Multi-material stereolithographic three dimensional printing

Information

  • Patent Grant
  • 11845225
  • Patent Number
    11,845,225
  • Date Filed
    Thursday, September 9, 2021
    2 years ago
  • Date Issued
    Tuesday, December 19, 2023
    6 months ago
Abstract
Methods, systems, and apparatus, including a method of multi-material stereolithographic three dimensional printing comprising, depositing a first material through a first material dispenser of a stereolithographic three dimensional printer onto an optical exposure window to form a first material layer; curing the first material layer to form a first material structure on a build head of the stereolithographic three dimensional printer; depositing a second material through the first material dispenser or a second material dispenser onto the optical exposure window to form a second material layer; and curing the second material layer to form a second material structure on the build head.
Description
FIELD

The present invention relates to three dimensional (3D) printing using photosensitive materials and digital light processing (DLP) stereolithographic (SLA) printing.


BACKGROUND

In recent years there has been a large increase in the number and type of 3D printers available to the hobbyist, jewelry makers, and consumers. A certain subsection of these SLA 3D printers use a configuration that requires light to be transmitted from underneath, through a transparent material (called the window), into the resin whereby the resin is cured, usually in thin layers. A few examples of such printers are the FormLabs Form 1+3D printer, the Pegasus Touch Laser 3D Printer by Full Spectrum Laser, the Solidator 3D Printer by Solidator, etc. The resin contains pigments or dyes that absorb (and/or scatter) light at the wavelength used to cure the resin. The window material needs to be transparent, free from optical defects, and inert to the resin especially during the curing of the resin. The most common window material is PDMS (polydimethylsiloxane).


DLP SLA 3D printers typically print in a single material. This limits the application space and also impacts the user experience. Notably it creates a support generation problem. Overhangs of the model need to be supported during the 3D printing process. When only one print material is available, the support material and part material are the same and therefore have the same material properties. This has two impacts: first, removing the supports becomes a challenge and there is a high risk of damaging the printed part or leaving undesirable marks on the surface of the printed part; and second, because of the first issue, when generating support you want to minimize the number of supports used. This represents a significant challenge that is difficult to solve through software algorithms.


Moreover, systems that use multi-materials in bottom-up DLP SLA use multiple resin trays, with each resin tray containing a different material. In addition, there is often a cleaning and drying station to prevent contamination between the different materials in the different resin trays. The cleaning and drying between the use of different materials, however, is performed separately and therefore significantly increases the print time, for example it can take 5-10 times longer to print a part with two materials as it does with one material.


SUMMARY

This specification describes technologies relating to three dimensional (3D) printing using photosensitive materials (e.g., photopolymers) and digital light processing stereolithographic (DLP SLA) printing.


Particular embodiments of the subject matter described in this specification can be implemented to realize one or more of the following advantages. In particular, the embodiments help to reduce support generation as a cause of print failure. Still further, development of support structure(s) can be simplified, enabling 3D printing of a part correctly with less iteration, even for experienced users. In addition, support removal, which is typically a manual process that significantly adds to the touch time required to produce a part using DLP SLA, can be made easier since a support material with different material properties from the main material(s) can be used.


In addition, independent of the building of supports during 3D printing, the ability to readily do DLP SLA printing with more than a single material can provide significant advantages. Many applications require the use of more than one material, e.g., the handle of a device that has rubber over-molded onto a rigid plastic to improve the grip. Using the systems and techniques described herein, the application space for a 3D printer can be increased. More than one material can be used in DLP SLA in a manner that is significantly quicker than existing implementations of multi-material DLP SLA. In addition, the issue of having to ensure that the optical windows of all the resin trays in a multi-resin tray system are co-planar can be avoided, thus reducing the opportunities for distortions in the printed part that can be caused by the optical windows not being coplanar.


Representatively, in one embodiment, the invention is directed to a process of multi-material stereolithographic three dimensional printing. The process may include depositing a first material through a first material dispenser of a stereolithographic three dimensional printer onto an optical exposure window to form a first material layer and curing the first material layer to form a first material structure on a build head of the stereolithographic three dimensional printer. The process may further include depositing a second material through the first material dispenser or a second material dispenser onto the optical exposure window to form a second material layer and curing the second material layer to form a second material structure on the build head. In some embodiments, the first material and the second material may include a photosensitive material, and curing may include positioning the build head over the optical exposure window and emitting a light from a light source positioned below the optical exposure window through the optical exposure window to the first material layer or the second material. In still further embodiments, the process may include performing a cleaning operation prior to depositing the second material layer. The cleaning operation may include moving the build head and the optical exposure window past one or more of a cleaning device to mechanically clean any uncured first material from the build head and the optical exposure window. The process may further include a separation operation after the curing of the first material and a cleaning operation. The separation operation may include separating the build head from the optical exposure window, and the cleaning operation may be performed simultaneously with the separation operation and include cleaning the optical exposure window or the build head of any uncured first material. In addition, the process may include a separation operation and a cleaning operation after the curing of the second material. The separation operation may include separating the build head from the optical exposure window, and the cleaning operation may be performed simultaneously with the separation operation and include cleaning the optical exposure window, the build head or the second material layer of the any uncured second material. In some cases, the second material is deposited through the first material dispenser.


In other embodiments, the invention is directed to a multi-material stereolithographic three dimensional printer including a light source adapted to perform stereolithography, a support member having an optical window, a build head, a material dispenser operable to dispense a photosensitive material on the optical window, and a plurality of cleaning devices operable to clean the optical window and the build head. In some cases, the support member may be the only support member. In some cases, the support member may have only one optical window. The material dispenser may be a syringe pump, a peristaltic pump, an ink-jet head, a roller transfer machine, or a film transfer machine. In addition, the printer may include a second material dispenser. Still further, the plurality of cleaning devices may be mechanically coupled with the printer. In addition, the plurality of cleaning devices may be active or passive cleaning devices. For example, the cleaning devices may include rubber blades, solvents, a brush, or a mechanized brush.


In another embodiment, the invention is directed to a stereolithographic three dimensional printing system including a light source adapted to perform stereolithography, a support member having an optical window, a build head, a material dispenser operable to hold a photosensitive material, a plurality of cleaning devices, and a controller operable to cause the material dispenser to dispense a photosensitive material on the optical window, cause the light source to perform stereolithography on the photosensitive material and cure the photosensitive material to the build head, and cause the plurality of cleaning devices to remove any uncured photosensitive material from the optical window and the build head. In some embodiments, the material dispenser is a first material dispenser and the photosensitive material is a first photosensitive material, and the first material dispenser is operable to hold the first photosensitive material, the system further comprising a second material dispenser operable to hold a second photosensitive material, wherein the second photosensitive material is different than the first photosensitive material. In some embodiments, the controller is operable to cause the second material dispenser to dispense the second photosensitive material, and cause the laser source to perform stereolithography on the second photosensitive material and cure the second photosensitive material to the build head or to the first photosensitive material. In some embodiments, the controller is further operable to, after the photosensitive material is dispensed, cause the build head to be positioned over the optical window, and in contact with the photosensitive material, such that the photosensitive material is cured to the build head. In addition, the controller may be operable to cause the cleaning devices to remove any uncured photosensitive material by causing the build head and the optical window to move past one or more of the plurality of cleaning devices. Still further, the controller may be operable to cause the cleaning devices to remove any uncured photosensitive material during an operation in which the build head is separated from the optical window.


The details of one or more embodiments of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the invention will become apparent from the description, the drawings, and the claims.





BRIEF DESCRIPTION OF THE DRAWINGS

The embodiments disclosed herein are illustrated by way of example and not by way of limitation in the figures of the accompanying drawings in which like references indicate similar elements. It should be noted that references to “an” or “one” embodiment in this disclosure are not necessarily to the same embodiment, and they mean at least one.



FIG. 1 shows a schematic diagram of one embodiment of a multi-material 3D printing system.



FIG. 2 shows a schematic diagram of one embodiment of a multi-material 3D printing system.



FIG. 3 shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out a printing operation.



FIG. 4 shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 5 shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 6 shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 7A shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 7B shows a bottom plan view of a cured material layer after the printing operation of FIG. 7A.



FIG. 8 shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 9 shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 10 shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 11A shows a schematic diagram of the multi-material 3D printing system of FIG. 2 carrying out another printing operation.



FIG. 11B shows a bottom plan view of a cured material layer after the printing operation of FIG. 11A.



FIG. 12 shows a schematic diagram of another embodiment of a 3D printing system.



FIG. 13 shows a flow chart of one embodiment of a 3D printing process.





DETAILED DESCRIPTION OF THE INVENTION

In this section we shall explain several preferred embodiments with reference to the appended drawings. Whenever the shapes, relative positions and other aspects of the parts described in the embodiments are not clearly defined, the scope of the embodiments is not limited only to the parts shown, which are meant merely for the purpose of illustration. Also, while numerous details are set forth, it is understood that some embodiments may be practiced without these details. In other instances, well-known structures and techniques have not been shown in detail so as not to obscure the understanding of this description.


The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Spatially relative terms, such as “beneath”, “below”, “lower”, “above”, “upper”, and the like may be used herein for ease of description to describe one element's or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the exemplary term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (e.g., rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.


As used herein, the singular forms “a”, “an”, and “the” are intended to include the plural forms as well, unless the context indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising” specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof.


The terms “or” and “and/or” as used herein are to be interpreted as inclusive or meaning any one or any combination. Therefore, “A, B or C” or “A, B and/or C” mean “any of the following: A; B; C; A and B; A and C; B and C; A, B and C.” An exception to this definition will occur only when a combination of elements, functions, steps or acts are in some way inherently mutually exclusive.



FIG. 1 shows a schematic diagram of one embodiment of a 3D printing system 100. System 100 includes a support tray, reservoir or vat 110 to hold a liquid 120. Liquid 120 may be a layer of material including one or more photosensitive, photoactive, or photoreactive materials or resins. Suitable photosensitive materials or resins may include any photosensitive material having a binding agent (e.g. a polymer), monomer(s) and photoinitiator(s) suitable for generating a 3D printed structure as discussed herein. The bottom portion of vat 110 may include a window 115 through which illumination is transmitted to cure a 3D printed object 160. The 3D printed object 160 is shown as a block, but as will be appreciated, a wide variety of complicated shapes can be 3D printed therefore other shapes and sizes are contemplated.


The 3D printed object 160 is 3D printed on a build plate (or head) 130, which is connected by a rod 135 to one or more 3D printing structures 140. The printing structure(s) 140 are used to move the build plate 130 within vat 110. This movement is relative movement, and thus the moving piece can be the build plate 130, the vat 110, or both, in various implementations. In some implementations, a controller for printing structure(s) 140 is implemented using integrated circuit technology, such as an integrated circuit board with embedded processor and firmware. Such controllers can connect with a computer or computer system. Representatively, in some implementations, system 100 includes a programmed computer 150 that connects to printing structure(s) 140 and operates as the controller for system 100.


Computer 150 may include a processor 152 and a memory 154. Processor 152 can be one or more hardware processors, which can each include multiple processor cores. Memory 154 can include both volatile and non-volatile memory, such as Random Access Memory (RAM) and Flash RAM. Computer 150 can include various types of computer storage media and devices, which can include memory 154, to store instructions of programs that run on the processor 152. For example, a 3D printing program 156 can be stored in the memory 154 and run on processor 152 to implement the techniques described herein. These techniques can include control of 3D printing structures 140 that move build head 130, vat 110 and/or window 115, as well as cleaning devices and/or material dispenser(s), as described in further detail below. In addition, these techniques can include algorithms to develop support structures and/or determine the order of printing of different materials within each respective layer of object 160.


One or more light sources 142 are positioned below the window 115 and are connected with computer 150 (or other controller). For example, light source(s) 142 can be a DLP projector that can output patterned light at different wavelengths. In one embodiment, light source 142 is a laser source adapted to perform stereolithography. Light source(s) 142 may direct at least a first light 180 into liquid 120 through the window 115. The light 180 has a wavelength selected to create 3D structure 160 on build plate 130 by curing the photosensitive resin in the liquid 120, in accordance with a defined pattern or patterns. In addition, the one or more light sources 142 can be a dual wavelength illumination source device or separate illumination devices.


In one embodiment, build plate 130 starts at a position near the bottom of vat 110, and a varying pattern of light 180 is directed through window 115 to create solid structure 160 as build plate 130 is raised out of the vat. In addition, computer 150 (or other controller) can build 3D structure 160 using multiple materials. In some implementations, one or more of the multiple materials are used as support structures of 3D structure 160 during the creation of 3D structure 160. In some implementations, two or more (or all) of the multiple materials are used as final components of 3D structure 160. In addition, a controller (e.g., computer 150) can direct cleaning and material dispensing operations, as described in detail below, in addition to controlling one or more lights 180 from one or more light sources 142. In some implementations, the controller for the 3D printer is implemented using a circuit board with integrated circuitry thereon, including an embedded processor and firmware.



FIG. 2 shows a schematic diagram of one embodiment of a multi-material 3D printing system. 3D printing system 200 shown in FIG. 2 may be substantially the same as system 100 shown in FIG. 1. In FIG. 2, however, various aspects of the printing components are shown in more detail. In particular, from this view it can be seen that system 200 includes a support tray 210 and an optical window 208 through which illumination is transmitted to cure the resin deposited onto optical window 208 to form a 3D printed structure 160. Support tray 210 may be substantially similar to vat 110 shown in FIG. 1 and include sidewalls (not shown) so that it can contain a liquid including a photosensitive resin as previously discussed. The 3D printed object 160 is shown as a block, but as previously discussed, a wide variety of complicated shapes can be 3D printed. The system 200 further includes at least one material dispenser 202 and a plurality of cleaning devices 204 and 206.


The object 160 is 3D printed on a build plate (or head) 130, which is connected by a rod 135 to one or more 3D printing structures 140, which are used to move build plate 130 or support tray 210, as previously discussed. In some implementations, a controller for the printing structure(s) 140 is implemented using integrated circuit technology, such as an integrated circuit board with embedded processor and firmware. Such controllers can connect with a computer or computer system. In some implementations, the system 200 includes a programmed computer 150 that connects to the printing structure(s) 140 and operates as the controller for the system 200.


One or more light sources 142 are positioned below the optical window 208 and are connected with the computer 150 (or other controller). For example, light source(s) 142 can be a DLP projector positioned below optical window 208 and that can output patterned light at different wavelengths. Light source(s) 142 directs at least a first light 180 through the optical window 208. The light 180 has a wavelength selected to create 3D structure 160 on build plate 130 by curing the photosensitive resin applied to optical window 208, in accordance with a defined pattern or patterns. In addition, the one or more light sources 142 can be a dual wavelength illumination source device or separate illumination devices, including laser light sources.


System 200 further includes dispenser 202 and cleaning devices 204, 206. Dispenser 202 and cleaning devices 204, 206 may be part of, or otherwise electrically coupled with, 3D printing structure(s) 140 and computer 150 such that they are controlled, or otherwise operated by, programmed computer 150. For example, dispenser 202 may be mechanically and/or electrically connected to 3D printing structure(s) 140 and computer 150 by support member 212, as shown. Support member 212 may be, for example, a rod through which a printing material can be passed to dispenser 202, and may include wiring running there through to provide an electrical connection between dispenser 202 and computer 150. In addition, cleaning devices 204 and 206 may be mechanically (and in some cases electrically) connected to 3D printing structure(s) 140 by support member 214 (e.g. a rod) and support tray 210, respectively, (e.g. such as by mounting to member 214 and/or support tray 210).


Dispenser 202 may be, for example, any type of dispensing mechanism suitable for dispensing a desired amount of material (for forming printed object 160) onto optical window 208 of support tray 210 in the desired amount. Representatively, dispenser 202 may be a positive pressure pump having valves to control the amount of material dispensed, a deposition extruder, a pick and place type dispenser, a syringe pump, a peristaltic pump, and/or a dispenser such as that found in an ink-jet head. The dispensing equipment may also include a Meyer rod, doctoring blade, or other device to spread the dispensed material across the window surface. The surface of optical window 208 may also be chemically functionalized to ease the spreading of the liquid across the window surface.


Cleaning devices 204 and 206 may be any type of device suitable for cleaning an uncured or undesirable material off of build plate 130 or support tray 210, respectively. For example, cleaning devices 204 and 206 may be passive or active mechanisms suitable for removal of the undesirable material. Representatively, in one embodiment, cleaning devices 204 and 206 are relatively rigid structures which have tip portions that are aligned with the desired surface such that they can mechanically remove (e.g., scrape) any undesirable material off the surface when devices 204, 206, build plate 130 and/or support tray 210 are moved with respect to one another. In addition, in some embodiments, cleaning devices 204 and 206 may include additional features that allow them to first apply a cleaning material to the appropriate surface (e.g. an isopropyl spray) to soften the material and then remove the softened material, such as by suction force. Specific details with respect to the operation of these aspects of printing system 200 will now be described in reference to FIG. 3 to FIG. 12.



FIG. 3 shows a schematic diagram of the multi-material 3D printing system of FIG. 1 and/or FIG. 2 carrying out a printing operation. Representatively, build head 130, support tray 210, optical window 208, a first material dispenser 202, and cleaning devices 204 and 206 of system 200 are shown. The remaining features of system 200 are omitted for ease of illustration, but it should be understood that these features are included and all the operations discussed herein may be automatically performed using, for example, the 3D printing structure, controller and/or computing device previously discussed in reference to FIG. 1 or FIG. 2.


More specifically, FIG. 3 shows a configuration of system 200 prior to applying a print material. In particular, from this view it can be seen that build head 130 is positioned over support tray 210, and slightly offset with respect to window 208, material dispenser 202 and cleaning devices 204, 206. In this aspect, a material surface 308 of optical window 208, upon which a print material can be applied, is exposed to material dispenser 202. In particular, material dispenser 202 is positioned over optical window 208 and oriented such that dispense head 302 faces optical window 208. Cleaning device 204 is mounted to the top side of support tray 210 and is oriented so that a cleaning end 304 faces the build surface 310 of build head 130. In this aspect, cleaning device 204 may be considered a build head cleaning device which is configured to clean build surface 310 of build head 130. Cleaning device 206, on the other hand, is positioned over optical window 208 and is oriented so that a cleaning end 306 faces a material surface 308 of optical window 208. In this aspect, cleaning device 206 may be considered an optical window-cleaning device, which is configured to clean a printing material off of optical window 208. It should be understood that in some embodiments, one or more of dispenser 202, cleaning device 204 and cleaning device 206 may be in a fixed position, while in other embodiments, one or more of these devices may move with respect to one another, build head 130 and/or optical window 208. In addition, although cleaning device 204 and cleaning device 206 are shown separated by material dispenser 202, other arrangements may be possible (e.g., devices 204, 206 may be side by side).



FIG. 4 shows the printing operation of applying a first print material onto the optical window. In particular, first print material 402 is shown deposited onto the optical window 208 via material dispenser 202. Representatively, in one embodiment, support tray 210 moves relative to the material dispenser 202 as shown by arrow 404 to aid deposition of first print material 402 onto optical window 208. This movement is relative movement, and thus the moving piece can be the support tray 210, the material dispenser 202, or both, in various implementations. In addition, in some embodiments, this movement also causes cleaning device 204 and cleaning device 206 to slide along their respective cleaning surfaces as shown and simultaneously perform a cleaning operation. First print material 402 may be a relatively thin layer of material that is deposited in a controlled amount, and in some cases, only on the optical window portion of support tray 210.



FIG. 5 shows the printing operation of curing first material 402 onto build head 130. Representatively, build head 130 is shown positioned over optical window 208 and in contact with first material 402 that was deposited onto the optical window 208. This alignment may be achieved by continuing the previously discussed movement of support tray 210 relative to build head 130 in the horizontal or lateral direction as shown by arrow 404 (of FIG. 4) until build head 130 and window 208 are vertically aligned as shown. In addition, build head 130 and support tray 210 may be moved relative to one another in a vertical direction as shown by arrow 502 so that build head 130 contacts first material 402 positioned on optical window 208 when the two structures are aligned. The light source 142, positioned below optical window 208, then directs a light 180 into first material 402 through the optical window 208. In one embodiment, light source 142 is a laser source adapted to perform stereolithography. Light 180 may have a wavelength selected to cure material 402 in a defined pattern or patterns. This, in turn, cures first material 402 in the desired configuration to build head 130. In addition, the light source 142 can be a dual wavelength illumination source device or separate illumination devices.



FIG. 6 shows the further printing operation of separating support tray 210 from build head 130, onto which the cured first material 402 is attached. In particular, support tray 210 moves relative to the build head 130 in a direction of arrow 602. This movement is relative movement, and thus the moving piece can be the support tray 210 as shown, the build head 130, or both, in various implementations. During separation, cleaning device 204, which may be mounted to support tray 210 and faces build head 130, simultaneously cleans portions of build head 130 and the cured first material structure or layer 606 (e.g. cured layer consisting of first material 402) of any excess uncured first material 608, while the oppositely oriented cleaning device 206 cleans the optical window 208 of any excess uncured first material 608. For example, in one embodiment, after the operation shown in FIG. 5 is performed, build head 130 and support tray 210 may move relative to one another in a vertical direction as shown by arrow 602 so that build head 130 and support tray 210 are moved farther apart. This, in turn, allows for cleaning device 204 to slide past the portion of the cured first structure or layer 606 (and should remain) without contacting this portion. Once cleaning device 204 is aligned with the material to be removed (e.g., excess uncured material 608), build head 130 and support tray 210 can be moved closer together (e.g., a direction opposite arrow 602) so that the cleaning head of cleaning device 204 contacts the excess material 608. In this aspect, when the movement of support tray 210 in the direction of arrow 604 continues, cleaning device 204 removes excess material 608 from that point on. In addition, as cleaning device 204 is removing excess material 608 from build head 130, cleaning device 206, which is positioned to the right of excess material 608 (as shown in FIG. 6), removes excess material 608 from optical window 208 as excess material 608 slides past. It should be understood that because these operations (e.g., separation and cleaning) are performed simultaneously, the process time associated with printing multiple materials is significantly reduced. In addition, since the support tray 210 and window 208 are automatically cleaned by the system, a single support tray 210 having optical window 208, which does not need to be replaced by the user, can be used for multiple materials. In addition to further reducing processing time, this eliminates the need for multiple support trays (one for each material) and the challenges associated with ensuring the trays are coplanar to avoid distortions, thus resulting in a more precise printing system.



FIG. 7A shows a subsequent printing operation in which first material structure or layer 606 is cured onto the build head 130 and optical window 208 is clean of any excess uncured material and ready for a subsequent printing material. In addition, as previously discussed, first material structure or layer 606 may be cured into a variety of shapes and/or patterns depending upon the 3D structure to be formed. Representatively, as can be seen from FIG. 7B, which is a bottom plan view of the cured first material structure or layer 606, the material may be cured onto build head 130 in a substantially hourglass or dual cone configuration having a first lobe 606A and a second lobe 606B. It should be understood, however, that because each of first lobe 606A and second lobe 606B are formed from the same material layer (e.g., layer of material 402), they will have substantially the same thickness (e.g. the thickness of the initial material layer). Once first material layer 606 is formed from first material 402, a second material layer may be formed, the processing operations of which are illustrated in FIG. 8 to FIG. 11.


In particular, FIG. 8 shows the deposition of a second material 802 onto the optical window 208 via material dispenser 202. Second printing material 802 may be a different material than printing material 402, or the same material in the case of, for example, a stacked deposition layer used to increase a thickness of the initial material layer. In addition, material dispenser 202 may be the same dispenser discussed in reference to FIG. 1 to FIG. 7B, or a different material dispenser. For example, in some embodiments, a separate dispenser may be used for each of the different materials. The support tray 210 moves relative to the material dispenser 202 to aid deposition of second material 802 onto the optical window 208. This movement is relative movement, and thus the moving piece can be the support tray 210 in a direction of arrow 804 as shown, the material dispenser 202, or both, in various implementations. The second material 802 may be deposited onto optical window 208 in a similar manner as previously discussed in reference to FIG. 4. In addition, support tray 210 may be moved in a direction of arrow 804 until second material is aligned with first material layer 606.


Once aligned, build head 130 and support tray 210 may be moved closer together (e.g., build head 130 moved in a downward vertical direction as shown by arrow 902) so that first material layer 606 is in contact with uncured second material 802 that is deposited onto the optical window 208 as shown in FIG. 9. Second material 802 may be, for example, a layer on a surface of first material structure or layer 606 facing optical window 208 and/or surround portions of layer 606 to form a single layer on surface 310 of build head 130. The light source 142 then directs at least a first light 180 into second material 802 through the optical window 208. The light 180 has a wavelength selected to cure second material 802 in a defined pattern or patterns. In addition, the light source 142 can be a dual wavelength illumination source device or separate illumination devices.


Once cured, second material 802 forms a cured second material structure or layer 1002 on build head 130, in addition to the cured first material structure or layer 606, as shown in FIG. 10. Second material layer 1002 may be directly or indirectly attached to build head 130. In this embodiment, both layer 606 and layer 1002 are shown cured directly to surface 310 of build head 130 in a side-by-side manner (e.g. within a same layer). Once first and second material layers 606 and 1002, respectively, are formed, support tray 210 may be moved relative to build head 130 (e.g., moved in a direction of arrow 1006) and a cleaning operation is simultaneously performed to remove any excess, uncured second material. In particular, during separation, cleaning device 204 cleans build head 130 and the newly printed second material layer 1002 of any excess uncured second material 1004, while cleaning device 206 cleans the optical window 208 of any excess uncured second material 1004 as previously discussed in reference to FIG. 6.



FIG. 11A shows a subsequent printing operation in which all of the excess material is removed, first material layer 606 and second material layer 1002 are cured onto the build head 130 and optical window 208 is clean. As previously discussed, first material layer 606 may be cured into a variety of shapes and/or patterns depending upon the 3D structure to be formed. In addition, second material layer 1002 may be cured into a complimentary shape and/or pattern, or other shape or pattern that is different from layer 606. Representatively, as can be seen from FIG. 11B, which is a bottom plan view of the cured first material layer 606 and cured second material layer 1002, the first material may be cured onto build head 130 in a substantially hourglass or dual cone configuration having a first lobe 606A and a second lobe 606B, and the second material is cured into a similar shape which includes complementary first lobe 1002A and second lobe 1002B. It should be understood, however, that although first material layer 606 and second material layer 1002 are shown in the same plane (e.g., adjacent layers), one layer may be stacked on top of the other layer, or in any other configured desired to form a 3D structure out of multiple materials.



FIG. 12 shows a schematic diagram of another embodiment of a multi-material 3D printing system, which uses one or more syringes as dispensers of materials. 3D printing system 1200 shown in FIG. 12 may be substantially similar to system 200 shown in FIG. 2, except that the material dispenser may be substituted by one or more syringes 910. In FIG. 12 various aspects of the printing components are shown in more detail. In particular, from this view it can be seen that system 1200 includes a support tray 210, optical window 208, cleaning devices 204, 206, build plate 130 connected to rod 135, similar to the system illustrated in FIG. 2. System 1200 shown in FIG. 12 differs from system 200 shown in FIG. 2 in that material dispenser is syringe 910. This syringe may be connected to 3D printing structure(s) 140. In one embodiment, syringe 910 may be used as dispenser for dispensing more than one material, by reusing the same syringe to dispense one material at a time. In another embodiment, multiple syringes may be used, such that each syringe dispenses only one type of material to build a 3D printed structure.



FIGS. 2-12 show an example of a process for multi-material DLP SLA 3D printing using exemplary 3D printing systems. For example, the system may be a material deposition system that eliminates the cleaning and drying phases in multi-material DLP SLA 3D printing and can therefore significantly increase the print speed. In addition, the elimination of the use of multiple resin trays and the use of only one optical window can eliminate the issue of ensuring that multiple optical windows are co-planar and therefore reduce the complexity and cost of the system.



FIG. 13 illustrates one embodiment of a printing process using the previously discussed printing systems. Representatively, process 1300 may include depositing a first material (e.g., first material 402) onto an optical exposure window of a 3D printing system (e.g., optical exposure window 208 using a material dispenser 202) as shown in block 1302. As shown in block 1304, a build head (e.g., build head 130) may be positioned such that the clean build surface (e.g., clean build surface 310) of the build head is in contact with the first material deposited onto the optical exposure window. Block 1306 shows the operation of curing the first material onto the build head by directing a light (e.g., first light 180) into the first material through the optical exposure window. As shown in block 1308, after curing the first material onto the build head, the build head is separated from a support tray (e.g., support tray 210). During separation of the build head from the support tray, the build head is cleaned of excess uncured first material (e.g., excess uncured first material 608) with a cleaning device (e.g., cleaning device 204). Simultaneously, the optical window is cleaned of excess uncured first material with a cleaning device (e.g., cleaning device 206). In one embodiment, the cleaning operation is coupled to the separation operation. As shown in block 1310, a second material (e.g., second material 802) is deposited onto the optical exposure window using a material dispenser. The material dispenser used to dispense the second material may be the same material dispenser described above or a different material dispenser. Block 1312 shows the operation of positioning the build head to be in contact with the second material deposited onto the optical exposure window. As shown in block 1314, the second material is cured by directing light into the second material through the optical exposure window. As shown in block 1316, the build head is separated from the support tray. During the separation operation, the build head is cleaned of excess uncured second material (e.g., excess uncured second material 1004) with a cleaning device (e.g., cleaning device 204). Simultaneously, the optical exposure window is cleaned of excess uncured second material with a cleaning device (e.g., cleaning device 206). In one embodiment, the cleaning operation is coupled to the separation operation. As shown in block 1318, the operations may be repeated for as many materials that are required for the layer, or the operations are repeated for a new layer.


Although a dispenser in general is disclosed herein for dispensing the material, it should be understood that the material can be deposited in many ways, for example, by a syringe pump (see FIG. 12), a peristaltic pump, an ink-jet head, roller transfer process or film transfer process.


The material can be bulk deposited or selectively deposited. In the case of bulk deposition, enough material is deposited to cover the whole area. In the case of selective deposition, material is only deposited where it will be cured. Selective deposition can be at a resolution greater than the XY resolution of the DLP as the cleaning devices will ensure that the excess material is removed. In addition, the cleaning devices can be passive cleaning devices such as blades, sponges, and/or brushes that can contain solvent. Further, a cleaning device can be an active cleaning device such as solvent sprays, mechanized brushes, or a combination thereof. In some implementations, only a single type of cleaning device is used in a 3D printer, and in other implementations, more than one type of cleaning device is used in a 3D printer.


In addition, it should be understood that in some embodiments, the 3D object printed using the 3D printing systems disclosed herein may be, or otherwise include, a self-supporting biocompatible structure (e.g., scaffold) to which biomaterials (e.g., cells) may later be added, or added simultaneously with the printing material. The structure may be removed after printing leaving behind a self-supporting biological structure. The term “scaffolding” as used herein may refer to any structure that is printed using a 3D printer. In some cases, the scaffolding or structure may be a temporary structure that is biologically compatible with any number of biomaterials such that it may be used as a support structure to which the biomaterials may be added and then grown into the desired biological structure. The scaffolding is then removed leaving behind a self-supporting three dimensional biological structure. In other cases, the scaffolding or structure is the final 3D printed object.


It should also be understood that the term “biological material” or “biomaterial” may refer to a biological material suitable for use in 3D printing technologies. For example, the material may be any biological material such as cells that can be printed with the aid of a computer controlled printing device to create a desired self-supporting biological structure. In some embodiments, a biomaterial includes cell solutions, cell aggregates, cell-comprising gels, proteins, multicellular bodies, or tissues. Representatively, in some embodiments, the biomaterial may include a plurality of cells, a component of extracellular matrix, a cellular material, a cellular component, a growth factor, a peptide, a protein, a synthetic molecule, or a combination thereof. In some embodiments, the cells may include cells derived from the endoderm. Representatively, the cells may include, but are not limited to, exocrine secretory epithelial cells, salivary gland cells (e.g., polysaccharide-rich secretion or glycoprotein enzyme-rich secretion), Von Ebner's gland cells, mammary gland cells, lacrimal gland cell, ceruminous gland cells, eccrine sweat gland cells, apocrine sweat gland cell, sebaceous gland cells, bowman's gland cells, brunner's gland cells, seminal vesicle cells, prostate gland cells, bulbourethral gland cell, bartholin's gland cell, uterus endometrium cell (carbohydrate secretion), isolated goblet cells of respiratory and digestive tracts, stomach lining mucous cell, gastric gland cells, pancreatic acinar cells, paneth cells, type II pneumocytes of lung, clara cells of the lung, hormone secreting cells, anterior pituitary cells, somatotropes, lactotropes, thyrotropes, gonadotropes, corticotropes, pituitary cells, magnocellular neurosecretory cells, gut and respiratory tract cells, thyroid gland cells, thyroid epithelial cell, parafollicular cell, parathyroid gland cells, parathyroid chief cell, oxyphil cell, adrenal gland cells, chromaffin cells, or kidney cells. In some embodiments, the cells may include cells derived from ectoderm. Representatively, the cells may include keratinizing epithelial cells, epidermal keratinocytes, epidermal basal cells (stem cell), keratinocytes of fingernails and toenails, nail bed basal cells, hair shaft cells, hair root sheath cells, hair matrix cells (stem cell), wet stratified barrier epithelial cells, surface epithelial cells, basal cells or urinary epithelium cells. In some embodiments, the cells may be nerve cells. Representative cells include, but are not limited to, sensory transducer cells, auditory inner hair cells, auditory outer hair cells, basal cells of olfactory epithelium, primary sensory neurons, merkel cells of epidermis, olfactory receptor neurons, sensory neurons, photoreceptor cells, autonomic neuron cells, cholinergic neural cell, adrenergic neural cells, peptidergic neural cells, sense organ and peripheral neuron supporting cells, cells of the organ of Corti, supporting cells (e.g. vestibular, taste bud, or olfactory epithelium), schwann cells, glial cells, astrocytes, or neuron cells. In some embodiments, the cells may be derived from the mesoderm. Representative cells may include, but are not limited to, metabolism and storage cells, hepatocytes, adipocytes, fat cells, liver lipocytes, kidney cells, pancreatic duct cells, exocrine gland striated duct cells, gall bladder epithelial cells, epididymal cells, extracellular matrix cells, epithelial cells, fibroblasts (e.g. connective tissue fibroblasts, tendon fibroblasts, bone marrow reticular tissue fibroblasts, or nonepithelial fibroblasts), hyaline cartilage chondrocyte, fibrocartilage chondrocyte, elastic cartilage chondrocyte, osteoblast/osteocytes, osteoprogenitor cell (stem cell of osteoblasts), hepatic stellate cell (Ito cell), pancreatic stellate cells, contractile cells, skeletal muscle cells, satellite cells, heart muscle cells, smooth muscle cells, myoepithelial cells, erythrocytes, megakaryocytes, monocytes, connective tissue macrophages, epidermal Langerhans cell, osteoclasts, dendritic cells, microglial cells, granulocytes, hybridoma cells, mast cells, T cells, B cells, reticulocytes, stem cells and committed progenitors for the blood and immune system, germ cells, oogonium/oocyte, spermatid, spermatocyte, spermatogonium cell (stem cell for spermatocyte), spermatozoon, follicle cells, thymus epithelial cells, or interstitial cells. The biomaterial may include one or a combination of any of the cells disclosed herein.


The term “self-supporting biological structure” may refer to any engineered tissue or organ that is viable and functional in the absence of a support structure or scaffolding. Representatively, the self-supporting biological structure may be a whole tissue, organ, or a portion thereof engineered to replicate wholly or in part its naturally occurring counterpart. Representative self-supporting biological structures may include, but are not limited to, connective tissues, muscle tissues, nervous system tissues, and epithelial tissues. Representative organs may include, but are not limited to, organ(s) associated with the cardiovascular system (e.g. heart), digestive system (e.g., esophagus, stomach, liver, gallbladder, pancreas, intestines, colon and rectum), the endocrine system (e.g., hypothalamus, pituitary gland, pineal body or pineal gland, thyroid, parathyroids and adrenals), the excretory system (e.g., kidneys, ureters, bladder and urethra), the immune system (e.g., bone marrow, thymus, spleen and lymph nodes), the integumentary system (e.g., skin, hair and nails), the muscular system (e.g., skeletal, smooth and cardiac muscles), the nervous system (e.g., brain and spinal cord), the reproductive system (e.g., ovaries, fallopian tubes, uterus, vagina, mammary glands, testes, vas deferens, seminal vesicles, prostate and penis), the respiratory system (e.g., pharynx, larynx, trachea, bronchi, lungs and diaphragm) and the skeletal system (e.g., bones, cartilage, ligaments and tendons).


In this aspect, in some cases, one or more of the 3D printing systems disclosed herein may be considered a “bioprinter.” A bioprinter may be any computer operated printing device operable to print a structure that includes biomaterials. The bioprinter may include several components that allow the bioprinter to print the resin at various locations along a Cartesian coordinate system so that a three dimensional biological structure is created. The printed three dimensional biological structure may be considered an engineered three dimensional biological structure in that it is formed by a computer-aided device (e.g. a bioprinter) according to a set of computer-implemented instructions. Representatively, as previously discussed, the printer may include a controller that manages the operation of the print head according to a set of computer-implemented instructions (e.g. computer software, computer instructions, a computer program or a computer application).


In addition the mechanical structures described, embodiments of the subject matter and the functional operations described in this specification can be implemented using digital electronic circuitry, or in computer software, firmware, or hardware, including the structures disclosed in this specification and their structural equivalents, or in combinations of one or more of them. Embodiments of the subject matter described in this specification can be implemented using one or more modules of computer program instructions encoded on a computer-readable medium for execution by, or to control the operation of, data processing apparatus. The computer-readable medium can be a manufactured product, such as hard drive in a computer system or an optical disc sold through retail channels, or an embedded system. The computer-readable medium can be a machine-readable storage device, a machine-readable storage substrate, a memory device, or a combination of one or more of them.


The term “data processing apparatus” encompasses all apparatus, devices, and machines for processing data, including by way of example a programmable processor, a computer, or multiple processors or computers. A computer program (also known as a program, software, software application, script, or code) can be written in any form of programming language, including compiled or interpreted languages, declarative or procedural languages, and it can be deployed in any form, including as a stand-alone program or as a module, component, subroutine, or other unit suitable for use in a computing environment. A computer program does not necessarily correspond to a file in a file system. A program can be stored in a portion of a file that holds other programs or data (e.g., one or more scripts stored in a markup language document), in a single file dedicated to the program in question, or in multiple coordinated files (e.g., files that store one or more modules, sub-programs, or portions of code). A computer program can be deployed to be executed on one computer or on multiple computers that are located at one site or distributed across multiple sites and interconnected by a communication network.


The processes described in this specification can be performed by, and/or under the control of, one or more programmable processors executing one or more computer programs to perform functions by operating on input data and generating output. The processes can also be performed by, and apparatus can also be implemented using, special purpose logic circuitry, e.g., an FPGA (field programmable gate array) or an ASIC (application-specific integrated circuit).


Processors suitable for the execution of a computer program include, by way of example, both general and special purpose microprocessors, and any one or more processors of any kind of digital computer. Generally, a processor will receive instructions and data from a read-only memory or a random access memory or both. The essential elements of a computer are a processor for performing instructions and one or more memory devices for storing instructions and data. Generally, a computer will also include, or be operatively coupled to receive data from or transfer data to, or both, one or more mass storage devices for storing data, e.g., magnetic, magneto-optical disks, or optical disks. However, a computer need not have such devices. Moreover, a computer can be embedded in another device, e.g., a mobile telephone, a personal digital assistant (PDA), a mobile audio or video player, a game console, a Global Positioning System (GPS) receiver, or a portable storage device (e.g., a universal serial bus (USB) flash drive), to name just a few. Devices suitable for storing computer program instructions and data include all forms of non-volatile memory, media and memory devices, including by way of example semiconductor memory devices, e.g., EPROM, EEPROM, and flash memory devices; magnetic disks, e.g., internal hard disks or removable disks; magneto-optical disks; and CD-ROM and DVD-ROM disks. The processor and the memory can be supplemented by, or incorporated in, special purpose logic circuitry.


In addition, in some embodiments, the programmable processors may execute instructions contained in a machine-readable medium, that, when executed cause the computing device to perform the processes disclosed herein. For example, the set of instructions may include depositing a first material through a first material dispenser onto an optical exposure window of a stereolithographic three dimensional printer. The instructions may further include curing the first material onto a build head or a previously cured material layer on the build head. Further instructions may include cleaning the optical exposure window of any uncured first material, cleaning the build head or the previously cured material layer on the build head of any uncured first material, depositing a second material through a first material dispenser or a second material dispenser onto the optical exposure window, curing the second material onto the build head or the cured first material layer on the build head, cleaning the optical exposure window of any uncured second material, and cleaning the build head and the cured second material of any uncured second material. Further instructions may include separation of the build head from the optical exposure window after the curing step.


To provide for interaction with a user, embodiments of the subject matter described in this specification can be implemented using a computer having a display device, e.g., a CRT (cathode ray tube) or LCD (liquid crystal display) monitor, for displaying information to the user and a keyboard and a pointing device, e.g., a mouse or a trackball, by which the user can provide input to the computer. Other kinds of devices can be used to provide for interaction with a user as well; for example, feedback provided to the user can be any form of sensory feedback, e.g., visual feedback, auditory feedback, or tactile feedback; and input from the user can be received in any form, including acoustic, speech, or tactile input.


It should also be appreciated that reference throughout this specification to “one embodiment”, “an embodiment”, or “one or more embodiments”, for example, means that a particular feature may be included in the practice of the invention. Similarly, it should be appreciated that in the description various features are sometimes grouped together in a single embodiment, Figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects may lie in less than all features of a single disclosed embodiment. Thus, the claims following the Detailed Description are hereby expressly incorporated into this Detailed Description, with each claim standing on its own as a separate embodiment of the invention.


In the foregoing specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes can be made thereto without departing from the broader spirit and scope of the invention as set forth in the appended claims. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense.

Claims
  • 1. A system for printing a three-dimensional (3D) object, comprising: a platform comprising a surface, wherein said surface is configured to hold (i) a first material layer comprising a first material or (ii) a second material layer comprising a second material;at least one dispenser configured to deposit said first material layer or said second material layer onto said surface;an optical source configured to provide a light towards said surface, wherein said light is for solidifying at least a portion of said first material layer or at least a portion of said second material layer; anda processor operatively coupled to said at least one dispenser and said optical source, wherein said processor is programmed to: (a) direct said at least one dispenser to deposit said first material layer over said surface;(b) direct said optical source to provide said light towards said surface to solidify said at least said portion of said first material layer, to form a first material structure of said 3D object;(c) subsequent to (b), direct said at least one dispenser to deposit said second material layer over said surface; and(d) direct said optical source to provide said light towards said surface to solidify said at least said portion of said second material layer, to form a second material structure of said 3D object,wherein, in (b), said surface is substantially free of a material different than said first material; andwherein, in (d), said surface is substantially free of a material different than said second material.
  • 2. The system of claim 1, wherein said at least one dispenser is configured to deposit said first material layer or said second material layer onto only a portion of said platform that comprises said surface.
  • 3. The system of claim 1, wherein said second material structure is formed adjacent to or over said first material structure.
  • 4. The system of claim 3, wherein said second material structure is formed adjacent to and over said first material structure.
  • 5. The system of claim 1, wherein said surface comprises a window.
  • 6. The system of claim 5, wherein said optical source is configured to provide said light through said window and towards said at least said portion of said first material layer or said at least said portion of said second material layer.
  • 7. The system of claim 5, wherein said optical source is positioned below said window.
  • 8. The system of claim 1, further comprising a build head configured to hold said first material structure and said second material structure.
  • 9. The system of claim 8, further comprising at least one cleaning device configured to clean (i) at least a portion of said surface, (ii) at least a portion of said first material structure, or (iii) a surface of said build head.
  • 10. The system of claim 9, wherein said processor is further configured to direct, prior to (c), said at least one cleaning device to clean (i), (ii), or (iii).
  • 11. The system of claim 10, wherein said processor is configured to direct said at least one cleaning device to clean (i).
  • 12. The system of claim 10, wherein said processor is configured to direct said at least one cleaning device to clean (ii).
  • 13. The system of claim 10, wherein said processor is configured to direct said at least one cleaning device to clean (iii).
  • 14. The system of claim 9, wherein said processor is further configured to direct a relative movement between said at least one cleaning device and said surface of said platform.
  • 15. The system of claim 9, wherein said processor is further configured to direct a relative movement between said at least one cleaning device and said build head.
  • 16. The system of claim 9, wherein said processor is further configured to simultaneously direct (1) said at least one cleaning device to clean (i), (ii), or (iii) and (2) said at least one dispenser to deposit said second material layer over said surface.
  • 17. The system of claim 9, wherein said at least one cleaning device comprises a blade, a sponge, a brush, or a solvent spray.
  • 18. The system of claim 8, wherein said processor is further configured to direct a relative movement between said build head and said surface.
  • 19. The system of claim 1, wherein said first material or said second material comprises (i) a polymeric precursor and (ii) and a photoinitiator.
  • 20. The system of claim 1, wherein said first material and said second material are different.
CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No. 15/374,734, filed Dec. 9, 2016, which claims the benefit of U.S. Provisional Patent Application No. 62/265,380, filed Dec. 9, 2015, each of which is incorporated herein by reference.

US Referenced Citations (293)
Number Name Date Kind
4252887 Dessauer Feb 1981 A
4269933 Pazos May 1981 A
4801477 Fudim Jan 1989 A
4814370 Kramer et al. Mar 1989 A
4961154 Pomerantz et al. Oct 1990 A
5006364 Fan Apr 1991 A
5096530 Cohen Mar 1992 A
5137662 Hull et al. Aug 1992 A
5143668 Hida et al. Sep 1992 A
5182056 Spence et al. Jan 1993 A
5184307 Hull et al. Feb 1993 A
5236326 Grossa Aug 1993 A
5248456 Evans, Jr. et al. Sep 1993 A
5330701 Shaw et al. Jul 1994 A
5474719 Fan et al. Dec 1995 A
5510162 Brown Apr 1996 A
5531958 Krueger Jul 1996 A
5545367 Bae et al. Aug 1996 A
5656297 Bernstein et al. Aug 1997 A
5676745 Kelly et al. Oct 1997 A
5877270 Takayama et al. Mar 1999 A
5902537 Almquist et al. May 1999 A
5922507 Van et al. Jul 1999 A
5998496 Hassoon et al. Dec 1999 A
6090865 Dudman et al. Jul 2000 A
6093761 Schofalvi et al. Jul 2000 A
6100007 Pang et al. Aug 2000 A
6204316 Schofalvi et al. Mar 2001 B1
6259962 Gothait Jul 2001 B1
6376585 Schofalvi et al. Apr 2002 B1
6399010 Guertin et al. Jun 2002 B1
6658314 Gothait Dec 2003 B1
6664354 Savu et al. Dec 2003 B2
6780472 Hamrock et al. Aug 2004 B2
6833043 Parsonage et al. Dec 2004 B1
6846862 Schofalvi et al. Jan 2005 B2
6850334 Gothait Feb 2005 B1
6852781 Savu et al. Feb 2005 B2
7022410 Tonapi et al. Apr 2006 B2
7079915 Huang et al. Jul 2006 B2
7101618 Coggio et al. Sep 2006 B2
7173778 Jing et al. Feb 2007 B2
7195472 John Mar 2007 B2
7209797 Kritchman et al. Apr 2007 B2
7223826 Ali et al. May 2007 B2
7267850 Coggio et al. Sep 2007 B2
7288469 Sharma et al. Oct 2007 B2
7288514 Scheuing et al. Oct 2007 B2
7332217 Coggio et al. Feb 2008 B2
7417099 Savu et al. Aug 2008 B2
7433627 German et al. Oct 2008 B2
7438846 John Oct 2008 B2
7491441 Pokorny et al. Feb 2009 B2
7511008 Scheuing et al. Mar 2009 B2
7575847 Jing et al. Aug 2009 B2
7632560 Filippini et al. Dec 2009 B2
7662896 Savu et al. Feb 2010 B2
7718264 Klun et al. May 2010 B2
7845930 Shkolnik et al. Dec 2010 B2
7907878 Takagi et al. Mar 2011 B2
7912411 Takagi et al. Mar 2011 B2
7961154 Qi et al. Jun 2011 B2
8110135 El-Siblani Feb 2012 B2
8133551 Claes Mar 2012 B2
8147966 Klun et al. Apr 2012 B2
8372330 El-Siblani et al. Feb 2013 B2
8372913 Claes Feb 2013 B2
8394313 Shkolnik et al. Mar 2013 B2
8476398 Klun et al. Jul 2013 B2
8551285 Ho et al. Oct 2013 B2
8623264 Rohner et al. Jan 2014 B2
8696971 Boot et al. Apr 2014 B2
8716377 Taden et al. May 2014 B2
8729211 Klun et al. May 2014 B2
8734715 Miller et al. May 2014 B2
8741203 Liska et al. Jun 2014 B2
8753464 Khanna Jun 2014 B2
8753714 Cheung et al. Jun 2014 B2
8801418 El-Siblani et al. Aug 2014 B2
8829070 Morita et al. Sep 2014 B2
8859642 Miyamoto Oct 2014 B2
8916335 Kitano et al. Dec 2014 B2
9108358 Herloski et al. Aug 2015 B1
9120270 Chen et al. Sep 2015 B2
9126446 Bonino Sep 2015 B1
9205601 DeSimone et al. Dec 2015 B2
9211678 DeSimone et al. Dec 2015 B2
9216546 DeSimone et al. Dec 2015 B2
9306218 Pyun et al. Apr 2016 B2
9360757 DeSimone et al. Jun 2016 B2
9367049 Jariwala et al. Jun 2016 B2
9415418 Sreenivasan et al. Aug 2016 B2
9452567 Syao et al. Sep 2016 B2
9453142 Rolland et al. Sep 2016 B2
9486944 El-Siblani et al. Nov 2016 B2
9492969 Spadaccini et al. Nov 2016 B2
9498920 DeSimone et al. Nov 2016 B2
9527244 El-Siblani et al. Dec 2016 B2
9533450 El-Siblani et al. Jan 2017 B2
9561623 El-Siblani et al. Feb 2017 B2
9567439 Pyun et al. Feb 2017 B1
9598606 Rolland et al. Mar 2017 B2
9676963 Rolland et al. Jun 2017 B2
9718096 Sreenivasan et al. Aug 2017 B2
9782934 Willis et al. Oct 2017 B2
9796138 Liska et al. Oct 2017 B2
9833839 Gibson et al. Dec 2017 B2
9975295 Rolland et al. May 2018 B2
9975296 El-Siblani et al. May 2018 B2
9982164 Rolland et al. May 2018 B2
9987653 Sreenivasan et al. Jun 2018 B2
9987804 El-Siblani et al. Jun 2018 B2
9993974 DeSimone et al. Jun 2018 B2
10011076 El-Siblani et al. Jul 2018 B2
10016938 DeSimone et al. Jul 2018 B2
10072921 Fu et al. Sep 2018 B2
10073424 Lin et al. Sep 2018 B2
10150280 Aghababaie et al. Dec 2018 B2
10166725 Willis et al. Jan 2019 B2
10213956 Willis et al. Feb 2019 B2
10245785 Adzima Apr 2019 B2
10354445 Greene et al. Jul 2019 B2
10421233 Lin et al. Sep 2019 B2
10464259 Lin et al. Nov 2019 B2
10882251 Lin et al. Jan 2021 B2
10935891 Lin et al. Mar 2021 B2
11141919 Lin et al. Oct 2021 B2
11161301 Lin et al. Nov 2021 B2
11351735 Greene et al. Jun 2022 B2
11400650 Adzima Aug 2022 B2
20010035597 Grigg et al. Nov 2001 A1
20030043360 Farnworth Mar 2003 A1
20030114936 Sherwood et al. Jun 2003 A1
20040138049 Yasrebi et al. Jul 2004 A1
20040187714 Napadensky et al. Sep 2004 A1
20060054039 Kritchman et al. Mar 2006 A1
20060127153 Menchik Jun 2006 A1
20060163774 Abels et al. Jul 2006 A1
20060257785 Johnson Nov 2006 A1
20070264481 DeSimone et al. Nov 2007 A1
20080169586 Hull et al. Jul 2008 A1
20080181977 Sperry et al. Jul 2008 A1
20080252682 Hernandez et al. Oct 2008 A1
20090020901 Schillen et al. Jan 2009 A1
20090130449 El-Siblani May 2009 A1
20090196946 Kihara et al. Aug 2009 A1
20090304952 Kritchman Dec 2009 A1
20100028994 DeSimone et al. Feb 2010 A1
20100029801 Moszner et al. Feb 2010 A1
20100122634 Doyle May 2010 A1
20100125356 Shkolnik et al. May 2010 A1
20100173096 Kritchman et al. Jul 2010 A1
20110089610 El-Siblani et al. Apr 2011 A1
20110181941 Henningsen Jul 2011 A1
20110182805 DeSimone et al. Jul 2011 A1
20110287185 Felstead et al. Nov 2011 A1
20110310370 Rohner et al. Dec 2011 A1
20110318595 Breiner et al. Dec 2011 A1
20120046376 Loccufier et al. Feb 2012 A1
20120107625 Smith et al. May 2012 A1
20120195994 El-Siblani et al. Aug 2012 A1
20130000553 Hoechsmann et al. Jan 2013 A1
20130001834 El-Siblani et al. Jan 2013 A1
20130056910 Houbertz-Krauss et al. Mar 2013 A1
20130123988 Jariwala et al. May 2013 A1
20130252178 McLeod et al. Sep 2013 A1
20130336884 DeSimone et al. Dec 2013 A1
20140084517 Sperry Mar 2014 A1
20140265032 Teicher Sep 2014 A1
20140339741 Aghababaie et al. Nov 2014 A1
20140361463 DeSimone et al. Dec 2014 A1
20150019000 Nakamura Jan 2015 A1
20150064298 Syao Mar 2015 A1
20150072293 DeSimone et al. Mar 2015 A1
20150077215 Ranky et al. Mar 2015 A1
20150097315 DeSimone et al. Apr 2015 A1
20150097316 DeSimone et al. Apr 2015 A1
20150102532 DeSimone et al. Apr 2015 A1
20150137426 Van et al. May 2015 A1
20150139608 Theobalt et al. May 2015 A1
20150183168 Liverman et al. Jul 2015 A1
20150202805 Saruhashi et al. Jul 2015 A1
20150210007 Durand et al. Jul 2015 A1
20150224710 El-Siblani et al. Aug 2015 A1
20150231828 El-Siblani et al. Aug 2015 A1
20150231831 El-Siblani Aug 2015 A1
20150273632 Chen Oct 2015 A1
20150287169 Ueda et al. Oct 2015 A1
20150290881 Ederer et al. Oct 2015 A1
20150328839 Willis et al. Nov 2015 A1
20150331402 Lin et al. Nov 2015 A1
20150343745 Pesek et al. Dec 2015 A1
20150344682 Ganapathiappan et al. Dec 2015 A1
20150360419 Willis et al. Dec 2015 A1
20160023403 Ramos et al. Jan 2016 A1
20160023467 Din et al. Jan 2016 A1
20160046075 DeSimone et al. Feb 2016 A1
20160059484 DeSimone et al. Mar 2016 A1
20160059486 Desimone et al. Mar 2016 A1
20160059487 DeSimone et al. Mar 2016 A1
20160067921 Willis et al. Mar 2016 A1
20160121547 Kobayashi May 2016 A1
20160122539 Okamoto et al. May 2016 A1
20160131974 Abe et al. May 2016 A1
20160136889 Rolland et al. May 2016 A1
20160141535 Snaith et al. May 2016 A1
20160158889 Carter et al. Jun 2016 A1
20160160077 Rolland et al. Jun 2016 A1
20160164031 Pieper et al. Jun 2016 A1
20160167301 Cole et al. Jun 2016 A1
20160170218 Johnson et al. Jun 2016 A1
20160193786 Moore et al. Jul 2016 A1
20160200052 Moore et al. Jul 2016 A1
20160214321 Tow et al. Jul 2016 A1
20160271870 Brown, Jr. Sep 2016 A1
20160271875 Brown, Jr. Sep 2016 A1
20160303793 Ermoshkin et al. Oct 2016 A1
20160303795 Liu et al. Oct 2016 A1
20160325493 DeSimone et al. Nov 2016 A1
20160332366 Donovan Nov 2016 A1
20160332386 Kuijpers Nov 2016 A1
20160368054 Ng et al. Dec 2016 A1
20160368210 Chen et al. Dec 2016 A1
20160368221 Ueda et al. Dec 2016 A1
20170015058 Ueda et al. Jan 2017 A1
20170021562 El-Siblani et al. Jan 2017 A1
20170022312 Liu et al. Jan 2017 A1
20170028644 Evans et al. Feb 2017 A1
20170080641 El-Siblani Mar 2017 A1
20170087765 Rundlett et al. Mar 2017 A1
20170087769 Lancaster-Larocque et al. Mar 2017 A1
20170106399 Sreenivasan et al. Apr 2017 A1
20170106603 Pobihun Apr 2017 A1
20170113406 Chen et al. Apr 2017 A1
20170113416 DeSimone et al. Apr 2017 A1
20170120326 Heikkila et al. May 2017 A1
20170120515 Rolland et al. May 2017 A1
20170151718 Rolland et al. Jun 2017 A1
20170173881 Dachs, II et al. Jun 2017 A1
20170182708 Lin et al. Jun 2017 A1
20170210077 Ermoshkin et al. Jul 2017 A1
20170239887 Rolland et al. Aug 2017 A1
20170246660 Thompson et al. Aug 2017 A1
20170246804 El-Siblani et al. Aug 2017 A1
20170266876 Hocker Sep 2017 A1
20170291356 Adachi et al. Oct 2017 A1
20170297099 Gibson et al. Oct 2017 A1
20170334129 Ebert et al. Nov 2017 A1
20170342182 Pesek et al. Nov 2017 A1
20170369633 Caruso et al. Dec 2017 A1
20180001552 Dachs, II et al. Jan 2018 A1
20180001581 Patel et al. Jan 2018 A1
20180015669 Moore et al. Jan 2018 A1
20180044448 Moser et al. Feb 2018 A1
20180071977 Tumbleston et al. Mar 2018 A1
20180079865 Pyun et al. Mar 2018 A1
20180100037 Pyun Apr 2018 A1
20180105649 Pyun et al. Apr 2018 A1
20180126630 Panzer et al. May 2018 A1
20180126631 Nauka et al. May 2018 A1
20180133959 Moore et al. May 2018 A1
20180162047 Gibson et al. Jun 2018 A1
20180162048 Gibson et al. Jun 2018 A1
20180194066 Ramos et al. Jul 2018 A1
20180200948 Kuijpers et al. Jul 2018 A1
20180208686 Pyun et al. Jul 2018 A1
20180264724 Feller et al. Sep 2018 A1
20180333912 Lin Nov 2018 A1
20180333913 Lin et al. Nov 2018 A1
20180348646 Lin et al. Dec 2018 A1
20180361666 Adzima Dec 2018 A1
20190023917 Drazba et al. Jan 2019 A1
20190126533 Thompson May 2019 A1
20190134886 Willis et al. May 2019 A1
20190134899 Mueller et al. May 2019 A1
20190176398 Adzima Jun 2019 A1
20190210285 Tomioka et al. Jul 2019 A1
20190212572 Tomioka Jul 2019 A1
20190224918 Zheng Jul 2019 A1
20190224919 Houben et al. Jul 2019 A1
20190291342 Chen et al. Sep 2019 A1
20190299283 Sheinman Oct 2019 A1
20190322033 Willis et al. Oct 2019 A1
20200031044 Lin et al. Jan 2020 A1
20200172748 Moussa Jun 2020 A1
20200316865 Adzima Oct 2020 A1
20200362157 Parkar et al. Nov 2020 A1
20210171701 Klun et al. Jun 2021 A1
20210186820 Chakraborty et al. Jun 2021 A1
20210238328 Wu et al. Aug 2021 A1
20210361389 Mac Murray et al. Nov 2021 A1
20220176622 Lin et al. Jun 2022 A1
20230082164 Greene et al. Mar 2023 A1
Foreign Referenced Citations (10)
Number Date Country
105122135 Dec 2015 CN
105924571 Sep 2016 CN
107573058 Jan 2018 CN
110914058 Mar 2020 CN
2015229349 Dec 2015 JP
WO-2018125596 Jul 2018 WO
WO-2019104072 May 2019 WO
WO-2020139858 Jul 2020 WO
WO-2020149831 Jul 2020 WO
WO-2022225854 Oct 2022 WO
Non-Patent Literature Citations (93)
Entry
EP18801929.3 Extended European Search Report dated Feb. 17, 2021.
Essemtec AG. Essemtec—Spider—Compact High Speed Jetter and Dispenser. YouTube Web Video. Published on Jul. 5, 2016. 2 pages. URL https://www.youtube.com/watch?v=NpgBurid2wU.
Essemtec AG. Essemtec Scorpion—Versatile High Speed Jetting of Solder Paste and Glue. YouTube Web Video. Published on Nov. 13, 2014. 2 pages. URL https://www.youtube.com/watch?v=SZ-Kq2Gkm5Y.
Fairbanks, et al. Photoinitiated polymerization of PEG-diacrylate with lithium phenyl-2,4,6-trimethylbenzoylphosphinate: polymerization rate and cytocompatibility. Biomaterials, 30 (2009): 6702-6707.
“Final Office action dated Jan. 7, 2019 for U.S. Appl. No. 14/967,055”.
“Flexography.” Wikipedia, Wikimedia Foundation, May 23, 2018, en.wikipedia.org/wiki/Flexography.
GB1809886.3 Office Action dated May 16, 2019.
German, et al. Injection Molding of Metals and Ceramics. Metal Powder Industries Federation, 1997.
Gonsalvi, et al. Novel synthetic pathways for bis(acyl)phosphine oxide photoinitiators. Angew. Chern. Int. Ed., 51 (2012): 7895-7897.
Green, Industrial photoinitiators-a technical guide, CRC Press,@ 2010 Taylor and Francis Group, LLC, 191 pages.
Houben. Equipment for printing of high viscosity liquids and molten metals. Universiteit Twente. Sep. 27, 2012.
Ikemura, et al. Design of a new dental adhesive-effect of a water-soluble sodium acyl phosphine oxide with crown ether on adhesion to dental hard tissues. Dental Materials Journal, 28.3 (2009): 267-276.
Kloxin, et al. Photodegradable hydro gels for dynamic tuning of physical and chemical properties. Science, 324 (2009): 59-63.
Kyzen. Stencil Cleaning & Misprinted PCB Cleaners. 2018. http://www.kyzen.com/electronics-manufacturing-cleaning/stencils-and-misprints/.
Lambert, et al. Design considerations for mask projection microstereolithography systems. (Jun. 22, 2016) [online] (retrieved from https://sffsymposium.engr.utexas.edu/Manuscripts/2013/2013-09-Lambert.pdf), 20 pages.
Lee, et al. Solvent Compatibility of Poly(dimethylsiloxane)-Based Microfluidic Devices, Anal. Chem. 75 (2003): 6544-6554.
Massey, L. Permeability Properties of Plastics and Elastomers—A Guide to Packaging and Barrier Materials. Published Jan. 1, 2003. pp. 1-5, 19-29.
Matyjaszewski, et al. Atom transfer radical polymerization. Chern. Rev., 101 (2001): 2921-2990.
McDonald, et al. Fabrication of microfluidic systems in poly(dimethylsiloxane). Electrophoresis, 21(2000): 27-40.
Miller. Slot Die Coating Technology. Aug. 3, 2009.
Moad, et al. Living radical polymerization by the RAFT process. Aust. J. Chern., 58 (2005): 379-410.
Murata, et al. Photopolymerization-induced phase separation in binary blends of photocurable/linear polymers. Polymer. vol. 43, Issue 9, Apr. 2002, pp. 2845-2859.
Myiconnect007. Taiyo's Inkjet Solder Mask Applied with Meyer Burger's PIXDRO IP410 Printer. YouTube Web Video. Published on Feb. 13, 2015. 2 pages. URL https://www.youtube.com/watch?v=jm_JteEkQWE.
Organic photoinitiators, [online] [Retrieved on Aug. 4, 2014]; Retrieved from the Internet URL: htts://www.sigmaaldrich.com/materials-science/material-scienceproducts.html?TablePage=16374997; 1 page.
Otsu, et al. Polymer design by iniferter technique in radical polymerization: synthesis of AB and ABA block copolymers containing random and alternating copolymer sequences. Polymer Journal, 17.1 (1985): 97-104.
Pan, et al. Rapid manufacturing in minutes: the development of a mask projection stereolithography process for high-speed fabrication. Proceedings of the ASME 2012 International Manufacturing Science and Engineering Conferences, Jun. 4-8, 2012, Notre Dame, Indiana, US, 10 pages.
PCT/US2018/032837 International Search Report and Written Opinion dated Sep. 24, 2018.
PCT/US2018/037630 International Search Report and Written Opinion dated Oct. 3, 2018.
PCT/US2019/068413 Search Report & Written Opinion dated Apr. 23, 2020.
Pinnau, et al. Gas and vapor properties of amorphous perfluorinated copolymer membranes based on 2,2-bistrifluoromethyl-4,5-difluoro-1 ,3-dioxole/tetrafluoroethylene. Journal of Membrane Science, 109: 125-133 (1996).
RAFT agents, [online] [Retrieved on Aug. 4, 2014]; Retrieved from the Internet URL: h !!Q ://www. sigmaaldrich.com/materials-science/material-scienceproducts.html?TablePage=I03936134; 4 pages.
“Reverse Roll Coating.” Wikipedia, Wikimedia Foundation, Apr. 10, 2018, en.wikipedia.org/wiki/Reverse_roll_coating.
Scott, et al. Two-color single-photon photoinitiation and photoinhibition for subdiffraction photolithography. Science, 324 (2009): 913-917.
“Screen Printing.” Wikipedia, Wikimedia Foundation, May 17, 2018, en.wikipedia.org/wiki/Screen_printing#1960s_to_present.
“Spin Coating.” Wikipedia, Wikimedia Foundation, Apr. 10, 2018, en.wikipedia.org/wiki/Spin_coating.
Szczepanski, et al. A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems. Polymer (Guildf). Sep. 28, 2012;53(21):4694-4701.
Temel, et al. Synthesis of main chain polymeric benzophenone photoinitiator via thiol-ene click chemistry and its use in free radical polymerization. J. Polym. Sci. A: Polym. Chern., 48 (2010): 5306-5312.
Unknown author, “DuPont™ Teflon® AF amorphous fluoroplastic resin,” (Jun. 22, 2016) [online] (retrieved from http://www2.dupont.com/Teflon_Industrial/en_US/assets/downloads/h44587.pdf), 4 pages.
Unknown author, “Teflon™ AF amorphous fluoroplastic resins,” (Jun. 22, 2016) [online] (retrieved from https://www.chemours.com/Teflon_Industrial/en_us/assets/downloads/teflon-af-product-information.pdf), 3 pages.
U.S. Appl. No. 15/983,962 Notice of Allowance dated Dec. 20, 2018.
U.S. Appl. No. 16/016,253 Notice of Allowance dated Oct. 2, 2020.
U.S. Appl. No. 14/711,703 Notice of Allowance dated Jun. 8, 2017.
U.S. Appl. No. 14/711,703 Office Action dated Apr. 22, 2016.
U.S. Appl. No. 14/711,703 Office Action dated Dec. 1, 2016.
U.S. Appl. No. 14/848,162 Notice of Allowance dated Oct. 3, 2018.
U.S. Appl. No. 14/848,162 Office Action dated Jun. 5, 2018.
U.S. Appl. No. 14/848,162 Office Action dated Sep. 18, 2017.
U.S. Appl. No. 14/967,055 Office Action dated May 19, 2017.
U.S. Appl. No. 14/967,055 Office Action dated Jan. 7, 2019.
U.S. Appl. No. 14/967,055 Office Action dated Jul. 12, 2018.
U.S. Appl. No. 14/967,055 Office Action dated Nov. 1, 2017.
U.S. Appl. No. 15/919,124 Notice of Allowance dated Nov. 27, 2020.
U.S. Appl. No. 15/919,124 Office Action dated Jun. 25, 2020.
U.S. Appl. No. 15/983,962 Notice of Allowance dated Oct. 12, 2018.
U.S. Appl. No. 16/016,253 Office Action dated Feb. 21, 2019.
U.S. Appl. No. 16/016,253 Office Action dated Oct. 16, 2018.
U.S. Appl. No. 16/016,253 Office Action dated Oct. 21, 2019.
U.S. Appl. No. 16/016,257 Notice of Allowance dated Jul. 17, 2019.
U.S. Appl. No. 16/016,257 Office Action dated Mar. 21, 2019.
U.S. Appl. No. 16/016,257 Office Action dated Sep. 27, 2018.
U.S. Appl. No. 16/016,262 Notice of Allowance dated Jul. 5, 2019.
U.S. Appl. No. 16/016,262 Office Action dated Mar. 21, 2019.
U.S. Appl. No. 16/016,262 Office Action dated Sep. 28, 2018.
U.S. Appl. No. 16/049,288 Notice of Allowance dated Jan. 3, 2019.
U.S. Appl. No. 16/049,288 Office Action dated Oct. 11, 2018.
U.S. Appl. No. 16/202,039 Office Action dated Apr. 15, 2020.
U.S. Appl. No. 16/276,148 Office Action dated May 20, 2019.
U.S. Appl. No. 16/276, 148 Office Action dated Nov. 29, 2019.
U.S. Appl. No. 16/539,333 Office Action dated Jan. 7, 2021.
Varma et al. Solution Combustion Synthesis of Nanoscale Materials. Chem Rev. Dec. 1, 20164;116(23):14493-14586.
Wei, et al. A highly efficient polyurethane-type polymeric photoinitiator containing in-chain benzophenone and coinitiator amine for photopolymerization of PU prepolymers. Macromol. Chern. Phys., 207 (2006): 2321-2328.
Yang, et al. Synthesis of 1 ,6-hexanediol diacrylate, 2010.
Yang, H. et al. “High Viscosity Jetting System for 3d Reactive Inkjet Printing.” (2013).
Zhang, Teflon AF composite materials in membrane separation and molecular recognition in fluorous media. Ph.D. dissertation, University of Pittsburgh, 2013, 207 pages.
Co-pending U.S. Appl. No. 18/078,211, inventors Willis; Karl et al., filed Dec. 9, 2022.
EP18816953.6 European Search Report dated May 18, 2021.
PCT/US2022/025229 International Search Report and Written Opinion dated Aug. 24, 2022.
PCT/US20/33279 International Search Report & Written Opinion dated Oct. 9, 2020.
U.S. Appl. No. 16/202,039 Office Action dated Aug. 27, 2020.
U.S. Appl. No. 16/202,039 Office Action dated Jul. 7, 2022.
U.S. Appl. No. 16/202,039 Office action dated Nov. 1, 2021.
U.S. Appl. No. 16/457,380 Office Action dated Jan. 21, 2022.
U.S. Appl. No. 16/539,333 Notice of Allowance dated Sep. 9, 2021.
U.S. Appl. No. 16/539,333 Office Action dated Jul. 20, 2021.
U.S. Appl. No. 16/842,082 Notice of Allowance dated Apr. 28, 2022.
U.S. Appl. No. 16/842,082 Notice of Allowance dated May 24, 2022.
U.S. Appl. No. 16/842,082 Office Action dated Jul. 22, 2021.
U.S. Appl. No. 17/355,394 Notice of Allowance dated Feb. 2, 2022.
U.S. Appl. No. 16/016,253 Notice of Allowance dated Aug. 18, 2020.
U.S. Appl. No. 15/374,734 Notice of Allowance dated Aug. 4, 2021.
U.S. Appl. No. 15/374,734 Office Action dated Feb. 26, 2020.
U.S. Appl. No. 15/374,734 Office Action dated Sep. 4, 2020.
U.S. Appl. No. 15/374,734 Office Action dated Sep. 6, 2019.
Related Publications (1)
Number Date Country
20220242043 A1 Aug 2022 US
Provisional Applications (1)
Number Date Country
62265380 Dec 2015 US
Continuations (1)
Number Date Country
Parent 15374734 Dec 2016 US
Child 17470648 US