected from the wavelength range of 380-780 nm). Hence, instead of the terms “absorption”, “conversion”, “transmission”, or “reflection” also the terms “light absorption”, “light conversion”, “light transmission”, or “light reflection”, respectively, may be applied. The phrase “having a wavelength”, and similar phrases, may specially indicate that the light has spectral power at such wavelength. White light may thus have a plurality of wavelengths in the wavelength range of 380-780 nm.
In embodiments, especially a first optical property of a first material of the k materials and a second optical property of a second material of the k materials are different, and may be selected from the group comprising: (a) >60% absorption of light having the first wavelength and the conversion of the absorbed light having the first wavelength is <10% of the absorbed light having the first wavelength; (b) >60% reflection of light having the first wavelength; (c) >60% transmission of light having the first wavelength; and (d) absorption and conversion of light having the first wavelength into second light having a spectral power distribution different from the absorbed light, wherein the conversion is at least 20% of the absorbed light having the first wavelength.
When optical properties differ, and a second material encloses a first material, then it may be useful when the second material is transmissive for visible light having the first wavelength, such as for white light. For instance, the transmission of visible light through the second material may in embodiments be at least 60% (one way), such as at least 80%, like even at least about 85%, such as at least about 90%. For instance, a second part may at least partially enclose a first part, like a core-shell arrangement of a core comprising the first material and a shell comprising the second material. Especially, a light transmissive material may be translucent or transparent.
In embodiments, the sheet-like material may be reflective for light having a wavelength in the visible wavelength range, such as white light. Especially, the other one or more shells may then be transmissive for visible light.
The optical features of the sheet-like material may include being reflective for visible light, absorptive for visible light, transmissive for visible light, and/or luminescent upon receiving visible light. Especially, in embodiments the sheet-like material may be reflective for visible light. The sheet-like material may especially be reflective to at least one color of visible light. Hence, the optical features of the sheet-like material may provide desired optical effects to the 3D printed item. Especially, the 3D printed item may be reflective to light of at least one color of visible light, hence when it receives light it may reflect it in other directions.
The terms “visible” light or “visible emission” refer to radiation (herein especially indicated as “light”) having a wavelength in the range of about 380-780 nm. The terms “violet light” or “violet emission” especially relates to light having a wavelength in the range of about 380-440 nm. The terms “blue light” or “blue emission” especially relates to light having a wavelength in the range of about 440-495 nm (including some violet and cyan hues). The terms “green light” or “green emission” especially relate to light having a wavelength in the range of about 495-570 nm. The terms “yellow light” or “yellow emission” especially relate to light having a wavelength in the range of about 570-590 nm. The terms “orange light” or “orange emission” especially relate to light having a wavelength in the range of about 590-620 nm. The terms “red light” or “red emission” especially relate to light having a wavelength in the range of about 620-780 nm. The term “pink light” or “pink emission” refers to light having a blue and a red component. The term “cyan” may refer to one or more wavelengths selected from the range of about 490-520 nm. The term “amber” may refer to one or more wavelengths selected from the range of about 585-605 nm, such as about 590-600 nm.
In embodiments, the sheet-like material may be flexible. This may allow winding the sheet-like material around the core. Hence, the final 3D printable filament may e.g. be bendable to a radius of 20 mm or smaller, such as a radius of 10 mm or smaller, such as a radius of 5 mm and smaller. Hence, the dimensions of the (metal comprising) sheet-like material, but also from the 3D core and other shell(s) may be selected such that the 3D printable filament may e.g. be bendable to a radius of 20 mm or smaller, such as a radius of 5 mm and smaller. Hence, the sheet-like material may be suitable for the 3D printing process.
Further, the sheet-like material may comprise multiple layers. Especially, in embodiments the sheet-like material may comprise a sheet layer and a coating layer. For instance, the sheet-like material may comprise a flexible white sheet. In (other) embodiments, the sheet-like material may be a flexible sheet with a white coating. In (other) embodiments, the sheet-like material may comprise a flexible sheet with a white reflective coating. The layers in the sheet-like material may be composed of different materials. For instance, the sheet-like material may comprise a flexible metal sheet layer. The sheet-like material may also be a flexible sheet with a metal coating or the sheet-like material may be a flexible sheet with a white reflective coating. The core and at least the outer shell, and optionally more shells, may have the same or may have different transition temperatures. Hence, two or more of the core and the outer shells may have different transition temperatures. The “transition temperature” of a material is herein defined as the lowest temperature from a glass-liquid transition temperature (or “glass transition temperature”) and a melting temperature of the material.
In embodiments, the core thermoplastic material has a core thermoplastic material transition temperature Tc. Further, the outer shell thermoplastic material may have an outer shell thermoplastic material transition temperature To. Especially, in embodiments Tc may be higher than To. Hence, during the 3D printing process the outer shell thermoplastic material may transition into a more fluid state before the core thermoplastic material. This may facilitate the adhesion between 3D printed layers by the outer shell thermoplastic material while the core thermoplastic material is able to provide structural support. In embodiments, the core thermoplastic material may have a core thermoplastic material transition temperature Tc. Tc may be a glass-liquid transition temperature in embodiments where the core thermoplastic material is a core amorphous polymer material and Tc may yet be a melting temperature in embodiments where the core thermoplastic material is a core semicrystalline thermoplastic material. The outer shell thermoplastic material may have an outer shell thermoplastic material transition temperature To. To may be a glass-liquid transition temperature in embodiments where the outer shell thermoplastic material is an amorphous shell thermoplastic material and To may yet be a melting temperature in embodiments where the outer shell thermoplastic material is an outer shell semicrystalline thermoplastic material. Further, in embodiments, To may especially be smaller than Tc. However, in other embodiments, To may yet be equal or higher than Tc.
Especially, during printing the temperature of the nozzle may be higher than the outer shell thermoplastic material transition temperature and/or lower than the core thermoplastic material transition temperature. Therefore, in embodiments the 3D printing stage may comprise heating a printer nozzle to a nozzle temperature TN, wherein TO<TN. Note that the material transition temperatures are not necessarily different and the material transition temperature of the outer shell is not necessarily lower than of the core.
In embodiments, TN may be (selected from the range of) 50 - 150 °C. Especially, TN may be higher than To. However, higher nozzle temperatures may also be possible, such as e.g. selected from the range of 150-300 °C. In embodiments |TN-TO|>0°C, more especially | TN-TO |>10°C. In yet other embodiments, 10°C <| TN-TO |<50°C. In embodiments |Tc-To|>0°C, more especially | Tc-To |>10°C. In yet other embodiments, 10°C <| Tc-To |<50°C.
In embodiments, the sheet-like material may have a lower permeability for a fluid than the other one or more shells. Especially, the sheet-like material may be impermeable to a fluid. Specifically, such fluid may include gases and liquids at ambient temperature and pressure.
In embodiments, the two or more shells may further comprise one or more adhesive shells. A first adhesive inner shell may comprise a first adhesive inner material. The first adhesive inner material may adhere the core and the sheet-like material. The first adhesive inner shell may at least partly cover the cover, as described above for a first shell covering the core. Hence, in embodiments where the selected core material and the selected sheet-like material will adhere to one another less than desired, a first adhesive inner shell may be used to improve the internal structure of the core-shell filament.
In further embodiments, a second adhesive inner shell may comprise a second adhesive inner material. The second adhesive inner material may adhere the sheet-like material and a shell surrounding the sheet-like material. Especially, the second adhesive inner material may adhere the sheet-like material and the outer shell. The second adhesive inner shell may at least partly cover the sheet-like material, as described above for a second shell covering a first shell. Hence, in embodiments where the selected sheet-like material and a selected outer shell thermoplastic material will adhere to one another less than desired, a second adhesive outer shell may be used to improve the internal structure of the core-shell filament.
Note that in embodiments there may be no adhesive shell, in other embodiments there may be the first adhesive inner shell and/or the second adhesive inner shell. Other embodiments may also be possible.
As indicated above, the method may comprise depositing during a printing stage 3D printable material. Instead of the term “fused deposition modeling (FDM) 3D printer” shortly the terms “3D printer”, “FDM printer” or “printer” may be used. The printer nozzle may also be indicated as “nozzle” or sometimes as “extruder nozzle”. Herein, the term “3D printable material” refers to the material to be deposited or printed, and the term “3D printed material” refers to the material that is obtained after deposition. These materials may be essentially the same, as the 3D printable material may especially refer to the material in a printer head or extruder at elevated temperature and the 3D printed material refers to the same material, but in a later stage when deposited. In embodiments, the 3D printable material may be printed as a filament and deposited as such. The 3D printable material may be provided as filament or may be formed into a filament. Hence, whatever starting materials are applied, a filament comprising 3D printable material may be provided by the printer head and 3D printed. The term “extrudate” may be used to define the 3D printable material downstream of the printer head, but not yet deposited. The latter may be indicated as “3D printed material”. In fact, the extrudate may be considered to comprises 3D printable material, as the material is not yet deposited. Upon deposition of the 3D printable material or extrudate, the material may thus be indicated as 3D printed material. Essentially, the materials may be the same material, as the thermoplastic material upstream of the printer head, downstream of the printer head, and when deposited, may essentially be the same material(s).
As indicated above, the present method comprises producing a 3D item by means of fused deposition modelling, wherein the 3D printing stages uses 3D printable filament to provide the 3D printed item.
Herein, the term “3D printable material” may also be indicated as “printable material”. The term “polymeric material” may in embodiments refer to a blend of different polymers, but may in embodiments also refer to essentially a single polymer type with different polymer chain lengths. Hence, the terms “polymeric material” or “polymer” may refer to a single type of polymers but may also refer to a plurality of different polymers. The term “printable material” may refer to a single type of printable material but may also refer to a plurality of different printable materials. The term “printed material” may refer to a single type of printed material but may also refer to a plurality of different printed materials.
Hence, the term “3D printable material” may also refer to a combination of two or more materials. In general, these (polymeric) materials have a glass transition temperature Tg and/or a melting temperature Tm. The 3D printable material will be heated by the 3D printer before it leaves the nozzle to a temperature of at least the glass transition temperature, and in general at least the melting temperature. Hence, in a specific embodiment the 3D printable material comprises a thermoplastic polymer having a glass transition temperature (Tg) and /or a melting point (Tm), and the printer head action may comprise heating the 3D printable material above the glass transition and in embodiments above the melting temperature (especially when the thermoplastic polymer is a semi-crystalline polymer). In yet another embodiment, the 3D printable material comprises a (thermoplastic) polymer having a melting point (Tm), and the 3D printing stage may comprise heating the 3D printable material to be deposited on the receiver item to a temperature of at least the melting point. The glass transition temperature is in general not the same thing as the melting temperature. Melting is a transition which may occur in crystalline polymers. Melting may happen when the polymer chains fall out of their crystal structures, and become a disordered liquid. The glass transition may be a transition which happens to amorphous polymers; that is, polymers whose chains are not arranged in ordered crystals, but are just strewn around in any fashion, even though they are in the solid state. Polymers can be amorphous, essentially having a glass transition temperature and not a melting temperature or can be (semi) crystalline, in general having both a glass transition temperature and a melting temperature, with in general the latter being larger than the former. The glass temperature may e.g. be determined with differential scanning calorimetry. The melting point or melting temperature can also be determined with differential scanning calorimetry.
As indicated above, the invention may thus provide a method comprising providing a filament of 3D printable material and printing during a printing stage said 3D printable material on a substrate, to provide said 3D item. Materials that may especially qualify as 3D printable materials may be selected from the group consisting of metals, glasses, thermoplastic polymers, silicones, etc.
The printer nozzle may include a single opening. In other embodiments, the printer nozzle may be of the core-shell type, having two (or more) openings. The term “printer head” may also refer to a plurality of (different) printer heads; hence, the term “printer nozzle” may also refer to a plurality of (different) printer nozzles. The 3D printable material providing device may provide a filament comprising 3D printable material to the printer head or may provide the 3D printable material as such, with the printer head creating the filament comprising 3D printable material. Hence, in embodiments the invention provides a fused deposition modeling 3D printer, comprising (a) a printer head comprising a printer nozzle, and (b) a filament providing device configured to provide a filament comprising 3D printable material to the printer head, wherein the fused deposition modeling 3D printer is configured to provide said 3D printable material to a substrate.
The printable material may be printed on a receiver item. Especially, the receiver item can be the building platform or can be comprised by the building platform. The receiver item can also be heated during 3D printing. However, the receiver item may also be cooled during 3D printing.
The phrase “printing on a receiver item” and similar phrases include amongst others directly printing on the receiver item, or printing on a coating on the receiver item, or printing on 3D printed material earlier printed on the receiver item. The term “receiver item” may refer to a printing platform, a print bed, a substrate, a support, a build plate, or a building platform, etc... Instead of the term “receiver item” also the term “substrate” may be used. The phrase “printing on a receiver item” and similar phrases include amongst others also printing on a separate substrate on or comprised by a printing platform, a print bed, a support, a build plate, or a building platform, etc... Therefore, the phrase “printing on a substrate” and similar phrases include amongst others directly printing on the substrate, or printing on a coating on the substrate or printing on 3D printed material earlier printed on the substrate. Here below, further the term substrate is used, which may refer to a printing platform, a print bed, a substrate, a support, a build plate, or a building platform, etc., or a separate substrate thereon or comprised thereby.
In embodiments, the invention provides a method for producing a 3D item by means of fused deposition modeling. Layer by layer printable material may be deposited, by which the 3D printed item may be generated (during the 3D printing stage). The 3D printed item may show a characteristic ribbed structures (originating from the deposited filaments). However, it may also be possible that after a printing stage, a further stage is executed, such as a finalization stage. This stage may include removing the printed item from the receiver item and/or one or more post processing actions. One or more post processing actions may be executed before removing the printed item from the receiver item and/or one more post processing actions may be executed after removing the printed item from the receiver item. Post processing may include e.g. one or more of polishing, coating, adding a functional component, etc... Post-processing may include smoothening the ribbed structures, which may lead to an essentially smooth surface.
Further, the invention relates to a software product that can be used to execute the method described herein. Therefore, in yet a further aspect the invention also provides a computer program product, when running on a computer which is functionally coupled to or comprised by a fused deposition modeling 3D printer, is capable of bringing about the method as described herein.
Hence, in an aspect the invention (thus) provides a software product, which, when running on a computer is capable of bringing about (one or more embodiments of) the method (for producing a 3D item by means of fused deposition modelling) as described herein.
Especially, the core-shell filament comprising 3D printable material may thus comprise one or more thermoplastic materials. Such thermoplastic polymer materials have been described above. The term 3D printable material is further also elucidated below, but may especially refer to a thermoplastic material, optionally including additives, to a volume percentage of at maximum about 60%, especially at maximum about 30 vol.%, such as at maximum 20 vol.% (of the additives relative to the total volume of the thermoplastic material and additives).
The printable material may thus in embodiments comprise two phases. The printable material may comprise a phase of printable polymeric material, especially thermoplastic material (see also below), which phase is especially an essentially continuous phase. In this continuous phase of thermoplastic material polymer additives such as one or more of antioxidant, heat stabilizer, light stabilizer, ultraviolet light stabilizer, ultraviolet light absorbing additive, near infrared light absorbing additive, infrared light absorbing additive, plasticizer, lubricant, release agent, antistatic agent, anti-fog agent, antimicrobial agent, colorant, laser marking additive, surface effect additive, radiation stabilizer, flame retardant, anti-drip agent may be present. The additive may have useful properties selected from optical properties, mechanical properties, electrical properties, thermal properties, and mechanical properties (see also above).
The printable material in embodiments may comprise particulate material, i.e. particles embedded in the printable polymeric material, which particles form a substantially discontinuous phase. The number of particles in the total mixture may especially not be larger than 60 vol.%, relative to the total volume of the printable material (including the (anisotropically conductive) particles) especially in applications for reducing thermal expansion coefficient. For optical and surface related effect number of particles in the total mixture is equal to or less than 20 vol.%, such as up to 10 vol.%, relative to the total volume of the printable material (including the particles). Hence, the 3D printable material may especially refer to a continuous phase of essentially thermoplastic material, wherein other materials, such as particles, may be embedded. Likewise, the 3D printed material especially refers to a continuous phase of essentially thermoplastic material, wherein other materials, such as particles, are embedded. The particles may comprise one or more additives as defined above. Hence, in embodiments the 3D printable materials may comprise particulate additives.
The present invention describes a 3D printing method which may be based on a specific filament. This filament may comprise a core and two or more shells, of which an inner shell comprises the sheet-like material. This filament can be introduced in a 3D printer, and can be 3D printed, to provide a 3D printed item. Such filament is herein also indicated as secondary filament or core-shell-shell filament (as will be further elucidated below). However, it is not excluded that such filament is introduced in a 3D printed with a core-shell nozzle, allowing 3D printing a 3D printed item wherein the extrudate comprises a core-shell extrudate, with the core being based on the core-shell filament (herein also indicated as primary filament, as will be further elucidated below), and with the (outer) shell based on other 3D printable material. The 3D printed items obtained thereby, are herein also included.
Hence, a 3D printing method may also be used to first 3D print a secondary filament which may then be used for 3D printing a 3D printed item. For instance, a core-shell filament comprising one or more shells, but not yet comprising one or more further shells, including the herein described outer shell, may be introduced into a 3D printer with a coreshell nozzle, with the primary filament being provided to the core, and 3D printable material to the shell of the core-shell nozzle. Such primary filament, as well as the method for producing the core-shell-shell filament (secondary filament) from the primary filament, as well as the thus obtained core-shell filament, are also part of the invention.
Here below, first the various filaments are discussed, followed by the various methods, and then the 3D printed item is discussed.
In an aspect, the present invention provides a filament for producing a 3D item by means of fused deposition modelling. The filament may comprise 3D printable material. In embodiments, the 3D printable material may comprise a core-shell filament which may comprise a core and two or more shells at least partly enclosing the core. The core may comprise a core thermoplastic material. The two or more shells may comprise an inner shell, which may comprise a sheet-like material at least partly enclosing the close. The two or more shells may further comprise an outer shell, which may comprise an outer shell thermoplastic material.
In a further aspect, the invention provides a primary filament for producing a 3D item by means of fused deposition modelling. The filament may comprise 3D printable material. In embodiments, the 3D printable material may comprise a primary core-shell filament which may comprise a core and one or more shells at least partly enclosing the core. The core may comprise a core thermoplastic material. The one or more shells may comprise an inner shell, which may comprise a sheet-like material at least partly enclosing the core. Such primary filament may be used in a core-shell printing process, wherein via the shell of the core-shell nozzle, an outer shell may be provided.
In yet a further aspect, the invention provides a second filament for producing a 3D item by means of fused deposition modelling according to the primary core-shell filament as described above. The 3D printable material may comprise a core-shell-shell filament comprising a core and two or more shells at least partly enclosing the core. The two or more shells may comprise an outer shell which may comprise outer shell thermoplastic material (and an inner shell, which may comprise a sheet-like material at least partly enclosing the core). Hence, in embodiments the 3D printable material may comprises a core- shell-shell filament (or secondary filament) comprising (i) the primary core-shell filament and (ii) an outer shell, comprising outer shell thermoplastic material, wherein the outer shell at least partly encloses the inner shell. Such secondary filament may be used as filament for producing a 3D item by means of fused deposition modelling.
In a further aspect, the present invention provides a method for producing a core-shell -shell filament. The method may comprise feeding a primary core-shell filament to a nozzle core of a core-shell nozzle of a fused deposition modeling 3D printer. The method may further comprise feeding outer shell thermoplastic material to a nozzle shell of the core shell of the fused deposition modeling 3D printer. Subsequently, the method may comprise 3D printing the core-shell-shell filament. The primary core-shell filament may comprise a core and one or more shells. The one or more shells may at least partly enclose the core. The core may comprise a core thermoplastic material. An inner shell of the one or more shells may comprise the sheet-like material. The sheet-like material may at least partly enclose the core. Hence, a core-shell-shell filament may be provided comprising a core and at least two or more shells as described above.
The method described as such may in embodiments comprise a core-[shell]n printer. The primary core-shell filament may have already been produced by the core-[shell]n printer, before being fed through the core nozzle of the core-[shell]n printer. Hence, additional shells up to the number of n may be added on to the core-shell filament. Here, n may be at least 1, like 1 or 2.
The core-shell filament may in embodiments have optical features. The optical features of the core-shell filament may include being reflective for visible light, absorptive for visible light, transmissive for visible light, and/or luminescent upon receiving visible light. Especially, in embodiments the core-shell filament may be reflective for visible light. The core-shell filament may especially be reflective to at least one color of visible light. Especially, the core-shell filament may be reflective to light of at least one color of visible light, hence when it receives light it may reflect it in other directions.
Further, the sheet-like material may comprise multiple layers. Especially, in embodiments the sheet-like material may comprise a sheet layer and a coating layer. For instance, the sheet-like material may comprise a flexible white sheet. In (other) embodiments, the sheet-like material may be a flexible sheet with a white coating. In (other) embodiments, the sheet-like material may comprise a flexible sheet with a white reflective coating. The layers in the sheet-like material may be composed of different materials. For instance, the sheet-like material may comprise a flexible metal sheet layer. The sheet-like material may also be a flexible sheet with a metal coating or the sheet-like material may be a flexible sheet with a white reflective coating.
The core-shell filament may have a low permeability. Especially, the coreshell filament may be partly impermeable to a fluid. Specifically, such fluid may include gases and liquids at ambient temperature and pressure.
In embodiments, the two or more shells comprised by the core-shell filament may further comprise one or more adhesive shells. A first adhesive inner shell may comprise a first adhesive inner material. The first adhesive inner material may adhere the core and the sheet-like material. The first adhesive inner shell may at least partly cover the cover, as described above for a first shell covering the core. Hence, in embodiments where the selected core material and the selected sheet-like material will adhere to one another less than desired, a first adhesive inner shell may be used to improve the internal structure of the core-shell filament.
In further embodiments, a second adhesive inner shell comprised by the coreshell filament may comprise a second adhesive inner material. The second adhesive inner material may adhere the sheet-like material and a shell surrounding the sheet-like material. Especially, the second adhesive inner material may adhere the sheet-like material and the outer shell. The second adhesive inner shell may at least partly cover the sheet-like material, as described above for a second shell covering a first shell. Hence, in embodiments where the selected sheet-like material and a selected outer shell thermoplastic material will adhere to one another less than desired, a second adhesive outer shell may be used to improve the internal structure of the core-shell filament.
In embodiments of the core-shell filament, the core may be defined by a core diameter (de). Further, the sheet-like material may be defined by a sheet-like material thickness ds. Yet further, the outer shell may be defined by an outer shell thickness (do). Especially, in embodiments do/dc < 0.5 and ds/dc < 0.5. Hence, the thickness of the at least two or more shells will preferably not exceed the core diameter, which may provide most of the structural support to the core-shell filament. Yet more especially, ds may be higher than do. Hence, the sheet-like material may be thicker than the outer shell, which provides adhesion between adjacent core-shell filaments. In specific embodiments, the core-shell filament may comprise one or more of polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), and semi-crystalline polytethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), poly(m ethyl methacrylate) (PMMA), polystyrene (PS), and styrene acrylic copolymers (SMMA) (as 3D printable material). However, other materials may also be possible (see also above). Hence, the 3D printed material may also comprise one or more of such materials.
The herein described method provides 3D printed items. Hence, the invention also provides in a further aspect a 3D printed item obtainable with the herein described method. In a further aspect a 3D printed item obtainable with the herein described method is provided. Especially, the invention provides a 3D item comprising 3D printed material. Especially, the 3D item may comprise one or more layers of 3D printed material. At least part of the one of the layers may comprise a core-shell layer. The core-shell layer may comprise a core and two or more shells. The two or more shells may at least partially enclose the core. The core may comprise a core thermoplastic material. An inner shell of the two or more shells may comprise the sheet-like material. The sheet-like material may at least partially enclose the core. An outer shell of the two or more shells may comprise an outer shell thermoplastic material. Therefore, in embodiments the invention also provides a 3D item comprising 3D printed material, wherein the 3D item comprises a plurality of layers of 3D printed material, wherein at least part of the one of the layers comprises a core-shell layer; wherein the core-shell layer comprises a core and two or more shells; wherein the two or more shells at least partly enclose the core ; wherein the core comprises a core thermoplastic material; wherein an inner shell of the two or more shells comprises a sheet-like material at least partly enclosing the core; and wherein an outer shell comprises an outer shell thermoplastic material. The phrase “at least part of the one of the layers may comprise a coreshell layer”, and similar phrases, may indicated that one or more layers may comprise a core shell layer, or a part of a layer (of the plurality of layers) may comprise a core shell layer, or different parts of a layer or different parts of different layers may comprise a core shell layers.
The 3D printed item may comprise a plurality of layers on top of each other, i.e. stacked layers. The width (thickness) and height of (individually 3D printed) layers may e.g. in embodiments be selected from the range of 100 - 5000 pm, such as 200-2500 pm, with the height in general being smaller than the width. For instance, the ratio of height and width may be equal to or smaller than 0.8, such as equal to or smaller than 0.6.
Layers may be core-shell layers or may consist of a single material. Within a layer, there may also be a change in composition, for instance when a core-shell printing process was applied and during the printing process it was changed from printing a first material (and not printing a second material) to printing a second material (and not printing the first material). At least part of the 3D printed item may include a coating.
Some specific embodiments in relation to the 3D printed item have already been elucidated above when discussing the method. Below, some specific embodiments in relation to the 3D printed item are discussed in more detail.
The 3D printed item may in embodiments have optical features. The optical features of the 3D printed item may include being reflective for visible light, absorptive for visible light, transmissive for visible light, and/or luminescent upon receiving visible light. Especially, in embodiments the 3D printed item may be reflective for visible light. The 3D printed item may especially be reflective to at least one color of visible light. Especially, the 3D printed item may be reflective to light of at least one color of visible light, hence when it receives light it may reflect it in other directions.
Further, the sheet-like material may comprise multiple layers. Especially, the sheet-like material may comprise a sheet layer and a coating layer. For instance, the sheetlike material may be a flexible sheet with a white coating. Especially, the sheet-like material may be a flexible sheet with a white reflective coating. The layers in the sheet-like material may be composed of different materials. For instance, the sheet-like material may comprise a flexible metal sheet layer. The sheet-like material may also be a flexible sheet with a metal coating. Especially, the sheet-like material may be a flexible sheet with a white reflective coating. The sheet-like material may comprise a flexible metal sheet layer with a white reflective coating.
The 3D printed item may have a low permeability. Especially, the 3D printed item may be partly impermeable to a fluid. Specifically, such fluid may include gases and liquids at ambient temperature and pressure.
In embodiments, the two or more shells comprised by the 3D printed item may further comprise one or more adhesive shells. A first adhesive inner shell may comprise a first adhesive inner material. The first adhesive inner material may adhere the core and the sheet-like material. The first adhesive inner shell may at least partly cover the cover, as described above for a first shell covering the core. Hence, in embodiments where the selected core material and the selected sheet-like material will adhere to one another less than desired, a first adhesive inner shell may be used to improve the internal structure of the core-shell filament.
In further embodiments, a second adhesive inner shell comprised by the 3D printed item may comprise a second adhesive inner material. The second adhesive inner material may adhere the sheet-like material and a shell surrounding the sheet-like material. Especially, the second adhesive inner material may adhere the sheet-like material and the outer shell. The second adhesive inner shell may at least partly cover the sheet-like material, as described above for a second shell covering a first shell. Hence, in embodiments where the selected sheet-like material and a selected outer shell thermoplastic material will adhere to one another less than desired, a second adhesive outer shell may be used to improve the internal structure of the core-shell filament.
In embodiments of the 3D printed item, the 3D printed core may be defined by a core diameter (de ). Here, the diameter of the core in the 3D printed item may be the circular equivalent as the core has not necessarily a perfect circular cross-sections but may also have a substantially oval or rounded square cross-sectional shape (due to the 3D printing process).
Further, the 3D printed sheet-like material may be defined by a sheet-like material thickness ds’. However, it is assumed that the thickness of the sheet-like material may essentially be the same in the filament as well as in the 3D printed layer(s). Yet further, the 3D printed outer shell may be defined by an outer shell thickness (do ). Especially, in embodiments do /dc’ < 0.5 and ds’/dc’ < 0.5. Hence, the thickness of the at least two or more shells may in embodiments not exceed the core diameter, which may provide most of the structural support to the core-shell filament. Yet more especially, ds’ may be lower than do’. Hence, the sheet-like material may be thinner than the outer shell, which provides adhesion between adjacent core-shell filaments.
In specific embodiments, see also above, the 3D printed material may comprise one or more of polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), and semicrystalline polytethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), poly(methyl methacrylate) (PMMA), polystyrene (PS), and styrene acrylic copolymers (SMMA). However, other materials may also be possible (see also above). The (with the herein described method) obtained 3D printed item may be functional per se. For instance, the 3D printed item may be a lens, a collimator, a reflector, etc... The thus obtained 3D item may (alternatively) be used for decorative or artistic purposes. The 3D printed item may include or be provided with a functional component. The functional component may especially be selected from the group consisting of an optical component, an electrical component, and a magnetic component. The term “optical component” especially refers to a component having an optical functionality, such as a lens, a mirror, a light transmissive element, an optical filter, etc... The term optical component may also refer to a light source (like a LED). The term “electrical component” may e.g. refer to an integrated circuit, PCB, a battery, a driver, but also a light source (as a light source may be considered an optical component and an electrical component), etc. The term magnetic component may e.g. refer to a magnetic connector, a coil, etc... Alternatively, or additionally, the functional component may comprise a thermal component (e.g. configured to cool or to heat an electrical component). Hence, the functional component may be configured to generate heat or to scavenge heat, etc...
As indicated above, the 3D printed item maybe used for different purposes. Amongst others, the 3D printed item maybe used in lighting. Hence, in yet a further aspect the invention also provides a lighting device comprising the 3D item as defined herein. In a specific aspect the invention provides a lighting system comprising (a) a light source configured to provide (visible) light source light and (b) the 3D item as defined herein, wherein 3D item may be configured as one or more of (i) at least part of a housing, (ii) at least part of a wall of a lighting chamber, and (iii) a functional component, wherein the functional component may be selected from the group consisting of an optical component, a support, an electrically insulating component, an electrically conductive component, a thermally insulating component, and a thermally conductive component. Hence, in specific embodiments the 3D item may be configured as one or more of (i) at least part of a lighting device housing, (ii) at least part of a wall of a lighting chamber, and (iii) an optical element. As a relative smooth surface may be provided, the 3D printed item may be used as mirror or lens, etc... In embodiments, the 3D item may be configured as shade. A device or system may comprise a plurality of different 3D printed items, having different functionalities.
Returning to the 3D printing process, a specific 3D printer may be used to provide the 3D printed item described herein. Therefore, in yet a further aspect the invention also provides a fused deposition modeling 3D printer, comprising (a) a printer head comprising a printer nozzle, and (b) a 3D printable material providing device configured to provide 3D printable material to the printer head, wherein the fused deposition modeling 3D printer is configured to provide said 3D printable material.
Especially, the 3D printer comprises a controller (or is functionally coupled to a controller) that is configured to execute in a controlling mode (or “operation mode”) the method as described herein. Instead of the term “controller” also the term “control system” (see e.g. above) may be applied.
The term “controlling” and similar terms especially refer at least to determining the behavior or supervising the running of an element. Hence, herein “controlling” and similar terms may e.g. refer to imposing behavior to the element (determining the behavior or supervising the running of an element), etc., such as e.g. measuring, displaying, actuating, opening, shifting, changing temperature, etc.. Beyond that, the term “controlling” and similar terms may additionally include monitoring. Hence, the term “controlling” and similar terms may include imposing behavior on an element and also imposing behavior on an element and monitoring the element. The controlling of the element can be done with a control system, which may also be indicated as “controller”. The control system and the element may thus at least temporarily, or permanently, functionally be coupled. The element may comprise the control system. In embodiments, the control system and element may not be physically coupled. Control can be done via wired and/or wireless control. The term “control system” may also refer to a plurality of different control systems, which especially are functionally coupled, and of which e.g. one control system may be a master control system and one or more others may be slave control systems. A control system may comprise or may be functionally coupled to a user interface.
The control system may also be configured to receive and execute instructions form a remote control. In embodiments, the control system may be controlled via an App on a device, such as a portable device, like a Smartphone or I-phone, a tablet, etc.. The device is thus not necessarily coupled to the lighting system, but may be (temporarily) functionally coupled to the lighting system.
Hence, in embodiments the control system may (also) be configured to be controlled by an App on a remote device. In such embodiments the control system of the lighting system may be a slave control system or control in a slave mode. For instance, the lighting system may be identifiable with a code, especially a unique code for the respective lighting system. The control system of the lighting system may be configured to be controlled by an external control system which has access to the lighting system on the basis of knowledge (input by a user interface of with an optical sensor (e.g. QR code reader) of the (unique) code. The lighting system may also comprise means for communicating with other systems or devices, such as on the basis of Bluetooth, WIFI, LiFi, ZigBee, BLE or WiMAX, or another wireless technology.
The system, or apparatus, or device may execute an action in a “mode” or “operation mode” or “mode of operation”. Likewise, in a method an action or stage, or step may be executed in a “mode” or “operation mode” or “mode of operation” or “operational mode”. The term “mode” may also be indicated as “controlling mode”. This does not exclude that the system, or apparatus, or device may also be adapted for providing another controlling mode, or a plurality of other controlling modes. Likewise, this may not exclude that before executing the mode and/or after executing the mode one or more other modes may be executed.
However, in embodiments a control system may be available, that is adapted to provide at least the controlling mode. Would other modes be available, the choice of such modes may especially be executed via a user interface, though other options, like executing a mode in dependence of a sensor signal or a (time) scheme, may also be possible. The operation mode may in embodiments also refer to a system, or apparatus, or device, that can only operate in a single operation mode (i.e. “on”, without further tunability).
Hence, in embodiments, the control system may control in dependence of one or more of an input signal of a user interface, a sensor signal (of a sensor), and a timer. The term “timer” may refer to a clock and/or a predetermined time scheme.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts, and in which:
Figs. 1A-1C schematically depict some general aspects of the 3D printer and of an embodiment of 3D printed material;
Figs. 2A-2D schematically depict some aspects of the method and/or of an embodiment of 3D printed material, and/or of an item;
Figs. 3 A-C schematically depict some aspects of the 3D printable filament.
Fig. 4 schematically depicts the 3D printing stages that can be used to provide 3D printable filament and 3D printed item.
Fig. 5 schematically depicts an application.
The schematic drawings are not necessarily to scale. DETAILED DESCRIPTION OF THE EMBODIMENTS
Fig. la schematically depicts some aspects of the 3D printer. Reference 500 indicates a 3D printer. Reference 530 indicates the functional unit configured to 3D print, especially FDM 3D printing; this reference may also indicate the 3D printing stage unit. Here, only the printer head for providing 3D printed material, such as an FDM 3D printer head is schematically depicted. Reference 501 indicates the printer head. The 3D printer of the present invention may especially include a plurality of printer heads (see below). Reference 502 indicates a printer nozzle. The 3D printer of the present invention may especially include a plurality of printer nozzles, though other embodiments are also possible. Reference 320 indicates a filament of printable 3D printable material (such as indicated above).
Instead of a filament also pellets may be used as 3D printable material. Both can be extruded via the printer nozzle.
For the sake of clarity, not all features of the 3D printer have been depicted, only those that are of especial relevance for the present invention (see further also below). Reference 321 indicates extrudate (of 3D printable material 201).
The 3D printer 500 is configured to generate a 3D item 1 by layer-wise depositing on a receiver item 550, which may in embodiments at least temporarily be cooled, a plurality of layers 322 wherein each layers 322 comprises 3D printable material 201, such as having a melting point Tm. The 3D printable material 201 may be deposited on a substrate 1550 (during the printing stage). By deposition, the 3D printable material 201 has become 3D printed material 202. 3D printable material 201 escaping from the nozzle 502 is also indicated as extrudate 321. Reference 401 indicates thermoplastic material.
The 3D printer 500 may be configured to heat the filament 320 material upstream of the printer nozzle 502. This may e.g. be done with a device comprising one or more of an extrusion and/or heating function. Such device is indicated with reference 573, and is arranged upstream from the printer nozzle 502 (i.e. in time before the filament material leaves the printer nozzle 502). The printer head 501 may (thus) include a liquefier or heater. Reference 201 indicates printable material. When deposited, this material is indicated as (3D) printed material, which is indicated with reference 202.
Reference 572 indicates a spool or roller with material, especially in the form of a wire, which may be indicated as filament 320. The 3D printer 500 transforms this in an extrudate 321 downstream of the printer nozzle which becomes a layer 322 on the receiver item or on already deposited printed material. In general, the diameter of the extrudate 321 downstream of the nozzle 502 is reduced relative to the diameter of the filament 320 upstream of the printer head 501. Hence, the printer nozzle is sometimes (also) indicated as extruder nozzle. Arranging layer 322 by layer 322 and/or layer 322t on layer 322, a 3D item 1 may be formed. Reference 575 indicates the filament providing device, which here amongst others include the spool or roller and the driver wheels, indicated with reference 576.
Reference Ax indicates a longitudinal axis or filament axis.
Reference 300 schematically depicts a control system. The control system may be configured to control the 3D printer 500. The control system 300 may be comprised or functionally coupled to the 3D printer 500. The control system 300 may further comprise or be functionally coupled to a temperature control system configured to control the temperature of the receiver item 550 and/or of the printer head 501. Such temperature control system may include a heater which is able to heat the receiver item 550 to at least a temperature of 50 °C, but especially up to a range of about 350 °C, such as at least 200 °C.
Alternatively or additionally, in embodiments the receiver plate may also be moveable in one or two directions in the x-y plane (horizontal plane). Further, alternatively or additionally, in embodiments the receiver plate may also be rotatable about z axis (vertical). Hence, the control system may move the receiver plate in one or more of the x-direction, y- direction, and z-direction.
Alternatively, the printer can have a head can also rotate during printing. Such a printer has an advantage that the printed material cannot rotate during printing.
Layers are indicated with reference 322, and have a layer height H and a layer width W.
Note that the 3D printable material is not necessarily provided as filament 320 to the printer head. Further, the filament 320 may also be produced in the 3D printer 500 from pieces of 3D printable material. Hence, the nozzle 502 may effectively produce from particulate 3D printable material 201 a filament 320, which upon deposition is indicated as layer 322 (comprising 3D printed material 202). Note that during printing the shape of the extrudate may further be changes, e.g. due to the nozzle smearing out the 3D printable material 201 / 3D printed material 202. Fig. lb schematically depicts that also particulate 3D printable material 201 may be used as feed to the printer nozzle 502.
Reference D indicates the diameter of the nozzle (through which the 3D printable material 201 is forced). However, the nozzle is not necessarily circular. Fig. lb schematically depicts in 3D in more detail the printing of the 3D item 1 under construction. Here, in this schematic drawing the ends of the layers in a single plane are not interconnected, though in reality this may in embodiments be the case.
Reference H indicates the height of a layer. Layers are indicated with reference 322. Here, the layers have an essentially circular cross-section. Often, however, they may be flattened, such as having an outer shape resembling a flat oval tube or flat oval duct (i.e. a circular shaped bar having a diameter that is compressed to have a smaller height than width, wherein the sides (defining the width) are (still) rounded).
Hence, Fig. la schematically depict some aspects of a fused deposition modeling 3D printer 500, comprising (a) a first printer head 501 comprising a printer nozzle 502, (b) a filament providing device 575 configured to provide a filament 320 comprising 3D printable material 201 to the first printer head 501, and optionally (c) a receiver item 550, which can be used to provide a layer of 3D printed material 202.
Fig. lb schematically depict some aspects of a fused deposition modeling 3D printer 500 (or part thereof), comprising a first printer head 501 comprising a printer nozzle 502, and optionally a receiver item (not depicted), which can be used to which can be used to provide a layer of 3D printed material 202. Such fused deposition modeling 3D printer 500 may further comprise a 3D printable material providing device, configured to provide the 3D printable material 201 to the first printer head.
In Figs, la-lb, the first or second printable material or the first or second printed material are indicated with the general indications printable material 201 and printed material 202, respectively. Downstream of the nozzle 502, the filament 320 with 3D printable material becomes, when deposited, layer 322 with 3D printed material 202. In Fig. lb, by way of example the extrudate is essentially directly the layer 322 of 3D printed material 202, due to the short distance between the nozzle 502 and the 3D printed material (or receiver item (not depicted).
Fig. 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 may differ for two or more layers 322. The layer width and/or layer height may also vary within a layer. Reference 252 in Fig. 1c indicates the item surface of the 3D item (schematically depicted in Fig. 1c).
Referring to Figs, la-lc, the filament of 3D printable material that is deposited leads to a layer having a height H (and width W). Depositing layer 322 after layer 322, the 3D item 1 is generated. Fig. 1c very schematically depicts a single-walled 3D item 1. Fig. 2A schematically depicts a method for producing a 3D item 1 by means of fused deposition modelling. The method comprises a 3D printing stage, wherein the 3D printing stage comprises layer-wise depositing 3D printable material 201 to provide the 3D item 1 comprising layers 322 of 3D printed material 202. The 3D printable material 201 comprises a core-shell filament 320. The core-shell filament 320 comprises a core 330 and two or more shells 340 at least partly enclosing the core. The core 330 comprises a core thermoplastic material 331. An inner shell 350 of the two or more shells 340 comprises a sheet-like material 351 at least partly enclosing the core 330. An outer shell 360 of the two or more shells 340 comprises outer shell thermoplastic material 361. Fig. 2A further schematically depicts an embodiment wherein the core-shell filament 320 of 3D printable material 201 is fed through the nozzle 502 of a 3D printer 500.
In embodiments, the sheet-like material 351 is one or more of (i) reflective for visible light, (ii) absorbs visible light, (iii) transmissive for visible light, (iv) luminescent upon receiving visible light; and wherein the other one or more shells (340) are transmissive for visible light.
In embodiments, the sheet-like material 351 may comprise multiple layers.
In embodiments, the 3D printing stage comprises heating a 3D nozzle 502 of a 3D printer 500 to a nozzle temperature TN. The outer shell thermoplastic material 361 has an outer shell thermoplastic material transition temperature To. To is a glass-liquid transition temperature of the amorphous shell thermoplastic material or a melting temperature of the outer shell semicrystalline thermoplastic material 361. In embodiments, TO<TN.
In embodiments, the 3D printable material 201 and the 3D printed material 202 comprise one or more of polycarbonate (PC), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polyoxymethylene (POM), polyethylene naphthalate (PEN), styrene-acrylonitrile resin (SAN), polysulfone (PSU), polyphenylene sulfide (PPS), and semi-crystalline polytethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), poly(methyl methacrylate) (PMMA), polystyrene (PS), and styrene acrylic copolymers (SMMA). However, other materials may also be possible (see also above).
The filament 320 schematically depicted in Fig. 2a may also be indicated as core-shell -shell filament or secondary filament 2320.
Fig. 2B schematically depicts how a filament 320 (or primary filament 1320) (for producing a 3D item by means of fused deposition modelling) may be provided. The filament 320 comprises printable material 201. The 3D printable material comprises a primary core-shell filament 1320 of 3D printable material 201. The primary core-shell filament 1320 comprises a core 1330 and one or more shells 1340 at least partly enclosing the core 1330; here by way of example a single shell 1340 is depicted. The core 1330 comprises a core thermoplastic material 1331. An inner shell 1350 of the one or more shells 1340 comprises a sheet-like material 1351 at least partly enclosing the core 1330. Fig. 2B further schematically depicts an embodiment wherein the primary core-shell filament 1320 is fed through the nozzle 502 of a 3D printer 500, wherein the core material is with sheet material wrapped around it is fed through a single nozzle 502, a to obtain 3D printable material 201 comprising the primary core-shell filament 1320.
Note that the primary core-shell filament 1320 may comprise an inner shell 1350 which is effectively an outer shell of the primary core-shell filament 1320, but which will be an inner shell in the core-shell-shell filament 2320 (see Fig. 2a).
Fig. 2C schematically depicts (also) a method for providing the filament 1320. The method comprises feeding a primary core-shell filament 320 to a nozzle core 503 of a core-shell nozzle 502 of a fused deposition modeling 3D printer 500. The method further comprises feeding sheet-like material 1351 to a nozzle shell 504 of the core-shell nozzle 502 of the fused deposition modeling 3D printer 500. Yet further the method comprises 3D printing the core-shell-shell filament 1320. The primary filament 1320 comprises a core 1330 and one or more shells 1340 at least partly enclosing the core 1330. The core 1330 comprises a core thermoplastic material 1331. An inner shell 1350 of the one or more shells 1340 comprises a sheet-like material 1351 at least partly enclosing the core 1330.
Fig. 2D schematically depicts a filament 320 for producing a 3D item (here effectively a layer 322 is depicted). The 3D printable material comprises a core-shell-shell filament 2320 comprising two or more shells 2340 at least partly enclosing the core 1330. An outer shell 2360 of the one or more shells 2340 comprises outer shell thermoplastic material 2361. Effectively here, a primary filament 1320 is provided to the nozzle core 503 of the core-shell nozzle 502, and 3D printable material for yet another shell, the outer shell, is provided to the nozzle shell 504 of the core-shell nozzle 502. Hereby, the secondary filament 2320 is effectively formed which is deposited to become 3D printed layer 322.
Hence, in embodiments, the printer 500 may be a core-[shell]n printer. The primary core-shell filament 1320 has already been produced by a core-shell printer 500 and is now fed through the core nozzle 502 of a 3D core-shell printer 500. Hence, additional shells 2340 up to the number of n may be added on to the filament 320.
Fig. 3 A-3B schematically depict a method to provide a 3D item 1 by means of fused deposition modelling. The method comprises a 3D printing stage. The 3D printing stage comprises layer-wise depositing 3D printable material 201 to provide the 3D item 1 comprising layers 322 of 3D printed material 202. The 3D printable material 201 comprises a core-shell filament 320. The core-shell filament comprises a core 330 and two or more shells 340 at least partly enclosing the core 330. The core 330 comprises a core thermoplastic material 1330. An inner shell 341 of the two or more shells 340 comprises a sheet-like material 1341 at least partly enclosing the core 330. An outer shell 342 of the two or more shells 340 comprises outer shell thermoplastic material 1342.
In embodiments, the sheet-like material 1341 is reflective for light having a wavelength in the visible wavelength range. The other one or more shells 340 are transmissive for visible light.
In embodiments, the sheet-like material 1341 comprises one or more of a flexible metal sheet, a flexible sheet with a metal coating, and a flexible white sheet.
In embodiments, the sheet-like material 1341 has a lower permeability for a fluid than the other one or more shells 340.
In embodiments, the core 330 has a core diameter de. The sheet-like material 1341 has a sheet-like material thickness ds. The outer shell 342 has an outer shell thickness do. In embodiments, do/dc<0.5 and ds/dc<0.5.
Fig. 3 A (cross-sectional view) depicts embodiments wherein the two or more shells 340 comprise a first adhesive inner shell 343. The first adhesive inner shell 343 comprises a first adhesive inner material 1343 adhering the core 330 and the sheet-like material 1341.
In embodiments, the two or more shells 340 comprise a second adhesive inner shell 344. wherein the second adhesive inner shell 344 comprises a second adhesive inner material 1344 adhering the sheet-like material 1341 and a shell surrounding the sheet-like material 1341.
Fig. 3B (cross-sectional view) depicts embodiments of filaments 320 wherein the two or more shells 340 comprise an inner shell 350 and an outer shell 360. The core 330 has a core diameter de. The inner shell 350 has a sheet-like material width Ws and a sheetlike material length Ls. The outer shell 360 has an outer shell thermoplastic material width Wo and an outer shell thermoplastic material length Lo. The filament has a filament width WF and a filament length LF.
Fig. 3C depicts embodiments wherein the layers 322 of 3D printed material 202 comprising the core 330, sheet-like material 350 and outer shell thermoplastic material 360. Each of the layers 322 in the 3D printed item 1 can be defined by a core thickness De’, a sheet-like material thickness Ds’, and an outer shell thickness Do’.
Fig. 4 schematically depicts embodiments of various filaments 320 used for 3D printing in this invention. A core thermoplastic material 331 may be provided with a sheet-like material 351 to provide a primary filament 1320 comprising a core 330 and an inner shell 350. The primary filament 1320 may subsequently be 3D printed with outer shell thermoplastic material 361 using a 3D printer nozzle 502 with core nozzle 503 and shell nozzle 504 to provide a secondary filament 2320 comprising a core 330, inner shell 350, and outer shell 360. The secondary filament 2320 may be 3D printed using a single 3D printer nozzle 502 in layers 322 to provide a 3D printed item 1.
In another aspect, via another route, the primary filament 1320 may be directly 3D printed in layers 322 with outer shell thermoplastic material 361 using a 3D printer nozzle 502 with core nozzle 503 and shell nozzle 504 to provide the 3D printed item 1.
Fig. 5 schematically depicts an embodiment of a lamp or luminaire, indicated with reference 2, which comprises a light source 10 for generating light 11. The lamp may comprise a housing or shade or another element, which may comprise or be the 3D printed item 1. Here, the half sphere (in cross-sectional view) schematically indicates a housing or shade. The lamp or luminaire may be or may comprise a lighting device 1000 (which comprises the light source 10). Hence, in specific embodiments the lighting device 1000 comprises the 3D item 1. The 3D item 1 may be configured as one or more of (i) at least part of a lighting device housing, (ii) at least part of a wall of a lighting chamber, and (iii) an optical element. Hence, the 3D item may in embodiments be reflective for light source light 11 and/or transmissive for light source light 11. Here, the 3D item may e.g. be a housing or shade. The housing or shade comprises the item part 400. For possible embodiments of the item part 400, see also above.
The term “plurality” refers to two or more.
The terms “substantially” or “essentially” herein, and similar terms, will be understood by the person skilled in the art. The terms “substantially” or “essentially” may also include embodiments with “entirely”, “completely”, “all”, etc. Hence, in embodiments the adjective substantially or essentially may also be removed. Where applicable, the term “substantially” or the term “essentially” may also relate to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%.
The term “comprise” includes also embodiments wherein the term
“comprises” means “consists of’. The term “and/or” especially relates to one or more of the items mentioned before and after “and/or”. For instance, a phrase “item 1 and/or item 2” and similar phrases may relate to one or more of item 1 and item 2. The term "comprising" may in an embodiment refer to "consisting of but may in another embodiment also refer to "containing at least the defined species and optionally one or more other species".
Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
The devices, apparatus, or systems may herein amongst others be described during operation. As will be clear to the person skilled in the art, the invention is not limited to methods of operation, or devices, apparatus, or systems in operation.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims.
In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim.
Use of the verb "to comprise" and its conjugations does not exclude the presence of elements or steps other than those stated in a claim. Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise”, “comprising”, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”.
The article "a" or "an" preceding an element does not exclude the presence of a plurality of such elements.
The invention may be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer. In a device claim, or an apparatus claim, or a system claim, enumerating several means, several of these means may be embodied by one and the same item of hardware. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
The invention also provides a control system that may control the device, apparatus, or system, or that may execute the herein described method or process. Yet further, the invention also provides a computer program product, when running on a computer which is functionally coupled to or comprised by the device, apparatus, or system, controls one or more controllable elements of such device, apparatus, or system.
The invention further applies to a device, apparatus, or system comprising one or more of the characterizing features described in the description and/or shown in the attached drawings. The invention further pertains to a method or process comprising one or more of the characterizing features described in the description and/or shown in the attached drawings.
The various aspects discussed in this patent can be combined in order to provide additional advantages. Further, the person skilled in the art will understand that embodiments can be combined, and that also more than two embodiments can be combined. Furthermore, some of the features can form the basis for one or more divisional applications.
It goes without saying that one or more of the first (printable or printed) material and second (printable or printed) material may contain fillers such as glass and fibers which do not have (to have) influence on the on Tg or Tm of the material(s).
Hence, amongst others the invention may especially provide a filament for 3D printing, especially for FDM printing. To this end, the invention provides a method for producing such filament. Yet, the invention also provides a 3D printed item, which may be based on such filament. To this end, the invention also provides a method for producing such 3D printed item on the basis of such filament.

Claims

CLAIMS:
1. A method for producing a 3D item (1) by means of fused deposition modelling, the method comprising a 3D printing stage, wherein the 3D printing stage comprises: layer-wise depositing 3D printable material (201) to provide the 3D item (1) comprising layers (322) of 3D printed material (202), wherein the 3D printable material (201) comprises a core-shell filament (320), comprising a core (330) and two or more shells (340) at least partly enclosing the core (330), wherein the core (330) comprises a core thermoplastic material (331), wherein an inner shell (350) of the two or more shells (340) comprises a sheetlike material (351) at least partly enclosing the core (330), wherein an outer shell (360) of the two or more shells (340) comprises outer shell thermoplastic material (361) at least partly enclosing the inner shell (350), wherein the core (330) has a core diameter (de), the sheet-like material (351) has a sheet-like material thickness (ds), and the outer shell (360) has an outer shell thickness (do), and wherein do/dc<0.5 and ds/dc<0.5.
2. The method according to claim 1, wherein the sheet-like material (351) is one or more of (i) reflective for visible light, (ii) absorbs visible light, (iii) transmissive for visible light, (iv) luminescent upon receiving visible light; and wherein the other one or more shells (340) are transmissive for visible light.
3. The method according to any one of the preceding claims, wherein the sheetlike material (351) is reflective for light having a wavelength in the visible wavelength range and wherein the other one or more shells (340) are transmissive for visible light.
4. The method according to any of the preceding claims, wherein the sheet-like material (351) comprises one or more of a flexible metal sheet, a flexible sheet with a metal coating, and a flexible white sheet.
5. The method according to any of the preceding claims, wherein the sheet-like material (351) is configured spirally wrapped around the core (330).
6. The method according to any one of the preceding claims, wherein the sheetlike material (351) has a lower permeability for a fluid than the other one or more shells (340).
7. The method according to any one of the preceding claims, wherein the two or more shells (340) comprise a first adhesive inner shell (370), wherein the first adhesive inner shell (370) comprises a first adhesive inner material (371) adhering the core (331) and the sheet-like material (351).
8. The method according to any one of the preceding claims, wherein the two or more shells (340) comprise a second adhesive inner shell (380), wherein the second adhesive inner shell (380) comprises a second adhesive inner material (381) adhering the sheet-like material (351) and a shell surrounding the sheet-like material (351).
9. A filament (320) for producing a 3D item (1) by means of fused deposition modelling, wherein the filament (320) comprises 3D printable material (201), wherein the 3D printable material (201) comprises a core-shell-shell filament (2320) comprising (i) a primary core-shell filament (1320) and (ii) an outer shell (360), wherein the primary core-shell filament (1320) comprises a core (330) and one or more shells (340) at least partly enclosing the core (1330), the core (330) comprising a core thermoplastic material (331) and the one or more shells (340) comprising an inner shell (350) comprising a sheet-like material (351) at least partly enclosing the core (1330), wherein the outer shell (360) comprises outer shell thermoplastic material (361), the outer shell (360) at least partly enclosing the inner shell (350), wherein the core (330) has a core diameter (de), the sheet-like material (351) has a sheet-like material thickness (ds), and the outer shell (360) has an outer shell thickness (do), and wherein do/dc<0.5 and ds/dc<0.5.
10. A method for producing the filament (320) according to claim 9, wherein: the method comprises feeding (i) the primary core-shell filament (1320) to a nozzle core (503) of a core-shell nozzle (502) of a fused deposition modeling 3D printer (500) and (ii) outer shell thermoplastic material (361) to a nozzle shell (504) of the core-shell nozzle (502) of the fused deposition modeling 3D printer (500).
11. A 3D item (1) comprising 3D printed material (202), wherein the 3D item (1) comprises a plurality of layers (322) of 3D printed material (202), wherein at least part of the one of the layers (322) comprises a core-shell layer (322); wherein the core-shell layer (322) comprises a core (330) and two or more shells (340); wherein the two or more shells at least partly enclose the core (330); wherein the core (330) comprises a core thermoplastic material (331); wherein an inner shell (350) of the two or more shells (340) comprises a sheet-like material (351) at least partly enclosing the core (330); wherein an outer shell (360) comprises an outer shell thermoplastic material (361), wherein the core (330) has a core diameter (de), the sheet-like material (351) has a sheet-like material thickness (ds), and the outer shell (360) has an outer shell thickness (do), and wherein do/dc<0.5 and ds/dc<0.5.
12. The 3D item according to claim 11, wherein for at least part of the 3D item (1) applies one or more of: the sheet-like material (351) is reflective for light having a wavelength in the visible wavelength range; wherein the other one or more shells (340) are transmissive for visible light; the sheet-like material (351) comprises one or more of a flexible metal sheet, a flexible sheet with a metal coating, and a flexible white sheet; the sheet-like material (351) has a lower permeability for a fluid than the other one or more shells (340); the two or more shells (340) comprise a first adhesive inner shell (370), wherein the first adhesive inner shell (370) comprises a first adhesive inner material (371) adhering the core (331) and the sheet-like material (351); the two or more shells (340) comprise a second adhesive inner shell (380), wherein the second adhesive inner shell (380) comprises a second adhesive inner material (381) adhering the sheet-like material (351) and a shell surrounding the sheet-like material (351); and the core (330) has a core diameter (de), wherein the sheet-like material (351) has a sheet-like material thickness (ds), and wherein the outer shell (360) has an outer shell thickness (do), wherein do/dc<0.5 and wherein ds/dc<0.5.
13. A lighting device (1000) comprising the 3D item (1) according to any one of the claims 11 and 12, wherein the 3D item (1) is configured as one or more of (i) at least part of a lighting device housing, (ii) at least part of a wall of a lighting chamber, and (iii) an optical element.
PCT/EP2023/064997 2022-06-07 2023-06-05 Functional filaments for 3d printing WO2023237494A1 (en)

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