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WO2008151063A2 - Procédé et matériau stéréolithique polyvalent haute définition - Google Patents

Procédé et matériau stéréolithique polyvalent haute définition Download PDF

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Publication number
WO2008151063A2
WO2008151063A2 PCT/US2008/065394 US2008065394W WO2008151063A2 WO 2008151063 A2 WO2008151063 A2 WO 2008151063A2 US 2008065394 W US2008065394 W US 2008065394W WO 2008151063 A2 WO2008151063 A2 WO 2008151063A2
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WO
WIPO (PCT)
Prior art keywords
monomer
catalyst
liquid
reactive
dimensional
Prior art date
Application number
PCT/US2008/065394
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English (en)
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WO2008151063A3 (fr
Inventor
Milton Meisner
Original Assignee
Milton Meisner
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Filing date
Publication date
Application filed by Milton Meisner filed Critical Milton Meisner
Publication of WO2008151063A2 publication Critical patent/WO2008151063A2/fr
Publication of WO2008151063A3 publication Critical patent/WO2008151063A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • 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

  • Stereolithography machines (those which create three-dimensional objects) are also a class of machines largely controlled by computer, but the unfortunate fact still remains that the cost and complexity of these devices are usually far too high for the general consumer.
  • stereolithography has been the focus mainly of industry for prototyping machine parts and commodity items, and other purposes, all far out of reach of the general populace.
  • stereolithography machines are dedicated for the express purpose of rapid prototyping, a direct three-dimensional representation of an item to be reproduced as a part of a production line or a decorative item in manufacturing.
  • the existing stereolithography techniques will be divided into either a "selective deposition,” wherein an item is successively layered in two dimensional planes, thereby forming a three dimensional object: by thermoplastic powder sintering; layered thermoplastic nozzle deposition; or layered thermoplastic fiber deposition, or layered photo-cured monomer; or "activated polymer separation,” wherein an item is successively layered in two dimensional planes thereby forming a three dimensional article by selective activation by ionic bombardment or light activated catalysis forming a solid matrix from within a liquid of adequate crosslinking species such as but not limited to, carboxyl or hydroxyl functional monomer.
  • Figure 1 illustrates a head depositing liquid monomer on a temperature controlled platen.
  • Figure 2 illustrates an ink jet head nearly simultaneously depositing liquid catalyst to immediately cure the monomer into the desired shape.
  • a hard shell being created at the same time as the rest of the object to create a holding bin for the partially cured monomer and catalyst.
  • Figure 3 illustrates curing of the liquid layers and serial deposition atop the hardened layers, where the layers fuse to create one solid object.
  • Figure 4 illustrates a finished three dimensional object that been created and is suspended in a moat of uncured liquid monomer, partially cured liquid monomer, or dry monomer sand in a sealed created at the same time as the object, which can then be washed away by the alternative embodiment of the washing/flocculating component of the machine and stored in a disposal tank or cartridge, or manually washed away as desired.
  • Figure 5 illustrates an example of a stereolithography machine.
  • Figure 6 illustrates an example of a stereolithography machine that includes a mechanism for direct UV illumination of droplets as they are ejected from a head of the machine.
  • Figure 7 illustrate a drop transit catalysis method.
  • Several embodiments of the present invention utilize a novel application of inkjet technology for the purpose of depositing precisely imaged and layered strata of rapidly catalyzed polymer thereby providing a new stereolithographic (three-dimensional) printing method.
  • Several embodiments include a stereolithic printing system utilizing x, y, and z axes to plot and deposit successive, additive layers of material representing cross sections of the object to be printed up to a resolution of l/10,000th of an inch in thickness or greater resolution.
  • Deposited materials are comprised of a two-part activated monomer or oligomer with an appropriate alternately deposited liquid catalyst, to create fully dimensional objects at various sizes.
  • Dispensing specifically tailored liquid monomer and catalyst, or the liquid to solid formation of other liquid reactants, for the purpose of three-dimensional layered rendering, is exploited by this invention in a novel and effective manner.
  • Several embodiments relate to inkjet printing in respect that the embodiments may utilize a head similar to that of a conventional inkjet head for the purposes of depositing reactive layers of monomer and catalyst or solutions of metal ion and reducing agents, both of which depend on the finished reaction byproducts to be of a substantially enhanced solid, taking the shape of a three dimensional object.
  • patents 4,962,391, 4,520,374, 4,525,728, and 4,546,362 demonstrate the refinements and characteristics of precise dispensing of micro droplets of ink for the specific purpose of printing onto a two- dimensional substrate such as paper which may find similar applicability to the deposition of three-dimensional objects according to the teachings disclosed herein.
  • Several embodiments also relate to a need for a more economical, and broader range application of stereolithgraphic technique.
  • the uses of this type of applied stereolithography technique are not limited to solid modeling, but are also unique because of the large variety of materials to be simultaneously employed, and can be of substantial dynamic modeling use as well.
  • dispensing specifically tailored liquid monomer and catalyst, or the liquid to solid formation of other liquid reactants, for the purpose of three-dimensional layered rendering is exploited by this invention in a novel, synergistic, and effective manner.
  • An embodiment of the invention includes a single axis track on which the inkjet head can travel back and forth rapidly with little inertial involvement. Because the ink jet head will move more rapidly than any other motor driven axis, it will not be filled with liquid but rather use liquid-supply catheters from isolated liquid reservoir sources not involved in the motion of the print head, thereby ensuring that the inertial moment of the print head assembly is relatively unhindered by the weight thereof.
  • the ink jet track rests on another carriage assembly capable of moving back and forth in an orthogonal axis relative to the rapidly oscillating inkjet track assembly. This carriage rests on sufficiently stable supports to render precise repetitions of motion and of sufficient height to clear substantial depth of a third axis platform that moves in small incremental steps in the vertical direction.
  • Catalyst is introduced simultaneously with monomer droplets and not onto a preexisting monomer reservoir.
  • a monomer reservoir represents a greater expense in unused monomer and a medium that transmits vibration induced error.
  • a monomer pool is far harder to control on a layer upon layer basis and is therefore unsuitable for very high tolerances, where as droplet groups have been found to create very precise tolerances and crisply delineated differentiation without bridging between close edges of an image/part.
  • the embodiments disclosed herein minimize excess waste of monomer wherein the created three-dimensional object is surrounded by a vertical moat concurrently formed of the same solidified material as the object being created.
  • the moat may be filled with uncured liquid monomer, partially cured monomer or a sand-like cured monomer.
  • the vertical moving platform may also have an inlet and outlet micro-tube assembly, which provides for the removal by pumping out of unused liquids, the infusion of washing liquids and their subsequent removal as well.
  • the entire mechanical assembly is stationed on a leveled platform, the means for which may be provided by screw-adjusted cleats preferably near the perimeter of the bottom chassis or other similar method which will ensure level stability.
  • Gravity provides for the leveling mechanism necessary for the establishment of uniform layering during the three-dimensional build up of the object. Each liquid layer will remain as a level surface and supporting layer for the solidifying linear infusion of another activating liquid substance that will create the final solid object.
  • the reliance on gravity as the liquid leveling mechanism also eliminates the need for a more expensive and complicated machine element to perform a leveling calibration.
  • the ink jet head can maintain reasonable control of the thickness of the consecutive layers by simple virtue of its established precision in the printing trade, wherein the resolution of the deposited dots can be controlled via the computer used to activate the printing. Lower resolution items are printed to test or prove a particular design as a draft, and when the draft model is approved the higher resolution full gamut of functions can then be activated.
  • Several embodiments relate to inkjet printing in that such embodiments utilize a similarly adapted head for the purposes of depositing reactive layers of monomer and catalyst.
  • nozzles and heads may be similar to nozzles and heads used in inkjet printing or may be specialized heads and sets of nozzles.
  • the head can also include built in alignment and cleaning mechanisms such that alignment of droplets of monomer and catalyst may be accurately controlled and residual monomer and catalyst is removed from the jets of the head.
  • Solutions of metal ion such as basic solutions of nickel sulfate, nickel chloride and copper sulfate, or metal salts established for electroless deposition such as cupric gluconate, ferrous sulfate and stannous chloride can likewise be deposited in a manner similar as the monomer layers are deposited by the head and reducing agents, such as those which are likewise established for electroless, or otherwise known as autocatalytic use, are deposited by another special set of nozzles similar to the way catalyst is deposited, that is, in selective linear/planar patterns which also correspond to a cross- sectioned area of a three dimensional object, thereby causing metallic deposition which is precipitated by means of selective reducing chemicals such as palladium chloride, platinum chloride, rhodium chloride, formaldehyde, glucose and many others of the metal plating art of which, depend on the reduced finished reaction byproducts becoming a substantially enhanced multilayered accretion and thus when finished, a homogeneous solid, which takes the shape
  • the platform floor of the z stage assembly is the electronegative collector or cathode and an externally applied anode metal bus tipped with carbon, platinum or a conductive plastic membrane and the deposition process is applied selectively thereby in a preformed solidified negative mold of plastic by the same invention by a precursor forming step which forms the mold. Then it is after this mold that metallic deposition with heavier rates of deposition is possible inside the preformed hollow mold with the precursor plastic mold having a microtube assembly both infusing fresh electrolyte and evacuating the exhausted portion of the same. In this manner, greater flux of metal ion are communicated in shorter amounts of time.
  • An embodiment of the invention includes a single axis track on which the inkjet head can travel back and forth rapidly with little inertial involvement. Because the ink jet head will move more rapidly than any other motor driven axis, it can use liquid supply catheters from stationary isolated reservoir sources not involved in the motion of the print head, thereby insuring that the inertial moment of the print head assembly is relatively unhindered by the weight thereof.
  • the ink jet track rests on another carriage assembly capable of moving back and forth on a Y axis track in an orthogonal axis relative to the rapidly oscillating inkjet track assembly. This carriage rests on sufficiently stable supports to render precise repetitions of motion and of sufficient height to clear substantial depth of a third axis platform that moves in small incremental steps in the vertical direction and is surrounded by a Z axis platform enclosure.
  • the Z axis platform travels upon three or more vertical screw elevators which are driven by a common drive belt through pulleys on free turning bearings and are powered by a gear reduced stepper motor.
  • the vertical moving platform also has an inlet and outlet micro-tube assembly which provides for the pumping out of unused liquids, the infusion of washing liquids and their removal as well.
  • the single reservoir of washing fluid is maintained by an internal filter and flocculating chemical system which ensures the economical and efficient fresh replenishment of the same.
  • the entire mechanical assembly can be stationed on a leveled platform, the means of which is provided for by screw adjusted cleats preferably near the perimeter of the bottom chassis.
  • Gravity provides for the leveling mechanism necessary for the establishment of uniform layering during the three-dimensional build up of the object. Each sequential liquid layer remains as a level surface and supporting layer for solidifying linear infusion of another activating liquid substance that will create the final solid object.
  • the reliance on gravity as the liquid leveling mechanism also eliminates the need for a more expensive and complicated machine element to perform a leveling calibration.
  • the ink jet head can maintain reasonable control of the thickness of the consecutive layers by simple virtue of its established mechanical precision in the printing trade for dispensing discrete droplet volumes and also from software control over the shape and number of droplets or resolution at which they may be dispensed.
  • a model of one square mile of Manhattan in 10 minutes can have resolution high enough to discern the wheels and windows of taxicabs on the streets below the skyscrapers or incorporate workable tolerances for a dynamic model of a V- 8 internal combustion engine on the same Z platform area as the Manhattan model with speeds as fast as one minute.
  • Rapid catalysis utilizing a dot monomer to dot catalyst deposition method is not as vulnerable to expansion deformity as large volume structures are. Catalysis may occur as rapidly as a few microseconds or even fifty milliseconds. Heat loss and material stability are controlled in the picoliter range and by the time anther layer is deposited in the "z" axis on top of the this layer latent heat of polymerization has already reached equilibrium.
  • Axes may be plotted through the use of a three dimensional drafting computer software in which a three dimensional rendering is abstracted using the x, y and z axes. Each layer corresponds to a cross section of the finished object.
  • the first is a local resolution limit established variously by optical refractive parameters, diffusion due to local light scattering or heat as is the problem in many methods heretofore employed.
  • the second is due to speed limitations set forth in powder sintering and many liquid solidification processes, by the need to make every successive layer leveled with a separate non imaging calibration pass.
  • the third is the requirement for massive amounts of liquid monomer, much of which is eventually non-image waste and the gross expense to cure through laser or similar method.
  • Fourth is an inability to simultaneously use a wide variety of structurally versatile materials suitable for dynamic modeling
  • fifth is an inability to create fully realistic objects in photographic color in opaque and transparent substrates.
  • the teachings relate to the resolution limits by experimentally applied use of an ink droplet delivery system with droplet size of monomer and catalyst with secondary heat coordination controlling the shape and uniformity of successive layers.
  • limited induced local reactivity has established resolution limits to within one ten thousandths of an inch.
  • An x/y two dimensional precisely deposited pattern of liquid monomer is deposited from one ink jet reservoir onto a platen by an ink jet dispenser at the same time as a catalyst is deposited selectively on top of the monomer dots by another ink jet dispensing head.
  • the platen is then lowered upon the z axis and the next successive dot layer of material and catalyst is likewise deposited atop the first.
  • An outside heat source or temperature controller may be employed to accelerate or retard polymerization.
  • the speed of this process is established mainly by the droplet delivery system which doesn't require time consuming alternate layer calibration, can be amplified by stacked arrays, additional image software support, and electromechanical hardware support.
  • the catalyst is introduced simultaneously with monomer droplets and not onto a preexisting monomer reservoir.
  • a monomer reservoir represents a medium that transmits vibration-induced error.
  • a monomer pool is far harder to control on a layer-upon-layer basis and is therefore unsuitable for very high tolerance work, whereas is employed in this new invention, droplet groups have been found to create very precise tolerances and crisply delineated differentiation without bridging between close edges of an image/part due to dendritic branches or other random formations.
  • a monomer pool creates a greater expense in unused monomer.
  • Waste management and support for the object as it is created can be simultaneously achieved and controlled by the employment of a novel "sand bed technique," whereby supportive material similar to powder sintering layers is deposited by catalyst droplet dithering, which prevents the fusion of adjacent droplets while contributing a solid, fluidized, open-celled sand-like volume by which to support island and negative angled portions of a built up three dimensional image, and also provide a means by which waste monomer is safely evacuated.
  • a moat or otherwise obvious shell like structure is simultaneously built up with the image/part and surrounds the three dimensional image/part thereby limiting also a great deal of excess investment in monomer.
  • the item created in a clear glass or plastic, sealed chamber of the machine and a washing system is employed.
  • the object has been created on the z platform, and it has been created within its own sealed catalyzed shell, which had been simultaneously formed with it.
  • the draining of the materials would take place within the sealed newly formed shell.
  • the internal flocculating / washing mechanism in the unit would then be employed to rinse the newly created item and drain away any uncured or partially cured material storing it in a cartridge for easy, non-hazardous disposal along with the fully cured sand-like support material. This is better for both the ease of the user and the environment.
  • the platen should be of a conductive material capable of functioning as cathode or electrode which is highly resistant to chemical erosion of strong acids or alkali.
  • the purpose of the electrically conductive platen is for the electrodeposition of metal salt solutions or of dissolved metal solutions into the direct formation of successively layered three dimensional parts. Virtually any metal or alloy may be tailored into the shape under construction with the native material properties of the resulting metal varied according to specification, and herein again, a platen capable of controlling heat in the reaction zone is of great benefit.
  • the z-axes platen is not preferred to move in either the x or y axes because the precise leveling effect of gravity upon the layers of liquid eliminates the need for a calibrating correction of another mechanical device. Any tangent motion introduced into the z-axes platen stage would contribute perturbed disturbances in the form of micro ripples thereby distorting the desired 3D image.
  • the preferred embodiment will for the same reason have leveling cleats attached to the bottom of the invention and these also, mounted on shock isolation pillows.
  • the degree of precision with which objects can be created with this invention is basically limited to the precision of the ink jet head. With regard to precision capacity 1200 dpi and greater are readily available in ink jet heads, and finer are available in certain others. Regarding materials used, it has been established by experiment that a dot of reactive catalyst will have its diffusion rate arrested by the surrounding reactive precursor and that the dot gain of the catalyst can be controlled by the limiting speed of the surrounding precursor reactants.
  • a piezo-delivery system is a more desirable method for the application of monomer in some embodiments.
  • Piezo jet heads are desirable because of droplet delivery, and also because the heating element common to a bubble-jet heads, such as is employed by Hewlett Packard, can create side reactions and charring with many of the substances and chemical combinations used by the embodiments disclosed herein. Therefore, the use of a peizo-delivery head may have additional advantages when used with the embodiments disclosed herein because of secondary and unexpected effects due to the side reactions and charring associated with ink jet heads. It is already well known by chemists in polymer science that usable plastic objects such as acrylic or styrene containers have catalyst emissions reduced to near zero amounts because of polymer entrapment.
  • inkjet heads containing inhibitors such as hydroquinone can be employed to quench the specific boundaries of reaction zones. Keeping the inhibitor separate rather than in combination with a monomer (which is also possible) is preferable to create the strongest boundary or "safety zone" for reaction control.
  • This method of localized inhibiting imagery can be employed also for the purpose of defining three dimensional objects, for example the quenching agent serves as a masking element to delineate deposited material borders.
  • An alternative embodiment employing multiple sets of ink jet heads can be used to create strata of various different substrates assembling three dimensional objects in multiple materials simultaneously in a dynamic form, providing the catalysis of one liquid is not unduly inhibited by another so as to prohibit accurate deposition.
  • Another alternative embodiment employing multiple sets of ink jet heads includes the use of tinted sets of monomer and catalyst to create objects in full lifelike color, with true photographic detail, in either opaque or transparent substrates. Utilizing either four- color process with resolution control and either opaque or transparent base monomer creates a heretofore unavailable degree of color replication and is completely unique to this invention.
  • Control of the droplet resolution settings provide the opportunity to first create a "rough” or lower resolution “draft” of an item before committing to the higher resolution finished item.
  • droplet size can be increased to create a lower resolution rough draft.
  • a honeycomb, or other pattern can create a more open celled structure for "rough" draft objects. Indeed the center of an object can be hollowed thereby conserving monomer.
  • a level of resolution may be selectable resulting in changes in droplet size, creating selective voids, patterns, and other manner in which the resolution may be reduced and/or monomer may be conserved while still generating an object at a desired lower resolution setting.
  • Objects can be built in the most economical way possible, including consideration for transparency versus opacity, color, and solid versus detail.
  • software may be configured to control droplet size, pattern, color, opaqueness, texture, and other aspects of the manner in which the object is generated.
  • These attributes can also be controlled base on other aspect, such as the size of the object generated. For example, where an object is larger, the droplet size can be increased such that the larger object is generated in a shorter amount of time than it would otherwise with a smaller droplet size.
  • These alternative embodiments can be combined to any degree or at any size to provide complete replication of real objects with remarkable accuracy.
  • An alternative embodiment employing multiple sets of ink jet heads can be used to create strata of various different substrates assembling three dimensional objects in multiple materials simultaneously in a dynamic form, providing the catalysis of one liquid is not unduly inhibited by another so as to prohibit accurate deposition.
  • Another alternative embodiment employing multiple sets of ink jet heads includes the use of tinted or pigmented sets of monomer and catalyst to create objects in full lifelike color, with true photographic detail, in either opaque or transparent substrates, all of which are comprised of the appropriate monomer and catalyst additives.
  • glitters and metalized pigments can be used to create the appearance of metal in a polymer base.
  • a B-staging catalysis curing cycle may be implemented to provide a first level of polymerization prior to a final catalysis curing cycle wherein a final level of polymerization is achieved.
  • Such embodiments may include multiple mechanisms for enabling each curing cycle.
  • a first curing cycle may include a UV-catalysis cycle accomplished using a UV irradiating mechanism followed by a second isolated heat-accelerated catalysis enabled using a heat conductive mechanism.
  • Each cycle can include any combination of reactive energy introduced to cause catalysis, such as UV irradiation and heat transfer.
  • the first curing cycle may be implemented to manipulate a first level of polymerization such that droplets of monomer more closely (or substantially) retain a three dimensional spherical shape. However, each droplet of monomer may be only partially polymerized such that each droplet retains a level of elasticity and the ability to adhere to subsequently applied droplets. Subsequently, a second curing cycle (or multiple subsequent curing cycles) can create a final hardening catalysis of the polymer such that the generated object substantially retains its intended final shape in a fully cured state.
  • a UV light source may be placed in a location such that a first catalysis curing cycle can be initiated by illumination prior to the reactants being applied to a substrate.
  • a head 600 is shown for application of a prepeg catalyst/monomer/diluent composition 605 as discussed in further detail in section 2 of this application.
  • the droplets 605 are irradiated by a source of light 610 that directs light 610 substantially perpendicular to a flow direction 615 of which the droplets 605 are applied.
  • the light 610 is irradiated directly upon the droplets 605 and at an intensity to initiate a first stage of catalysis of the droplets 605.
  • Radiation of any electromagnetic radiation of various wavelengths may be used and may be tailored to the particular reactants being ejected from the head 600.
  • the light source 610 can include a silicon based light source, such as a laser or light emitting diode in combination with a waveguide for directing such light.
  • the light source 610 can be incorporated into the head 600 such that the light source 610 travels in the x-axis and y-axis with the head 600 to deliver the direct irradiation to the airborne droplets 605 prior to application of the droplets 605 to a surface of a heated Z-stage 620.
  • UV irradiation on the deposited surface 625 may not be desirable as the droplets 605 of the prepeg composition are only catalyzed for the purpose of creating a more localized lobe shaped nucleus for a second droplet of monomer which surrounds the catalyst nucleation lobe and thereby forms its own surrounding polymer material layer in similar shaped fashion.
  • This form of extended catalysis is initiated under the first UV influence cracks a cationic catalyst which can further finish catalysis without the aid of UV light, but controlled very precisely with the addition of application of heat in the deposit zone by the heated Z-stage 620, for example.
  • the multi-stage catalysis curing cycle can be activated by separate monomer and catalyzed droplets.
  • a view of a drop transit catalysis method is illustrated.
  • UV light 700 irradiates a catalyst droplet 705 at right angles only exposing it before it at the beginning of its path to a substrate 710.
  • a monomer droplet 715 from another nozzle lands over a nucleus catalyst droplet target 720, coating it where it is held captive for final diffused curing.
  • the catalyst chemical material is composed of a UV activated lewis acid. The lewis acid will continue a heat accelerated cure cycle even after it is no longer under the influence of UV irradiation.
  • the monomer droplet 715 may be colored by a transparent dye or by opaque micro pigments and will cure readily after combining around the catalyst nucleus 720.
  • the nuclear catalyst droplet 705 can be finely tailored with ingredients that retard curing, disperse catalyst concentration, disperse monomer concentration or any combination thereof.
  • the nuclear catalyst droplet 705 can be hereby designed to acquire just enough gel like properties after UV irradiation, that it does not flatten out upon impact with the substrate 710 and maintains a small highly localized voxel position but is still liquid enough to permit catalyst diffusion
  • encapsulant bead Into the monomer droplet 715 which lands over the catalyst droplet nucleus 720 as an encapsulant bead.
  • the polymerized encapsulant bead has many times the strength and adds significant volume to the finished voxel.
  • Multiple voxels build up serially in layers to form 3D objects and retarded cure gel voxels can substitute as support media in a way similar to the 'sand bed' theme and also wash away later with the use of detergent/solvent mixtures.
  • Epoxies comprise a very large part of the material benefits available to the monomer chemicals which are available. Cationic curing will cure virtually all of the epoxy monomers and oligamers in the market.
  • Latent heat free radicals can also be employed for such monomers such as acrylics and acrylated urethanes and combined to great advantage with cationic systems.
  • Epoxy, Elastomers, Acrylics, Silicones and many other plastic materials can be used in this type of curing system or in conjunction with others as symbiotic materials.
  • the selection and formulation of monomers for homopolymer and copolymer formation need to and can have adaptive chemical and environmental compensation for tuning the reaction rates, exothermic accumulation and density modulations.
  • Such chemical manipulation includes a thermostatically controlled conductive core under the Z stage platform that virtually tunes in the peak values needed for rapid polymerization and also supplies a more even temperature gradient which greatly reduces the exothermic density distortions across the reaction threshold.
  • This invention relies on a head, such as a conventional inkjet printing head or specialized printing head, adapted for the purpose of generating discreet, single or multiple consecutive laminar strata which generate three dimensional representations or models of an object.
  • a head such as a conventional inkjet printing head or specialized printing head, adapted for the purpose of generating discreet, single or multiple consecutive laminar strata which generate three dimensional representations or models of an object.
  • Such printing heads may be integrated with an appropriate mechanism for generating a geometrical x axis, y axis, and z axis and with a variety of software capable of executing machine codes by computer consistent with real deposition of that corresponding three dimensional representation.
  • the liquids deposited by a first head are activated by a chemical reaction by another liquid of at least one other head to precipitate from a concentrated solution a metal, or to crosslink an unsaturated species of chemical precursor so that it solidifies thereby, will be comprised of materials such as but not limited to acrylate liquids.
  • the monomer liquids can be comprised of member of the acrylate family, such as the following examples:
  • monofunctional acrylates such as methylmethacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate;
  • difunctional acrylates such as polyethylene glycol diacrylate, alkoxylated aliphatic dioldiacrylate, or any difunctional diol of alkoxylated aliphatic dioldiacrylic;
  • trifunctional acrylates such as trimethol propane triacrylate, glyceryl propoxy triacrylate, or any propoxylated group between 3 and 9 of glyceryl triacrylate; • the highly alkoxylated triacrylates and tetrafunctional acrylates such as di- trimethylol propane tetraacrylate;
  • the acrylates can be catalyzed by free radical catalysts, wherein the catalysts are comprised of any hydrocarbon based peroxide with pendant peroxide group which are easily liberated such as methylethylketone peroxide, acetone, or peroxide.
  • Epoxy liquids can be used where the epoxy liquids are comprised of members of the epoxy family.
  • epoxies including Bisphenol A epoxies, Bisphenol F epoxies, epoxy creosol novolacs, epoxy phenol novolacs, cycloaliphatic epoxies, aliphatic epoxies, or any unsaturated hydrocarbon molecule with at least one oxyrain ring that is liquid can be used.
  • Epoxies can be catalyzed by specific initiators. Examples of such initators include:
  • Lewis Acids which are initiating homopolymerization through either blocked or unblocked cationic initators, such as iodonium salts of hexofluoro antimonates, hexafluoro phosphate, or hexacloro phosphate;
  • cycloaliphatic amines family of co-reactive or copolymerization initiators such as aliphatic amines, cycloaliphatic amines, unsaturated polyamids, aromatic amines, or phenaalkamines;
  • the vinyl ether family of co-reactive or copolymerization initiators may be from the cyanate ester family of co-reactive or copolymerization initiators;
  • the initiators may be from the diisocyanate family of co-reactive or copolymerization initiators
  • the anhydrides family of co-reactive or copolymerization initiators such as methyl tetrahydrophthalic anhydride, or hexahydrophthalic anhydride; and • The polyester family of co-reactive or copolymerization initiators having reactive double bonds.
  • Catalyzations can also be improved through the use of hardeners.
  • the hardeners increase the speed and efficiency of reaction such as an amine coinitiator.
  • Polyester liquids can be implemented, wherein the liquids are comprised of members of the Polyester family such as polyesters including aliphatic and cycloaliphatic polyesters, or polyester which are viscosity modified by styrene monomer.
  • Polyesters can be catalyzed by specific initiators wherein initiators are can be catalyzed by free radical catalysts.
  • Such catalysts are comprised of any hydrocarbon based peroxide with pendant peroxide group which are easily liberated such as methylethylketone peroxide, acetone, or peroxide.
  • Catalyzations can also be improved through the use of reactive synergists.
  • the reactive synergists increase the speed and efficiency of reaction such as an amine coinitiator, or vinyl ether.
  • Any other monomer and catalyst combination may mimic the functionality of those named herein so as to have similar polyester acrylate functionality.
  • Styrene monomers which may be coreacted with the monomer and catalyst combination.
  • Complete polymerization reactions can vary in speed from several hours such as an epoxy potting formula, to reactions so rapid that they occur in femtosecond flashes of time such as polyacetalyne created after pressure autodetonation of acetylene monomer.
  • the liquids used can be formulated to cure to varying durometers and tints anywhere from materials such as smooth soft rubbery flesh tone, to rigid brightly hued plastic that looks like stained glass or pigmented to look like gold, or even deposited of metal salts to create real metal objects.
  • a 3-part chemical prepeg catalyst material may be used.
  • the 3-part chemical prepeg catalyst material can be specifically formulated with a portion of monomer (for the purpose of starting a partially cured B stage polymer network), a portion of nonreactive diluent (for the purpose of retarding 100% cure of the monomer and compromising the polymers full strength and other material properties), and a photosensitive cationic catalyst of a percentage sufficient to initiate partial polymerization but also of a percentage which is sufficient to remain latent until a final cure of second surrounding monomer material is deposited on it.
  • Cationic catalysts have a property whereby, unlike free-radical curing processes, the cationic released lewis acids will continue to promote polymerization after primary initiation with the UV irradiation. Secondary additional heat is very effective at extending the finished curing process over a longer period of time, thereby allowing exothermic reactions to continue in a more relaxed manner.
  • Polymer surfaces with a slightly more controlled catalysis reaction are also smoother, less reticulated, and generally have better material properties than other method previously used. According to this method, upon microscopic examination, the droplets formed in the former embodiment, have wider less localized pancake-like structures. However, the refined embodiment herein forms smaller, higher resolution polymer dots.
  • the purposeful multi-staging catalysis method becomes of increased importance in many applications. As disclosed herein, in such applications it is not necessary to maintain local shape integrity to have 100% curing occur in a fraction of a second, droplet upon droplet. As objects become larger and larger, for example, exothermic distortions will predominantly influence structures which require high resolution with resolution- limiting inclusions and warping.
  • the application of a first activating UV-catalysis coupled with second UV isolated second heat-accelerated catalysis is unique as a single design intent and design function.
  • This invention may surpass the resolution limits of the conventional stereolithographic methods by incorporating a monomer dot to catalyst dot resolution. Using this method, small discreet smooth edged structures of high uniformity and repeatability are rendered. This invention also permits the use of more than one catalyzable material simultaneously with another. Thus, several embodiments permit object formation in full photorealistic color in both transparent and fully opaque materials.
  • the catalyst is introduced simultaneously with monomer droplets and not onto a preexisting monomer reservoir.
  • a conventional monomer reservoir as discussed in the background section represents a medium that transmits vibration-induced error.
  • a monomer pool is much more difficult to control on a layer-upon-layer basis and is therefore unsuitable for very high tolerance work.
  • droplet groups have been found to create very precise tolerances and crisply delineated differentiation without bridging between close edges of an image/part.
  • a monomer pool creates a greater expense in unused monomer.
  • the embodiments disclosed herein reduce the expense and complexity of precision stereolithography by the elimination of previous mechanisms and techniques that produce the highest expense or inhibition of speed, accuracy and/or ease of use.
  • the embodiments disclosed herein allow for use of more than one material simultaneously forming three dimensional objects and creation of full color, photorealistic three dimensional objects in opaque or transparent materials.
  • the creation of this economical process for stereolithography enables the general populace to access this technology for engineering, research, artistic and hobby applications via the common personal computer.
  • CAD CAD
  • Solid Works or other three dimensional modeling software is used to create objects in the industrial sector however with the advent of three dimensional gaming programs, animation and other software the general populace by means of a simple interface enables a user to utilize the availability of object downloads off of the worldwide web to print out three dimensional objects at home.
  • one aspect of the present invention relates to a point of sale enabling a consumer to remotely purchase and download digital instructions for locally fabricating a product using the stereolithographic printer disclosed herein.
  • This invention in its smaller form, will easily serve as a peripheral extension analogous to a desktop printer.
  • it is created to function as a two- or three-dimensional printer to give the user complete freedom in one unit, with replaceable monomer cartridges.
  • peripheral extensions also enable a new point for licensing 3D art from toy, hobby, restaurant or other theme generated objects of a copyrighted nature that are popular for general consumer use.
  • a McDonald's Happy Meal Action Figure a Disney animated character, a Power Rangers action figure, Mattel Barbie doll accessories, such as shoes or belts, Special Martha Stewart Christmas tree ornaments, rubber stamps, Swarovsky Crystal jewelry items, or any other copyrighted objects for sale may be made utilizing the capacity of the internet to permit consumers to download via an exclusive licensing agreement with revenue generated for both licensor and licensee.
  • the licensing and exclusivity to different manufacturers or owners of commercially viable and popular entertainment or novelty items intellectual property may be enabled at a new point of sale as a result of the convenience offered by the embodiments disclosed herein.
  • the ability to download such copyrighted, or otherwise proprietary, designs for manufacture by the stereolithographic printer can be enabled by use of a computer connected to both the stereolithographic printer and an internet connection along with software stored on the computer for downloading the data files representing instructions for controlling the stereolithographic printer to construct the three dimensional objects.
  • the computer may also store licenses for later access.
  • stereolithography units of this invention can also be made to create industrial rapid prototyped items as large as an automobile with several types of materials in place, in color, in a way that heretofore was thought of as impossible, or impossibly expensive.
  • the invention may improve both the ease and economic viability of stereolithography, as well as increase the capability currently available form existing stereolithography methods. These benefits may extend to both the industrial sector for quality, speed, cost and versatility, and for the private general consumer who will have a completely new arena for creativity and utility available to them.
  • this invention greatly expands the versatility and variety of materials and provides the ability for users at both professional and consumer levels to create items in photorealistic color in both transparent and opaque versions, metallic objects, and objects comprised of more than one type of material simultaneously deposited.

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Abstract

L'invention concerne une nouvelle application d'une technologie de jet d'encre pour l'objectif express de déposer une strate imagée et en couches de manière précise d'un polymère rapidement catalysé, fournissant ainsi un nouveau procédé d'impression stéréolithographique (tridimensionnel). Il s'agit d'un système d'impression stéréolithique utilisant des axes x, y et z pour tracer et déposer des couches d'additif successives de matériau jusqu'à une résolution de 1/10 000 de pouce d'épaisseur ou plus, où les matériaux déposés sont composés d'un monomère activé de deux parties ou oligomère avec un catalyseur approprié, pour créer des objets de pleine dimension à diverses tailles. Un plan déposé précisément bidimensionnel de x/y de monomère liquide, représentant une section transversale de l'objet à rendre, est déposé à partir d'un réservoir de jet d'encre sur un plateau à chaleur régulée par un dispositif de jet d'encre au même moment qu'un catalyseur est déposé de manière sélective sur le dessus de la couche de monomère par une autre tête de distribution de jet d'encre. Lorsque chaque couche a des zones imagées durcies établies, le plateau est ensuite abaissé sur l'axe z et la couche successive suivante de matériau catalysé est également déposée au-dessus de la première. Le catalyseur est introduit simultanément avec des gouttelettes de monomère et pas sur un réservoir de monomère préexistant. De sels de métaux dissous qui sont amenés à précipiter hors de la solution par le biais d'une application de goutte d'agent réducteur créent des objets tridimensionnels métalliques réels. Des procédés de contrôle des déchets, d'élimination des déchets et de support d'objet créé sont une partie intégrante de la présente invention. L'utilisation de multiples ensembles de têtes à jet d'encre peut être utilisée pour créer une strate de divers substrats différents assemblant des objets tridimensionnels dans de multiples matériaux simultanément dans une forme dynamique tels que des joints statiques en place sur un objet en plastique dur. De plus, l'utilisation de multiples ensembles de têtes à jet d'encre peut comprendre l'utilisation d'ensembles teintés ou pigmentés de couleur de la quadrichromie de monomère et de catalyseur pour créer des objets dans une couleur complètement réelle, avec un vrai détail photographique, soit dans des substrats opaques, soit transparents. L'utilisation soit d'un processus à quatre couleurs avec un contrôle de résolution, soit d'un monomère de base opaque transparent crée un degré de reproduction de couleur jusqu'à non disponible et est complètement unique à la présente invention. Le contrôle des réglages de résolution de gouttelettes donne l'occasion de créer tout d'abord une « maquette » ou un « brouillon » de résolution inférieure d'un article avant de s'engager avec l'article fini de résolution supérieure. L'invention utilise également un nouveau procédé commercial utilisant Internet pour des fichiers d'article tridimensionnels téléchargeables pour l'impression client. Cette machine, ce procédé et ces matériaux introduisent un nouveau procédé de faible coût, de haute définition, hautement polyvalent pour créer des objets tridimensionnels, rendant cette technologie plus facilement disponible pour le consommateur de masse ainsi que l'industrie.
PCT/US2008/065394 2007-05-31 2008-05-30 Procédé et matériau stéréolithique polyvalent haute définition WO2008151063A2 (fr)

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CN102529096A (zh) * 2010-12-20 2012-07-04 卡尔·赫尔 用于制造三维的物品的装置
CN102529096B (zh) * 2010-12-20 2015-10-14 卡尔·赫尔 用于制造三维的物品的装置
CN105873743A (zh) * 2013-12-30 2016-08-17 三星电子株式会社 三维打印机及其操作方法
EP2889125A1 (fr) * 2013-12-30 2015-07-01 Samsung Electronics Co., Ltd Imprimante tridimensionnelle et procédé de fonctionnement correspondant
US10452038B2 (en) 2014-01-16 2019-10-22 Hewlett-Packard Development Company, L.P. Build material profile
US10583612B2 (en) 2014-01-16 2020-03-10 Hewlett-Packard Development Company, L.P. Three-dimensional (3D) printing method
CN105916663A (zh) * 2014-01-16 2016-08-31 惠普发展公司，有限责任合伙企业 产生三维对象
CN105916664A (zh) * 2014-01-16 2016-08-31 惠普发展公司，有限责任合伙企业 产生三维物体
US11679560B2 (en) 2014-01-16 2023-06-20 Hewlett-Packard Development Company, L.P. Generating a three-dimensional object
US11203155B2 (en) 2014-01-16 2021-12-21 Hewlett-Packard Development Company, L.P. Build material profile
US10252474B2 (en) 2014-01-16 2019-04-09 Hewlett-Packard Development Company, L.P. Temperature determination based on emissivity
CN105916664B (zh) * 2014-01-16 2019-04-19 惠普发展公司，有限责任合伙企业 产生三维物体
US11167475B2 (en) 2014-01-16 2021-11-09 Hewlett-Packard Development Company, L.P. Generating three-dimensional objects
US10518476B2 (en) 2014-01-16 2019-12-31 Hewlett-Packard Development Company, L.P. Generating a three-dimensional object
US10544311B2 (en) 2014-01-16 2020-01-28 Hewlett-Packard Development Company, L.P. Polymeric powder composition for three-dimensional (3D) printing
US11273594B2 (en) 2014-01-16 2022-03-15 Hewlett-Packard Development Company, L.P. Modifying data representing three-dimensional objects
EP3626434A1 (fr) * 2014-01-16 2020-03-25 Hewlett-Packard Development Company, L.P. Génération d'un objet tridimensionnel
US10625468B2 (en) 2014-01-16 2020-04-21 Hewlett-Packard Development Company, L.P. Generating a three-dimensional object
US11673314B2 (en) 2014-01-16 2023-06-13 Hewlett-Packard Development Company, L.P. Generating three-dimensional objects
US10730237B2 (en) 2014-01-16 2020-08-04 Hewlett-Packard Development Company, L.P. Generating a three-dimensional object
US11618217B2 (en) 2014-01-16 2023-04-04 Hewlett-Packard Development Company, L.P. Generating three-dimensional objects
WO2015106816A1 (fr) * 2014-01-16 2015-07-23 Hewlett-Packard Development Company, L.P. Génération d'un objet tridimensionnel
US10889059B2 (en) 2014-01-16 2021-01-12 Hewlett-Packard Development Company, L.P. Generating three-dimensional objects
WO2015175651A1 (fr) * 2014-05-13 2015-11-19 Massachusetts Institute Of Technology Systèmes, dispositifs et procédés permettant l'impression en trois dimensions
US10052824B2 (en) 2014-05-13 2018-08-21 Massachusetts Institute Of Technology Systems, devices, and methods for three-dimensional printing
CN114734628A (zh) * 2014-06-23 2022-07-12 卡本有限公司 由具有多重硬化机制的材料制备三维物体的方法
CN114131923A (zh) * 2014-06-23 2022-03-04 卡本有限公司 由具有多重硬化机制的材料制备聚氨酯三维物体的方法
US12179435B2 (en) 2014-06-23 2024-12-31 Carbon, Inc. Methods of producing three-dimensional objects with apparatus having feed channels
US12172382B2 (en) 2014-06-23 2024-12-24 Carbon, Inc. Methods for producing three-dimensional objects
CN114131923B (zh) * 2014-06-23 2024-05-24 卡本有限公司 由具有多重硬化机制的材料制备聚氨酯三维物体的方法
WO2016170030A1 (fr) * 2015-04-21 2016-10-27 Covestro Deutschland Ag Procédé de fabrication d'objets en 3d
US10806208B2 (en) 2015-04-21 2020-10-20 Covestro Deutschland Ag Method for producing 3D objects
US10987856B2 (en) 2015-12-21 2021-04-27 Wacker Chemie Ag Method and device for producing an object by using a 3D printing device
EP3666500A1 (fr) * 2018-12-13 2020-06-17 Canon Production Printing Holding B.V. Procédé d'impression à jet d'encre en 3d
US11407176B2 (en) 2019-03-20 2022-08-09 Magnum Venus Products, Inc. Pumping system and method for 3D printing
EP3711921A1 (fr) * 2019-03-20 2020-09-23 Magnum Venus Products Système de pompage et procédé d'impression 3d
US20210094226A1 (en) * 2019-09-26 2021-04-01 The Curators Of The University Of Missouri Oxidation polymerization additive manufacturing
CN113484531B (zh) * 2021-06-30 2022-08-26 中国热带农业科学院橡胶研究所 一种橡胶树排胶自动监测系统及方法
CN113484531A (zh) * 2021-06-30 2021-10-08 中国热带农业科学院橡胶研究所 一种橡胶树排胶自动监测系统及方法
KR102580627B1 (ko) 2021-09-30 2023-09-21 한국세라믹기술원 광중합 3d 프린터, 광중합 3d 프린팅 방법, 및 광중합 3d 프린팅용 조성물
KR20230047269A (ko) * 2021-09-30 2023-04-07 한국세라믹기술원 광중합 3d 프린터, 광중합 3d 프린팅 방법, 및 광중합 3d 프린팅용 조성물

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