Patent Application
20230264414
Three-dimensional (3D) printing may be an additive printing process used to make three-dimensional solid parts from a digital model. 3D printing is often used in rapid product prototyping, mold generation, and mold master generation. 3D printing techniques are considered additive processes because they involve the application of successive layers of material. This is unlike traditional machining processes, which often rely upon the removal of material to create the final part. Materials used in 3D printing often require curing or fusing, which for some materials may be accomplished using heat-assisted sintering, and for other materials may be accomplished using digital light projection technology.
Features of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.
Building and/or embedding electronics on and/or within a dense part may require multiple steps to assemble several different components. For example, three-dimensional printing techniques, such as extrusion or additive manufacturing, have been used to create the dense part, and then other techniques, such as electroplating or the application of conducting materials, have been used to create the electronics. Many of the materials used to create the electronics require specific activation procedures, which may utilize specialized (e.g., proprietary, expensive, etc.) equipment, such as annealing equipment.
Examples of the three-dimensional (3D) printing method disclosed herein utilize multi jet fusion (MJF) to impart an electronic property within, and/or upon the surface of a layer of a 3D objects/parts at a voxel level.
During MJF, an entire layer or several layers of a build material (also referred to as build material particles) is/are exposed to electromagnetic radiation, but a selected region (in some instances less than the entire layer(s)) of the build material is fused and hardened to become a layer or several layers of a 3D object/part. A fusing agent is selectively deposited in contact with the selected region of the build material. The fusing agent(s) is/are capable of penetrating into the layer of the build material and spreading onto the exterior surface of the build material. This fusing agent is capable of absorbing electromagnetic radiation and converting the absorbed radiation to thermal energy, which in turn melts or sinters the build material that is in contact with the fusing agent. This causes the build material to fuse, bind, cure, etc. to form the layer of the 3D object/part.
In the examples disclosed herein, an electronic agent is also selectively deposited on the build material and/or on the layer of the 3D object/part to impart the electronic property within, and/or upon the surface of the layer of the 3D objects/parts at the voxel level. To impart the electronic property/properties, the MJF platform may be used without modification. This is due, in part, to the electronic agents being jettable via thermal and/or piezoelectric inkjet printheads. As such, no specialized electroplating or other deposition equipment is needed. In some instances, this is also due, in part, to the fact that the heat and light provided by the MJF process is suitable to anneal any of the material(s) that may be used to impart the electronic property. As such, no specialized equipment (e.g., annealing equipment) is needed. However, it is to be understood that off-bed annealing may also be utilized.
The method(s) disclosed herein also enable control over where the electronic property is introduced (e.g., at the voxel surface and/or through the voxel volume). By combining electronic voxels in a controlled fashion using MJF, a variety of devices with different electronic properties can be created. As examples, the methods disclosed herein may be used to form anti-static surface coatings (e.g., scratch-tolerant surface conductivity for static-related applications), capacitors, conductive traces, and more complex geometry electronic components.
The electronic property that is imparted to/on the object/part may be electrical conductivity, semi-conductivity, and/or an electrically insulating property. The electronic property may be imparted upon the build material by selectively depositing a suitable electronic agent on the build material. The electronic property may also be the property of at least a portion of an electronic component or feature that is formed on the surface of the layer of the 3D object/part by selectively depositing a suitable electronic agent on the layer.
It is to be understood that in the examples disclosed herein, a single electronic property or several electronic properties may be imparted to a single layer of build material and/or a single layer of the 3D object/part. As an example of the latter instance, to form a capacitor upon the surface of the layer of the 3D object/part, an electronic agent including a conductive material or a material whose electronic property is enhanced or activated when exposed to a treatment may be applied in a certain pattern on the layer, and then an electronic agent including an insulating material may be applied in a different area on the layer. As another example, to form a multi-layered structure (e.g., a capacitor, a via, etc.) in the build material or on the 3D object/part/layer, different electronic agents may be sequentially applied upon one another. In these types of structures, electrical continuity may be provided from one plane of electrically active material to another plane of electrically active material and then potentially on to subsequent planes. As an example, a first electronic agent may be selectively applied (on at least a portion of the build material or on an area of a 3D object/part/layer) to impart a first electronic property (e.g., conductivity) and then a second electronic agent may be selectively applied on the first electronic agent to impart a second electronic property (e.g., insulation) that is different than the first electronic property. It is to be understood that if the different electronic agents require different annealing conditions (e.g., no annealing and annealing, or annealing at different temperatures), then the electronic agents may be applied and annealed separately. If, however, the different electronic agents require similar annealing conditions, then the electronic agents can be selectively deposited and annealed together.
Referring now to
Referring now to
The build material 16 may be a powder, a liquid, a paste, or a gel. Examples of the build material 16 include semi-crystalline thermoplastic materials with a wide processing window of greater than 5° C. (i.e., the temperature range between the melting point and the re-crystallization temperature). Some specific examples of the build material 16 include polyamides (PAs) (e.g., PA 11 / nylon 11, PA 12 / nylon 12, PA 6 / nylon 6, PA 8 / nylon 8, PA 9 / nylon 9, PA 66 / nylon 66, PA 612 / nylon 612, PA 812 / nylon 812, PA 912 / nylon 912, etc.). Other specific examples of the build material 16 include polyethylene, polyethylene terephthalate (PET), and an amorphous variation of these materials. Still other examples of suitable build materials 16 include polystyrene, polyacetals, polypropylene, polycarbonate, polyester, thermal polyurethanes, other engineering plastics, and blends of any two or more of the polymers listed herein. Core shell polymer particles of these materials may also be used.
Other examples of the build material 16 include ceramic particles. Examples of suitable ceramic particles include oxides, carbides, and nitrides. Some specific examples include alumina (Al2O3), glass, silicon mononitride (SiN), silicon dioxide (SiO2), zirconia (ZrO2), titanium dioxide (TiO2), or combinations thereof. As an example, 30 wt% glass may be mixed with 70 wt% alumina.
The build material 16 may have a melting point ranging from about 50° C. to about 2100° C. As examples, alumina particles having a melting point of 2072° C. may be used, glass having a melting point ranging from about 200° C. to about 1700° C. may be used, a polyamide having a melting point of 180° C. may be used, or thermal polyurethanes having a melting point ranging from about 100° C. to about 165° C. may be used.
The build material 16 may be made up of similarly sized particles or differently sized particles. In the examples shown herein, the build material 16 includes particles of two different sizes.
The term “size” or “particle size” is used herein to describe at least the build material 16. The size or particle size generally refers to the diameter or average diameter, which may vary, depending upon the morphology of the individual particle. In an example, the respective particle may have a morphology that is substantially spherical. A substantially spherical particle (i.e., spherical or near-spherical) has a sphericity of >0.84. Thus, any individual particles having a sphericity of <0.84 are considered non-spherical (irregularly shaped). The particle size of the substantially spherical particle may be provided by its largest diameter, and the particle size of a non-spherical particle may be provided by its average diameter (i.e., the average of multiple dimensions across the particle) or by an effective diameter, which is the diameter of a sphere with the same mass and density as the non-spherical particle.
In an example, the average size of the particles of the build material 16 ranges from about 1 µm to about 500 µm. In another example, the build material 16 is a particle having a particle size ranging from about 5 µm to less than 200 µm.
It is to be understood that build material 16 may include, in addition to the polymer or ceramic particles, a charging agent, a flow aid, or combinations thereof. Charging agent(s) may be added to suppress tribo-charging. Examples of suitable charging agent(s) include aliphatic amines (which may be ethoxylated), aliphatic amides, quaternary ammonium salts (e.g., behentrimonium chloride or cocamidopropyl betaine), esters of phosphoric acid, polyethylene glycol esters, or polyols. Some suitable commercially available charging agents include HOSTASTAT® FA 38 (natural based ethoxylated alkylamine), HOSTASTAT® FE2 (fatty acid ester), and HOSTASTAT® HS 1 (alkane sulfonate), each of which is available from Clariant Int. Ltd.). In an example, the charging agent is added in an amount ranging from greater than 0 wt% to less than 5 wt% based upon the total wt% of the build material 16.
Flow aid(s) may be added to improve the coating flowability of the build material 16. Flow aid(s) may be particularly desirable when the particles of the build material 16 are less than 25 µm in size. The flow aid improves the flowability of the build material 16 by reducing the friction, the lateral drag, and the tribocharge buildup (by increasing the particle conductivity). Examples of suitable flow aids include tricalcium phosphate (E341), powdered cellulose (E460(ii)), magnesium stearate (E470b), sodium bicarbonate (E500), sodium ferrocyanide (E535), potassium ferrocyanide (E536), calcium ferrocyanide (E538), bone phosphate (E542), sodium silicate (E550), silicon dioxide (E551), calcium silicate (E552), magnesium trisilicate (E553a), talcum powder (E553b), sodium aluminosilicate (E554), potassium aluminium silicate (E555), calcium aluminosilicate (E556), bentonite (E558), aluminium silicate (E559), stearic acid (E570), or polydimethylsiloxane (E900). In an example, the flow aid is added in an amount ranging from greater than 0 wt% to less than 5 wt% based upon the total wt% of the build material 16.
In the example shown in
The delivery piston 26 and the fabrication piston 28 may be the same type of piston, but are programmed to move in opposite directions. In an example, when a first layer of the 3D object is to be patterned or formed, the delivery piston 26 may be programmed to push a predetermined amount of the build material 16 out of the opening in the supply bed 22 and the fabrication piston 28 may be programmed to move in the opposite direction of the delivery piston 26 in order to increase the depth of the fabrication bed 24. The delivery piston 26 will advance enough so that when the roller pushes the build material 16 into the fabrication bed 24, the depth of the fabrication bed 24 is sufficient so that a layer 18 of the build material 16 may be formed in the bed 24. The roller is capable of spreading the build material 16 into the fabrication bed 24 to form the layer 18, which is relatively uniform in thickness. In an example, the thickness of the layer 18 ranges from about 90 µm to about 110 µm, although thinner or thicker layers may also be used. For example, the thickness of the layer 18 may range from about 50 µm to about 1 mm. In an example, the layer 18 thickness ranges from about 100 µm to about 200 µm.
It is to be understood that the roller is a build material distributor that may be replaced by other tools, such as a blade that may be desirable for spreading different types of powders, or a combination of a roller and a blade.
The supply bed 22 that is shown is one example, and could be replaced with another suitable delivery system to supply the build material 16 to the fabrication bed 24. Examples of other suitable delivery systems include a hopper, an auger conveyer, or the like.
The fabrication bed 22 that is shown is also one example, and could be replaced with another support member, such as a platen, a print bed, a glass plate, or another build surface.
After the layer 18 of the build material 16 is applied in the fabrication bed 24, the layer 18 may be exposed to heating (not shown). Heating may be performed to pre-heat the build material 16, and thus the heating temperature may be below the melting point of the build material 16. As such, the temperature selected will depend upon the build material 16 that is used. As examples, the heating temperature may be from about 5° C. to about 50° C. below the melting point of the build material 16.
Pre-heating the layer 18 of the build material 16 may be accomplished using any suitable heat source that exposes all of the build material 16 in the fabrication bed 24 to the heat. Examples of the heat source include a thermal heat source or an electromagnetic radiation source (e.g., infrared (IR), microwave, ultraviolet, etc.).
As shown in
The printhead 32 may include an array of nozzles through which it is able to selectively eject drops of fluid. In one example, each drop may be in the order of about 10 pico liters (pl) per drop, although it is contemplated that a higher or lower drop size may be used. In some examples, printhead 32 is able to deliver variable size drops of the fusing agent 30.
The printhead 32 may be attached to a moving XY stage or a translational carriage (neither of which is shown) that moves the printhead 32 adjacent to the fabrication bed 24 in order to deposit the fusing agent 30 in desirable area(s). In other examples, the printhead 32 may be fixed while a support member (similar to the fabrication bed 24) is configured to move relative thereto. The printhead 32 may be programmed to receive commands from a central processing unit and to deposit the fusing agent 30 according to a pattern of a cross-section for the layer of the 3D object/part that is to be formed. As used herein, the cross-section of the layer of the part to be formed refers to the cross-section that is parallel to a contact surface of the fabrication bed 24.
In an example, the printhead 32 may have a length that enables it to span the whole width of the fabrication bed 24 in a page-wide array configuration. As used herein, the term ‘width’ generally denotes the shortest dimension in the plane parallel to the X and Y axes of the contact surface, and the term ‘length’ denotes the longest dimension in this plane. However, it is to be understood that in other examples, the term ‘width’ may be interchangeable with the term ‘length’. In an example, the page-wide array configuration is achieved through a suitable arrangement of multiple printheads 32. This configuration may be desirable for single pass printing. In still other examples of the printing system 20, the printhead 32 may have a shorter length that does not enable them to span the whole width of the fabrication bed 24. In these other examples, the printhead 32 be movable bi-directionally across the width of the fabrication bed 24. This configuration enables selective delivery of the fusing agent 30 across the whole width and length of the fabrication bed 24 using multiple passes.
Examples of the fusing agent 30 are water-based dispersions including a radiation absorbing binding agent (i.e., an active material). The active material may be any infrared light absorbing colorant. In an example, the active material is a near infrared light absorber. Any near infrared colorants, e.g., those produced by Fabricolor, Eastman Kodak, or Yamamoto, may be used in the fusing agent 30. As one example, the fusing agent 30 may be an ink formulation including carbon black as the active material. Examples of this ink formulation are commercially known as CM997A, 516458, C18928, C93848, C93808, or the like, all of which are available from Hewlett-Packard Company. As another example, the fusing agent 30 may be an ink formulation including near infrared absorbing dyes as the active material. Examples of this ink formulation are described in U.S. Pat. No. 9,133,344, incorporated herein by reference in its entirety. Some examples of the near infrared absorbing dye are water soluble near infrared absorbing dyes selected from the group consisting of:
and mixtures thereof. In the above formulations, M can be a divalent metal atom (e.g., copper, etc.) or can have OSO3Na axial groups filling any unfilled valencies if the metal is more than divalent (e.g., indium, etc.), R can be any C1-C8 alkyl group (including substituted alkyl and unsubstituted alkyl), and Z can be a counterion such that the overall charge of the near infrared absorbing dye is neutral. For example, the counterion can be sodium, lithium, potassium, NH4+, etc.
Some other examples of the near infrared absorbing dye are hydrophobic near infrared absorbing dyes selected from the group consisting of:
and mixtures thereof. For the hydrophobic near infrared absorbing dyes, M can be a divalent metal atom (e.g., copper, etc.) or can include a metal that has Cl, Br, or OR′ (R′=H, CH3, COCH3, COCH2COOCH3, COCH2COCH3) axial groups filling any unfilled valencies if the metal is more than divalent, and R can be any C1-C8 alkyl group (including substituted alkyl and unsubstituted alkyl).
The aqueous nature of the fusing agent 30 enables the fusing agent 30 to penetrate, at least partially, into the layer 18 of the build material 16. The build material 16 may be hydrophobic, and the presence of a co-solvent and/or a surfactant in the fusing agent 30 may assist in obtaining a particular wetting behavior.
As shown in
In an example, the electromagnetic radiation R may include wavelengths ranging from about 100 nm (UV) to about 10 µm. In yet another example, the electromagnetic radiation R wavelengths range from about 400 nm to about 3 µm or 4 µm (which includes near-infrared and mid-infrared radiation). As an example, the electromagnetic radiation 36 is blackbody radiation with a maximum intensity at a wavelength of about 1100 nm.
The radiation R is emitted from a radiation source 34, such as an IR (e.g., near-IR) curing lamp, a UV or UV-Vis curing lamp, IR (e.g., near-IR), UV, or visible light emitting diodes (LED), Vertical Cavity Surface Emitting Laser (VCSEL) arrays, or lasers with specific wavelengths. Any radiation source 34 may be used that emits a suitable wavelength for the 3D printing process. The radiation source 34 may be attached, for example, to a carriage that also holds the printhead(s) 32. The carriage may move the radiation source 34 into a position that is adjacent to the fabrication bed 24. The radiation source 34 may be programmed to receive commands from the central processing unit and to expose the layer 18, including the fusing agent 30 and build material 16, to radiation R.
The length of time the radiation R is applied for, or energy exposure time, may be dependent, for example, on one or more of: characteristics of the radiation source 34; characteristics of the build material 16; and/or characteristics of the fusing agent 30.
The fusing agent 30 enhances the absorption of the radiation R, converts the absorbed radiation to thermal energy, and promotes the transfer of the thermal heat to the build material 16 in contact therewith. In an example, the fusing agent 30 sufficiently elevates the temperature of the build material 16 above the melting point(s), allowing curing (e.g., sintering, binding, fusing, etc.) of the build material particles to take place. Exposure to radiation R forms a layer 14 of the 3D object/part.
While not shown in
As shown in
The electronic agent 38 may be an aqueous formulation that includes a conductive material, a material whose electronic property is enhanced or activated when exposed to a treatment, a semiconductive material, and/or an insulating material. The electronic agent may include one of the materials, or a combination of the materials in order to enhance the compatibility with a particular build material and/or to enhance the electronic property. For examples, the electronic agent 38 may include a combination of conductive materials to enhance the conductive electronic property, or may include a combination of a semiconductive material and an insulating material to modify the electronic property. Some specific examples of material combinations include: a combination of carbon nanotubes, silver nanoparticles and a PEDOT:PSS polymer to enhance conductive properties; a combination of quantum dots and semi-conducting polymers to enhance semi-conducting properties; a combination of insulating polymer and insulating nanoparticles to enhance insulating properties; and a combination of silver nanoparticles and carbon black to create an electronic feature with a specific conductivity, for instance, a resistor of specific resistance.
In addition to the electronic material, the aqueous formulation of the electronic agent 38 may also include water, a co-solvent, and/or a pH adjuster. As an example, conducting polymers may be incorporated into an aqueous formulation including water and a co-solvent. Other examples of the aqueous formulation may include a surfactant. As examples, carbonaceous nanomaterials and metal nanoparticles may be incorporated into an aqueous formulation including water, a co-solvent, and a surfactant.
Examples of the conductive materials include metallic (e.g., silver, copper, gold, platinum, palladium, tungsten, iron, etc.) nanomaterials (e.g., nanoparticles, nanorods, nanowires, nanotubes, nanosheets, etc.), conductive oxides (e.g., indium tin oxide, antimony oxide, zinc oxide, etc.), conducting polymers (e.g., poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), polyacetylene, polythiophenes, any any other conjugated polymer, etc.), carbonaceous nanomaterials (e.g., graphene (single or multi-layer), carbon-nanotubes (CNTs, single or multi-walled), graphene nanoribbons, fullerenes, etc.), and reactive metal systems (e.g., metal oxide nanoparticles, which are reduced once deposited). Carbonaceous nanomaterials and metallic materials are stable at very high temperatures (i.e., at the sintering/processing temperatures for 3D printing polymers and ceramics, e.g., up to 3400° C.), and thus may be suitable for forming electronic component(s) 14 on and/or in ceramic build materials 16.
Examples of the semiconductive material include semiconducting nanomaterials (nanoparticles, nanorods, nanowires, nanotubes, nanosheets, etc.), semiconducting metal oxides (e.g., tin oxide, antimony oxide, indium oxide, etc.), semiconducting polymers (e.g., PEDOT:PSS, polythiophenes, poly(p-phenylene sulfide), polyanilines, poly(pyrrole)s, poly(acetylene)s, poly(p-phenylene vinylene), polyparaphenylene, any any other conjugated polymer, etc.), and semiconducting small molecules (i.e., having a molecular mass less than 5,000 Daltons, e.g., rubrene, pentacene, anthracene, aromatic hydrocarbons, etc.). Some specific examples of the semiconducting nanomaterials include quantum dots, III-V or II-VI semiconductors, Si, Ge, transition metal dichalcogenides (WS2, WSe2, MoSes, etc.), graphene nanoribbons, semiconducting carbon nanotubes, and fullerenes and fullerene derivatives.
The nanoparticles may have weakly bound ligands at their surface. Weakly bound ligands include molecules that attach to the nanoparticle surface through an amine, carboxylic acid, or pyridine functional group. Examples of such molecules include dodecanoic acid, triethylenetetramine, or 4-dimethylaminopyridine.
The previously described fullerenes, conducting or semi-conducting metal oxides, and conducting or semi-conducting polymers may be semi-conductive, in that they have a finite conductivity. However, this conductivity may often be sufficient for conductive applications. The material may be considered conductive or semi-conductive depending upon the geometry and/or in what combination with other electronic components it is utilized.
Some of the conductive or semiconductive materials are inherently electronically active or become electronically active after evaporation of the aqueous formulation. Others of the conductive or semiconductive materials have their electronic property enhanced or activated when exposed to a treatment. The treatment may be annealing or a chemical treatment (e.g., chemical interaction with another activating agent). In the examples disclosed herein, the activating agent may be contained in a separate fluid from electronic agent 38 (e.g., the fusing agent 30), and may be deposited before, after, or simultaneously with the electronic agent 28 to activate the material in the electronic agent 38.
Some examples of the material whose electronic property is enhanced or activated when exposed to a treatment may include conductive or semiconductive materials that become more electronically active following annealing (e.g., graphene, carbon nanotubes, WS2, WSe2, MoSe2, graphene nanoribbons, fullerenes, and semiconducting metal oxides). A surfactant may be used to incorporate these materials into the electronic agent 38, and removal of the surfactant during annealing results in suitable electronic property/properties. Other examples of the material whose electronic property is enhanced or activated when exposed to a treatment may exhibit conductivity or semiconductivity after annealing or chemical treatment (e.g., metal nanoparticles, metal organic decomposition systems which become conductive following annealing or chemical treatment). Still other examples of the material whose electronic property is enhanced or activated when exposed to a treatment may include those materials that decompose into metallic features (e.g., metal salts). The decomposition may be initiated via heat, light, or chemical treatment (e.g., reduction).
Examples of the insulating (dielectric) material include insulating nanomaterials (nanoparticles, nanorods, nanowires, nanotubes, nanosheets, etc.), colloids, or sol-gel precursors, such as hexagonal boron nitride, metal and semiconducting oxides, metal and semiconducting nitrides, metal oxide sol-gel precursors (e.g., metal alkoxides, metal chlorides, etc.), silicon sol-gel precursors (silicates), or solid electrolytes. Other examples of the insulating material include insulating polymers (e.g., polylactic acid, fluoropolymers, polycarbonate, acrylics, polystyrene, SU-8, etc.) and insulating small molecules (i.e., having a molecular mass less than 5,000 Daltons, e.g., benzocyclobutane, paraffins, organic dyes, etc.).
As mentioned above, the aqueous formulation of the electronic agent 38 may include water, co-solvent(s), pH adjuster(s), and/or surfactant(s). The aqueous formulation may also include other additives, such as a biocide and/or an anti-kogation agent.
Examples of suitable co-solvents include 2-pyrrolidinone, N-methylpyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1,6-hexanediol or other diols (e.g., 1,5-Pentanediol, 2-methyl-1,3-propanediol, etc.), triethylene glycol, tetraethylene glycol, tripropylene glycol methyl ether, or the like, or combinations thereof. Whether used alone or in combination, the total amount of the co-solvent(s) ranges from about 1 wt% to about 60 wt% of the total wt% of the electronic agent 38.
Examples of suitable surfactants include a self-emulsifiable, nonionic wetting agent based on acetylenic diol chemistry (e.g., SURFYNOL® SEF from Air Products and Chemicals, Inc.), a nonionic fluorosurfactant (e.g., CAPSTONE® fluorosurfactants from DuPont, previously known as ZONYL FSO), and combinations thereof. In other examples, the surfactant is an ethoxylated low-foam wetting agent (e.g., SURFYNOL® 440 or SURFYNOL® CT-111 from Air Products and Chemical Inc.) or an ethoxylated wetting agent and molecular defoamer (e.g., SURFYNOL® 420 from Air Products and Chemical Inc.). Still other suitable surfactants include non-ionic wetting agents and molecular defoamers (e.g., SURFYNOL® 104E from Air Products and Chemical Inc.) or water-soluble, non-ionic surfactants (e.g., TERGITOL™ TMN-6 from The Dow Chemical Company). In some examples, it may be desirable to utilize a surfactant having a hydrophilic-lipophilic balance (HLB) less than 10.
Whether a single surfactant is used or a combination of surfactants is used, the total amount of surfactant(s) in the electronic agent 38 may range from about 0.5 wt.% to about 1.5 wt.% based on the total wt.% of the electronic agent 38.
pH adjusters may be used to control the pH of the electronic agent 38. From 0 wt% to about 2 wt% (of the total wt% of the electronic agent 38) of the pH adjuster, for example, can be used.
Examples of suitable biocides include an aqueous solution of 1,2-benzisothiazolin-3-one (e.g., PROXEL® GXL from Arch Chemicals, Inc.), quaternary ammonium compounds (e.g., BARDAC® 2250 and 2280, BARQUAT® 50-65B, and CARBOQUAT® 250-T, all from Lonza Ltd. Corp.), and an aqueous solution of methylisothiazolone (e.g., KORDEK® MLX from The Dow Chemical Co.). The biocide or antimicrobial may be added in any amount ranging from about 0.1 wt.% to about 5 wt.% with respect to the total wt.% of the electronic agent 38.
An anti-kogation agent may be included in the electronic agent 38. Kogation refers to the deposit of dried ink (e.g., electronic agent 38) on a heating element of a thermal inkjet printhead. Anti-kogation agent(s) is/are included to assist in preventing the buildup of kogation. Examples of suitable anti-kogation agents include oleth-3-phosphate (e.g., commercially available as CRODAFOS™ O3A or CRODAFOS™ N-3 acid from Croda), or a combination of oleth-3-phosphate and a low molecular weight (e.g., < 5,000) polyacrylic acid polymer (e.g., commercially available as CARBOSPERSE™ K-7028 Polyacrylate from Lubrizol). Whether a single anti-kogation agent is used or a combination of anti-kogation agents is used, the total amount of anti-kogation agent(s) in the electronic agent 38 may range from about 0.1 wt.% to about 5 wt.% based on the total wt.% of the electronic agent 38.
The electronic agent 38 may also be dispensed from any suitable applicator, such as an inkjet printhead 32′, similar to inkjet printhead 32. As shown in
After the electronic agent 38 is selectively applied, the applied electronic agent 38 may be exposed to a subsequent treatment, such as annealing (as shown in phantom in
Annealing may be used to accelerate evaporation of the aqueous formulation, to enhance the electronic property, and/or to activate the electronic property. It is to be understood that some electronic agents 38 have an aqueous formulation that evaporates upon being dispensed or by the heat of the fabrication bed 24, and also do not require property enhancement or activation, and thus the treatment may not be performed with all of the electronic agents 38. As an example, electronic agents 38 made with conducting polymers, such as PEDOT:PSS, involve solvent evaporation at a temperature of about 100° C. or less, but do not involve property enhancement or activation. Even in these instances, however, annealing may be performed in order to accelerate the evaporation process.
Annealing may be accomplished utilizing the radiation source 34, another overhead annealing lamp, and/or a heater (not shown) of the fabrication bed 24 that is used to pre-heat the build material 16. The additional annealing lamp may be mounted to printing system 20, for example, with the radiation source 34 and/or upon the printing carriage. The additional annealing lamp may be an arc-lamp, a flash lamp, or the like. The layer 14 and the electronic agent 38 thereon may be exposed to annealing in the fabrication bed 24, or the printing system 20 may include an additional bed or platform where annealing takes place.
Annealing takes place for a specified time and at a specified energy output determined, at least in part, by the surfactant(s), solvent system, and/or sintering conditions for the material used in the electronic agent 38. When metal nanoparticles are used in the electronic agent 38, annealing may also be dependent upon the particle size and/or a ligand system associated with then nanoparticles. Annealing may take place at a temperature below the melting temperature of the build material 16, but at a temperature that is suitable to evaporate the aqueous formulation (water, co-solvent, and in some instances surfactant), or to enhance or activate the material in the electronic agent 38. Annealing may also take place at a temperature at or above the melting temperature of the build material 16 (which may range from 50° C. to 2000° C. depending upon the build material 12). At temperatures higher than the melting temperature of the build material 16, the build material 16 may melt, which is acceptable. Following this type of higher temperature anneal, a delay in the print process can be employed to allow for the part 14 to cool before additional build material 16 is supplied for the next layer. In other instances, the temperature rise may be quick, which is useful to cause annealing but leaves the build material 16 largely unaffected (in terms of exhibiting a similar temperature rise).
The following are a few examples of the annealing process. When annealing is utilized to drive off solvent (e.g., water and co-solvent) and/or surfactant(s), relatively low temperatures (about 350° C. or less) may be utilized. When the electronic agent 38 includes graphene, the annealing temperature may be less than 150° C. When the electronic agent 38 includes small metal nanoparticles (e.g., diameter ≤ 10 nm) or nanoparticles with weakly bound ligands, the annealing temperature may be about 200° C. or less. At these temperatures, the small metal nanoparticles or nanoparticles with weakly bound ligands are capable of sintering and becoming electronically active. When the electronic agent 38 includes silver nanoparticles, the annealing temperature may be greater than 100° C. Larger metal nanoparticles may require higher temperatures and/or longer annealing times.
During annealing, the resistance of the electronic component 12 may be monitored to determine the minimum time for obtaining the suitable electronic property.
Some examples of the electronic agents 38 that are thermal inkjet jettable and the corresponding annealing utilized with the electronic agents are shown in Table 1.
As previously mentioned, chemical treatment may be used to enhance the electronic property and/or to activate the electronic property. An example of the chemical treatment involves ligand destabilization of nanoparticles having ligands weakly bound thereto. Ligand destabilization removes the ligands from the metal nanoparticles to enhance sintering. Examples of ligand destabilizers include sodium chloride and potassium iodide. Another example of the chemical treatment is doping. Doping may enhance the electronic property. Benzyl viologen and sodium azide may be suitable dopants for the carbonaceous materials. Another example of the chemical treatment is a reduction process. Reducing agent(s), such as hydrazine, sodium borohydride, formaldehyde, etc., may be used to reduce metal salts or metal oxide nanoparticles.
The thickness of the electronic component 12 (or portion thereof) may be built up by applying more of the electronic agent 38 on the previously applied electronic agent 38. In some instances, after each application of the electronic agent, 38, the electronic agent may be exposed to annealing. These processes may be repeated until a desirable thickness of the electronic component 12 is achieved. If annealing is not desired or required, the deposited electronic agent 38 may be allowed to dry before a subsequent layer of the electronic agent 38 is selectively applied thereon. The electronic agent 38 may also be deposited layer by layer until a suitable thickness is achieved, and a single annealing step (if desired or required) may be performed. In an example, the electronic agent 38 may be applied in an amount ranging from about 0.1 picoliters to about 36 picoliters per pixel at 600 dots per inch.
While
Examples of the electronic component 12 that may be formed include conductors, insulators, resistors, capacitors, inductors, memristors, diodes, transistors, rectifiers, transducers, relays, chemical or electronic sensors, transformers, antennas, radio frequency identifiers (RFID), batteries, switches, light emitting diodes (LED), thermoelectric devices, piezo-responsive devices, photovoltaics, or the like.
An example of the device 10, including the 3D printed layer 14 and electronic component 12 formed thereon, is shown in
In some examples of the method, the electronic component 12 may be at least partially embedded in another layer of the 3D object/part. An example of this is shown in
As shown in
As shown in
It is to be understood that heat absorbed, during the application of energy, by the build material 16 in the additional layer 18′ on which fusing agent 30 has been delivered or has penetrated may propagate to a previously solidified layer, such as layer 14, causing at least some of that layer 14 to heat up above its melting point. This effect helps create strong interlayer bonding between adjacent layers 14, 40 of the device 10′.
Rather than covering the electronic component 12 and the exposed surfaces of the layer 14 with additional build material 16 (as shown in
Referring now to
Also as shown in
The application of the electronic agent(s) 38 forms a build material portion 42 having the electronic property. The electronic agent(s) 38 may be applied in a single pass or in multiple passes using the printhead 32′. The thickness of the build material portion 42 may be increased as more electronic agent(s) 38 is applied. In an example, the electronic agent 38 may be applied in an amount up to about 200 picoliters per pixel at 600 dots per inch and with a build material thickness of up to about 100 µm.
After each pass, or after the desired amount of the electronic agent 38 is applied to the build material 16, the build material 16 and the electronic agent 38 may be exposed to a treatment (e.g., annealing, chemical treatment, etc.) to accelerate evaporation of the aqueous formulation, to enhance the electronic property, and/or to activate the electronic property. In other examples, before or during each pass, the electronic agent 38 may be exposed to a chemical treatment to enhance the electronic property and/or to activate the electronic property. It is to be understood that some electronic agents 38 have an aqueous formulation that evaporates upon being dispensed, and also do not require property enhancement or activation, and thus the treatment may not be performed with all of the electronic agents 38. Annealing takes place at any suitable temperature, depending, at least in part, on the surfactant(s), solvent system, and/or sintering conditions for the material used in the electronic agent 38.
In some examples, the electronic agent 38 occupies such a small space that there is little build material 16 within the volume of the electronic agent 38. In other examples, the electronic agent 38 occupies enough space that there is a significant amount of build material 16 within the volume. The dried electronic agent 38 is capable of holding the build material 16 in contact therewith together. In the example shown in
As shown in both
As shown in both
Exposure to radiation R forms a layer 14′ of the 3D object/part. In the example shown in
Referring back briefly to
Referring now to
Also as shown in
The application of the electronic agent(s) 38 forms a build material portion 42 having the electronic property. The electronic agent(s) 38 may be applied in a single pass or in multiple passes using the printhead 32′. The thickness of the build material portion 42 may be increased by adding additional electronic agent 38.
After each pass, or after the desired amount of the electronic agent 38 is applied to the build material 16, the build material 16 and the electronic agent 38 may be exposed to a treatment (e.g., annealing, chemical treatment, etc.) to accelerate evaporation of the aqueous formulation, to enhance the electronic property, and/or to activate the electronic property. In other examples, before or during each pass, the electronic agent 38 may be exposed to a chemical treatment to enhance the electronic property and/or to activate the electronic property. It is to be understood that some electronic agents 38 have an aqueous formulation that evaporates upon being dispensed, and also do not require property enhancement or activation, and thus the treatment may not be performed with all of the electronic agents 38. Annealing takes place at any suitable temperature, depending, at least in part, on the surfactant(s), solvent system, and/or sintering conditions for the material used in the electronic agent 38.
As shown in
As shown in
Exposure to radiation R forms a layer 44 of the 3D object/part having the electronic property of the electronic agent 38 imparted thereto. The layer 44 may be referred to as a “volume feature,” in part because the electronic property is imparted throughout at least a portion of the volume of the layer 44 that is formed. This volume approach is useful for creating scratch resistant static-dissipative or antistatic parts.
Any unfused build material 16 may be removed from the layer 44.
While all of the build material 16 in the fabrication bed 24 is shown forming the layer 44 in
Still further, in the example of the method shown in
The electronic agent 38 including the conductive material, the semiconductive material, or the material whose electronic property is enhanced or activated when exposed to treatment may function similar to the fusing agent or be used as (i.e., in place of) the fusing agent 30. When the electronic agent 38 functions as a fusing agent 30 or is used in place of the fusing agent 30, the electronic property may be imparted to the bulk of the layer(s) (e.g., layer 14, 40, etc.) and the electronic agent 38 may actually aid in fusing the build material 16 upon which it is applied. For example, in
To further illustrate the present disclosure, examples are given herein. It is to be understood that these examples are provided for illustrative purposes and are not to be construed as limiting the scope of the present disclosure.
A layer (100 µm thick) of polyamide-12 (PA-12) build material was applied to a fabrication bed and was pre-heated 150° C. Silver nanoparticle ink (86 wt% METALON® Ink: Silver* and 14 wt% aqueous formulation) was used as the fusing agent. The aqueous formulation included 1 wt% - 50 wt% 2-pyrrolidinone, 0.1 wt% - 5 wt% anti-kogation agent, 0.1 wt% - 5 wt% biocide, 0.01 wt% - 5 wt% other additives, and a balance of DI water. The silver nanoparticle ink was thermal inkjet printed with a 9 ng printhead on the PA-12 layer. The PA-12 (with silver nanoparticle ink applied thereto) was subjected to selective fusion with a 300 W halogen light bulb using a prototype Multi jet Fusion™ Machine (Hewlett Packard). This process was repeated 4 more times to form a part with 5 fused layers (total thickness ~ 500 µm).
5 layers of silver nanoparticle ink was jetted directly onto the surface of the part, creating a surface horizontal feature. The thin film on the top of the part was not conductive when initially taken off the build bed, but became conductive when the entire part was annealed in an oven at 150° C. for 4 hours. For the thin film, the measured sheet resistance was ~120 Ohms/sq with a bulk conductivity of ~20,000 Siemens/m. The underlying part was not conductive.
Four commercially available electronic inks were tested. Three of the four inks were mixed with an aqueous formulation, which included 1 wt% - 50 wt% 2-pyrrolidinone, 0.1 wt% - 5 wt% anti-kogation agent, 0.1 wt% - 5 wt% biocide, 0.01 wt% - 5 wt% other additives, and a balance of DI water to form the electronic agent. The fourth commercially available ink (i.e., the carbon nanotube ink shown in Table 2) was used as received (i.e., was not mixed with the aqueous formulation). A graphene based electronic agent was also prepared with 3 wt% Nano99 powder, 2.5 wt% JONCRYL® 683 resin, 14 wt% of the aqueous formulation, and 80.5 wt% additional water. Table 2 illustrates the commercially available inks that were used, the advertised conductivity, and the concentration in the aqueous thermal inkjet vehicle.
Experiment 1: For this experiment, ~30 µL of each of inks 1, 2, 3, 4, and the in-house graphene ink were spotted on one side of a silicon substrate (~15 mm in width and ~40 mm in length). A draw-down rod (#11 wire, ~30 µm liquid film) was used to spread the ink upon the silicon substrate. The substrates were annealed under different conditions, as shown in Table 3. Resistance measurements were taken of the films to obtain sheet resistance and resistivity.
The films created on the silicon substrates were used to establish a baseline for films formed on other surfaces, as described in experiments 2-5. By using drying/annealing conditions similar to those recommended by the ink suppliers, films with sheet resistances and resistivities within an order of magnitude of the supplier spec were able to be created for inks 1, 2, and 4. The films formed with the in-house graphene ink and ink 3 did not correspond with advertised values, however, this may be due to the fact that graphene in the ink is not in a fully crystallized form. The graphene structure may be deformed, which could degrade the electronic properties. The graphene ink may be suitable for forming a resistor or a heater.
Experiment 2: For this experiment, ~30 µL of each of inks 1, 2, 3 and 4 was spotted on one side of a PA 12 surface. A draw-down rod (#11 wire, ~30 µm liquid film) was used to spread the ink upon the PA 12 surface. The substrates were annealed under different conditions, as shown in Table 4. Resistance measurements were taken of the films to obtain sheet resistivity.
When applied to PA 12, there was little change in the conductivity for the PEDOT:PSS film (Sample F) and CNT film (Sample H) (when comparing the results from experiment 1), but the Ag NP film (Sample E) lost around an order of magnitude of conductivity (when comparing the results from experiment 1). Even with this loss, the conductivity of Sample E is still the highest among the samples tested.
Experiment 3: For experiment 3, ~30 µL of ink 2 was spotted on one side of a PA 12 surface. A draw-down rod (#11 wire, ~30 µm liquid film) was used to spread the ink upon the PA 12 surface. A second PA 12 surface was applied to sandwich the film. The substrate was annealed. Resistance measurements were taken of the films to obtain sheet resistivity (shown in Table 5).
When sandwiched between two PA 12 substrates, the PEDOT:PSS film (Sample I) lost around an order of magnitude of conductivity (when comparing the results from experiments 1 and 2). Even with this loss, the conductivity of Sample I is reasonable.
Experiment 4: For experiment 4, 20 wt% of inks 2 and 4 were mixed with bulk PA 12 powder. The ink/bulk mixture was annealed at 210° C. for 5 minutes. Resistance measurements were taken of the bulk polymer films to obtain bulk resistance (shown in Table 6).
With 20 wt% of inks 2 and 4 mixed with bulk PA 12 powder, there was measurable conductivity of the bulk polymer film (~0.5 mm thick), although it was lower than the film measurements in other experiments. However, the volume-based conductivity measured in experiment 5 is sufficient for creating scratch-resistant part surfaces which are anti-static (109-1012 Ω/sq) or static dissipative (106-109 Ω/sq).
Reference throughout the specification to “one example”, “another example”, “an example”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the example is included in at least one example described herein, and may or may not be present in other examples. In addition, it is to be understood that the described elements for any example may be combined in any suitable manner in the various examples unless the context clearly dictates otherwise.
It is to be understood that the ranges provided herein include the stated range and any value or sub-range within the stated range. For example, a range from about 50° C. to about 2100° C. should be interpreted to include not only the explicitly recited limits of about 50° C. to about 2100° C., but also to include individual values, such as 57° C., 95° C., 225° C., 1350° C., etc., and sub-ranges, such as from about 75° C. to about 2025° C., from about 100° C. to about 1900° C., etc. Furthermore, when “about” is utilized to describe a value, this is meant to encompass minor variations (up to +/-10%) from the stated value.
In describing and claiming the examples disclosed herein, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.
While several examples have been described in detail, it is to be understood that the disclosed examples may be modified. Therefore, the foregoing description is to be considered non-limiting.
This application is a divisional of U.S. Pat. Application No. 15/763,200, filed on Mar. 26, 2018, which claims priority to PCT/US2015/058094, filed on Oct. 29, 2015. U.S. Pat. Application 15/763,200 and PCT/US2015/058094 are incorporated in their entirety herein.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15763200 | Mar 2018 | US |
| Child | 18132821 | US |
