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
  • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
  • B29C64/205—Means for applying layers
  • B29C64/209—Heads; Nozzles
• • 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
• • 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
  • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor

Definitions

• THREE-DIMENSIONAL PRINTER WITH MULTIHEAD EXTRUDER AND COMPOSITIONS FOR USE THEREIN CROSS-REFERENCE TO RELATED APPLICATIONS [0001]
• This application claims priority to U.S. Provisional Application No. 62/923,244 filed on October 18, 2019, the entire content of which is incorporated herein by reference.
• FIELD [0002]
• the present disclosure relates to three-dimensional printer having a multihead extruder.
• the present disclosure further relates to methods of three-dimensional printing, filament to be used in three-dimensional printing, and methods of making the same. Additionally, the present disclosure describes electronic components and parts thereof which are produced using such filament compositions described herein.
• 3D printing is any of various processes in which a material is joined or solidified under computer control to create a three-dimensional object, with the material being added together (such as liquid molecules or powder grains being fused together). 3D printing can be used in both rapid prototyping and additive manufacturing. Objects typically are produced using digital model data from a 3D model or another electronic data source such as an Additive Manufacturing File (AMF).
• AMF Additive Manufacturing File
• Additive manufacturing is becoming a leading method for reducing costs, increasing quality, and shortening schedules for production of innovative parts and components that were previously not possible using more traditional methods of manufacturing.
• Known additive manufacturing technologies are based on computer-controlled layer-by-layer building of the parts.
• 3D printing electronics can involve “directly” writing an electronic circuit using an inkjet printing process.
• Known 3D printing processes for electronic devices are limited to planar only printing with possible adjustments in a third dimension (2.5 Dimensional printing).
• the development of aerosol jet printing technology provides advantages over current inkjet printing processes.
• Aerosol jet printing provides that fine feature electronic prints can be obtained by means of pneumatically or ultrasonically atomizing and transferring formulated inks to and through an aerodynamically focused jet nozzle to the substrate.
• the aerosol jet printing process uses proprietary inks to print small-scale electronics in three axis (x, y, z) with up to 10 microns single-pass layer thickness.
• This non-contact printing strategy allows for precise printing on non-conformal surfaces, down into trenches, and overtop of 3D electronic components with complex geometries.
• aerosol jet printing requires the post- processing oven or laser treatment of the printed product in order to remove the binder agents added to the materials.
• Post processing techniques such as oven heating or laser treatment can adversely affect the electrical and mechanical properties of materials that have been formed by the additive manufacturing process.
• post processing techniques using extreme heat can alter Young’s modulus of the material.
• Electrical properties such as the IV (current–voltage) characteristics, the resistivity/conductivity, or the dielectric constant can be altered by excess heat. This can significantly impact the desired performance of an electrical or electronic circuit.
• Known polymer binding agents can include 100% Polylactide acetone solution (PLA) and 100% Acrylonitrile Butadiene Styrene (ABS) acetone solution.
• PLA Polylactide acetone solution
• ABS Acrylonitrile Butadiene Styrene
• Semiconductor based electronic circuits can be created by doping a base layer of silicon with various dopants. The entire base layer (and the doped portions) is then overlaid with an insulator compound (typically silicon dioxide). The insulator compound is masked, and the unmasked portions of the insulator compound are removed. The entire surface is then covered with an electrically conductive material (e.g., aluminum or polysilicon) and selectively masked. Excess or undesired portions of the conductive material layer that are not masked are then removed. The insulator layer and metal (i.e., conductive material) layer may be repeated as necessary to build the desired electronic circuit.
• an electrically conductive material e.g., aluminum or polysilicon
• the existing and most advanced technology of 3D printing of electronic components primarily combines the conventional layer-by-layer printing of conductors and insulators with embedded interconnected and pre-fabricated electronic components to create cost-efficient manufacturing of electronic devices in three dimensions.
• the productions of electronic devices are a combination assembly of a 3D printing cavity along with highly conductive paste and pre-manufactured individual circuit components.
• the direct writing technologies available for the printing electronics include the inkjet, aerosol jet, or screen- printing.
• the 3D planar printing of electronic circuit devices can be accomplished using the jet or screen printing technologies, all technologies require the thermal or laser post- processing treatment.
• Direct 3D printing involves the laying down of layers of material without additional treatment.
• Technology challenges for Direct 3D printing include (1) preparation of ink-based printing materials necessary for realizing the desired electrical properties for the 3D electronic devices; (2) deposition and process of the ink-based materials for 3D electronics, and (3) the complexity of computer aided design software control to produce a functional 3D electronic device.
• the present disclosure provides a direct answer to these key technology challenges.
• 3D printing is primarily focused on single material manufacturing, such as plastics, polymers, metals, and even concrete. Materials with electronic properties beyond insulation and conduction has so far eluded the 3D printing industry. However, the present inventors have discovered certain capabilities of multi-material printing.
• extruder assembly for a three-dimensional printer.
• the extruder assembly comprising: a carriage having one or more apertures; a plurality of extruders, each extruder being attached to the carriage via at least one of the one or more apertures; and a fan assembly configured to induce air flow around the plurality of extruders.
• An exemplary three dimensional printer is disclosed.
• the three-dimensional printer comprising: a housing; a platform for supporting a component being processed within the housing, the platform configured to move vertically within the housing for processing the component; and an extruder assembly, the extruder assembly configured to move horizontally in the housing to process the component on the platform.
• An exemplary method for processing a component in a three-dimensional printer is disclosed.
• the three-dimensional printer having a movable platform and a movable extruder assembly arranged in a housing.
• compositions for use in 3D printing are disclosed.
• a composition which comprises ash. These compositions can be used to 3D print objects. Additionally, these compositions can be used to prepare further compositions to be used in 3D printing.
• a method of preparing a composition for use in 3D printing of electronic devices comprising sifting ashes to a particle size of about 0.01 to 200 microns, mixing TPA and ash for between 10 and 90 minutes at a temperature of between 75 and 100°C, extruding said TPA and ash mixture at a temperature of between 50 and 75°C, allowing said extruded mixture and ash to cool, and rolling said cooled and extruded TPA and ash.
• a composition for use in 3D printing of electronic devices comprising at least ash and Triphenylamine (TPA), wherein the TPA is used as a powder binding agent in the composition, and the composition is to be melted and extruded.
• TPA Triphenylamine
• FIG. 2A illustrates an isometric view of a physical implementation of an electronic circuit according to an exemplary embodiment.
• Fig. 2B illustrates an isometric view of a physical implementation of an electronic circuit according to an exemplary embodiment.
• Fig. 2C illustrates an isometric view of a physical implementation of an electronic circuit according to an exemplary embodiment.
• Fig. 3 illustrates one mixing procedure utilizing nanopowder in solution according to an exemplary embodiment. Bismuth nanopowders can be mixed with liquid epoxy to form the printing medium or electronic ink;
• Fig. 4A illustrates ultraviolet (UV) cured semiconductor mixtures according to an exemplary embodiment.
• Fig. 1 illustrates an isometric view of a physical implementation of an electronic circuit according to an exemplary embodiment.
• FIG. 4B illustrates ultraviolet (UV) cured semiconductor mixtures according to an exemplary embodiment.
• Fig. 5A illustrates TPA mixtures in various thicknesses for testing according to an exemplary embodiment.
• Fig. 5B illustrates ultraviolet testing of TPA mixtures according to an exemplary embodiment.
• Fig. 6 shows a resistance curve for a cured graphite and TPA adhesive mixture according to an exemplary embodiment.
• Fig. 7 shows mixing nanopowder and ABS-acetone to create printing media (i.e., electronic ink) according to an exemplary embodiment.
• Fig. 8 shows an exemplary user interface of a 3D circuit design program according to an exemplary embodiment.
• Fig. 8 shows an exemplary user interface of a 3D circuit design program according to an exemplary embodiment.
• FIG. 9 shows an exemplary user interface of a 3D circuit design program depicting a temperature sensor according to an exemplary embodiment.
• Fig.10 shows a measured IV characteristic curve for a TPA-Graphite mixture showing a resistance of approximately 250 Ohms for a 2mm length 0.4mm diameter material sample.
• Fig.11 illustrates a temperature vs resistance curve for 0.4mm sample of TPA-Graphite mixture showing an accurate temperature sensing capability.
• Fig. 12 shows an IV characteristic curve for an N-type TPA-Si mixture sample.
• Fig. 13 shows a multi-material station using magnetic coupling and mechanical grips to attach and detach material filament cartridges to and from the print arm to the material holding arm.
• Fig. 14A shows an exemplary helmet impact sensor that is conceptualized using a 3D printed capacitive pressure sensor array using a combination of capacitive, resistive, and insulating mixtures.
• Fig. 14B shows an exemplary 3D printed capacitive pressure sensor array using a combination of capacitive, resistive, and insulating mixtures.
• Fig.15A shows an exemplary starting image from which an object 3D may be prepared via a process described herein and a composition described herein.
• Fig. 15B shows an exemplary design prepared from the image depicted in Fig. 15A. The design depicted in Fig.
• Fig. 15B may serve as a basis for preparing a 3D printed object via a process described herein and a composition described herein.
• Fig.15C shows an exemplary 3D printed object prepared via a process described herein and a composition described herein.
• Figs. 16A-16C show various embodiments of blocks (carriages) which house extruder heads, the different blocks holding different numbers of nozzles.
• Figs.17A-17O show various embodiments and views of 3D printing devices described herein which employ extruder head blocks as described herein. Also depicted are views of filament being fed or otherwise connected to the extruder heads housed in the interchangeable block of nozzles.
• Fig. 16A-16C show various embodiments of blocks (carriages) which house extruder heads, the different blocks holding different numbers of nozzles.
• Figs.17A-17O show various embodiments and views of 3D printing devices described herein which employ extruder head blocks as described herein. Also depicted are views of filament
• FIG. 18 depicts a 3D printer sub-assembly view.
• Figs. 19A-19D show various views of an extruder head assembly.
• DETAILED DESCRIPTION An exemplary extruder assembly for a three-dimensional printer is disclosed.
• the extruder assembly comprising: a carriage having one or more apertures; a plurality of extruders, each extruder being attached to the carriage via at least one of the one or more apertures; and a fan assembly configured to induce air flow around the plurality of extruders.
• the plurality of extruders can be independently controlled via a processing device. Each extruder is configured to be retractable within the carriage via a respective aperture.
• the extruders are configured to be smart devices having automatic speed and oscillation controls to reduce material contamination.
• the optimized cooling fans of the extruder assembly and precision nozzle openings allow the filaments to exit through friction controlled systems for quality print every time.
• An exemplary three dimensional printer is disclosed.
• the three-dimensional printer comprising: a housing; a platform for supporting a component being processed within the housing, the platform configured to move vertically within the housing for processing the component; and an extruder assembly, the extruder assembly configured to move horizontally in the housing to process the component on the platform.
• the extruder assembly contains a plurality of heads, for example six heads.
• nozzles are temperature-controlled (and are each individually controller), and six heaters, six sensors and four fans are present, the fans being centrally located.
• a temperature accuracy of one degree Celsius can be achieved, with a temperature range of from room temperature to 250°C.
• the extruder block allows for X/Y/Z movement with one material being extruded at a time. The block movement allows for the same belt for speed of print, reduced complexity in the movement, and improved stability for the extruders. See Fig. 16A. [0052] In other embodiments, eight extruder heads may be present on the block, for example. See Fig. 16B. [0053] Additionally, extruder heads may be planned for in an existing machine.
• the three-dimensional can print both electronic and mechanical materials and/or components.
• the sensor components can include temperature, pressure, impact, vibration, optical haptic, chemical (e.g., CO2), electromagnetic, radiofrequency (e.g., Wi-Fi, Bluetooth), radiation or any other sensors as desired.
• the three-dimensional printer can print luminescent components.
• the three-dimensional printer can be configured to print on various material substrates including fabrics and circuit boards.
• the printable components can also include photo/solars, PN diodes, PNP/NPN transistors and amplifier circuits.
• the three-dimensional printer according to an exemplary embodiment of the present disclosure can be configured to print fully-functional electronics via the plurality of extruders (e.g., 8), retractable smart nozzles of the extruders, and an extra-large build platform.
• the printed electronics and components can be used in various industries, which include but are not limited to: Food & Beverage, automatic, petrochemical, Internet of Things, Hardware, Biomedical, Telemedicine & Healthcare, Defense, Home Security, Aerospace, and Logistics.
• the components can be printed at a resolution accuracy ranging from 1.35 to 20 microns and a build speed of less than 80 mm 3 /s and up to 120 mm/s. Each extruder can be connected to a different printing material.
• the components can be built at an expandable volume of as little as one cubic foot or smaller as well as larger volumes.
• the processing device of the three-dimensional printer can be configured for printing on-demand in which it receives (e.g., download) instruction code for printing the various components and/or devices from a remote computing device (e.g., server) over a network connection.
• the instructions can be in the form of a downloadable design, which can be accessed on the server via a graphical interface resident on the three-dimensional printer or through an external computing device.
• the processing device can be configured to individually control each of the extruders and perform level adjustment of the build platform as necessary.
• the extruders can be controlled individually to retract and extend from an extruder carriage to eliminate material contamination of the component and permit the precision use of individual materials. This allows for precision printing.
• the platform can be formed of tempered glass and equipped with auto level detection and PID sensors for heating and cooling regulation by the processing device.
• the plurality of extruder nozzles can be activated or deactivated using a single control (e.g., button).
• the processing device can be configured to control automatic feeding of filament material to each extruder and detect power loss in any of the motors and/or components of the three-dimensional printer.
• An exemplary three-dimensional printer can be configured as follows: [0061] Print technology: Fused deposition modeling (FDM) [0062] Build volume: 10.75” x 7.85” x 11.8” [0063] Number of Nozzles (Heads): 8 materials [0064] Compatible Materials: 6 electronic materials + 3.0mm standard materials [0065] Print file type: Gcode [0066] Minimum nozzle temperature: 0C [0067] Maximum nozzle temperature: 265C [0068] Maximum bed temperature 120C [0069] Minimum print speed: 1 mm/s [0070] Maximum print speed: 80 mm/s [0071] Construction: Aluminum, POM, PP, ABS, steel [0072] Build plate leveling: Factory leveled + manual level + bed level check on touch screen [0073] Nozzle function: 8 retractable nozzles (automatic) [0074] Power supply: 100-240V, 50-60 Hz [0075] Maximum power: 360W [0076] Power switch: On/Off [
• the three-dimensional printer having a movable platform and a movable extruder assembly arranged in a housing.
• the method comprising: receiving, in a processing device of the three-dimensional printer, one or more sensor measurements from the movable extruder assembly during printing of a component; controlling, via the processing device, a property of one or more extruders of the extruder assembly based on the one or more sensor measurements; adjusting, via the processing device, a position of at least one of the movable platform and the movable extruder assembly based on printing instructions received from a memory device.
• An exemplary embodiment of the present disclosure is directed to systems and methods for directly printing and creating complete functional 3D electronic circuits and devices without the need to undergo any thermal or laser post-processing treatment.
• the systems and methods can use TPA as a powder binding agent.
• TPA by itself, can be used as the powder binding agent in a composition for use in 3D printing of electronic devices, or it can be used in combination with other materials.
• the TPA can be mixed with one or more powders for 3D printing based on the desired electrical and mechanical properties of the composition, such that the composition can be melted and extruded onto a structure, while maintaining the desired electrical characteristics.
• the three-dimensional printer can print components and other objects comprising ash.
• the ash may be derived from any source.
• the ash is derived from a cellulose-containing source.
• Non- limiting examples of a cellulose-containing source include wood, paper, and/or any vegetation, such as trees, bamboo, crops, or any other plant.
• the ash is derived from any organic source.
• Non-limiting examples of organic sources include wood, coal, charcoal, and incinerated or otherwise burned plants, animals, humans (e.g., cremated individuals), or any other organism.
• Exemplary compositions and methods for preparing the same are set forth below in detail.
• Exemplary Materials and Compositions A composition for use in 3D printing is disclosed, the composition comprising at least, in certain embodiments, Triphenylamine (TPA).
• TPA Triphenylamine
• TPA can be used in a novel manner as a powder binding agent in a composition to be melted and extruded either on a structure or to form a three-dimensional object.
• TPA is a polymer compound having a lower melting point than that of Polylactide (PLA) and Acrylonitrile butadiene styrene (ABS). Further, at room temperature a state of TPA can be both pliable and malleable. When exposed to high temperature, the TPA material can melt into relatively high viscosity fluid. The viscosity of the melted TPA varies inversely with the temperature. TPA by itself or when combined with other materials is suitable to be used as a binder agent for 3D printing mixtures.
• TPA crosses the threshold of the mechanical flexibility required so that a print can be made with a thermal material printer (standard) in conjunction with one or more powders necessary for achieving the desired electrical properties.
• This allows a composition with TPA to be melted and extruded on a structure without breaking.
• 3D ink filaments with a composition that includes, for example, ABS mixed with nanopowders is brittle. Therefore, such filaments can easily break when extruded on a structure. Additionally, these ABS filaments do not allow for easy storage and transport because of their brittleness.
• filaments are fed into a printing nozzle to create the 3D object.
• a substantially specific mixture ratio of powder to polymer is required for each filament so that the 3D printed electronic devices behave appropriately with respect to the desired electrical and physical characteristics.
• a mixture of PLA and graphite powder in specific amounts can exhibit the properties of a resistor. Increasing the proportion of PLA in that mixture, however, can cause the resistance property to be lost. Increasing the proportion of graphite powder can make the mixture too brittle to be used as a filament.
• An exemplary composition of the present disclosure can be made to exhibit any of a number of electrical properties as desired.
• an exemplary composition can be formed of a mixture to exhibit insulating electrical characteristics that restricts or blocks the flow of current.
• An exemplary composition can also be formed to have conducting electrical characteristics that freely conduct electric current.
• An exemplary composition can be formed to have resistive-electrical characteristics that resist current flow but do not completely block the flow of current.
• An exemplary composition can be formed to have capacitive electrical characteristics that can store electrical charge. Further, an exemplary material can be formed to have semi-conducting electrical characteristics that can resist or conduct current dependent upon the voltage potential across it. The electrical characteristics described herein can be realized, enhanced, and/or diminished in a material based on the proportion of TPA and other components of the composition. [0098] In an exemplary embodiment, the composition can be insulating when the TPA forms about 99% of the material by weight. [0099] In an exemplary embodiment, the composition can be insulating when the TPA forms about 25% of the material by weight and PLA forms about 75% of the weight.
• the composition can be conducting when graphene forms at least about 5% of the composition by weight, and silver (Ag) forms at least about 15% of the composition by weight, such that the graphene and Ag can be in a powder form with particle size ranging from about 100 nm to about 100,000 nm.
• the composition can be resistive when graphite forms at least about 25% of the composition by weight, and silver (Ag) forms at least about 10% of the composition by weight, such that the graphite and Ag can be in a powder form with particle size ranging from about 100 nm to about 100,000 nm.
• the composition can be resistive when PLA forms at least about 25% of the composition by weight, graphite forms at least about 25% of the composition by weight, and silver (Ag) forms at least about 10% of the composition by weight, such that the graphite and Ag can be in a powder form with particle size ranging from about 100 nm to about 100,000 nm.
• the composition can be capacitive when Titanium dioxide (TiO2) forms at least about 35% of the composition by weight, such that the TiO2 can be in a powder form with particle size ranging from about 100 nm to about 100,000 nm.
• the composition can be capacitive when PLA forms at least about 30% of the composition by weight and Titanium dioxide (TiO2) forms at least about 35% of the composition by weight, such that the TiO2 is in a powder form with particle size ranging from about 100 nm to about 100,000 nm.
• the composition can be semiconducting, when silver (Ag) forms at least about 5% of the composition by weight, and n-type Silicon semiconductor (Si-N) forms at least about 50% of the composition by weight, such that the Si-N is in a wafer form with a particle size of about 100 um.
• the composition can be semiconducting, when silver (Ag) forms at least about 5% of the composition by weight, and p-type Silicon semiconductor (Si-P) forms at least about 50% of the composition by weight, such that the Si-P is in a wafer form with a particle size of about 100 um.
• Si-P p-type Silicon semiconductor
• Semiconductor particle weight fraction can affect the electrical properties of a semiconductor ink-based material, and may vary in various aspects of the present disclosure.
• Semiconductor ink-based compositions can be semiconducting and self-supporting after injection, and can have relatively low viscosity.
• the particle size of the powder used in the semiconductor ink can be very fine for precision ink dispensing, having a size of10 microns or smaller.
• Another exemplary embodiment of the present disclosure provides a process of manufacturing a 3D printing composition.
• the process can include melting the TPA at a temperature of at least about 140 oC in an enclosed container for at least about 15 minutes, adding one or more powders to the container and stirring for about two hours for homogeneity, reducing the temperature to about 100 oC, applying a filament cap to the container, extruding a predefined length of a filament at a particular diameter, and cooling the filament into rolls for use in the 3D printing of electronic devices.
• the semiconductor ink is dispensed in a liquid suspension. Once the ink is dispensed from an injector it rapidly solidifies (cures) into a self-supporting mechanical structure.
• the ink can be pre-treated so that it remains wet enough after injection to seamlessly merge with previously deposited 3D-printed layers and adjacent material.
• the exemplary semiconductor ink can be printed at about room temperature so that significant thermal control is not necessary.
• semiconductor ink can be printed at various temperatures above or below the room temperature.
• Second embodiment using UV curable liquid epoxy Liquid epoxy can affect the conductivity of the semiconductor ink, and may vary in various aspects of the present disclosure.
• the UV curing intensity and curing time can also affect the electrical properties of a semiconductor ink-based composition, and may vary in various aspects of the present disclosure.
• An exemplary embodiment of the present disclosure is directed to a process of manufacturing an electronic device using ultraviolet (UV) curable liquid epoxy.
• the process can involve mixing UV curable liquid epoxy with at least one nanopowder to form a mixture, dispensing the mixture on a non-conducting glass surface, curing the dispensed mixture using an UV light emitting diode (LED) source, and melting the cured mixture to a semi-liquid state that is extruded from a print head to form the device.
• the LED source can have a maximum intensity of about 16 MW/cm2 and duration for the curing can be between about 20 seconds and about 120 seconds.
• Another exemplary embodiment of the present disclosure is directed to a process of manufacturing an electronic device using TPA in combination with ultraviolet (UV) curable liquid epoxy.
• the process can involve mixing UV curable liquid epoxy with TPA and at least one nanopowder to form a mixture, dispensing the mixture on a non-conducting glass surface, curing the dispensed mixture using an UV light emitting diode (LED) source, and melting the cured mixture to a semi-liquid state that is extruded from a print head to form the device.
• the LED source can have a maximum intensity of about 16 MW/cm2 and duration for the curing can be between about 20 seconds and about 120 seconds.
• Liquid epoxy is a staple material of the electronics industry, which has been widely employed in motors, generators, transformers, switchgear, bushings, and insulators.
• fast UV curable liquid epoxy specifies a long natural time or heat treatment for curing, which prevents liquid epoxies from being used as a 3D printing ink solution and binding agent.
• the fast UV curable liquid epoxy is an exception and has unexpected properties because it specifies a short curing time (usually seconds) under UV light activation.
• fast UV curable liquid epoxy is a unique, one component, low viscosity, UV curable liquid adhesive that offers unexpected properties.
• the viscosity of such an epoxy is in the range of 200-450 cPs, which is suitable for ink-based material printing. Due to its excellent adhesion and fast curing property under UV light, a fast UV curable liquid epoxy is mixed with appropriate nanopowder materials to create the various basic electronic inks.
• the process of forming semiconductor ink based materials for 3D printing involves mixing by fast blending action to evenly combine nanopowders and liquid epoxy whose viscosities differ. Before mixing, the liquid epoxy and selected nanopowders are measured precisely to the accuracy of about 0.001 gram to form an appropriate weight ratio.
• the mixture can be produced using a high speed centrifugal mixer in a short duration mixing process (generally about 60 seconds).
• the exemplary mixing device e.g., mixer
• the exemplary mixing device can efficiently mix small amounts of nanopowders with liquid epoxy for repeated use.
• the process of making a semiconductor ink can include at least the following considerations: 1) the UV curable epoxy can behave like an electric insulator, therefore, modifications of the epoxy fluid are necessary; 2) the liquid semiconductor ink mixture should be cured completely to bring semiconductor particles in close contact; and 3) the IV curve measurement technique should be able to handle a thin layer of cured mixture without creating a short between voltage probes.
• the properties of a liquid epoxy can be modified by adding conducting silver nanopowder. This mixture results in a fast UV curable epoxy that can enable the epoxy to behave as an insulator and brings the semiconductor particles in close contact.
• an ash-based filament described herein is prepared using ash which has been blended and/or sifted to a particle size of about 0.01 to 200 microns, or about 1 to 175 microns, or about 10 to 150 microns, [0119] In certain embodiments, an ash-based filament described herein is prepared using ash which has been blended and/or sifted to a particle size of about 1 to 250 microns or about 1 to 175 microns, or about 1 to 150 microns, or about 1 to 100 microns.
• an ash-based filament described herein is prepared using ash which has been blended and/or sifted to a particle size of about 0.1 to 25 microns, or about 0.5 to 15 microns, or about 1 to 10 microns.
• an ash-based filament described herein comprises 0.01% to 75% ash by weight, or 0.1% to 50% ash by weight, or 1% to 40% ash by weight, based on the total weight of the filament composition.
• an ash-based filament described herein comprises 0.01% to 75% TPA by weight, or 0.1% to 65% TPA by weight, or 1% to 55% ash by weight, based on the total weight of the filament composition.
• an ash-based filament described herein comprises at least 50% TPA by weight, based on the total weight of the filament composition. In other embodiments, an ash-based filament described herein comprises approximately 50% TPA by weight, based on the total weight of the filament composition [0124] In certain embodiments, an ash-based filament described herein further comprises 0.01% to 75% TiO by weight, or 0.1% to 50% TiO by weight, or 1% to 40% TiO by weight, based on the total weight of the filament composition.
• an ash-based filament described herein further comprises 0.01% to 75% TiO2 by weight, or 0.1% to 50% TiO2 by weight, or 1% to 40% TiO2 by weight, based on the total weight of the filament composition.
• an ash-based filament described herein further comprises 0.01% to 75% silver by weight, or 0.1% to 50% silver by weight, or 1% to 40% silver by weight, based on the total weight of the filament composition.
• an ash-based filament described herein further comprises 0.01% to 75% graphite by weight, or 0.1% to 50% graphite by weight, or 1% to 40% graphite by weight, based on the total weight of the filament composition.
• an ash-based filament described herein further comprises 0.01% to 75% grapheme by weight, or 0.1% to 50% grapheme by weight, or 1% to 40% grapheme by weight, based on the total weight of the filament composition.
• an ash-based filament described herein further comprises 0.01% to 75% silver by weight, or 0.1% to 50% silver by weight, or 1% to 40% silver by weight, based on the total weight of the filament composition.
• an ash-based filament described herein is prepared by mixing ashes with TPA.
• an ash-based filament described herein is prepared by mixing ashes with TPA and graphite and/or grapheme.
• an ash-based filament described herein is prepared by mixing ashes with TPA and silver. [0131] In certain embodiments, an ash-based filament described herein is prepared by mixing ashes with TPA and TiO2. [0132] In certain embodiments, an ash-based filament described herein is prepared by mixing ashes with TPA and TiO. [0133] In certain embodiments, an ash-based filament described herein is prepared by mixing ashes with TPA, TiO and graphite and/or grapheme. In certain embodiments, an ash-based filament described herein is prepared by mixing ashes with TPA, TiO2 and graphite and/or grapheme.
• an ash-based filament described herein is prepared by mixing ashes with TPA, TiO, TiO2 and graphite and/or grapheme. [0134] In certain embodiments, an ash-based filament described herein is prepared by mixing ashes with TPA, and one or more of TiO2 and/or TiO and/or silver and/or graphite and/or grapheme and/or other power(s).
• ash-based filament compositions described above may be prepared by first sifting ashes to a desired particle size, followed by mixing at least TPA and ash for between 10 and 90 minutes at a temperature of between 75 and 100°C, followed by extruding said ash-containing mixture at a temperature of between 50 and 75°C, followed by allowing said extruded ash-containing mixture to cool and finally rolling said cooled and extruded TPA and ash.
• TPA and ash are mixed with one or more of TiO2 and/or TiO and/or silver and/or graphite and/or grapheme and/or other power(s).
• said mixing is conducted for between 10 and 90 minutes, or between 15 and 80 minutes, or between 20 and 75 minutes, or between 25 and 60 minutes, or approximately 30 minutes.
• mixing is conducted at a temperature of 75-100°C, or 75- 95°C, or 75-90°C, or 75-85°C, or approximately 80°C.
• the extruding is conducted at a temperature of 50-75°C, or 55-75°C, or 55-70°C, or 55-65°C, or approximately 60°C.
• the system can enable a user design, layout, and print various 3D electronic circuits in a multitude of form factors, thus providing on demand, customized, production that meets the specific need at the specific time.
• the exemplary system and methods can be used in a variety of applications, for example, to form sensors and biomedical detectors, to perform circuit layout and design and, insitu production, for use as educational and training tools and in research and development, toys, games, enhanced electronic components, replacement parts, communications devices, computing equipment, household electronic components, industrial electronic components, over land electronic components, aerospace electronic components, nautical electronic components, sports equipment, construction equipment, robotic equipment, networking devices, Wi-Fi devices, Bluetooth devices, decorative components, lighting equipment, audio equipment, satellite components, spacecraft components, devices that utilize artificial intelligence, mobile devices, military equipment, wearable technology, devices utilizing Blockchain technology, devices utilizing finance, banking, and monitory technology, electronic jewelry, electronic time- keeping devices, internet of things (IoT) devices, or in any other application or implementation as desired.
• IoT internet of things
• the exemplary embodiments disclosed herein can be for nano-electronic materials development such that any raw material mixed under the exemplary processes described herein can be converted into a range of electronic inks to be deposited for the formation of 3D electronic components through the use of various 3D printing processes.
• the driving variable in how the resulting semiconductor based inks are then deposited is determined by their intended application and fluid viscosity ranges.
• Semiconductor inks that range from about 1 to 1,000 centipoise in viscosity are precisely deposited using 3D Aerosol Jet printing technology. When ink viscosities rise within ranges of about 1,000 to 10,000 centipoise then it is more desirable to move to higher viscosity pneumatic spraying or dispensing techniques.
• Semiconductor materials can be deposited using spraying technologies where the materials can be held in a pressurized reservoir and delivered to a pneumatic spray head that is controlled through computer software to turn on and off to regulate the dispensing of the material.
• Spraying capabilities can provide a high volume deposition process for printing a wide variety of electronic coatings, adhesives, and resins to provide protective encapsulation and adhesion of parts to surfaces.
• pneumatic dispensing of inks and thick film pastes provide for a more controlled direct write approach.
• An exemplary embodiment of the present disclosure can provide a significant advantage over known printing techniques in applying thick film material development processes to manufacture a variety of electronic thick film devices by employing the practice of screen printing.
• 3D printing of functional electronics is in-sole sensing devices that can be printed using three materials - conductive, capacitive, insulating.
• the sensing devices can be a matrix of pressure and temperature sensors made from isolated capacitive and conductive elements connected by conductive wires across a surface.
• the surface can be formed into any desired shape. In this case the shape of a foot is desired at various lengths and widths. Pressure can be sensed by the change in geometry of the sensor elements by pressure applied by the wearer.
• the geometry change can result in a capacitance change which can further cause a change in a voltage applied across the elements.
• a temperature can be sensed by a change in the resistivity of the conductive material when a significant change in temperature occurs.
• a voltage change can be created because of the change in resistance across the material.
• a pressure sensor array as shown in Fig. 14B, that can be printed using a combination of an insulator mixture, a capacitive mixture, and conductive/low resistive mixture.
• the sensor array can be made of a lattice of individual capacitive elements connected on top and on the bottom by the conductive lines. It can be enclosed in an insulating housing in the shape of a foot sole.
• FIG. 14A Yet another example of 3D printing of functional electronics (3De) is a football helmet impact sensor, as shown in Fig. 14A.
• the helmet impact sensor is conceptualized using a 3D printed capacitive pressure sensor array using a combination of capacitive, resistive, and insulating mixtures. Impacts on front, side, back or any localized area can be measured and uploaded to a server giving real-time, multiple player data on force and pressure.
• the resistivity For an insulating material, the resistivity, which can be measured in ohms/meter (inverse of conductivity), should be high. For a resistive material, the resistivity should vary from moderate to high. Resistivity can be measured by producing a line of known geometry and measuring the total resistance. [0151] For a capacitive material, the relative dielectric constant (unit less) should be greater than 1. This dielectric constant is directly proportional to the amount of capacitance available in the structure. It can be measured by producing a sample of known geometry then passing a known sinusoidal signal of known frequency through it. The variation of the phase and the amplitude of the signal are functionally related to the capacitance.
• the material should act as a switch, changing its overall resistance depending upon the voltage applied across it, or the current flowing through it. At low voltages, the resistance is high, and at high voltages the resistance is low.
• the electrical response or behavior of the semiconducting material can be captured in the form of an IV curve, which typically has an exponential behavior as dependent upon applied voltage. Important measures are turn-on voltage and saturation current.
• the materials also have mechanical properties by virtue of their composition. Because the foundation of the composition is polymer based, they have stress/strain characteristics that are dependent upon them. Also, the melting points of the materials are also dependent largely upon the polymer base. Stress and strain are measures of how much deformity a material can stand before failure.
• the current (I) -Voltage (V) characteristic curve (IV) defines the relationship between the current flowing through an electronic device and the applied voltage across its terminals. For a fixed value resistor, the IV curve is approximately a straight line. However, the IV curve for a semiconductor material is not linear. Starting from the zero applied voltage, the current value increases but the magnitude is extremely small. The current passing through semiconductor will increase rapidly for a small increment of voltage when the “kick-off” voltage reached.
• the filaments can include Conductive, Insulative, Capacitive, Resistive, N-Type Semi-conductive and P-Type Semi-conductive properties.
• Table 1 illustrates the exemplary base mixtures with approximate relative amounts for forming various 3D print electronics of the present disclosure. These are merely illustrative of the present disclosure and should not be construed as limiting the scope of the disclosure in any way as many variations and equivalents that are encompassed by the present disclosure will become apparent to those skilled in the art upon reading the present disclosure.
• Table 1 [0157] Table 2 and Table 3 below illustrate further exemplary mixtures with approximate amounts (in grams) for forming various 3D print electronics of the present disclosure, which do not contain ABS. These are merely illustrative of the present disclosure and should not be construed as limiting the scope of the disclosure in any way as many variations and equivalents that are encompassed by the present disclosure will become apparent to those skilled in the art upon reading the present disclosure.
• the present disclosure provides for filament compositions useful for printing electronic components and parts of electronic components.
• Non-limiting examples include resistors and parts thereof, capacitors and parts thereof, n-type semiconductors and parts thereof, p-type semiconductors and parts thereof, insulators and parts thereof, and magnetic components and parts thereof. Additionally, ash-based components or objects may be printed.
• filament compositions described herein comprise one or more of acrylonitrile butadiene styrene (ABS), polylactide acetone solution (PLA), triphenylamine (TPA), graphite, graphene, TiO2, TiO, n-type silicon, p-type silicon, silver (Ag), Sn/Al, magnet powder, and/or ash.
• ABS acrylonitrile butadiene styrene
• PLA polylactide acetone solution
• TPA triphenylamine
• graphite graphene
• TiO2 TiO2
• n-type silicon p-type silicon
• silver silver
• Sn/Al silver
• magnet powder and/or ash.
• Any type of ash or source of ash may be used.
• the ash is wood ash.
• Any type of magnet powder may be used in formulations described herein.
• Formulations described herein may comprise one or more of acrylonitrile butadiene styrene (ABS), polylactide acetone solution (PLA), triphenylamine (TPA), graphite, graphene, TiO, TiO2, n-type silicon, p-type silicon, silver (Ag), Sn/Al, magnet powder, and/or ash in any amounts or ratios.
• ABS acrylonitrile butadiene styrene
• PLA polylactide acetone solution
• TPA triphenylamine
• graphite graphene
• TiO TiO2
• TiO2 titanium oxide
• silver silver
• Sn/Al magnet powder
• Certain preferred formulations described herein comprise PLA, TPA, or both PLA and TPA.
• the filament composition contains either Sn/Al; PLA and TPA; PLA and graphite; PLA and graphene; PLA and TiO; PLA and TiO2; PLA, TiO and TiO 2 ; PLA and n-type silicon; PLA and p-type silicon; PLA and silver; PLA and Sn/Al; PLA and magnet powder; PLA and wood ash; PLA, n-type silicon and silver; PLA, p-type silicon and silver; PLA, graphite and graphene; PLA, graphite and silver; PLA, graphene and silver; TPA and TiO; TPA and TiO2; TPA, TiO and TiO2; TPA and graphite; TPA and graphene; TPA and silver; TPA and n-type silicon; TPA and p-type silicon; TPA, n-type silicon and silver; TPA, p-type silicon and silver; TPA and magnet powder; TPA and wood ash; TPA, graphite and silver; TPA, graphene and silver; TPA, graphene and
• compositions described herein may contain any amount of PLA, i.e., 0-100% by weight of the composition.
• Compositions described herein may contain any amount of TPA, i.e., 0-100% by weight of the composition.
• Compositions described herein may contain any amount of magnetic powder, i.e., 0- 100% by weight of the composition.
• compositions described herein may contain any amount of graphite, i.e., 0-100% by weight of the composition. In certain embodiments, graphite is present in an amount of 0-50% by weight of the composition. [0171] Compositions described herein may contain any amount of graphene, i.e., 0-100% by weight of the composition. In certain embodiments, graphene is present in an amount of 0-50% by weight of the composition. [0172] Compositions described herein may contain any amount of TiO, i.e., 0-100% by weight of the composition. In certain embodiments, TiO is present in an amount of 0-66% by weight of the composition.
• compositions described herein may contain any amount of TiO 2 , i.e., 0-100% by weight of the composition. In certain embodiments, TiO 2 is present in an amount of 0-66% by weight of the composition. [0174] In embodiments containing both TiO and TiO2, the total amount of TiO+ TiO2 may be any amount. In certain embodiments, the total amount of TiO+ TiO2 is 0-66% of the total weight of the composition. [0175] Compositions described herein may contain any amount of silicon (n-type), i.e., 0-100% by weight of the composition. In certain embodiments, silicon (n-type) is present in an amount of 0-66% by weight of the composition.
• compositions described herein may contain any amount of silicon (p-type), i.e., 0-100% by weight of the composition. In certain embodiments, silicon (p-type) is present in an amount of 0-66% by weight of the composition.
• Compositions described herein may contain any amount of silver, i.e., 0-100% by weight of the composition. In certain embodiments, silver is present in an amount of 0-50% by weight of the composition, or 0-25% by weight of the composition.
• Compositions described herein may contain any amount of Sn/Al, i.e., 0-100% by weight of the composition.
• compositions described herein may contain any amount of ash, i.e., 0-100% by weight of the composition. In certain embodiments, ash is present in an amount of 0-33% by weight of the composition. [0180] In certain embodiments containing two of the above-described ingredients, the two ingredients may be present in any ratio by mass. [0181] Exemplary Method of Preparing Ash-Based Filament [0182] In an exemplary embodiment of ash-based filament compositions prepared according to methods described herein, ashes were sifted to a small size of 100 microns.

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• Optics & Photonics (AREA)
• Producing Shaped Articles From Materials (AREA)
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• Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

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• 2020
  • 2020-10-19 WO PCT/US2020/056333 patent/WO2021077087A1/en unknown
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