WO2022055904A1 - System for obtaining a photopolymerized prepolymer - Google Patents
System for obtaining a photopolymerized prepolymer Download PDFInfo
- Publication number
- WO2022055904A1 WO2022055904A1 PCT/US2021/049328 US2021049328W WO2022055904A1 WO 2022055904 A1 WO2022055904 A1 WO 2022055904A1 US 2021049328 W US2021049328 W US 2021049328W WO 2022055904 A1 WO2022055904 A1 WO 2022055904A1
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- WO
- WIPO (PCT)
- Prior art keywords
- prepolymerization
- station
- chamber
- conveyor
- stations
- Prior art date
Links
- 239000000463 material Substances 0.000 claims abstract description 150
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- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 5
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 3
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- 230000004075 alteration Effects 0.000 description 1
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- CQAIBOSCGCTHPV-UHFFFAOYSA-N bis(1-hydroxycyclohexa-2,4-dien-1-yl)methanone Chemical class C1C=CC=CC1(O)C(=O)C1(O)CC=CC=C1 CQAIBOSCGCTHPV-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- ZIMKJLALTRLXJO-UHFFFAOYSA-N hioc Chemical compound C12=CC(O)=CC=C2NC=C1CCNC(=O)C1CCCNC1=O ZIMKJLALTRLXJO-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Definitions
- the present disclosure relates generally to prepolymers, and more particularly to the creation of photopolymerized prepolymers suitable for use as construction materials.
- 3D printing has become a big buzz term in the industry and starts penetrating even into such a field as the construction sector.
- 3D printers now capable of printing building walls and processing cements, the technology could help reshape the traditional construction technique and products.
- the history of 3D printing in construction is not yet rich.
- 2004, a University of South Carolina made an attempt to produce a wall by 3D printing which was widely accepted as the technology’s first entry into construction.
- a full canal house built using 3D printing was completed in Amsterdam.
- a 3D-printed mansion was completed in China.
- the Dubai Future Foundation built its office via 3D printing which is considered as a major milestone for the technology in the commercial construction sector.
- the fully functioning 2,700-square foot building was built in just 17 days by a large 3D printer that measured 120 x 40 x 20 feet.
- US Patent No. 9,394,441 issued on July 19, 2016 to P. Xu, et al. discloses a build material for use in a three-dimensional printing system.
- the material consists of a curable oligomeric material, a reactive component, a non-reactive component comprising one or more urethane waxes, and at least one diluent.
- the reactive component of the material is at least one chemical moiety that is polymerizable with a chemical moiety contained in the oligomeric curable material and/or at least one diluent.
- the reactive component is present in the build material as crystalline regions.
- suitable photoinitiators comprise those operable for use with an Ar laser radiation source including benzyl ketals, such as benzyl dimethyl ketal.
- a photoinitiator comprises an a-hydroxyphenyl ketone, benzyl dimethyl ketal or 2,4,6- trimethylbenzoyl diphenylphosphine oxide or a mixture thereof.
- US Patent No. 6,927,018 issued on August 9, 2005 to R. Burgess relates to three-dimensional printing using photo-activated building materials.
- the publication discloses a method, an article of manufacture, and a system for fabricating an article using photo-activatable building material.
- the method includes the steps of applying a layer of a photo-activatable building material to a preselected surface, scanning the layer using a plurality of light-emitting centers to photo-activate the layer of photo- activatable building material in accordance with a predetermined photo-initiation process to obtain polymerization of the building material, wherein scanning is accomplished at a predetermined distance using a predetermined light intensity, and repeating the steps of applying the layer, with each layer being applied to an immediately previous layer, and scanning the layer with the plurality of light-emitting centers to polymerize the building material until the article is fabricated.
- Photo-activatable building materials exemplified herein as materials suitable for the manufacture of building components in the proposed 3D printing method are the Shipley Microposit SI 800 Series Photo Resists.
- the Shipley Microposit SI 800 Series Photo Resists are optimized for G-line (0.436 microns) exposure, effective for broadband exposure, and have high-resolution process parameters.
- Shipley Microposit S 1813 has a 12.3 micrometer thickness, requires 150 mJ/cm 2 for polymerization (“printing”), and may be polymerized at the G-line (0.54 NA).
- the present disclosure relates to systems and methods for obtaining photopolymerized prepolymers as materials suitable for manufacturing buildings or building components using 3D printing processes.
- building components can include walls, floors, exterior and interior cladding, furniture, other outdoor and indoor features, and the like.
- This can be accomplished using a system that includes a closed loop conveyor, such as a flexible belt, stretched between a precursor loading station and a prepolymerization material receiver from which the product is unloaded to a mixer for the inorganic fdlers to be added and then to the construction 3D printing machine.
- the conveyor can carry a plurality of flexible trays that loop around pulleys of the closed loop conveyor.
- One pulley can be a driving pulley having a driving motor.
- the trays are shallow troughs that have open tops and carry dosed portions of the precursor, which is photopolymerized on its way from the loading station to the unloading station by sequentially passing under light sources of two photopolymerization stations.
- the conveyor can have a loading station for untreated (i.e., precursor) material and unloading position on the side opposite to the loading station. Trays can receive material facing upward at the loading station, pass through the unloading station, and then return face down back to the loading station on the underside of the conveyor.
- Photopolymerization stations can include a plurality of light-emitting devices operating at predetermined wavelength(s) and irradiating the material in the trays with a predetermined dosed amount of light energy to precure the material to a desired viscosity. Parameters of the process, such as viscosity, radiation dose, exposure time, exposure intensity, temperature, and the like, can be automatically controlled by a central processing unit. Prior to unloading, uncured liquid can be separated from the precured prepolymer and is returned to the loading station for reuse.
- a photopolymerized prepolymer manufacturing system can include at least a conveyor, a prepolymerization chamber, and one or more processors.
- the conveyor can be configured to move untreated material from a loading area to an unloading area.
- the prepolymerization chamber can be positioned proximate the conveyor and can have multiple prepolymerization stations arranged in sequence with respect to the conveyor.
- the prepolymerization chamber can convert at least a portion of the untreated material into photopolymerized prepolymer material as the conveyor moves the untreated material past the prepolymerization chamber.
- the processor(s) can be configured to control operations of the conveyor, the prepolymerization chamber, or both, and can alter operations of the conveyor, the prepolymerization chamber, or both, in response to a detected system event.
- the photopolymerized prepolymer material (after adding the inorganic fillers) can be suitable for use in the 3D printing of buildings or building components.
- Each of the multiple prepolymerization stations can include one or more light sources that irradiate the untreated material as the conveyor moves the untreated material past the prepolymerization chamber.
- Each of the multiple prepolymerization stations further includes a lid that facilitates access to the one or more light sources, and the light sources can be contained within the lid.
- Some or all of the light sources can include an array of light-emitting diodes (“LEDs”).
- the detected system event can involve a halted operation of one of the multiple prepolymerization stations.
- the processor(s) can be configured to increase the intensity of the one or more light sources in the remaining prepolymerization stations in response to the halted operation of one of the multiple prepolymerization stations.
- Each of the multiple prepolymerization stations can also include at least one fan and one or more ventilation holes to facilitate air circulation as the conveyor moves the untreated material past the prepolymerization chamber.
- a prepolymerization chamber configured to convert material into photopolymerized prepolymer material can include a first prepolymerization station and a second prepolymerization station.
- the first prepolymerization station can include a first light source configured to irradiate material at a first intensity level as a separate conveyor moves the prepolymer material past the first prepolymerization chamber
- the second prepolymerization station can include a second light source configured to irradiate the material at a second intensity level as the separate conveyor moves the material past the second prepolymerization chamber.
- the prepolymerization chamber can be configured to automatically increase the first intensity level when operation of the second prepolymerization station is halted, and can also be configured to automatically increase the second intensity level when operation of the first prepolymerization station is halted.
- the prepolymerization chamber can also include a first lid at the first prepolymerization station that facilitates access to the first light source and a second lid at the second prepolymerization station that facilitates access to the second light source.
- the first light source can be contained within the first lid and the second light source can be contained within the second lid, and both light sources can include an array of LEDs.
- the prepolymerization chamber can also include a processor configured to automatically increase the first intensity level when operation of the second prepolymerization station is halted and to automatically increase the second intensity level when operation of the first prepolymerization station is halted.
- the processor may also be configured to interface with a separate processor controlling the separate conveyor, which can involve providing an instruction to the separate processor to slow the separate conveyor when operation of the first prepolymerization station is halted or operation of the second prepolymerization station is halted.
- a separate processor controlling the separate conveyor can involve providing an instruction to the separate processor to slow the separate conveyor when operation of the first prepolymerization station is halted or operation of the second prepolymerization station is halted.
- Such halted operation of one of the first or second prepolymerization stations while the other prepolymerization station continues operation can include performing maintenance on the halted prepolymerization station.
- the prepolymerization chamber can also include a first fan at the first prepolymerization station, a second fan at the second prepolymerization station, and a plurality of ventilation holes at the first and second prepolymerization stations. The fans and ventilation holes can facilitate air circulation as the separate conveyor moves the material past the prepolymerization chamber.
- Pertinent method steps can include introducing an uncured liquid material onto a conveyor at a loading position, moving the conveyor until the material is at a first prepolymerization station of an overall prepolymerization chamber, exposing the material to a first dose of radiation at the first prepolymerization station, moving the conveyor until the material is at a second prepolymerization station of the overall prepolymerization chamber, and exposing the material to a second dose of radiation at the second prepolymerization station.
- the second dose of radiation can result in curing at least a portion of the material into a photopolymerized prepolymer material.
- Additional method steps can include separating the cured portion of photopolymerized prepolymer material from remaining uncured liquid material, returning the remaining uncured liquid material to the loading position of the conveyor, feeding the cured portion of photopolymerized prepolymer material through a shredder, and delivering the shredded photopolymerized prepolymer to a receiver.
- FIG. 1 illustrates in side elevation view a schematic for an example system for obtaining a photopolymerized prepolymer according to one embodiment of the present disclosure.
- FIG. 2 illustrates in front perspective view an example tray for use on a conveyor of the system of FIG. 1 according to one embodiment of the present disclosure.
- FIG. 3 illustrates in front perspective view an example conveyor and prepolymerization chamber for use with the system of FIG. 1 according to one embodiment of the present disclosure.
- FIG. 4 illustrates in top plan view the conveyor and prepolymerization chamber of FIG. 3 according to one embodiment of the present disclosure.
- FIG. 5 illustrates in rear end elevation view the conveyor and prepolymerization chamber of FIG. 3 according to one embodiment of the present disclosure.
- FIG. 6A illustrates in side cross-section view the conveyor and prepolymerization chamber of FIG. 3 according to one embodiment of the present disclosure.
- FIG. 6B illustrates in side elevation view the conveyor and prepolymerization chamber of FIG. 3 according to one embodiment of the present disclosure.
- FIG. 7 illustrates in back perspective view the conveyor and prepolymerization chamber of FIG. 3 with one prepolymerization station lid opened according to one embodiment of the present disclosure.
- FIG. 8A illustrates in front elevation view an example prepolymerization chamber according to one embodiment of the present disclosure.
- FIG. 8B illustrates in bottom plan view the prepolymerization chamber of FIG. 8A according to one embodiment of the present disclosure.
- FIG. 9 illustrates a flow diagram of an example method of obtaining photopolymerized prepolymer material according to one embodiment of the present disclosure.
- the present disclosure relates in various embodiments to features, apparatuses, systems, and methods for obtaining photopolymerized prepolymers.
- the disclosed embodiments can be used to obtain photopolymerized prepolymers that are suitable for use (after adding inorganic fillers) as 3D printing material in the 3D printing of buildings and building components such as walls, floors, exterior and interior cladding, furniture, other outdoor and indoor features, and the like.
- the disclosed systems can include a conveyor, a prepolymerization chamber, and one or more processors for this purpose.
- the prepolymerization chamber can have multiple prepolymerization stations arranged in sequence to convert untreated material into photopolymerized prepolymer material as the conveyor moves the prepolymer past the prepolymerization chamber.
- Each polymerization station can include a light source that irradiates material, and each light source can be in a lid of the prepolymerization station.
- the system processor(s) can increase the light source intensity of the remaining polymerization stations, slow the conveyor speed, or both.
- System 20 is intended for the preparation of a photopolymerized organic material for use in a mixture with other components in the manufacture of buildings or building parts by 3D printing.
- the system 20 is intended for providing a continuous and effective prepolymerization of photocurable photopolymerizable material by irradiating the prepolymerizable material under the effect of light emitted from light sources installed on the way of the photopolymerizable material, which is transported from a starting material loader to the prepolymerized material output station.
- the system 20 contains a transporting unit in the form of a closed loop conveyor 22, e.g., a flexible belt that extends from a loading position, i.e., a prepolymerizable material input station 24, to an unloading position on the side opposite to the loading position, i.e., a prepolymerized material output station 26.
- the input station is provided with a tank 27, which contains a starting photo-prepolymerizable material 28 in a liquid state and a solid PEG 4000 powder (in some formulations) suspended in the liquid media.
- the closed loop conveyor 22 i.e., a flexible belt, is guided around pulleys 30 and 32, one of which, e.g., the pulley 30, is a driving pulley and another, i.e., the pulley 32, is a driven pulley.
- the pulley 30 is driven into rotation by a motor 34 via a driver (not shown).
- the upper run of the conveyor 22 moves in the direction of arrow A (FIG. 1).
- Attached to the surface of the conveyor 22 is a plurality of prepolymerization trays (hereinafter referred to as “material-receiving trays”) 36a, 36b, ... 36n (FIG. 1).
- the trays may be spaced from one another at a predetermined distance or may be connected to each other as links of a tractor tracks.
- Tray 36a can be a shallow rectangular trough, which has an open top, side walls 36al, 36a2, 36a3, and 36a4 and a bottom plate 38. It is understood that the material-receiving tray is shown as a rectangular body only as an example and that the tray may be square, hexagonal, or of any other suitable shape. Since the trays 36a, 36b, . . .
- the conveyor 22 i.e., the belt
- the pulleys 34 and 36 they are made of a flexible material, e.g., silicone, which is chemically inert to the liquid photopolymerizable material 28 and is able to loop around the pulleys.
- the inner surfaces of the side walls 36al, 36a2, 36a3, and 36a4 and the bottom plate 38 can be coated with a reflective coating.
- the conveyor 22 has a loading position on the side of the untreated material loading station and unloading position on the side opposite to the loading position, wherein, when the material-receiving trays pass through the unloading position, the material receiving trays are turned into upside-down positions, i.e., into position in which the open tops of the trays face down.
- System 20 can include a stationary prepolymerization chamber 38 that may have a first prepolymerization station 38a and a second prepolymerization station 38b arranged in sequence above the conveyor 22 for passing through them the material-receiving trays 36a, 36b, ... 36n on the way from the loading material input station 24 to the prepolymerized material output station 26.
- the material -receiving trays 36a, 36b, . . . 36n pass through the prepolymerization stations 38a and 38b in a continuous or an intermittent manner under control of a central processing unit 40 that, among other things, controls the operation speed of the drive motor 34 of the drive pulley 30 via a feedback line 42.
- Two prepolymerization stations 38a and 38b can be used rather than just one in order not to interrupt the process. If one of the stations fails, the other continues to work, and the process is not interrupted.
- dividing the photo-prepolymerization process into two or more stages can allow for finer selection of the viscosity in the final product, since a photopolymerization kinetics curve can have an exponential form.
- their light energy doses can be shared as 50% / 50%. If only one station operates, the load on it increases.
- the photopolymerizable material that fills the material -receiving trays 36a, 36b, ... 36n is supplied to these trays from the input station tank 37 via a dosing valve 44.
- the material contained in the trays is prepolymerized by photopolymerization under the effect of light emitted from light sources 46 and 48 installed in the respective stations 38a and 38b just above the path of the material -receiving trays 36a, 36b, . . . 36n.
- Each light source 46 and 48 can include multiple LEDs, for example.
- the light sources 46 and 48 of both stations 38a and 38b can provide a total light illumination power in the range of 2 to 50 Wt, for example.
- the LEDs are arranged in the form of a flat matrix of a rectangular or square-shaped configuration.
- the LEDs may operate on various lengths, such as 405 nm, 440 nm, etc.
- the main requirement to the light sources 46 and 48 is to provide high uniformity of illumination of the material in the trays with an accuracy within the range of ⁇ 5%.
- Each light source 46 and 48 may contain, e.g., 300 LEDs. It is understood that this amount is given only as an example and the final result will be defined by the total dose with which the prepolymerizable material is irradiated.
- the light sources 46 and 48 may be replaceable and operate on the same or different wavelengths.
- the light sources 46 and 48 may be replaceable and consist of LEDs of different wavelengths.
- the light sources 46 and 48 may operate on the wavelength of 405 nm or on the wavelength of 440 nm, or one of them may operate on the wavelength of 405 nm and another on the wavelength of 440 nm. It is understood that the specific wavelengths are given only as examples.
- the optimal dose for obtaining the final product with optimal parameters acceptable for subsequent use of the obtained prepolymer for mixing with other components used in 3D printing may be reached by adjusting the time of exposure and the power of the illuminators.
- the value of D may be adjusted by changing the power W, the exposure time t exp , or both.
- the curing time of staying of the photopolymerizable material under the light emitters and the intensity of the emitted light power, i.e., the radiation dose can be adjusted (e.g., within the range of 2 sec to 60 sec) and depends on the material used and the viscosity of the prepolymerized material to receive.
- the prepolymerized material obtained after passage through the second exposure station 38b is a gelatinous substance having viscosity in the range of 10,000 to 100,000 cPs (after homogenization).
- the material obtained in this stage consists of a gelatinous substance and a liquid.
- the viscosity is selected to provide flowability of the 3D printing material prepared in a mixture with the obtained prepolymer through pipelines of the 3D printing machine (not shown in the drawings).
- the prepolymerized material output station 26 contains a separator 50 into which the prepolymerized product that has passed through the second station 38b falls from the tray when the latter loops over the driven pulley 32.
- the separator’s interior is divided into two sections 50a and 50b by a tiltable sieve 50c, which passes the liquid phase of the prepolymerized material into the section 50b and retains the gelatinous phase in the section 50a.
- the gelatinous phase is fed through a funnel 51 into a prepolymerized material receiver.
- the prepolymerized material receiver is shown as a crusher such as a shredder 52.
- the shredder 52 may be a conventional industrial shredder such as Twin Shaft Wagner Shredder WTS500 (Austria), or the like.
- the shredder breaks the gelatinous substance into small pieces having dimensions, e.g., in the range of 1-10 mm.
- the final shredded prepolymerized product which is one of the components to be mixed with minerals or other substances needed for 3D printing of buildings or parts of buildings, is unloaded from the system (after adding mineral fillers (not shown)) to a 3D printing machine (not shown) from a final prepolymer receiver 54.
- the liquid phase of the prepolymerized material accumulated in the section 50b may be returned to the prepolymerizable material input station 24 under the action of a pumping unit 56 via a return pipeline 58.
- the final prepolymer receiver 54 is provided with an online viscometer 60 that measures viscosity of the obtained crushed and homogenized prepolymerized mass prior to unloading thereof.
- An example of a viscometer is a TT-100 lECEx Viscometer that allows fast and accurate viscosity readings. Brand: AMETEK BrookfieldTM.
- the viscometer 60 is linked to the central processing unit 40 via a feedback line 62.
- the central processing unit 40 may control and adjust the speed of rotation of the motor 34 and, hence, the linear speed of the conveyor 22, and the power of the light emitters 38a and 38b, and hence the radiation dose of the photopolymerizable material.
- the predetermined degree of prepolymerization which affects the viscosity and other performance properties of the final flowable mass of crushed and homogenized prepolymer, depends on the dose of irradiation of the material during the process of photopolymerization, and that such a dose is defined by the power of light emitted from the prepolymerization stations 38a and 38b.
- the viscosity of the final product depends on such variables as the exposure time at the first station 38a, the exposure time at the second station, viscosity of the starting material in the container 28, the thickness of the layer of the photopolymerizable material, etc., it would be advantageous to select these parameters experimentally prior to setting the system to a continuous and automatic operation in a steady mode.
- the required thickness of the material layer in each tray can be predetermined by calculations based on the Beer-Lambert law, which determines the attenuation of a parallel monochromatic beam of light when it propagates in an absorbing medium.
- the light emitted from the illuminators of the photopolymerization stations 38a and 38b decreases in the layer depth direction exponentially, knowing the constant of light absorption of the components, it is possible to evaluate a thickness of the layer of the material in the trays.
- System 20 can again include a closed-loop conveyor 22 that is run by pulleys 30, 32, to move multiple trays 36a holding material through the system.
- Prepolymerization chamber 38 can include at two photopolymerization stations 38a and 38b, although a different number of stations may be used in some embodiments. Using multiple prepolymerization stations 38a, 38b can be advantageous, as the system 20 can continue to operate even when the operation of one of the stations is halted, such as due to station failure, maintenance, or the like.
- a central processing unit 40 can be located at prepolymerization chamber 38 and may be considered as part of the prepolymerization chamber in some arrangements. Central processing unit 40 can be located between the prepolymerization stations 38a, 38b atop the prepolymerization chamber 38, for example. Central processing unit 40 can have an internal processor (not shown), as well as a display screen 41 and buttons 43 to provide input and output capabilities for system users. Such inputs can include, for example, adjusting the intensity of the light sources, adjusting the times of exposure, adjusting the conveyor speed and timing, and the like. In some embodiments, central processing unit 40 may not directly control the speed or timing of conveyor 22, but rather may include an interface to communicate with another processor that controls conveyor 22. In such arrangements, central processing unit 40 can instruct a separate conveyor processor to adjust operations of the conveyor 22 as needed.
- a first prepolymerization station 38a can include a fan 35, ventilation holes 45, a lid 39a, a handle 49a coupled to the lid 39a, and hinges or bearings 47 that facilitate opening of the lid 39a while keeping the lid attached to the prepolymerization chamber 38.
- a second prepolymerization station 38b can also include a fan 35, ventilation holes 45, a lid 39b, a handle 49b coupled to the lid 39b, and hinges or bearings 47 that facilitate opening of the lid 39b while keeping the lid attached to the prepolymerization chamber 38.
- prepolymerization chamber 38 can remain stationary while conveyor 22 moves the various trays such as tray 36a from the material loading station through the prepolymerization chamber 38.
- each prepolymerization station 38a, 38b can have its own internal light source (not shown in FIG. 3) that is used to irradiate the material as it passes therethrough, as noted above.
- Each internal light source can be an ultraviolet LED array, such as a 30 x 20 LED array, for example.
- One or more temperature sensors may be disposed within or internally about one or both prepolymerization stations 38a, 38b.
- the central processing unit 40 may monitor the internal temperature of the stations 38a, 38b by way of signals from the temperature sensor(s).
- the central processing unit 40 may independently control the speed of the fans 35 to adjust the amount of airflow drawn into the stations 38a, 38b.
- the air flow regulates the internal temperature of stations 38a, 38b.
- Each prepolymerization station door or lid 39a, 39b can be opened by way of an attached handle 49a, 49b respectively, to provide access to an internal region of the prepolymerization station. This can allow for maintenance or replacement of various dead or malfunctioning LEDs or other light source components, for example.
- central processing unit 40 can be configured to detect a system event, such as when a light source is not operating properly or when one or lids 39a, 39b is open, such that the central processing unit can alter operations of the system, as detailed below.
- FIGS. 4-7 depict the conveyor and prepolymerization chamber of FIG. 3 in various alternative views for purposes of added illustration.
- FIG 4 provides a top plan view
- FIG. 5 provides a rear end elevation view
- FIG. 6A provides a side cross-section view
- FIG. 6B provides a side elevation view
- FIG. 7 provides a back perspective view with one prepolymerization station lid opened.
- lid 39b of prepolymerization station 38b has been opened about hinges
- light source 48 can be fitted within lid 39b such that the light source 48 readily irradiates material passing beneath it inside prepolymerization station
- Light source 46 of prepolymerization station 38a can be similarly situation within the lid 39a of its prepolymerization station.
- the lid 39b when closed may rest upon a lip 53 surrounding an opening 55.
- a clear panel 57 e.g., a panel made of glass, plexi-glass or other suitable clear material
- the clear panel 57 may be removed to allow cleaning of the surfaces of the panel.
- the clear panel 57 may have a refractive index of less than 1.5 so as not to impede the ultraviolet radiation emitted from the light source 48.
- the clear panel 57 may be translucent yet still capable of passing ultraviolet radiation or other curing light from the light source to polymeric material being treated within prepolymerization station.
- an alternative and/or additional clear or translucent panel may be coupled to the underside of lid 39b. Identical or substantially similar features such as lip 53, opening 55, and clear panel 57 may also be present within polymerization station 38a.
- FIG. 8A illustrates in front elevation view an example prepolymerization chamber
- FIG. 8B illustrates in bottom plan view the same prepolymerization chamber.
- both light sources 46, 48 of both prepolymerization stations are visible and can be activated to irradiate material as it passes therebeneath.
- light sources 46, 48 are shown as having 30 x 20 LED arrays, it will be understood that other sizes and shapes of arrays may be used, and that other types of light sources may alternatively be used to precure and cure the materials.
- Temperature sensors 59 can be located within each of the prepolymerization stations to measure internal temperatures during processing, and these temperature sensors 59 can be coupled to the central processing unit or other processing component for internal temperature monitoring and appropriate system actions. For example, a first temperature sensor 59 can be located proximate the fan 35 within one prepolymerization station, and a second temperature sensor 59 can be located proximate the fan 35 within another prepolymerization station. Temperature readings can be sent from each temperature sensor 59 to the central processing unit or other system processor, and the central processing unit or other processor can adjust the speed of one or more fans accordingly based on the temperature readings to increase or decrease airflow as appropriate through the prepolymerization chamber.
- Light intensity sensors 69 can also be located within each of the prepolymerization stations to measure light intensities during processing, and these light intensity sensors 69 can also be coupled to the central processing unit or other processing component for internal light intensity monitoring and appropriate system actions. For example, four light intensity sensors 69 can be located proximate the internal comers of prepolymerization station. Light intensity readings can be sent from each light intensity sensor 69 to the central processing unit or other system processor, and the central processing unit or other processor can adjust the intensity of the relevant LEDs or other light sources accordingly based on the light intensity readings to increase or decrease power to the LEDs as appropriate through each respective prepolymerization chamber.
- central processing unit 40 can be configured to detect certain system events, such as when a light source 46, 48 is not operating properly, when a prepolymerization station 38a, 38b is not functioning correctly, when one of the lids 39a, 39b is open, a manual override input, or any other situation where irradiation is not properly taking place from a light source 46, 48 to underlying material passing therethough.
- system events such as when a light source 46, 48 is not operating properly, when a prepolymerization station 38a, 38b is not functioning correctly, when one of the lids 39a, 39b is open, a manual override input, or any other situation where irradiation is not properly taking place from a light source 46, 48 to underlying material passing therethough.
- the central processing unit 40 can automatically take action to alter operations of the system such that overall system processing can continue even with a halted operation of one of the prepolymerization stations.
- such action can include increasing the intensity of the light source of the still operable prepolymerization station. In the case of more than two prepolymerization stations, this can include increasing the intensity of some or all of the remaining operable prepolymerization stations. For example, when operation of prepolymerization station 38a is halted for any reason, then central processing unit 40 can detect such an event and automatically double the intensity of the light emitted from light source 48 of still operable prepolymerization station 38b. In this manner, the overall system 20 can continue to operate and produce photopolymerized prepolymer of a similar quality while the effective operation of prepolymerization station 38a remains halted. A similar adjustment can be made when operation of prepolymerization station 38b is halted for any reason.
- central processing unit 40 can involve altering the function of the conveyor 22. This may involve sending an instruction to a separate controller for conveyor 22 to achieve the desired alteration in function. Such an altered function can involve, for example, a longer period of time spent with the conveyor not moving while the material is beneath and being irradiated by the functioning light source. Other altered functions of the system may also be possible to achieve the desired result of continuing overall system operations while operation of one of the prepolymerization stations is halted.
- central processing unit 40 can also be configured to detect when a previously halted prepolymerization station is back online, such that system operations can be realtered back to normal.
- the feedstock material 28 that is fed into the input station 24 can be a liquid mixture of components presented in Table 1 below, for example.
- the viscosity of the material 28 can be in the range of 5 to 15 cPs, and its density can be in the range of 1.0 to 1.2 kg/1.
- the produced prepolymerized material is a gelatinous homogeneous substance having viscosity in the range of 10,000 to 100,000 cPs, for example.
- This material has an improved adhesiveness, resistance to environment, low shrinkage properties, and a short solidification time. A combination of these properties makes it possible to achieve a desired 3D printing result for a time shorter than with the use of conventional prepolymerized material.
- FIG. 9 illustrates a flow diagram of an example method 100 of obtaining photopolymerized prepolymer material according to one embodiment of the present disclosure.
- a first process step 104 can involve introducing uncured liquid photopolymerizable material into each movable tray in a predetermined dosed amount controlled through the dosing valve in a manner known in the art.
- each tray stops by the command sent to the conveyor motor from the central processing unit.
- the conveyor belt can assume its motion after the filling operation is completed and move until the tray is aligned with the position directly under the light source of the first prepolymerization station.
- the material can be exposed to a predetermined first dose of radiation at the first prepolymerization station. This can provide prepolymerization of the photopolymerizable material to a first desired degree of prepolymerization.
- the conveyor belt can again assume its motion and align the tray that contains the precured material with the light source of the second station.
- the material precured on the stage can then be subjected to a predetermined second dose of radiation for final curing to achieve the desired degree of prepolymerization.
- Process steps 104-112 can proceed continuously with the conveyor continuing its way along an endless looped path around the pulleys.
- the tray reaches the edge of the conveyor and changes its direction by looping around the pulley, where the tray drops the final gelatinous prepolymerized material to a first section of the separator.
- the obtained material may contain a liquid uncured phase.
- process step 116 the liquid uncured phase flows into a second section of the separator and returns to the tank via the pipeline under the action of the pumping unit.
- process step 116 can be optional.
- the separated homogenous prepolymerized material which is obtained with a preset viscosity of 10,000 to 100,000 cPs and a temperature in the range of 30 to 40°C, is fed from the first section of the separator via a funnel to the crusher or shredder, and from the shredder to the prepolymer receiver, where the viscosity of the prepolymer is controlled by the online viscometer.
- process step 118 can be optional.
- the final prepolymer is unloaded from the receiver in the direction of the arrow B to the mixer of a 3D printing machine. The method then ends at end step 122.
- TPO phenylbis (2,4,6-trimethylbenzoyl)phosphine oxide
- PEG polyethylene glycol HiOC fECfEjnOH
- the first prepolymerization station contained 600 LEDs with a maximal light emission energy 5 W, of which only about 90% (4.5 W) was used for irradiation of the prepolymerizable mixture.
- the irradiation time was 27 sec.
- the mixture pretreated on the first prepolymerization was transferred to the second prepolymerization station 38b, which contained 600 LEDs with a total light emission energy 5 W, of which only about 90% (4.5 W) was used for irradiation of the prepolymerizable mixture.
- the irradiation time was 27 sec.
- the viscosity of the final prepolymerized material which was unloaded after filtration through the sieve 50c and the shredder 52, was 70,000 cP. Since in this case the viscosity of the final product was within the prescribed range, the product was suitable for use in construction 3D printing.
- TPO phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide
- PEG polyethylene glycol H(OCH2CH2) n OH
- the filled trough was then sent to the first prepolymerization station 38a.
- the first prepolymerization station contained 600 LEDs with a total light emission energy 5 W, of which only about 90% (4.5 W) was used for irradiation of the prepolymerizable mixture.
- the irradiation time was 10 sec.
- the mixture pretreated on the first prepolymerization was transferred to the second prepolymerization station 38b, which contained 600 LEDs with a total light emission energy 5 W, of which only about 90% (4.5 W) was used for irradiation of the prepolymerizable mixture.
- the irradiation time was 10 sec.
- the viscosity of the final prepolymerized material, which was unloaded after filtration through the sieve 50c and the shredder 52 was 9000 cP. Since in this case the viscosity of the final product was beyond the prescribed range, the product was unsuitable for use in construction 3D printing.
- TPO phenylbis (2,4,6-trimethylbenzoyl)phosphine oxide
- PEG polyethylene glycol H(OCH2CH2) n OH
- the filled trough was then sent to the first prepolymerization station 38a.
- the first prepolymerization station contained 600 LEDs with a total light emission energy 5 W, of which only about 90% (4.5 W) was used for irradiation of the prepolymerizable mixture.
- the irradiation time was 40 sec.
- the mixture pretreated on the first prepolymerization was transferred to the second prepolymerization station 38b, which contained 600 LEDs with a total light emission energy 5 W, of which only about 90% (4.5 W) was used for irradiation of the prepolymerizable mixture.
- the irradiation time was 40 sec.
- the viscosity of the final prepolymerized material which was unloaded after filtration through the sieve 50c and the shredder 52 was 112,000 cP. Since in this case the viscosity of the final product was beyond the prescribed range, the product was unsuitable for use in construction 3D printing.
- a pulsing pump can be used instead of the dosing valve for loading the trays with a dosed amount of the precursor material.
Abstract
Description
Claims
Priority Applications (6)
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KR1020237011938A KR20230065320A (en) | 2020-09-10 | 2021-09-07 | Systems for obtaining photopolymerized prepolymers |
MX2023002891A MX2023002891A (en) | 2020-09-10 | 2021-09-07 | System for obtaining a photopolymerized prepolymer. |
CA3191771A CA3191771A1 (en) | 2020-09-10 | 2021-09-07 | System for obtaining a photopolymerized prepolymer |
CN202180062093.9A CN116171289A (en) | 2020-09-10 | 2021-09-07 | System for obtaining photopolymerized prepolymers |
JP2023515737A JP2023541591A (en) | 2020-09-10 | 2021-09-07 | System for obtaining photopolymerized prepolymers |
EP21867461.2A EP4210949A1 (en) | 2020-09-10 | 2021-09-07 | System for obtaining a photopolymerized prepolymer |
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US17/017,669 US11891465B2 (en) | 2019-04-29 | 2020-09-10 | System for obtaining a photopolymerized prepolymer |
US17/017,669 | 2020-09-10 |
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JP (1) | JP2023541591A (en) |
KR (1) | KR20230065320A (en) |
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Citations (6)
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US6174070B1 (en) * | 1998-03-02 | 2001-01-16 | Elna Kabushiki Kaisha | Portable lighting instrument having a light emitting diode assembly |
WO2015105762A1 (en) * | 2014-01-08 | 2015-07-16 | Carbon3D, Inc. | Materials and methods for three-dimensional fabrication |
US20150273520A1 (en) * | 2014-03-26 | 2015-10-01 | Seiko Epson Corporation | Method of manufacturing three-dimensional structure and three-dimensional structure |
WO2016025579A1 (en) * | 2014-08-12 | 2016-02-18 | Carbon3D, Inc. | Three-dimensional printing with build plates having a smooth or patterned surface and related methods |
WO2020120986A1 (en) * | 2018-12-14 | 2020-06-18 | Secure Micro Solutions Limited | Safety apparatus and method |
US20200407472A1 (en) * | 2019-04-29 | 2020-12-31 | Mighty Buildings, Inc. | System for Obtaining a Photopolymerized Prepolymer |
-
2021
- 2021-09-07 EP EP21867461.2A patent/EP4210949A1/en active Pending
- 2021-09-07 KR KR1020237011938A patent/KR20230065320A/en unknown
- 2021-09-07 JP JP2023515737A patent/JP2023541591A/en active Pending
- 2021-09-07 CA CA3191771A patent/CA3191771A1/en active Pending
- 2021-09-07 WO PCT/US2021/049328 patent/WO2022055904A1/en active Application Filing
- 2021-09-07 MX MX2023002891A patent/MX2023002891A/en unknown
- 2021-09-07 CN CN202180062093.9A patent/CN116171289A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6174070B1 (en) * | 1998-03-02 | 2001-01-16 | Elna Kabushiki Kaisha | Portable lighting instrument having a light emitting diode assembly |
WO2015105762A1 (en) * | 2014-01-08 | 2015-07-16 | Carbon3D, Inc. | Materials and methods for three-dimensional fabrication |
US20150273520A1 (en) * | 2014-03-26 | 2015-10-01 | Seiko Epson Corporation | Method of manufacturing three-dimensional structure and three-dimensional structure |
WO2016025579A1 (en) * | 2014-08-12 | 2016-02-18 | Carbon3D, Inc. | Three-dimensional printing with build plates having a smooth or patterned surface and related methods |
WO2020120986A1 (en) * | 2018-12-14 | 2020-06-18 | Secure Micro Solutions Limited | Safety apparatus and method |
US20200407472A1 (en) * | 2019-04-29 | 2020-12-31 | Mighty Buildings, Inc. | System for Obtaining a Photopolymerized Prepolymer |
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EP4210949A1 (en) | 2023-07-19 |
MX2023002891A (en) | 2023-04-04 |
KR20230065320A (en) | 2023-05-11 |
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