Polymeric structures with microvoid spaces and systems and methods for making same

Abstract

Aspects of the present disclosure include methods for fabricating polymer structures with microvoid spaces. The method, according to certain embodiments, includes irradiating a polymerizable composition positioned between a build elevator and a build surface to produce a polymerizable composition having polymerized regions of the polymerizable composition with microvoid spaces in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface; displacing the build elevator away from the build surface; contacting the generated microvoid spaces with a non-reactive composition; and repeating in a manner sufficient to produce a polymer structure with resolved microvoid spaces. Systems for preparing polymer structures according to the subject methods are also described. Polymer structures with resolved microvoid spaces, for example, where the microvoid spaces are filled with a non-polymerizable composition, are also provided.

Description

[Background technology]

[0001] Government Rights This invention was made with government support under contract NSF GRFP(FELLOWSHIP) awarded by the National Science Foundation. The government has certain rights in this invention.

[0002] Additive manufacturing techniques for printing polymer resins are used in applications such as personalized human protection, wearable electronics, and functionally graded materials.

[0003] The printed materials have been shown to have desirable mechanical, electrical, and chemically stable properties. Continuous liquid interface generation (CLIP), like other digital light projection (DLP) methods, projects rapid succession of ultraviolet (UV) patterns to photopolymerize the resin layer by layer. Other DLP methods require layer-by-layer delamination between each exposure. CLIP generates polymer structures by regenerating the resin below the build surface through a continuous liquid interface (dead zone) formed by oxygen, a polymerization inhibitor, supplied through a highly oxygen-permeable window at the bottom of the resin reservoir. The combination of improved optical projection and CLIP technology allows printers to reach submicron lateral (XY) resolution at speeds 100 times faster than other 3D printing methods.

[0004] The fabrication of negative spaces (channels, voids, etc.), a common feature of microelectronic, microsensor, and microfluidic devices, requires the ability to achieve high Z-resolution. Despite CLIP's ability to resolve submicron features in the XY plane, its ability to resolve features of this scale in the build (Z) direction is severely limited by the negative feature size. This is due to UV light penetrating previously fabricated layers and causing polymerization of unpolymerized resin trapped in the negative spaces. Summary of the Invention

[0005] The inventors of the present disclosure have discovered that penetration curing (e.g., UV penetration) of a reactive polymerizable composition (e.g., through channels into a build surface) can trap polymerizable resin when it forms void spaces within the polymer structure being built. This penetration curing can hinder or prevent the formation of microvoid spaces within the polymer structure created by continuous liquid interfacing (including infused continuous liquid interfacing). The present disclosure eliminates the negative polymerization and print-through effects of UV penetration.

[0006] Aspects of the present disclosure include methods for fabricating polymer structures with microvoid spaces. The method, according to certain embodiments, includes irradiating a polymerizable composition positioned between a build elevator and a build surface to produce a polymerizable composition having polymerized regions of the polymerizable composition with microvoid spaces in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface; displacing the build elevator away from the build surface; contacting the generated microvoid spaces with a non-reactive composition; and repeating in a manner sufficient to produce a polymer structure with resolved microvoid spaces. Systems for preparing polymer structures according to the subject methods are also described. Polymer structures with resolved microvoid spaces, for example, where the microvoid spaces are filled with a non-polymerizable composition, are also provided.

[0007] When practicing the subject method according to some embodiments, a quantity of polymerizable composition is conveyed through the generated microvoid space in a manner sufficient to displace any polymerized material (e.g., trapped resin) within the microvoid space. In some cases, the polymerizable composition is injected into the microvoid space, e.g., the microvoid space is a microchannel formed within the polymer structure. In certain cases, conveying the polymerizable composition is sufficient to flush out trapped resin within the microvoid space to maintain a negative space and eliminate print-through of the polymer structure. In some cases, the polymerizable composition is continuously conveyed through the generated microvoid space into the space between the build elevator and the build surface of the liquid interface-generating module. In some cases, a non-reactive composition is continuously conveyed (e.g., through a conduit) into the microvoid space while displacing the build elevator away from the build surface as the polymer structure is generated.

[0008] In some embodiments, the method includes contacting the generated microvoid space with a non-polymerizable composition. In some cases, the non-polymerizable composition continuously contacts the microvoid space while generating the polymer structure. In some embodiments, the method includes filling at least a portion of the void volume of the microvoid space with the non-polymerizable composition. In some embodiments, the method includes filling 5% or more, e.g., 10% or more, e.g., 25% or more, e.g., 50% or more (including 75% or more) of the void volume of the microvoid space with the non-polymerizable composition. In some embodiments, the method includes filling the entire void volume of the microvoid space with the non-polymerizable composition. In certain cases, the non-polymerizable composition is non-reactive with the polymerizable composition of the polymer structure. In some cases, the microvoid space comprises a microchannel within the polymer structure, e.g., the microchannel extends through the polymer structure. In some cases, the polymer structure comprises a plurality of microvoid spaces. In some cases, the non-polymerizable composition is a composition selected from water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electro-responsive liquid, and a gas.

[0009] In some embodiments, the polymerizable composition is in contact with the build elevator and the build surface. In some cases, the method includes irradiating the polymerizable composition for a period of time sufficient to bond a first polymerized region of the polymerizable composition to the build elevator. In some cases, the build elevator is displaced in predetermined increments of 0.5 μm to 1.0 μm. In some cases, the method includes applying the polymerizable composition to the build surface after each displacement of the build elevator away from the build surface. In some cases, the method includes continuously applying the polymerizable composition to the build surface. In some cases, the polymerizable composition is continuously applied to the build surface by injection through a conduit. In some embodiments, the method includes contacting the generated microvoid space with a non-reactive composition (e.g., through a conduit) after each displacement of the build elevator away from the build surface. In some embodiments, the polymerizable composition is continuously polymerized while the build elevator is displaced away from the build surface. In some embodiments, the non-reactive composition is continuously conveyed through microvoid spaces (e.g., microchannels formed within the polymeric structure) while displacing the build elevator away from the build surface. In some embodiments, the non-reactive composition is injected (e.g., continuously) into the microvoid spaces through a conduit. In some cases, the method includes continuously applying the non-reactive composition to the build region. In some cases, the non-reactive composition is continuously applied to the build region by injection through a conduit. In certain embodiments, the method includes removing the non-reactive composition (e.g., non-polymerizable composition) from the generated microvoid spaces of the polymeric structure.

[0010] Aspects of the present disclosure also include systems for fabricating polymer structures having microvoid spaces. The system, according to certain embodiments, includes a light source and an optical interface polymerization module configured to generate a polymer structure having resolved microvoid spaces therein from a polymerizable composition positioned therebetween, the polymer structure having a build elevator and a build surface. In some embodiments, the optical interface polymerization module is configured to generate a polymer structure having one or more microchannels within the polymer structure. In some cases, one or more of the microchannels extend through the polymer structure. In some embodiments, the system includes a processor having a memory operatively coupled to the processor, the memory including instructions stored thereon that, when executed by the processor, cause the processor to: a) irradiate a polymerizable composition positioned between a build elevator and a build surface to generate a polymerizable composition having polymerized regions of the polymerizable composition having microvoid spaces in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface; b) displace the build elevator away from the build surface; c) contact the generated microvoid spaces with a non-reactive composition; and d) repeat steps a)-c) in a manner sufficient to generate a polymer structure having resolved microvoid spaces. In some instances, the system is configured to generate a polymer structure having microvoid spaces containing a non-polymerizable composition positioned therein.

[0011] In some embodiments, the memory includes instructions for contacting the generated microvoid space with a quantity of polymerizable composition in a manner sufficient to displace polymerized material within the microvoid space. In some cases, the memory includes instructions for continuously conveying the polymerizable composition through the generated microvoid space to displace polymerized material within the microvoid space. In some cases, the memory includes instructions for injecting the polymerizable composition into the generated microvoid space to displace polymerized material within the microvoid space. In some cases, the polymerizable composition is injected into the generated microvoid space using a syringe. In certain cases, the system further includes a syringe pump. In some cases, the memory includes instructions for continuously conveying the polymerizable composition through the generated microvoid space to a space between a build elevator and a build surface of the liquid interface-generating module.

[0012] In some cases, the system further includes a source of non-polymerizable composition operably coupled to the optical interface polymerization module such that the non-polymerizable composition continuously contacts the microvoid space while generating the polymer structure. In some cases, the source is in communication with the build region of the optical interface polymerization module through a conduit. In some cases, the non-polymerizable composition is provided to the build region through the conduit, e.g., the non-polymerizable composition is injected into the build region through the conduit. In some cases, the memory includes instructions for filling at least a portion of the void volume of the microvoid space with the non-polymerizable composition, e.g., 5% or more, e.g., 10% or more, e.g., 25% or more, e.g., 50% or more (including 75% or more) of the void volume of the microvoid space, e.g., filling the entire void volume of the microvoid space with the non-polymerizable composition. In some embodiments, the memory includes instructions for generating a polymer structure having multiple microvoid spaces. In certain cases, the memory includes instructions for irradiating the polymerizable composition for a period of time sufficient to couple a first polymerization region of the polymerizable composition to the build elevator. In some cases, the memory includes instructions for displacing the build elevator in predetermined increments from 0.5 μm to 1.0 μm. In some embodiments, the memory includes instructions for applying a polymerizable composition to the build surface after each displacement of the build elevator away from the build surface. In some cases, the memory includes instructions for applying a non-polymerizable composition to the generated microvoid spaces after each displacement of the build elevator away from the build surface. In some cases, the memory includes instructions for continuously polymerizing the polymerizable composition while displacing the build elevator away from the build surface. In some embodiments, the memory includes instructions for continuously applying a non-polymerizable composition to the generated microvoid spaces while displacing the build elevator away from the build surface. In certain embodiments, the memory includes instructions for removing the non-polymerizable composition from the generated microvoid spaces of the polymer structure.

[0013] In certain embodiments, the system includes a micro-digital light projection system having a light beam generator component and a light projection monitoring component. In some embodiments, the light beam generator includes two projection lenses, such as magnification lenses. In some embodiments, the light projection monitoring component includes a light detector, such as a charge-coupled device (CCD).

[0014] Aspects of the present disclosure also include polymer structures having microvoid spaces containing a non-polymerizable composition positioned therein. In some cases, the non-polymerizable composition fills 75% or more of the void volume of the microvoid space, e.g., the non-polymerizable composition fills the entire volume of the void volume of the microvoid space. In some cases, the non-polymerizable composition is non-reactive with the polymer structure. In some cases, the microvoid spaces are microchannels within the polymer structure, e.g., extending through the polymer structure. In some cases, the polymer structure comprises a plurality of microvoid spaces. In some cases, the non-polymerizable composition is selected from water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electro-responsive liquid, and a gas. In some cases, the polymeric structure is formed from a polymerizable material such as polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-enes, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl esters, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof. In certain embodiments, aspects of the present disclosure include polymeric structures having resolved microvoid spaces from which non-polymerizable compositions have been removed.

[0015] Aspects of the present disclosure also include a non-transitory computer-readable storage medium for creating a polymer structure in a liquid interface-generating module. In some cases, the non-transitory computer-readable storage medium includes instructions stored thereon, the instructions including: an algorithm for irradiating a polymerizable composition positioned between a build elevator and a build surface to generate a polymerizable composition having polymerized regions of the polymerizable composition with microvoid spaces in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface; an algorithm for displacing the build elevator away from the build surface; an algorithm for contacting the generated microvoid spaces with a non-reactive composition; and an algorithm for repeating one or more steps in a manner sufficient to generate a polymer structure with resolved microvoid spaces. In some cases, the non-transitory computer-readable storage medium includes an algorithm for injecting the polymerizable composition through a conduit using a syringe pump. In some instances, the non-transitory computer-readable storage medium includes an algorithm for generating a polymer structure with microvoid spaces containing a non-polymerizable composition positioned therein.

[0016] In some embodiments, the non-transitory computer-readable storage medium has an algorithm for contacting the generated microvoid space with an amount of polymerizable composition in a manner sufficient to displace polymerized material within the microvoid space. In some cases, the non-transitory computer-readable storage medium has an algorithm for continuously delivering the polymerizable composition through the generated microvoid space to displace polymerized material within the microvoid space. In some cases, the non-transitory computer-readable storage medium has an algorithm for injecting the polymerizable composition into the generated microvoid space to displace polymerized material within the microvoid space. In some cases, the non-transitory computer-readable storage medium has an algorithm for injecting the polymerizable composition into the generated microvoid space with a syringe. In some cases, the non-transitory computer-readable storage medium includes an algorithm for continuously delivering the polymerizable composition through the generated microvoid space to a space between a build elevator and a build surface of a liquid interface-generating module.

[0017] In some cases, the non-transitory computer-readable storage medium includes an algorithm for contacting a non-polymerizable composition with the generated microvoid space of the polymer structure. In some cases, the non-transitory computer-readable storage medium includes an algorithm for filling at least a portion of the void volume of the microvoid space with the non-polymerizable composition, e.g., 5% or more, e.g., 10% or more, e.g., 25% or more, e.g., 50% or more (including 75% or more) of the void volume of the microvoid space, e.g., filling the entire void volume of the microvoid space with the non-polymerizable composition. In some embodiments, the non-transitory computer-readable storage medium includes an algorithm for generating a polymer structure having multiple microvoid spaces. In certain cases, the non-transitory computer-readable storage medium includes an algorithm for irradiating the polymerizable composition for a period of time sufficient to bond a first polymerized region of the polymerizable composition to the build elevator. In some cases, the non-transitory computer-readable storage medium includes an algorithm for displacing the build elevator in predetermined increments from 0.5 μm to 1.0 μm. In some embodiments, the non-transitory computer-readable storage medium has an algorithm for applying a polymerizable composition to the build surface after each displacement of the build elevator away from the build surface. In some cases, the non-transitory computer-readable storage medium has an algorithm for applying a non-polymerizable composition to the generated microvoid spaces after each displacement of the build elevator away from the build surface. In some cases, the non-transitory computer-readable storage medium has an algorithm for continuously polymerizing the polymerizable composition while displacing the build elevator away from the build surface. In some embodiments, the non-transitory computer-readable storage medium has an algorithm for continuously applying a non-polymerizable composition to the generated microvoid spaces while displacing the build elevator away from the build surface. In certain embodiments, the non-transitory computer-readable storage medium has an algorithm for removing the non-polymerizable composition from the generated microvoid spaces of the polymer structure. [Brief explanation of the drawings]

[0018] The invention can be best understood from the following detailed description when read in conjunction with the accompanying drawings, in which:

[0019] [Figure 1] 1 illustrates the injection of a non-polymerizable composition into the generated microvoid space (eg, microchannel), according to certain embodiments. [Figure 2A] 1 shows a schematic of the conventional CLIP 3D printing approach and the resulting print-through effect. [Figure 2B] 1 illustrates a process for producing polymer structures and the resulting resolved microvoid spaces (i.e., negative structures) according to certain embodiments of the present disclosure. [Figure 2C] 1 illustrates the relationship between light penetration depth and minimum channel height for a process for producing polymer structures according to certain embodiments and other digital light processing systems. [Figure 2D] 1 shows generated polymer structures according to certain embodiments, including a microfluidic distributor, a vascular perfusion bed, and a microfluidic-enabled microarray patch, with channels filled with dye for contrast. Scale bar is 5 mm. [Figure 3A] 1 shows a comparison of model and experimental print-through effects, according to certain embodiments. 2 shows the accumulation of UV light in the formed microchannels (i.e., microvoid spaces) that results in the print-through effect. [Figure 3B] 3A shows a comparison of model and experimental print-through effects, according to certain embodiments. FIG. 3B shows the resulting polymer structure of FIG. 3A with the microvoid spaces filled. [Figure 3C] 10 shows a comparison of model and experimental print-through effects, according to certain embodiments. 11 shows the accumulation of UV light as a polymerizable composition is continuously conveyed through formed microchannels of a polymer structure. [Figure 3D]3C shows a comparison of model and experimental print-through effects, according to certain embodiments. FIG. 3D shows the resulting polymer structure of FIG. 3C, in which wavy microvoid spaces are resolved. [Figure 4A] 10A-10C show print-through mitigation in producing polymer structures with different microfluidic channel shapes and sizes, according to certain embodiments. Different microchannel pitches are shown in polymer structures produced with (iCLIP) and without (CLIP) injecting a polymerizable composition through the microchannels during fabrication. The scale bar is 1 mm. [Figure 4B] 1 shows the mitigation of print-through when generating polymer structures with different microfluidic channel shapes and sizes, according to certain embodiments. Different microchannel diameters are shown for polymer structures generated with (iCLIP) and without (CLIP) injecting a polymerizable composition through the microchannel during fabrication. Scale bar is 1 mm. [Figure 4C] 10A-10C show the mitigation of print-through in producing polymer structures with varying microfluidic channel shapes and sizes, according to certain embodiments. 10B shows the resolution of various microchannel pitch geometries produced with (iCLIP) and without (CLIP) injecting a polymerizable composition through the microchannels during fabrication. 10C shows the resolution of various microchannel pitch geometries produced with (iCLIP) and without injecting a polymerizable composition through the microchannels during fabrication. 10D shows the resolution of various microchannel pitch geometries produced with (iCLIP) and without injecting a polymerizable composition through the microchannels during fabrication. 10D shows the resolution of various microchannel pitch geometries produced with (iCLIP) and without (CLIP) ... injecting a polymerizable composition through the microchannels during fabrication. 10D shows the resolution of various microchannel pitch geometries produced with (iCLIP) and without injecting a polymerizable composition through the microchannels during fabrication. 10D shows the resolution of various microchannel pitch geometries produced with (iCLIP) and without injecting a polymerizable composition through the microchannels during fabrication. 10D shows the resolution of various microchannel pitch geometries produced with [Figure 4D] 10A-10C show the mitigation of print-through in generating polymer structures with varying microfluidic channel shapes and sizes, according to certain embodiments. 10B-10C show the resolution of various microchannel diameters in polymer structures generated with (iCLIP) and without (CLIP) injecting a polymerizable composition through the microchannel during fabrication. 10C-10D show the resolution of various microchannel diameters in polymer structures generated with (iCLIP) and without injecting a polymerizable composition through the microchannel during fabrication. 10D-10C show the resolution of various microchannel diameters in polymer structures generated with (iCLIP) and without injecting a polymerizable composition through the microchannel during fabrication. 10D-10C show the resolution of various microchannel diameters in polymer structures generated with (iCLIP) and without (CLIP) ... [Figure 5A] 1 shows microchannel resolution as a function of resin turnover number when producing polymeric structures with microchannels, according to certain embodiments. 1 shows the resolution of a resin with a penetration depth of 237 μm as a function of turnover number. [Figure 5B]10A-10C show microchannel resolution in relation to resin turnover when producing polymeric structures with microchannels, according to certain embodiments. 10B show resolution of various microchannel sizes as a function of turnover number. [Figure 5C] 10A-10C show microchannel resolution in relation to resin turnover when producing polymeric structures with microchannels, according to certain embodiments. 10B show resolution of various microchannel shapes as a function of turnover number. [Figure 5D] 1 shows microchannel resolution in relation to resin turnover when producing polymeric structures with microchannels, according to certain embodiments. 2 shows the relationship between resin penetration depth and minimum turnover rate. [Figure 6A] 1A-1C show polymer structures with microvoid spaces (e.g., microchannels) positioned therein produced in accordance with certain embodiments. 1B show microfluidic microneedle patches. Scale bar is 1 mm. [Figure 6B] 1A-1C show polymer structures with microvoid spaces (e.g., microchannels) positioned therein produced in accordance with certain embodiments. 1B-1C show microneedle patches with interconnected microfluidic channels. Scale bar is 1 mm. [Figure 6C] 1A-1C show polymer structures with microvoid spaces (e.g., microchannels) positioned therein produced in accordance with certain embodiments. 1B-1C show microfluidic inductors backfilled with conductive gallium. Scale bar is 1 mm. [Figure 6D] 1A-1C show polymer structures with microvoid spaces (e.g., microchannels) positioned therein produced according to certain embodiments. 1D shows a microfluidic microneedle patch with a 3D micromixer. Scale bar is 1 mm. [Figure 6E] 1A-1C show polymeric structures having microvoid spaces (e.g., microchannels) positioned therein, produced in accordance with certain embodiments. [Figure 6F] 1A-1C show polymeric structures with microvoid spaces (e.g., microchannels) positioned therein produced in accordance with certain embodiments. 1B-1C show porous media separation columns with various porosity unit cells. 1B-1C show the scale bar is 1 mm. DETAILED DESCRIPTION OF THE INVENTION

[0020] Aspects of the present disclosure include methods for fabricating polymer structures with microvoid spaces. The method, according to certain embodiments, includes irradiating a polymerizable composition positioned between a build elevator and a build surface to produce a polymerizable composition having polymerized regions of the polymerizable composition with microvoid spaces in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface; displacing the build elevator away from the build surface; contacting the generated microvoid spaces with a non-reactive composition; and repeating in a manner sufficient to produce a polymer structure with resolved microvoid spaces. Systems for preparing polymer structures according to the subject methods are also described. Polymer structures with resolved microvoid spaces, for example, where the microvoid spaces are filled with a non-polymerizable composition, are also provided.

[0021] Before the present invention is described in more detail, it is to be understood that this invention is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

[0022] Where a range of values ​​is provided, unless the context clearly indicates otherwise, it is understood that each intervening value is included, to the tenth of the unit of the lower limit, between the upper and lower limit of that range and any other stated or intervening value in that stated range. The upper and lower limits of these smaller ranges may individually be included in the smaller ranges and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.

[0023] Certain ranges are presented herein with the term "about" preceding the numerical value. As used herein, the term "about" is used to provide literal support for the exact number it precedes, as well as a number that is near or approximately the number it precedes. In determining whether a number is near or approximately a specifically recited number, the near or approximately unrecited number may be a number that, in the context provided, provides substantial equivalence to the specifically recited number.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, representative illustrative methods and materials are now described.

[0025] All publications and patents cited herein are incorporated by reference as if each individual publication or patent was specifically and individually indicated to be incorporated by reference, and their incorporation by reference discloses and describes the methods and / or materials in connection with which the publications are cited. The citation of any publication is for its disclosure prior to the filing date of the present application and should not be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided may be different from the actual publication dates which may need to be independently confirmed.

[0026] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It should be further noted that the claims may be drafted to exclude any optional element. Accordingly, this statement is intended to serve as a predicate to the use of such exclusive terminology as "solely," "only," and the like, or the use of a "negative" limitation in connection with the recitation of claim elements.

[0027] As will be apparent to those skilled in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has distinct components and features which may be readily separated from or combined with the features of any of the other embodiments without departing from the scope or spirit of the invention. Any recited method can be carried out in the order of events recited or in any other order which is logically possible.

[0028] Although apparatus and methods have been or will be described in functional terms for grammatical fluidity, it is expressly understood that the claims should in no way be construed as necessarily limited by the syntax of "means" or "step" limitations unless expressly recited under 35 U.S.C. 112, but should be accorded the full scope of meaning and equivalents of the definitions provided by the claims under the doctrine of judicial equivalents, and that if the claims are expressly recited under 35 U.S.C. 112, they should be accorded the full statutory equivalents under 35 U.S.C. 112.

[0029] Method for making polymer structures with microvoid spaces Aspects of the present disclosure also include methods for producing polymer structures with microvoid spaces. The method, according to certain embodiments, includes irradiating a polymerizable composition positioned between a build elevator and a build surface to produce a polymerizable composition having polymerized regions of the polymerizable composition in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface, displacing the build elevator away from the build surface, contacting the produced microvoid spaces with a non-reactive composition, and repeating in a manner sufficient to produce a polymer structure with resolved microvoid spaces. These steps are repeated in a manner sufficient to produce a polymer structure with resolved microvoid spaces. For example, the steps may be repeated 2 or more times, such as 3 or more times, for example, 4 or more times, for example, 5 or more times, for example, 10 or more times, for example, 20 or more times, for example, 30 or more times, for example, 40 or more times, for example, 50 or more times, for example, 100 or more times, for example, 250 or more times, for example, 500 or more times (including 1000 or more times). In certain cases, the produced polymeric structure has a non-polymerizable composition located therein.

[0030] In some embodiments, the polymerizable composition is irradiated with a light beam generator component of a micro-digital light projection system. In some cases, the light source is a broadband light source emitting light having a wavelength between 400 nm and 1000 nm. In some cases, the broadband light source is a halogen lamp, a deuterium arc lamp, a xenon arc lamp, a stabilized fiber-coupled broadband light source, a broadband LED with a continuous spectrum, an ultra-bright light emitting diode, a semiconductor light emitting diode, a broad-spectrum LED white light source, a multi-LED integrated white light source, or any combination thereof, among other broadband light sources. In some cases, the light source is a narrowband light source emitting a specific wavelength or a narrow range of wavelengths. In some cases, a narrowband light source includes a light source emitting light having a narrow range of wavelengths, such as 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 25 nm or less, e.g., 20 nm or less, e.g., 15 nm or less, e.g., 10 nm or less, e.g., 5 nm or less, e.g., 2 nm or less, and emitting light of a specific wavelength. In some cases, the polymerizable composition is irradiated with a narrow band light source, such as a narrow wavelength LED, a laser diode, or a broad band light source coupled to one or more optical band pass filters, a diffraction grating, a monochromator, or any combination thereof.

[0031] In certain embodiments, the light source is a strobe light source, and the polymerizable composition is illuminated with a periodic light beam, for example, the polymerizable composition is illuminated with a frequency of 0.01 kHz or greater, such as 0.05 kHz or greater, for example, 0.1 kHz or greater, for example, 0.5 kHz or greater, for example, 1 kHz or greater, for example, 2.5 kHz or greater, for example, 5 kHz or greater, for example, 10 kHz or greater, for example, 25 kHz or greater, for example, 50 kHz or greater (including 100 kHz or greater). In certain cases, the polymerizable composition is illuminated with a laser, such as a pulsed laser or a continuous wave laser.

[0032] In some embodiments, the polymerizable composition is in contact with the build elevator and the build surface. In some cases, the method includes irradiating the polymerizable composition for 1 second or more, e.g., 5 seconds or more, e.g., 10 seconds or more, e.g., 20 seconds or more, e.g., 30 seconds or more, e.g., 1 minute or more, e.g., 5 minutes or more, including 10 minutes or more, to bond a first polymerized region of the polymerizable composition to the build elevator.

[0033] In some embodiments, the build elevator is displaced away from the build surface after the first polymerized region of the polymerizable composition is bonded to the build elevator. In some cases, the build elevator is displaced in increments of 0.001 μm or more, such as 0.005 μm or more, for example, 0.01 μm or more, such as 0.05 μm or more, for example, 0.1 μm or more, such as 0.5 μm or more, for example, 1 μm or more, such as 2 μm or more, for example, 3 μm or more, such as 4 μm or more, for example, 5 μm or more (including increments of 10 μm or more). In certain cases, the build elevator is displaced in increments of 0.001 μm to 20 μm, such as 0.005 μm to 19 μm, for example, 0.01 μm to 18 μm, for example, 0.05 μm to 17 μm, for example, 0.1 μm to 16 μm, for example, 0.2 μm to 17 μm, for example, 0.3 μm to 16 μm, for example, 0.4 μm to 15 μm, for example, 0.5 μm to 14 μm, for example, 0.6 μm to 13 μm, for example, 0.7 μm to 12 μm, for example, 0.8 μm to 11 μm (including 0.9 μm to 10 μm).

[0034] In certain cases, the polymerizable composition is applied to the build surface after each displacement of the build elevator away from the build surface. In some cases, the polymerizable composition is applied to the build surface continuously. In other cases, the polymerizable composition is applied to the build surface at discrete intervals, each having a predetermined amount. In some embodiments, the polymerizable composition is selected from polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-ene, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl ester, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof. In certain cases, one or more of the polymerizable materials comprises carbon nanotubes, such as single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs). In some cases, the polymerizable composition has a viscosity of from 100 cP to 7000 cP, such as from 150 cP to 6500 cP, for example, from 200 cP to 6000 cP, for example, from 250 cP to 5500 cP, for example, from 300 cP to 5000 cP, for example, from 350 cP to 4500 cP, for example, from 400 cP to 4000 cP, for example, from 450 cP to 3500 cP (including a viscosity of from 500 cP to 3000 cP).

[0035] In some embodiments, the polymerizable composition is irradiated through the build surface. In some cases, the polymerizable composition is irradiated in the presence of a polymerization inhibitor. In certain embodiments, the polymerizable composition is polymerized continuously while displacing the build elevator away from the build surface. In certain cases, the polymerization inhibitor is oxygen, and the build surface is permeable to oxygen. In certain cases, polymerizing the polymerizable composition in the presence of a polymerization inhibitor such as oxygen allows for the continuous (i.e., not layer-by-layer) production of polymer structures with microvoid spaces, with a liquid "dead zone" at the interface between the build surface and the built polymer structure with microvoid spaces. In some cases, the dead zone is produced because oxygen acts as a polymerization inhibitor and penetrates through the oxygen-permeable build surface. Photopolymerization cannot occur in the oxygen-containing "dead zone" region; therefore, this region remains fluid, the polymerizing components contact the build surface, and therefore the built polymer structure does not physically adhere to the build surface.

[0036] In some embodiments, the polymerizable composition is in contact with a build elevator and a build surface. In some cases, the method includes irradiating the polymerizable composition for a period of time sufficient to bond a first polymerized region of the polymerizable composition to the build elevator. In some cases, the build elevator is displaced in increments of 0.001 μm or more, such as 0.005 μm or more, for example, 0.01 μm or more, such as 0.05 μm or more, for example, 0.1 μm or more, such as 0.5 μm or more, for example, 1 μm or more, such as 2 μm or more, for example, 3 μm or more, such as 4 μm or more, for example, 5 μm or more (including increments of 10 μm or more). In certain cases, the build elevator is displaced in increments of 0.001 μm to 20 μm, such as 0.005 μm to 19 μm, for example, 0.01 μm to 18 μm, for example, 0.05 μm to 17 μm, for example, 0.1 μm to 16 μm, for example, 0.2 μm to 17 μm, for example, 0.3 μm to 16 μm, for example, 0.4 μm to 15 μm, for example, 0.5 μm to 14 μm, for example, 0.6 μm to 13 μm, for example, 0.7 μm to 12 μm, for example, 0.8 μm to 11 μm (including 0.9 μm to 10 μm).

[0037] In some cases, the method includes applying a polymerizable composition to the build surface after each displacement of the build elevator away from the build surface. In some cases, the method includes continuously applying the polymerizable composition to the build surface. In some cases, the polymerizable composition is continuously applied to the build surface by injection through a conduit.

[0038] In some cases, the polymerizable composition can be provided directly to the build plate from a liquid conduit and reservoir system. In some embodiments, the carrier includes one or more feed channels therein. The carrier feed channels are in fluid communication with a polymerizable composition source, e.g., a reservoir, and an associated pump. Different carrier feed channels can be in fluid communication with the same supply and operate simultaneously with one another, or different carrier feed channels can be separately controllable from one another (e.g., by providing a pump and / or valve for each). Separately controllable feed channels can be in fluid communication with sources (e.g., reservoirs) containing the same polymerizable composition, or can be in fluid communication with reservoirs containing different polymerizable compositions. In some embodiments, through the use of a valve assembly, different polymerizable compositions can be alternately fed through the same feed channel as needed.

[0039] In some embodiments, the polymerizable composition is transported to the space between the build elevator and the build surface through two or more conduits, e.g., three or more, e.g., four or more, e.g., five or more, e.g., six or more, e.g., seven or more, e.g., eight or more, e.g., nine or more (including ten or more) different conduits. In some cases, the conduits are positioned internal to the generated polymer structure. In other cases, the conduits are positioned external to the generated polymer structure. In certain cases, one or more of the conduits, e.g., two or more of the conduits, e.g., three or more of the conduits, pass through the build elevator, including when the polymerizable composition is transported through five or more of the conduits passing through the build elevator.

[0040] In some embodiments, the method includes conveying two or more different polymerizable materials to a space between a build elevator and a build surface. In some cases, a first polymerizable material is conveyed to the space between the build elevator and the build surface through a first conduit, and a second polymerizable material is conveyed to the space between the build elevator and the build surface through a second conduit. In certain embodiments, multiple different polymerizable materials are conveyed to the space between the build elevator and the build surface through multiple different conduits. For example, the number of different polymerizable materials conveyed can be two or more, such as three or more, such as four or more, such as five or more, such as six or more, such as seven or more, such as eight or more, such as nine or more (including ten or more). In some cases, the multiple polymerizable materials are conveyed through two or more different conduits, such as three or more, such as four or more, such as five or more, such as six or more, such as seven or more, such as eight or more, such as nine or more (including ten or more) different conduits.

[0041] Two or more different polymerizable materials can be delivered to the space between the build elevator and the build surface simultaneously or in a predetermined sequence. In some cases, two or more different polymerizable materials are delivered to the space between the build elevator and the build surface, for example, to form a blend or mixture (i.e., a mixed resin) of two or more different polymerizable materials. In other cases, two or more different polymerizable materials are delivered to the space between the build elevator and the build surface sequentially, for example, to form layers of different polymerizable materials.

[0042] The polymerizable composition can be delivered through each conduit at a rate ranging from, for example, 0.01 μL / sec to 200 μL / sec, for example, 0.05 μL / sec to 150 μL / sec, for example, 0.1 μL / sec to 100 μL / sec, for example, 0.5 μL / sec to 90 μL / sec, for example, 1 μL / sec to 80 μL / sec, for example, 2 μL / sec to 70 μL / sec, for example, 3 μL / sec to 60 μL / sec, for example, 4 μL / sec to 50 μL / sec, for example, 5 μL / sec to 40 μL / sec, for example, 6 μL / sec to 30 μL / sec (including 7 μL / sec to 27 μL / sec). In some cases, the rate for delivering the polymerizable composition is controlled by a syringe pump. In some cases, the rate can be controlled by a rate-limiting valve positioned at the proximal or distal end of the conduit. In certain embodiments, the polymerizable composition is conveyed into the space between the build elevator and the build surface at a rate of 0.01 mm / hr or more, such as 0.05 mm / hr or more, for example 0.1 mm / hr or more, such as 0.5 mm / hr or more, for example 1 mm / hr or more, such as 2 mm / hr or more, for example 3 mm / hr or more, such as 4 mm / hr or more, for example 5 mm / hr or more, such as 6 mm / hr or more, for example 7 mm / hr or more, such as 8 mm / hr or more, for example 9 mm / hr or more, such as 10 mm / hr or more, for example 15 mm / hr or more, such as 20 mm / hr or more, for example 25 mm / hr or more, such as 50 mm / hr or more, for example 75 mm / hr or more, such as 100 mm / hr or more, for example 150 mm / hr or more, comprising conveying the polymerizable composition through one or more conduits into the space between the build elevator and the build surface at a rate sufficient to produce a polymeric structure at a rate of 250 mm / hr or more. For example, the polymerizable material may be conveyed through one or more conduits at a rate sufficient to produce a polymeric structure at a rate of from 1 mm / hr to 250 mm / hr, such as from 2 mm / hr to 225 mm / hr, for example from 3 mm / hr to 200 mm / hr, for example from 4 mm / hr to 175 mm / hr, for example from 5 mm / hr to 150 mm / hr, including from 10 mm / hr to 125 mm / hr.

[0043] In some embodiments, the method provides the polymerizable composition to a liquid interfacial polymerization module by injection continuous liquid interface generation, such as described in International Patent Application No. PCT / US23 / 15406, filed March 16, 2023, the disclosure of which is incorporated herein by reference. In certain embodiments, the polymerizable composition is polymerized using a liquid interfacial polymerization module that is a continuous liquid interface generation (CLIP) system, such as described in International Patent Publication No. WO2014 / 126837, U.S. Patent Publication Nos. 2018 / 0064920, 2017 / 0095972, 2021 / 0246252, and U.S. Patent Publication Nos. 10,155,882 and 10,792,857, the disclosures of which are incorporated herein by reference.

[0044] In some cases, the microvoid space generated within the polymeric structure comprises one or more microchannels. In some cases, one or more of the microchannels comprises one or more branches, e.g., two or more branches, e.g., three or more, e.g., four or more, e.g., five or more (including ten or more) different branches. In some cases, the microchannels extend through the polymeric structure. In some cases, the microchannels are fluidically interconnected. In some cases, the polymeric structure has a single network of fluidically interconnected microchannel networks. In other cases, the polymeric structure has multiple fluidically interconnected microchannel networks.

[0045] When practicing the methods of the present disclosure according to some embodiments, a quantity of polymerizable composition is delivered through the generated microvoid space in a manner sufficient to displace any material within the microvoid space (e.g., residual or trapped polymerized resin). In embodiments, the polymerizable composition used to displace material from the microvoid space can be the same polymerizable material used to form the polymer structure, or optionally, a different polymerizable material. In some cases, the polymerizable composition delivered through the microvoid space is non-reactive when injected through the microvoid space. By "non-reactive," we mean that the polymerizable composition delivered through the microvoid space does not react with or polymerize within the formed polymer structure (e.g., does not fill the microvoid space). In some cases, the polymerizable composition is injected into the microvoid space, e.g., the microvoid space is a microchannel within the forming polymer structure. The polymerizable composition may be conveyed through the generated microvoid space at a velocity sufficient to displace material within the microvoid space, for example at a rate of 0.01 μL / sec or more, such as 0.05 μL / sec or more, for example 0.1 μL / sec or more, for example 0.5 μL / sec or more, such as 1 μL / sec or more, for example 2 μL / sec or more, for example 3 μL / sec or more, such as 4 μL / sec or more, for example 5 μL / sec or more, for example 6 μL / sec or more, such as 7 μL / sec or more, for example 8 μL / sec or more, for example 9 μL / sec or more, such as 10 μL / sec or more, for example 15 μL / sec or more, such as 20 μL / sec or more, for example 25 μL / sec or more, such as 50 μL / sec or more, for example 75 μL / sec or more, for example 100 μL / sec or more (including rates of 250 μL / sec or more). For example, the polymerizable composition can be transported through the generated microvoid space at a rate of 0.01 μL / sec to 200 μL / sec, for example, 0.05 μL / sec to 150 μL / sec, for example, 0.1 μL / sec to 100 μL / sec, for example, 0.5 μL / sec to 90 μL / sec, for example, 1 μL / sec to 80 μL / sec, for example, 2 μL / sec to 70 μL / sec, for example, 3 μL / sec to 60 μL / sec, for example, 4 μL / sec to 50 μL / sec, for example, 5 μL / sec to 40 μL / sec, for example, 6 μL / sec to 30 μL / sec (including 7 μL / sec to 27 μL / sec).In certain cases, delivering the polymerizable composition is sufficient to flush away any resin or residual resin trapped within the microvoid spaces to maintain the negative space and eliminate print-through of the polymer structure.

[0046] In some embodiments, the polymerizable composition is delivered through the generated microvoid space at predetermined intervals while generating the polymer structure (e.g., while displacing the build elevator away from the build surface while generating the polymer structure). In some cases, the polymerizable composition is delivered through the microvoid space every 1 second or more, e.g., every 5 seconds or more, e.g., every 10 seconds or more, e.g., every 15 seconds or more, e.g., every 30 seconds or more, e.g., every 1 minute or more, e.g., every 5 minutes or more, e.g., every 10 minutes or more (including every 30 minutes or more) to displace any material (e.g., trapped polymerized resin) within the microvoid space. In some cases, the polymerizable composition is continuously delivered through the generated microvoid space into the space between the build elevator and the build surface of the liquid interface-generating module. In some cases, a non-reactive composition is continuously delivered (e.g., through a conduit) into the microvoid space while displacing the build elevator away from the build surface while generating the polymer structure.

[0047] In some embodiments, the method includes contacting the generated microvoid space with a non-polymerizable composition. In practicing the subject method, in some cases, the non-polymerizable composition continuously contacts the microvoid space while generating the polymer structure. In some embodiments, the method includes filling at least a portion of the void volume of the microvoid space with the non-polymerizable composition, for example, 5% or more, for example, 10% or more, for example, 15% or more, for example, 20% or more, for example, 25% or more, for example, 50% or more, for example, 75% or more (including 90% or more) of the void volume of the microvoid space. In some embodiments, the method includes filling the entire void volume of the microvoid space with the non-polymerizable composition. In certain cases, the non-polymerizable composition is non-reactive with the polymerizable composition of the polymer structure. In some cases, the non-polymerizable composition fills one or more microchannels within the polymer structure, for example, the non-polymerizable composition fills one or more microchannels extending through the polymer structure. In some cases, the polymer structure comprises multiple microvoid spaces. In some cases, the non-polymerizable composition is a composition selected from water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electro-responsive liquid, and a gas.

[0048] In some cases, the method includes applying a non-polymerizable composition to the build surface after each displacement of the build elevator away from the build surface to fill the microvoid spaces created. In some cases, the method includes continuously applying the non-polymerizable composition to the build surface to fill the microvoid spaces created. In some cases, the non-polymerizable composition is continuously applied to the build surface by injection through a conduit to fill the microvoid spaces created.

[0049] In some cases, the non-polymerizable composition can be provided directly to the build plate from a liquid conduit and reservoir system. In some embodiments, the carrier includes one or more feed channels therein. The carrier feed channels are in fluid communication with a non-polymerizable composition supply, e.g., a reservoir, and an associated pump. Different carrier feed channels can be in fluid communication with the same supply and operate simultaneously with each other, or different carrier feed channels can be separately controllable from each other (e.g., by providing a pump and / or valve for each). Separately controllable feed channels can be in fluid communication with reservoirs containing the same polymerizable composition, or with reservoirs containing different polymerizable compositions. In some embodiments, through the use of a valve assembly, different polymerizable compositions can be alternately fed through the same feed channel as needed.

[0050] FIG. 1 illustrates the injection of a non-polymerizable composition into generated microvoid spaces, e.g., microchannels, according to certain embodiments. As shown in FIG. 1, polymer structures are generated layer by layer by irradiating a polymerizable composition between a build elevator and a build surface. Microvoid spaces, here microchannels, are formed within the polymer structure. During the formation of the microchannels in each layer, a non-polymerizable composition is injected into the forming microvoid spaces through a conduit passing through the build elevator. The non-polymerizable composition in this embodiment is sufficient to prevent polymerization of excess polymerizable material in the forming microvoid spaces. Removal of the non-polymerizable composition is sufficient to generate resolved microvoid spaces, such as the microchannels through the illustrated polymer structure. As mentioned above, in some cases, additional polymerizable material (e.g., fresh resin used to form the polymer structure) can instead be injected through the forming microchannels in each layer to flush out any residual or trapped polymerized material.

[0051] System for fabricating polymer structures with microvoid spaces Aspects of the present disclosure also include a system for fabricating polymer structures having microvoid spaces. The system, according to certain embodiments, includes a light source and a light interface polymerization module having a build elevator and a build surface, configured to generate a polymer structure having resolved microvoid spaces therein from a polymerizable composition positioned therebetween.

[0052] In some embodiments, the system includes a light source. In some embodiments, the light source is a broadband light source that emits light having a broad range of wavelengths, e.g., 50 nm or greater, such as 100 nm or greater, such as 150 nm or greater, such as 200 nm or greater, such as 250 nm or greater, such as 300 nm or greater, such as 350 nm or greater, or 400 nm or greater, including 500 nm or greater. For example, one suitable broadband light source emits light having a wavelength between 200 nm and 1500 nm. Another example of a suitable broadband light source includes a light source that emits light having a wavelength between 400 nm and 1000 nm. Any convenient broadband light source protocol may be employed, such as a halogen lamp, a deuterium arc lamp, a xenon arc lamp, a stabilized fiber-coupled broadband light source, a broadband LED with a continuous spectrum, an ultra-bright light-emitting diode, a semiconductor light-emitting diode, a broad-spectrum LED white light source, a multi-LED integrated white light source, or any combination thereof, among other broadband light sources.

[0053] In some embodiments, the light source is a narrowband light source that emits a specific wavelength or a narrow range of wavelengths. In some cases, a narrowband light source includes a light source that emits light having a narrow range of wavelengths, such as 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 25 nm or less, e.g., 20 nm or less, e.g., 15 nm or less, e.g., 10 nm or less, e.g., 5 nm or less, e.g., 2 nm or less, and emits light of a specific wavelength (i.e., monochromatic light). Any convenient narrowband light source protocol can be used, such as a narrow wavelength LED, a laser diode, or a broadband light source coupled to one or more optical bandpass filters, a diffraction grating, a monochromator, or any combination thereof. The subject systems can include one or more light sources, such as two or more light sources, e.g., three or more light sources, e.g., four or more light sources, e.g., five or more light sources (including ten or more light sources), as desired. The light source may include a combination of light source types; for example, if two light sources are used, the first light source may be a broadband white light source (e.g., a broadband white light LED) and the second light source may be a broadband near-infrared light source (e.g., a broadband near-infrared LED). In other cases where two light sources are used, the first light source may be a broadband white light source (e.g., a broadband white light LED) and the second light source may be a narrow spectrum light source (e.g., a narrowband visible or near-infrared LED). In still other cases, the light source is a narrowband light source, each emitting a specific wavelength, for example, an array of two or more LEDs, for example, an array of three or more LEDs, for example, an array of five or more LEDs (including an array of ten or more LEDs).

[0054] In certain embodiments, the light source is a strobe light source, in which the polymerizable composition is illuminated with a periodic flash of light. Depending on the light source (e.g., flash lamp, pulsed laser), the frequency of the strobe light can vary and can be 0.01 kHz or higher, e.g., 0.05 kHz or higher, e.g., 0.1 kHz or higher, e.g., 0.5 kHz or higher, e.g., 1 kHz or higher, e.g., 2.5 kHz or higher, e.g., 5 kHz or higher, e.g., 10 kHz or higher, e.g., 25 kHz or higher, e.g., 50 kHz or higher (including 100 kHz or higher). In these embodiments, the strobe light can be operably coupled to a processor having a frequency generator that adjusts the strobe frequency. In some cases, the strobe light frequency generator is operably coupled to the projection monitoring component of the micro-digital light projection system so that the strobe light frequency is synchronized with the frequency of image capture on the build surface of the optical interface polymerization module. In certain instances, suitable strobe light sources and frequency controllers include, but are not limited to, those described in U.S. Pat. Nos. 5,700,692 and 6,372,506, the disclosures of which are incorporated herein by reference.

[0055] In some embodiments, the light source includes one or more lasers. Lasers of interest may include pulsed or continuous wave lasers. The type and number of lasers used in the subject methods may be gas lasers, such as helium-neon lasers, argon lasers, krypton lasers, xenon lasers, nitrogen lasers, CO lasers, CO lasers, argon-fluorine (ArF) excimer lasers, krypton-fluorine (KrF) excimer lasers, xenon-chlorine (XeCl) excimer lasers, or xenon-fluorine (XeF) excimer lasers, or combinations thereof. In other cases, the light beam generator includes a dye laser, such as a stilbene, coumarin, or rhodamine laser. In still other cases, the optical beam generator includes a metal vapor laser, such as a helium-cadmium (HeCd) laser, a helium-mercury (HeHg) laser, a helium-selenium (HeSe) laser, a helium-silver (HeAg) laser, a strontium laser, a neon-copper (NeCu) laser, a copper laser, or a gold laser, and combinations thereof. In still other cases, the optical beam generator includes a solid-state laser, such as a ruby ​​laser, a Nd:YAG laser, a NdCrYAG laser, an Er:YAG laser, a Nd:YLF laser, a Nd:YVO4 laser, a Nd:YCa4O(BO3)3 laser, a Nd:YCOB laser, a titanium sapphire laser, a thulium YAG laser, a ytterbium YAG laser, a ytterbium2O3 laser, or a cerium-doped laser, and combinations thereof. In still other cases, the light source comprises a semiconductor diode laser, an optically pumped semiconductor laser (OPSL), or a frequency-doubled or frequency-tripled implementation of any of the aforementioned lasers.

[0056] In some embodiments, the light source includes one or more tube lenses configured with an adjustable focal length. In some cases, the tube lens is a telecentric lens. In certain cases, the tube lens is configured for wide-field imaging. In some cases, the tube lens has an adjustable focal length in the range of 10 mm to 1000 mm, e.g., 20 mm to 900 mm, e.g., 30 mm to 800 mm, e.g., 40 mm to 700 mm, e.g., 50 mm to 600 mm, e.g., 60 mm to 500 mm, e.g., 70 mm to 400 mm, e.g., 80 mm to 300 mm (including an adjustable focal length of 100 mm to 200 mm).

[0057] In some embodiments, the light source includes one or more projection lenses, e.g., two or more projection lenses, e.g., three or more projection lenses, e.g., four or more projection lenses (including five or more projection lenses). In some cases, the projection lenses provide a magnification of 2x or more, e.g., 3x or more, e.g., 4x or more, e.g., 5x or more, e.g., 6x or more, e.g., 7x or more, e.g., 8x or more, e.g., 9x or more (including 10x or more magnification). In some instances, the projection lenses provide a reduction having a magnification in the range of 0.1 to 0.95, e.g., 0.2 to 0.9, e.g., 0.3 to 0.85, e.g., 0.35 to 0.8, e.g., 0.5 to 0.75 (including 0.55 to 0.7), e.g., 0.6.

[0058] In some embodiments, the light source includes one or more beam splitters. A beam splitter may be any optical component configured to propagate a beam of light along two or more distinct, spatially separated optical paths, such that a predetermined portion of the light is propagated along each optical path. The beam splitter may be any convenient beam splitter protocol, such as a triangular prism, a semitransparent mirror prism, or a dichroic mirror prism, among other types of beam splitters. The beam splitter may be formed from any suitable material, so long as it is capable of propagating the desired amount and wavelength of light along each optical path. For example, beam splitters of interest may be formed from glass (e.g., N-SF10, N-SF11, N-SF57, N-BK7, N-LAK21, or N-LAF35 glass), silica (e.g., fused silica), quartz, crystal (e.g., CaF2 crystal), zinc selenide (ZnSe), F2, germanium titanate (Ge) (e.g., S-TIH11), or borosilicate (e.g., BK7). In certain embodiments, the beamsplitter is formed from a polymeric material such as, but not limited to, polycarbonate, polyvinyl chloride (PVC), polyurethane, polyether, polyamide, polyimide, or copolymers of these thermoplastics such as PETG (glycol-modified polyethylene terephthalate), among other polymeric plastic materials. In certain embodiments, the beamsplitter is formed from a polyester, including, but not limited to, poly(ethylene terephthalate) (PET), bottle-grade PET (a copolymer made based on monoethylene glycol, terephthalic acid, and other comonomers such as isophthalic acid and cyclohexanedimethanol), poly(butylene terephthalate) (PBT), and poly(alkylene terephthalates) such as poly(hexamethylene terephthalate), poly(ethylene adipate), poly(1,poly(alkylene adipates) such as poly(4-butylene adipate) and poly(hexamethylene adipate), poly(alkylene suberates) such as poly(ethylene suberate), poly(alkylene sebacates) such as poly(ethylene sebacate), poly(ε-caprolactone) and poly(β-propiolactone), poly(alkylene isophthalates) such as poly(ethylene isophthalate), poly(ethylene 2,6-naphthalene-dicarboxylate), poly(alkylene 2,6-naphthalene dicarboxylate), poly(alkylenesulfonyl-4,4'-dibenzoate) such as poly(ethylenesulfonyl-4,4'-dibenzoate), poly(p-phenylene alkylene dicarboxylate) such as poly(p-phenylene ethylene dicarboxylate), poly(trans-1,4-cyclohexanediyl alkylene dicarboxylate) such as poly(trans-1,4-cyclohexanediyl ethylene dicarboxylate), poly(1,4-cyclohexane-dimethylene alkylene dicarboxylate) such as poly(1,4-cyclohexane-dimethylene ethylene dicarboxylate), poly([2.2.2]-bicyclooctane-1,4-dimethylene alkylene dicarboxylate) such as poly([2.2.2]-bicyclooctane-1,4-dimethylene ethylene dicarboxylate), (S)-polylactide, (R,S)-polylactide, poly(tetramethyl glycolide), and Examples of suitable polycarbonates include lactic acid polymers and copolymers such as poly(lactide-co-glycolide), polycarbonates of bisphenol A, 3,3'-dimethylbisphenol A, 3,3',5,5'-tetrachlorobisphenol A, 3,3',5,5'-tetramethylbisphenol A, polyamides such as poly(p-phenylene terephthalamide), polyethylene terephthalate (e.g., Mylar™ polyethylene terephthalate), combinations thereof, and the like.

[0059] In an embodiment, the micro-digital light projection system includes a light projection monitoring component having a photodetector. The photodetector may be any convenient light detection protocol, including, but not limited to, a light sensor or photodetector such as an active pixel sensor (APS), an avalanche photodiode (APD), a quadrant photodiode, an image sensor, a charge-coupled device (CCD), an intensified charge-coupled device (ICCD), a light-emitting diode, a photon counter, a bolometer, a pyroelectric detector, a photoresistor, a solar cell, a photodiode, a photomultiplier tube, a phototransistor, a quantum dot photoconductor or photodiode, and combinations thereof, among other photodetectors. In one particular embodiment, the photodetector is a photomultiplier tube, e.g., a 0.01 cm 2 ~10cm 2 , e.g., 0.05 cm 2 ~9cm 2 , e.g., 0.1 cm 2 ~8cm 2 , e.g., 0.5 cm 2 ~7cm 2 (1cm 2 ~5cm 2 The photomultiplier tube has an active detection surface area in each region of the range including the area of ​​the active detection surface area.

[0060] In certain embodiments, the optical projection monitoring component includes one or more photodetectors optically coupled to the slit. Depending on the size of the active detection surface of the photodetector, the slit in certain cases has a rectangular (or other polygonal) opening with a width of 0.01 mm to 2 mm, e.g., 0.1 mm to 1.9 mm, e.g., 0.2 mm to 1.8 mm, e.g., 0.3 mm to 1.7 mm, e.g., 0.4 mm to 1.6 mm (including a width of 0.5 mm to 1.5 mm), and a length of 0.01 mm to 2 mm, e.g., 0.1 mm to 1.9 mm, e.g., 0.2 mm to 1.8 mm, e.g., 0.3 mm to 1.7 mm, e.g., 0.4 mm to 1.6 mm (including a length of 0.5 mm to 1.5 mm). In certain cases, the width of the slit is 1 mm or less, e.g., 0.9 mm or less, e.g., 0.8 mm or less, e.g., 0.7 mm or less, e.g., 0.6 mm or less, e.g., 0.5 mm or less (including widths of 0.4 mm or less). In certain cases, the optical detection system includes an optical detector optically coupled to a slit having multiple apertures, e.g., two or more apertures, e.g., three or more apertures, e.g., four or more apertures, e.g., five or more apertures, e.g., six or more apertures, e.g., seven or more apertures, e.g., eight or more apertures, e.g., nine or more apertures (including slits having ten or more apertures).

[0061] The light may be measured by a photodetector at one or more wavelengths, e.g., two or more wavelengths, e.g., five or more different wavelengths, e.g., ten or more different wavelengths, e.g., twenty-five or more different wavelengths, e.g., fifty or more different wavelengths, e.g., one hundred or more different wavelengths, e.g., two hundred or more different wavelengths, e.g., three hundred or more different wavelengths (including measuring light at four hundred or more different wavelengths). The light may be measured continuously or at discrete intervals. In some cases, the detector in question is configured to measure the light continuously. In other cases, the detector in question is configured to measure at discrete intervals, e.g., measuring light every 0.001 millisecond, e.g., every 0.01 millisecond, e.g., every 0.1 millisecond, e.g., every 1 millisecond, e.g., every 10 milliseconds, e.g., every 100 milliseconds, including every 1000 milliseconds, or some other interval.

[0062] In certain embodiments, the micro digital light projection system is a digital light processing (DLP) system having a digital micromirror device as described in U.S. Patent Publication Nos. 2017 / 0095972, 2022 / 0250313, 2022 / 0048242, and U.S. Patent Nos. 11,358,342 and 11,141,910, the disclosures of which are incorporated herein by reference.

[0063] In some embodiments, the system includes a processor having a memory operatively coupled to the processor, the memory including instructions stored thereon that, when executed by the processor, cause the processor to: a) irradiate a polymerizable composition positioned between a build elevator and a build surface to generate a polymerizable composition having polymerized regions of the polymerizable composition with microvoid spaces in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface; b) displace the build elevator away from the build surface; c) contact the generated microvoid spaces with a non-reactive composition; and d) repeat steps a)-c) in a manner sufficient to generate a polymer structure having resolved microvoid spaces. In some instances, the system is configured to generate a polymer structure having microvoid spaces containing a non-polymerizable composition positioned therein. These steps are repeated in a manner sufficient to generate a polymer structure having microvoid spaces with a non-polymerizable composition positioned therein. For example, the steps may be repeated 2 or more times, such as 3 or more times, for example 4 or more times, for example 5 or more times, for example 10 or more times, such as 20 or more times, for example 30 or more times, for example 40 or more times, for example 50 or more times, such as 100 or more times, for example 250 or more times, for example 500 or more times (including 1000 or more times).

[0064] In some embodiments, the memory includes instructions for irradiating the polymerizable composition for a period of time sufficient to bond a first polymerized region of the polymerizable composition to the build elevator. In some cases, the memory includes instructions for irradiating the polymerizable composition for 1 second or more, e.g., 5 seconds or more, e.g., 10 seconds or more, e.g., 20 seconds or more, e.g., 30 seconds or more, e.g., 1 minute or more, e.g., 5 minutes or more, including 10 minutes or more, to bond the first polymerized region of the polymerizable composition to the build elevator.

[0065] In some embodiments, the memory includes instructions to displace a build elevator that builds the polymer structure in predetermined increments, hi some cases, the memory includes instructions to displace the build elevator in increments of 0.001 μm or more, e.g., 0.005 μm or more, e.g., 0.01 μm or more, e.g., 0.05 μm or more, e.g., 0.1 μm or more, e.g., 0.5 μm or more, e.g., 1 μm or more, e.g., 2 μm or more, e.g., 3 μm or more, e.g., 4 μm or more, e.g., 5 μm or more (including increments of 10 μm or more). In certain cases, the memory includes instructions to displace the build elevator in increments of 0.001 μm to 20 μm, such as 0.005 μm to 19 μm, for example, 0.01 μm to 18 μm, for example, 0.05 μm to 17 μm, for example, 0.1 μm to 16 μm, for example, 0.2 μm to 17 μm, for example, 0.3 μm to 16 μm, for example, 0.4 μm to 15 μm, for example, 0.5 μm to 14 μm, for example, 0.6 μm to 13 μm, for example, 0.7 μm to 12 μm, for example, 0.8 μm to 11 μm (including 0.9 μm to 10 μm).

[0066] In certain cases, the memory includes instructions for applying the polymerizable composition to the build surface after each displacement of the build elevator away from the build surface. In some cases, the memory includes instructions for continuously applying the polymerizable composition to the build surface. In other cases, the memory includes instructions for continuously applying the polymerizable composition to the build surface in discrete intervals in predetermined amounts. In some embodiments, the polymerizable composition is selected from polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-ene, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl ester, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof. In certain cases, one or more of the polymerizable materials includes carbon nanotubes, such as single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs). In some cases, the polymerizable composition has a viscosity of from 100 cP to 7000 cP, such as from 150 cP to 6500 cP, for example, from 200 cP to 6000 cP, for example, from 250 cP to 5500 cP, for example, from 300 cP to 5000 cP, for example, from 350 cP to 4500 cP, for example, from 400 cP to 4000 cP, for example, from 450 cP to 3500 cP (including a viscosity of from 500 cP to 3000 cP).

[0067] In some cases, the polymerizable composition can be provided directly to the build plate from a liquid conduit and reservoir system. In some embodiments, the carrier includes one or more feed channels therein. The carrier feed channels are in fluid communication with a polymerizable composition source, e.g., a reservoir, and an associated pump. Different carrier feed channels can be in fluid communication with the same supply and operate simultaneously with one another, or different carrier feed channels can be separately controllable from one another (e.g., by providing a pump and / or valve for each). Separately controllable feed channels can be in fluid communication with sources (e.g., reservoirs) containing the same polymerizable composition, or can be in fluid communication with reservoirs containing different polymerizable compositions. In some embodiments, through the use of a valve assembly, different polymerizable compositions can be alternately fed through the same feed channel as needed.

[0068] In some embodiments, the system includes two or more conduits, e.g., three or more, e.g., four or more, e.g., five or more, e.g., six or more, e.g., seven or more, e.g., eight or more, e.g., nine or more (including ten or more) different conduits, for transporting the polymerizable composition to the space between the build elevator and the build surface. In some cases, the conduits are positioned internal to the generated polymer structure. In other cases, the conduits are positioned external to the generated polymer structure. Certain cases include when one or more of the conduits, e.g., two or more of the conduits, e.g., three or more of the conduits, pass through the build elevator, and the polymerizable composition is transported through five or more of the conduits that pass through the build elevator.

[0069] In some embodiments, the system is configured to deliver two or more different polymerizable materials to the space between the build elevator and the build surface. In some cases, the system is configured to deliver a first polymerizable material to the space between the build elevator and the build surface through a first conduit and a second polymerizable material to the space between the build elevator and the build surface through a second conduit. In certain embodiments, the system is configured to deliver multiple different polymerizable materials to the space between the build elevator and the build surface through multiple different conduits. For example, the number of different polymerizable materials delivered can be two or more, such as three or more, such as four or more, such as five or more, such as six or more, such as seven or more, such as eight or more, such as nine or more (including ten or more). In some cases, the system is configured to transport multiple polymerizable materials through two or more different conduits, such as three or more, for example four or more, for example five or more, for example six or more, for example seven or more, for example eight or more, for example nine or more (including ten or more) different conduits.

[0070] In some embodiments, the system is configured to deliver two or more different polymerizable materials to the space between the build elevator and the build surface simultaneously or in a predetermined sequence. In some cases, the system is configured to deliver two or more different polymerizable materials to the space between the build elevator and the build surface, for example, to form a blend or mixture (i.e., a mixed resin) of two or more different polymerizable materials. In other cases, the system is configured to deliver two or more different polymerizable materials to the space between the build elevator and the build surface sequentially, for example, to form layers of different polymerizable materials.

[0071] In some cases, the system is configured to deliver the polymerizable composition through each conduit at a rate that varies, e.g., from 0.01 μL / sec to 200 μL / sec, e.g., from 0.05 μL / sec to 150 μL / sec, e.g., from 0.1 μL / sec to 100 μL / sec, e.g., from 0.5 μL / sec to 90 μL / sec, e.g., from 1 μL / sec to 80 μL / sec, e.g., from 2 μL / sec to 70 μL / sec, e.g., from 3 μL / sec to 60 μL / sec, e.g., from 4 μL / sec to 50 μL / sec, e.g., from 5 μL / sec to 40 μL / sec, e.g., from 6 μL / sec to 30 μL / sec (including from 7 μL / sec to 27 μL / sec). In some cases, the rate for delivering the polymerizable composition is controlled by a syringe pump. In some cases, the conduits include rate-limiting valves at their proximal or distal ends to control the rate at which the polymerizable composition is delivered. In certain embodiments, the system is configured to deliver the polymerizable composition to the space between the build elevator and the build surface at a rate sufficient to produce a polymeric structure at a rate of 0.01 mm / hr or more, such as 0.05 mm / hr or more, for example 0.1 mm / hr or more, such as 0.5 mm / hr or more, for example 1 mm / hr or more, such as 2 mm / hr or more, for example 3 mm / hr or more, such as 4 mm / hr or more, for example 5 mm / hr or more, such as 6 mm / hr or more, for example 7 mm / hr or more, such as 8 mm / hr or more, for example 9 mm / hr or more, such as 10 mm / hr or more, for example 15 mm / hr or more, such as 20 mm / hr or more, for example 25 mm / hr or more, such as 50 mm / hr or more, for example 75 mm / hr or more, such as 100 mm / hr or more, for example 150 mm / hr or more, including wherein the system is configured to deliver the polymerizable composition to the space between the build elevator and the build surface through one or more conduits at a rate sufficient to produce a polymeric structure at a rate of 250 mm / hr or more. For example, the polymerizable material may be conveyed through one or more conduits at a rate sufficient to produce a polymeric structure at a rate of from 1 mm / hr to 250 mm / hr, such as from 2 mm / hr to 225 mm / hr, for example from 3 mm / hr to 200 mm / hr, for example from 4 mm / hr to 175 mm / hr, for example from 5 mm / hr to 150 mm / hr, including from 10 mm / hr to 125 mm / hr.

[0072] In some embodiments, the system includes a source of polymerizable composition in communication with the build region to apply the polymerizable composition to the build surface. In some cases, the source is configured to apply the polymerizable composition to the build region through a conduit, such as by injecting the polymerizable composition through the conduit. In certain embodiments, a subject system includes a light-interface polymerization module having an injection system for providing the polymerizable composition to the build surface, as described in International Patent Application No. PCT / US23 / 15406, filed March 16, 2023, the disclosure of which is incorporated herein by reference. In certain embodiments, liquid interfacial polymerization modules that are continuous liquid interface generation (CLIP) systems include those described in International Patent Publication No. WO2014 / 126837, U.S. Patent Publication Nos. 2018 / 0064920, 2017 / 0095972, 2021 / 0246252, and U.S. Patent Publication Nos. 10,155,882 and 10,792,857, the disclosures of which are incorporated herein by reference.

[0073] In some embodiments, the system includes a processor having a memory operably coupled to the processor, the memory including instructions stored thereon for contacting the generated microvoid space with a quantity of a polymerizable composition in a manner sufficient to displace polymerized material within the microvoid space. In embodiments, the polymerizable composition used to displace material from the microvoid space can be the same polymerizable material used to form the polymer structure, or optionally, can be a different polymerizable material. In some cases, the polymerizable composition delivered through the microvoid space is non-reactive when injected through the microvoid space.

[0074] In some cases, the memory includes instructions for injecting the polymerizable composition into a microvoid space, for example, the microvoid space is a microchannel formed within the polymer structure. In some cases, the memory includes instructions for conveying the polymerizable composition m through the generated microvoid space at a rate sufficient to displace material within the microvoid space, e.g., at a rate of 0.01 μL / sec or more, such as 0.05 μL / sec or more, for example 0.1 μL / sec or more, for example 0.5 μL / sec or more, such as 1 μL / sec or more, for example 2 μL / sec or more, for example 3 μL / sec or more, such as 4 μL / sec or more, for example 5 μL / sec or more, for example 6 μL / sec or more, such as 7 μL / sec or more, for example 8 μL / sec or more, for example 9 μL / sec or more, such as 10 μL / sec or more, for example 15 μL / sec or more, such as 20 μL / sec or more, for example 25 μL / sec or more, for example 50 μL / sec or more, for example 75 μL / sec or more, such as 100 μL / sec or more (including rates of 250 μL / sec or more). In certain instances, the memory includes instructions for delivering the polymerizable composition through the generated microvoid space at a rate of 0.01 μL / sec to 200 μL / sec, e.g., 0.05 μL / sec to 150 μL / sec, e.g., 0.1 μL / sec to 100 μL / sec, e.g., 0.5 μL / sec to 90 μL / sec, e.g., 1 μL / sec to 80 μL / sec, e.g., 2 μL / sec to 70 μL / sec, e.g., 3 μL / sec to 60 μL / sec, e.g., 4 μL / sec to 50 μL / sec, e.g., 5 μL / sec to 40 μL / sec, e.g., 6 μL / sec to 30 μL / sec (including 7 μL / sec to 27 μL / sec). In certain instances, the memory includes instructions for delivering sufficient polymerizable composition to flush out resin trapped within the microvoid space to maintain a negative space and eliminate print-through of the polymer structure.

[0075] In some embodiments, the memory includes instructions for conveying the polymerizable composition through the generated microvoid space at predetermined intervals while generating the polymer structure (e.g., while displacing the build elevator away from the build surface as the polymer structure is generated). In some cases, the memory includes instructions for conveying the polymerizable composition through the microvoid space every 1 second or more, e.g., every 5 seconds or more, e.g., every 10 seconds or more, e.g., every 15 seconds or more, e.g., every 30 seconds or more, e.g., every 1 minute or more, e.g., every 5 minutes or more, e.g., every 10 minutes or more (including every 30 minutes or more), to displace any material (e.g., trapped polymerized resin) within the microvoid space. In some cases, the memory includes instructions for conveying the polymerizable composition continuously through the generated microvoid space to a space between a build elevator and the build surface of a liquid interface-generating module. In some cases, the memory includes instructions for conveying a non-reactive composition continuously (e.g., through a conduit) into the microvoid space while displacing the build elevator away from the build surface as the polymer structure is generated.

[0076] In some embodiments, the memory includes instructions for contacting the generated microvoid space with a non-polymerizable composition. In some cases, the memory includes instructions for continuously contacting the non-polymerizable composition with the microvoid space while generating the polymer structure. In some embodiments, the system further includes a source of non-polymerizable composition operably coupled to the optical interface polymerization module such that the non-polymerizable composition can contact the microvoid space continuously or at predetermined intervals while generating the polymer structure. In some cases, the system includes a source of non-polymerizable composition selected from water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electric field-responsive liquid, and a gas.

[0077] In some cases, the memory includes instructions for applying a non-polymerizable composition to the build surface to fill the generated microvoid spaces after each displacement of the build elevator away from the build surface. In some cases, the memory includes instructions for continuously applying the non-polymerizable composition to the build surface to fill the generated microvoid spaces. In some cases, the non-polymerizable composition is continuously applied to the build surface by injection through a conduit to fill the generated microvoid spaces. In certain embodiments, the memory includes instructions for removing the non-polymerizable composition from the generated microvoid spaces of the polymer structure.

[0078] In some cases, the memory includes instructions for filling at least a portion of the void volume of the microvoid space with the non-polymerizable composition, e.g., 5% or more, such as 10% or more, for example 15% or more, such as 20% or more, for example 25% or more, such as 50% or more, for example 75% or more (including 90% or more) of the void volume of the microvoid space. In some cases, the system is configured to deliver the non-polymerizable composition through the conduit at a rate that varies from, e.g., 0.01 μL / sec to 200 μL / sec, e.g., 0.05 μL / sec to 150 μL / sec, e.g., 0.1 μL / sec to 100 μL / sec, e.g., 0.5 μL / sec to 90 μL / sec, e.g., 1 μL / sec to 80 μL / sec, e.g., 2 μL / sec to 70 μL / sec, e.g., 3 μL / sec to 60 μL / sec, e.g., 4 μL / sec to 50 μL / sec, e.g., 5 μL / sec to 40 μL / sec, e.g., 6 μL / sec to 30 μL / sec (including 7 μL / sec to 27 μL / sec) to fill at least a portion of the void volume of the microvoid space. In some cases, the rate at which the non-polymerizable composition is delivered to fill at least a portion of the void volume of the microvoid space is controlled by a syringe pump.

[0079] In some embodiments, the system also includes a source of polymerizable composition. In some cases, the source is configured to continuously deliver the polymerizable composition to the build surface. In some cases, the system is configured to apply the polymerizable composition to the build surface after each displacement of the build elevator away from the build surface. In some embodiments, the polymerizable composition is selected from polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-ene, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl ester, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof. In certain cases, one or more of the polymerizable materials includes carbon nanotubes, such as single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs). In some cases, the polymerizable composition has a viscosity of from 100 cP to 7000 cP, such as from 150 cP to 6500 cP, for example, from 200 cP to 6000 cP, for example, from 250 cP to 5500 cP, for example, from 300 cP to 5000 cP, for example, from 350 cP to 4500 cP, for example, from 400 cP to 4000 cP, for example, from 450 cP to 3500 cP (including a viscosity of from 500 cP to 3000 cP).

[0080] In some embodiments, the light source is configured to illuminate through the build surface, and in some cases, at least a portion of the build surface is permeable to the polymerization inhibitor, for example, the polymerization inhibitor is oxygen.

[0081] In certain embodiments, the liquid interfacial polymerization module comprises a continuous liquid interface generation (CLIP) system, such as those described in International Patent Publication No. WO2014 / 126837, U.S. Patent Publication Nos. 2018 / 0064920, 2017 / 0095972, 2021 / 0246252, and U.S. Patent Publication Nos. 10,155,882 and 10,792,857, the disclosures of which are incorporated herein by reference.

[0082] Aspects of the present disclosure further include computer control systems, where the system further includes one or more computers for full or partial automation of the methods described herein. In embodiments, the system includes an input module, a processing module, and an output module. The subject systems may include both hardware and software components, where the hardware components may take the form of one or more platforms, e.g., in the form of servers, such that the functional elements of the system, i.e., those elements of the system that perform specific tasks (e.g., managing the input and output of information, processing information, etc.), may be performed by the execution of software applications on and across one or more computer platforms represented in the system.

[0083] The system may include a display and an operator input device. The operator input device may be, for example, a keyboard, a mouse, etc. The processing module includes a processor that accesses a memory having stored instructions to perform the steps of the subject method. The processing module may include an operating system, a graphical user interface (GUI) controller, a system memory, a memory storage device, and an input / output controller, a cache memory, a data backup unit, and many other devices. The processor may be a commercially available processor or one of other processors that is or will become available. The processor executes an operating system, which interfaces with firmware and hardware in a well-known manner and facilitates the processor's coordination and execution of functions of various computer programs, which may be written in a variety of programming languages, such as Java, Perl, C++, other high-level or low-level languages, and combinations thereof, as is known in the art. The operating system typically cooperates with the processor to coordinate and execute functions of the other components of the computer. The operating system also provides scheduling, input / output control, file and data management, memory management, and communication control and related services, all in accordance with known techniques. The processor may be any suitable analog or digital system.

[0084] The system memory may be any of a variety of known or future memory storage devices. Examples include any commonly available random access memory (RAM), magnetic media such as a resident hard disk or tape, optical media such as a read-and-write compact disk, flash memory devices, or other memory storage devices. The memory storage device may be any of a variety of known or future devices, including a compact disk drive, tape drive, removable hard disk drive, or disk drive. Such types of memory storage devices typically read from and / or write to a program storage medium (not shown), such as a compact disk, magnetic tape, removable hard disk, or floppy disk, respectively. Any of these program storage media, or others now in use or that may later be developed, may be considered a computer program product. As will be appreciated, these program storage media typically store computer software programs and / or data. Computer software programs, also referred to as computer control logic, are typically stored in system memory and / or program storage devices used in conjunction with memory storage devices.

[0085] In some embodiments, a computer program product is described having a computer-usable medium storing control logic (a computer software program including program code). When the control logic is executed by a processor, the computer causes the processor to perform the functions described herein. In other embodiments, some functions are implemented primarily in hardware, for example, using hardware state machines. Implementation of hardware state machines to perform the functions described herein will be apparent to those skilled in the relevant art.

[0086] The memory may be any suitable device from which the processor can store and retrieve data, such as a magnetic, optical, or solid-state storage device (including a magnetic or optical disk, or tape, or RAM, or any other suitable device, either fixed or portable). The processor may include a general-purpose digital microprocessor suitably programmed from a computer-readable medium carrying the necessary program code. The programming may be provided remotely to the processor via a communications channel, or may be pre-stored in a computer program product, such as memory or some other portable or fixed computer-readable storage medium, using any of these devices together with the memory. For example, a magnetic or optical disk may carry the programming and be readable by a disk writer / reader. The system of the present invention also includes programming in the form of a computer program product, e.g., algorithms for use in implementing the above-described methods. The programming according to the present invention may be recorded on a computer-readable medium, e.g., any medium that can be directly read and accessed by a computer. Such media include, but are not limited to, magnetic storage media such as floppy disks, hard disk storage media, and magnetic tape, optical storage media such as CD-ROMs, electrical storage media such as RAM and ROM, portable flash drives, and hybrids of these categories such as magnetic / optical storage media.

[0087] The processor may also have access to a communication channel for communicating with a user at a remote location, meaning that the user does not have direct contact with the system but rather relays input information to the input manager from an external device, such as a computer connected to a wide area network ("WAN"), a telephone network, a satellite network, or any other suitable communication channel, including a mobile phone (i.e., a smartphone).

[0088] In some embodiments, a system according to the present disclosure may be configured to include a communications interface. In some embodiments, the communications interface includes a receiver and / or a transmitter for communicating with a network and / or another device. The communications interface may be configured for wired or wireless communications, including, but not limited to, radio frequency (RF) communications (e.g., radio frequency identification (RFID), ZigBee communications protocol, WiFi, infrared, wireless universal serial bus (USB), ultra-wideband (UWB), Bluetooth® communications protocol, and cellular communications such as code division multiple access (CDMA) or Global System for Mobile Communications (GSM).

[0089] In one embodiment, the communications interface is configured to include one or more communications ports, e.g., physical ports or interfaces such as a USB port, an RS-232 port, or any other suitable electrical connection port, to enable data communications between the subject system and other external devices, such as computer terminals (e.g., in a clinic or hospital environment), configured for similar complementary data communications.

[0090] In one embodiment, the communication interface is configured for infrared communication, Bluetooth® communication, or any other suitable wireless communication protocol, allowing the subject system to communicate with other devices, such as computer terminals and / or networks, communication-enabled mobile phones, personal digital assistants, or any other communication devices that a user may use in conjunction with the subject system.

[0091] In one embodiment, the communication interface is configured to provide a connection for data transfer utilizing the Internet Protocol (IP) via a cellular network, short message service (SMS), a wireless connection to a personal computer (PC) on a local area network (LAN) connected to the Internet, or a WiFi connection to the Internet at a WiFi hotspot.

[0092] In one embodiment, the subject system is configured to communicate wirelessly with a server device via a communications interface using common standards such as, for example, 802.11 or Bluetooth® RF protocols, or the IrDA infrared protocol. The server device may be another portable device, such as a smartphone, personal digital assistant (PDA), or notebook computer, or a larger device, such as a desktop computer, appliance, etc. In some embodiments, the server device has a display, such as a liquid crystal display (LCD), and input devices, such as buttons, a keyboard, a mouse, or a touchscreen.

[0093] In some embodiments, the communications interface is configured to automatically or semi-automatically communicate data stored within the subject system, e.g., in the optional data storage unit, with a network or server device using one or more of the communications protocols and / or mechanisms described above.

[0094] The output controller may include a controller for any of a variety of known display devices for presenting information to a user, whether human or machine, local or remote. When one of the display devices provides visual information, this information may typically be logically and / or physically organized as an array of pixels. The graphical user interface (GUI) controller may include any of a variety of known or future software programs for providing a graphical input and output interface between the system and the user and for processing user input. The functional elements of the computer may communicate with each other via a system bus. Some of these communications may, in alternative embodiments, be achieved using a network or other type of remote communication. The output manager may also provide information generated by the processing module to a user at a remote location, for example, via the Internet, telephone, or satellite network, in accordance with known techniques. Presentation of data by the output manager may be performed in accordance with various known techniques. As some examples, the data may include SQL, HTML, or XML documents, emails or other files, or other forms of data. The data may include Internet URL addresses so that the user can retrieve additional SQL, HTML, XML, or other documents or data from remote sources. The one or more platforms present in the subject system will typically be of the class of computers commonly referred to as servers, but may be any type of known or future-developed computer platform. Alternatively, they may be mainframe computers, workstations, or other computer types. They may be connected via any known or future type of cabling or other communication systems, including wireless systems, either networked or not. They may be co-located or physically separate.In some cases, various operating systems may be employed on any of the computer platforms, depending on the type and / or configuration of the computer platform selected. Suitable operating systems include Windows NT, Windows XP, Windows 7, Windows 8, iOS, Sun Solaris, Linux, OS / 400, Compaq Tru64 Unix, SGI IRIX, Siemens Reliant Unix, etc.

[0095] Polymer structures with resolved microvoid spaces Aspects of the present disclosure also include polymer structures having resolved microvoid spaces prepared by the methods of the subject matter described herein. In some cases, the polymer structures include multiple microvoid spaces. In some cases, the microvoid spaces include one or more different microchannels, such as two or more, such as three or more, such as four or more, such as five or more (including ten or more) different microchannels. In some cases, one or more of the microchannels include one or more branches, such as two or more branches, such as three or more, such as four or more, such as five or more (including ten or more) branches. In some cases, the microchannels extend through the polymer structure. In some cases, the microchannels are fluidically interconnected. In some cases, the polymer structure has a single network of fluidically interconnected microchannel networks. In other cases, the polymer structure has multiple fluidically interconnected microchannel networks. In some embodiments, each microchannel has a diameter of 0.01 μm or more, such as 0.05 μm or more, for example 0.1 μm or more, for example 0.5 μm or more, such as 1 μm or more, for example 2 μm or more, for example 3 μm or more, such as 4 μm or more, for example 5 μm or more, such as 10 μm or more, for example 15 μm or more, for example 20 μm or more, such as 25 μm or more, for example 50 μm or more, such as 75 μm or more (including 100 μm or more). In certain cases, each microchannel has a diameter of 0.01 μm to 75 μm, for example 0.05 μm to 50 μm, for example 0.1 μm to 25 μm, for example 0.5 μm to 20 μm.

[0096] Depending on the polymer structure and the size of the microvoid space, each resolved microvoid space may have a volume of 0.001 μL or more, such as 0.005 μL or more, for example 0.01 μL or more, for example 0.05 μL or more, such as 0.1 μL or more, for example 0.2 μL or more, such as 0.3 μL or more, for example 0.4 μL or more, such as 0.5 μL or more, for example 1 μL or more, such as 2 μL or more, for example 3 μL or more, such as 4 μL or more, for example 5 μL or more, such as 6 μL or more, for example 7 μL or more, such as 8 μL or more, for example 9 μL or more, such as 10 μL or more, for example 15 μL or more, for example 20 μL or more (including 25 μL or more). In some cases, the volume of each microvoid space is between 0.01 μL and 2.5 μL, for example, between 0.02 μL and 2.4 μL, for example, between 0.03 μL and 2.3 μL, for example, between 0.04 μL and 2.2 μL, for example, between 0.05 μL and 2.1 μL, for example, between 0.06 μL and 2.0 μL, for example, between 0.07 μL and 1.9 μL, for example, between 0.08 μL and 1.8 μL, for example, between 0.09 μL and 1.7 μL, including each microvoid space having a volume of between 1 μL and 1.5 μL. In some cases, the resolved microvoid spaces in the polymeric structure have a cumulative volume (i.e., the combined volume of all of the microvoid spaces) of 0.1 μL or more, such as 0.2 μL or more, for example 0.3 μL or more, for example 0.4 μL or more, such as 0.5 μL or more, for example 1 μL or more, such as 2 μL or more, for example 3 μL or more, such as 4 μL or more, for example 5 μL or more, such as 6 μL or more, for example 7 μL or more, such as 8 μL or more, for example 9 μL or more, such as 10 μL or more, for example 15 μL or more, for example 20 μL or more (including 25 μL or more).

[0097] In some cases, the subject polymeric structures include a non-polymerizable composition positioned therein. In some cases, the non-polymerizable composition fills 5% or more, e.g., 10% or more, e.g., 15% or more, e.g., 20% or more, e.g., 25% or more, e.g., 50% or more, e.g., 75% or more, e.g., 90% or more, e.g., 95% or more, e.g., 97% or more, e.g., 99% or more of the void volume of the microvoid spaces (i.e., the negative space within the polymeric structure), including filling the entire volume of the void volume of the microvoid spaces. In some cases, the non-polymerizable composition is non-reactive with the polymeric structure. In some cases, the non-polymerizable composition within the void volume of the polymeric structure is water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electro-responsive liquid, or a gas. In certain embodiments, aspects of the present disclosure include polymeric structures having microvoid spaces from which the non-polymerizable composition has been removed.

[0098] In embodiments, the polymeric structure is formed from a polymerizable material that may include, but is not limited to, polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, thiol-ene, anhydrides, polyacrylic acid, polymethyl methacrylate, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl esters, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethyl cellulose, and blends or copolymers thereof. In certain embodiments, the polymeric structure is formed from polyethylene glycol dimethacrylate (PEGDMA). In certain embodiments, the polymeric structure is formed from trimethylolpropane triacrylate (TMPTA) monomer. In certain embodiments, the polymeric material is selected from polycarbonate, polyvinyl chloride (PVC), polyurethane, polyether, polyamide, polyimide, or copolymers of these thermoplastics, such as PETG (glycol-modified polyethylene terephthalate), among other polymeric plastic materials. In certain embodiments, the beamsplitter is formed from a polyester, including, but not limited to, poly(ethylene terephthalate) (PET), bottle-grade PET (a copolymer made based on monoethylene glycol, terephthalic acid, and other comonomers such as isophthalic acid, cyclohexanedimethanol), poly(alkylene terephthalates) such as poly(butylene terephthalate) (PBT) and poly(hexamethylene terephthalate), poly(ethylene adipate), poly(1,4-butylene terephthal ... poly(alkylene adipates) such as poly(ethylene adipate) and poly(hexamethylene adipate), poly(alkylene suberates) such as poly(ethylene suberate), poly(alkylene sebacates) such as poly(ethylene sebacate), poly(ε-caprolactone) and poly(β-propiolactone), poly(alkylene isophthalates) such as poly(ethylene isophthalate), poly(alkylene 2,6-naphthalene-dicarboxylate) such as poly(ethylene 2,6-naphthalene-dicarboxylate), poly(ethylenesulfonyl-4,poly(alkylenesulfonyl-4,4'-dibenzoates) such as poly(4'-dibenzoate), poly(p-phenylene alkylene dicarboxylates) such as poly(p-phenylene ethylene dicarboxylate), poly(trans-1,4-cyclohexanediyl alkylene dicarboxylates) such as poly(trans-1,4-cyclohexanediyl ethylene dicarboxylate), poly(1,4-cyclohexane-dimethylene alkylene dicarboxylates) such as poly(1,4-cyclohexane-dimethylene ethylene dicarboxylate), poly([2.2.2]-bicyclooctane-1,4-dimethylene ethylene dicarboxylate),

[0023] Examples of suitable polymeric materials include lactic acid polymers and copolymers such as (S)-polylactide, (R,S)-polylactide, poly(tetramethylglycolide), and poly(lactide-co-glycolide), as well as polycarbonates of bisphenol A, 3,3'-dimethylbisphenol A, 3,3',5,5'-tetrachlorobisphenol A, 3,3',5,5'-tetramethylbisphenol A, polyamides such as poly(p-phenylene terephthalamide), polyethylene terephthalate (e.g., Mylar™ polyethylene terephthalate), combinations thereof, and the like. In some embodiments, the polymeric structure is formed from one or more polymerizable materials, e.g., two or more different polymerizable materials, e.g., three or more (including four or more) different polymerizable materials. In certain instances, one or more of the polymerizable materials comprises carbon nanotubes, such as single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs).

[0099] Non-transitory computer-readable storage medium Aspects of the present disclosure further include non-transitory computer-readable storage media having instructions for practicing the subject methods. The computer-readable storage medium may be employed on one or more computers for fully or partially automating systems for practicing the methods described herein. In certain embodiments, instructions according to the methods described herein may be encoded on a computer-readable medium in the form of "programming," in which case the term "computer-readable medium," as used herein, refers to any non-transitory storage medium involved in providing instructions and data to a computer for execution and processing. Examples of suitable non-transitory storage media include floppy disks, hard disks, optical disks, magnetic optical disks, CD-ROMs, CD-Rs, magnetic tape, non-volatile memory cards, ROMs, DVD-ROMs, Blue-ray disks, solid-state disks, and network-attached storage devices (NAS), regardless of whether such devices are internal or external to the computer. A file containing information may be "stored" on a computer-readable medium, where "storing" means recording information so that it can be accessed and retrieved at a later date by a computer. The computer-implemented methods described herein may be performed using programming that can be written in one or more of any number of computer programming languages, including, for example, Python, Java, Java Script, C, C#, C++, Go, R, Swift, PHP, as well as any of many others.

[0100] In some cases, a non-transitory computer-readable storage medium includes instructions stored thereon, the instructions including an algorithm for irradiating a polymerizable composition positioned between a build elevator and a build surface to generate a polymerizable composition having polymerized regions of the polymerizable composition with microvoid spaces in contact with the build elevator and non-polymerized regions of the polymerizable composition in contact with the build surface, an algorithm for displacing the build elevator away from the build surface, an algorithm for contacting the generated microvoid spaces with a non-reactive composition, and an algorithm for repeating one or more steps in a manner sufficient to generate a polymer structure with resolved microvoid spaces. In some cases, the non-transitory computer-readable storage medium includes an algorithm for injecting the polymerizable composition through a conduit using a syringe pump. In some instances, the non-transitory computer-readable storage medium includes an algorithm for generating a polymer structure with microvoid spaces containing a non-polymerizable composition positioned therein.

[0101] In some embodiments, the non-transitory computer-readable storage medium has an algorithm for contacting the generated microvoid space with an amount of polymerizable composition in a manner sufficient to displace polymerized material within the microvoid space. In some cases, the non-transitory computer-readable storage medium has an algorithm for continuously delivering the polymerizable composition through the generated microvoid space to displace polymerized material within the microvoid space. In some cases, the non-transitory computer-readable storage medium has an algorithm for injecting the polymerizable composition into the generated microvoid space to displace polymerized material within the microvoid space. In some cases, the non-transitory computer-readable storage medium has an algorithm for injecting the polymerizable composition into the generated microvoid space with a syringe. In some cases, the non-transitory computer-readable storage medium includes an algorithm for continuously delivering the polymerizable composition through the generated microvoid space to a space between a build elevator and a build surface of a liquid interface-generating module.

[0102] In some cases, the non-transitory computer-readable storage medium includes an algorithm for contacting a non-polymerizable composition with the generated microvoid space of the polymer structure. In some cases, the non-transitory computer-readable storage medium includes an algorithm for filling at least a portion of the void volume of the microvoid space with the non-polymerizable composition, e.g., 5% or more, e.g., 10% or more, e.g., 25% or more, e.g., 50% or more (including 75% or more) of the void volume of the microvoid space, e.g., filling the entire void volume of the microvoid space with the non-polymerizable composition. In some embodiments, the non-transitory computer-readable storage medium includes an algorithm for generating a polymer structure having multiple microvoid spaces. In certain cases, the non-transitory computer-readable storage medium includes an algorithm for irradiating the polymerizable composition for a period of time sufficient to bond a first polymerized region of the polymerizable composition to the build elevator. In some cases, the non-transitory computer-readable storage medium includes an algorithm for displacing the build elevator in predetermined increments from 0.5 μm to 1.0 μm. In some embodiments, the non-transitory computer-readable storage medium has an algorithm for applying a polymerizable composition to the build surface after each displacement of the build elevator away from the build surface. In some cases, the non-transitory computer-readable storage medium has an algorithm for applying a non-polymerizable composition to the generated microvoid spaces after each displacement of the build elevator away from the build surface. In some cases, the non-transitory computer-readable storage medium has an algorithm for continuously polymerizing the polymerizable composition while displacing the build elevator away from the build surface. In some embodiments, the non-transitory computer-readable storage medium has an algorithm for continuously applying a non-polymerizable composition to the generated microvoid spaces while displacing the build elevator away from the build surface. In certain embodiments, the non-transitory computer-readable storage medium has an algorithm for removing the non-polymerizable composition from the generated microvoid spaces of the polymer structure.

[0103] The non-transitory computer-readable storage medium may be employed on one or more computer systems having a display and an operator input device. The operator input device may be, for example, a keyboard, a mouse, etc. The processing module includes a processor that accesses a memory having stored instructions to perform the steps of the subject method. The processing module may include an operating system, a graphical user interface (GUI) controller, a system memory, a memory storage device, and an input / output controller, a cache memory, a data backup unit, and many other devices. The processor may be a commercially available processor or one of other processors that are available or that will become available. The processor executes an operating system, which interfaces with firmware and hardware in a well-known manner to facilitate the processor's coordination and execution of the functions of various computer programs, which may be written in a variety of programming languages, such as those mentioned above, as well as other high-level or low-level languages, and combinations thereof, as known in the art. The operating system typically cooperates with the processor to coordinate and execute the functions of the other components of the computer. The operating system also provides scheduling, input / output control, file and data management, memory management, and communication control and related services, all in accordance with known techniques.

[0104] kit Kits for use in practicing certain methods described herein are also provided. In certain embodiments, the kits include one or more of the polymer structures described above. In some cases, the kits include a polymerizable composition for preparing the polymer structures. In certain embodiments, the kits include a non-reactive composition, such as a non-polymerizable composition, for contacting the generated microvoid space. For example, the kits may further include a quantity of one or more of water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electric field-responsive liquid, and a gas.

[0105] In certain embodiments, the kits further include instructions for practicing the subject methods or means for obtaining them (e.g., a website URL that directs the user to a web page providing the instructions), which may be printed on a substrate, which may be one or more of a package insert, packaging, reagent containers, etc. Yet another form for these instructions is a computer-readable medium having the information recorded thereon, such as a diskette, compact disc (CD), portable flash drive, USB storage, DVD, Blu-ray disc, etc. Yet another form for these instructions that may be present is a website address that may be used via the internet to access the information at the removed site.

[0106] Notwithstanding the appended claims, the present disclosure is also defined by the following clauses.

[0107] 1. A method for making a polymer structure containing microvoid spaces, comprising: a) irradiating a polymerizable composition positioned between a build elevator of a liquid interface-generating module and a build surface to generate a polymerizable composition comprising polymerized regions of the polymerizable composition including microvoid spaces in contact with the build elevator and unpolymerized regions of the polymerizable composition in contact with the build surface; b) displacing the build elevator away from the build surface; and c) contacting the generated microvoid spaces with a non-reactive composition; d) repeating steps a) through c) in a manner sufficient to produce a polymer structure having resolved microvoid spaces.

[0108] 2. The method of clause 1, wherein the generated microvoid space comprises one or more microchannels within the polymer structure.

[0109] 3. The method of clause 2, wherein one or more of the microchannels extend through the polymer structure.

[0110] 4. The method of any one of clauses 1-3, comprising contacting the generated microvoid spaces with a quantity of a polymerizable composition in a manner sufficient to displace polymerized material within the microvoid spaces.

[0111] 5. The method of clause 4, wherein a quantity of polymerizable composition is continuously conveyed through the generated microvoid spaces to displace polymerized material within the microvoid spaces.

[0112] 6. The method of any one of clauses 2 to 5, wherein the polymerizable composition is injected through the generated microvoid space.

[0113] 7. The method of any one of clauses 2 to 6, wherein the polymerizable composition is conveyed through the generated microvoid space into the space between the build elevator of the liquid interface generating module and the build surface.

[0114] 8. The method of clause 6 or 7, wherein the polymerizable composition is injected through the generated microvoid space using a syringe.

[0115] 9. The method of clause 8, wherein the syringe is operably coupled to a syringe pump.

[0116] 10. The method of any one of clauses 1 to 3, comprising contacting the generated microvoid spaces with a non-polymerizable composition.

[0117] 11. The method of claim 10, wherein the non-polymerizable composition contacts the generated microvoid spaces while generating the polymer structure.

[0118] 12. The method of claim 11, wherein the non-polymerizable composition is continuously contacted with the microvoid spaces while producing the polymeric structure.

[0119] 13. The method of any one of clauses 10-12, comprising filling at least a portion of the void volume of the microvoid space with a non-polymerizable composition.

[0120] 14. The method of clause 13, comprising filling 5% or more of the void volume of the microvoid space with the non-polymerizable composition.

[0121] 15. The method of any one of clauses 10 to 14, wherein the non-polymerizable composition is non-reactive with the polymerizable composition of the polymeric structure.

[0122] 16. The method of any one of clauses 10-15, wherein the non-polymerizable composition is selected from the group consisting of water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electro-responsive liquid, and a gas.

[0123] 17. The method of any one of clauses 10-16, further comprising removing the non-polymerizable composition from the generated microvoid spaces of the polymer structure.

[0124] 18. The method of any one of clauses 1 to 17, wherein the polymer structure comprises a plurality of microvoid spaces.

[0125] 19. The method of any one of clauses 1-18, wherein the polymerizable composition is in contact with a build elevator and a build surface.

[0126] 20. The method of clause 19, comprising irradiating the polymerizable composition for a period of time sufficient to bond a first polymerized region of the polymerizable composition to the build elevator.

[0127] 21. The method of any one of clauses 1 to 20, wherein the build elevator is displaced in predetermined increments of 0.5 μm to 1.0 μm.

[0128] 22. The method of any one of clauses 1-21, further comprising applying a polymerizable composition to the build surface after each displacement of the build elevator away from the build surface.

[0129] 23. The method of clause 22, further comprising contacting the generated microvoid spaces with a non-reactive composition after each displacement of the build elevator away from the build surface.

[0130] 24. The method of any one of clauses 1-23, wherein the polymerizable composition is polymerized continuously while displacing the build elevator away from the build surface.

[0131] 25. The method of clause 24, wherein the non-reactive composition continuously contacts the generated microvoid spaces while displacing the build elevator away from the build surface.

[0132] 26. The method of any one of clauses 1-25, wherein the polymerizable composition comprises a polymerizable material selected from the group consisting of polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-enes, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl esters, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof.

[0133] 27. The method of clause 26, wherein the polymerizable composition comprises polyethylene glycol dimethacrylate (PEGDMA).

[0134] 28. The method of clause 26 or 27, wherein the polymerizable material comprises carbon nanotubes.

[0135] 29. The method of clause 28, wherein the polymerizable material comprises one or more of single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs).

[0136] 30. A system for fabricating polymer structures containing microvoid spaces, comprising: A light source and a light interface polymerization module configured to generate a polymer structure having resolved microvoid spaces therein from a polymerizable composition positioned between a build elevator and a build surface.

[0137] 31. The system of clause 30, wherein the optical interface polymerization module is configured to generate a polymer structure having one or more microchannels within the polymer structure.

[0138] 32. The system of clause 31, wherein one or more of the microchannels extend through the polymer structure.

[0139] 33. The system further comprises a processor comprising a memory, the memory operatively coupled to the processor, the memory comprising instructions stored therein, the instructions, when executed by the processor, causing the processor to: a) irradiating a polymerizable composition positioned between a build elevator and a build surface to produce a polymerizable composition comprising polymerized regions of the polymerizable composition including microvoid spaces in contact with the build elevator and unpolymerized regions of the polymerizable composition in contact with the build surface; b) displacing the build elevator away from the build surface; c) contacting the generated microvoid spaces with a non-reactive composition; d) repeating steps a) through c) in a manner sufficient to produce a polymer structure having resolved microvoid spaces.

[0140] 34. The system of clause 33, wherein the memory includes instructions for contacting the generated microvoid space with a quantity of a polymerizable composition in a manner sufficient to displace polymerized material within the microvoid space.

[0141] 35. The system of clause 34, wherein the memory includes instructions for continuously conveying the polymerizable composition through the generated microvoid space to displace the polymerized material within the microvoid space.

[0142] 36. The system of any one of clauses 33 to 35, wherein the polymerizable composition is injected through the generated microvoid space.

[0143] 37. The system of any one of clauses 33-36, wherein the memory comprises instructions for continuously conveying the polymerizable composition through the generated microvoid space into the space between the build elevator of the liquid interface generating module and the build surface.

[0144] 38. The system of any one of clauses 30 to 37, wherein the system further comprises a syringe pump.

[0145] 39. The system of any one of clauses 30-33, wherein the memory includes instructions for contacting the generated microvoid spaces with a non-polymerizable composition.

[0146] 40. The system of clause 39, further comprising a source of non-polymerizable composition operably coupled to the optical interface polymerization module such that the non-polymerizable composition is in continuous contact with the microvoid space while producing the polymer structure.

[0147] 41. The system of any one of clauses 39-40, wherein the memory includes instructions for filling at least a portion of the void volume of the microvoid space with a non-polymerizable composition.

[0148] 42. The system of clause 41, wherein the memory includes instructions for filling 5% or more of the void volume of the microvoid space with the non-polymerizable composition.

[0149] 43. The system of any one of clauses 39-42, wherein the non-polymerizable composition is non-reactive with the polymerizable composition of the polymer structure.

[0150] 44. The system of any one of clauses 39-43, wherein the non-polymerizable composition is selected from the group consisting of water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electric field-responsive liquid, and a gas.

[0151] 45. The system of any one of clauses 33-44, wherein the memory includes instructions for generating a polymer structure comprising a plurality of microvoid spaces.

[0152] 46. ​​The system of any one of clauses 33-45, wherein the memory includes instructions for irradiating the polymerizable composition for a period of time sufficient to bond a first polymerized region of the polymerizable composition to the build elevator.

[0153] 47. The system of any one of clauses 33 to 46, wherein the memory comprises instructions for displacing the build elevator in predetermined increments of 0.5 μm to 1.0 μm.

[0154] 48. A system according to any one of clauses 33 to 47, wherein the memory includes instructions for contacting the generated microvoid space with a fluid composition after each displacement of the build elevator away from the build surface.

[0155] 49. The system of any one of clauses 33-48, wherein the memory includes instructions for applying a polymerizable composition to the build surface after each displacement of the build elevator away from the build surface.

[0156] 50. The system of clause 49, wherein the memory includes instructions for applying a non-polymerizable composition to the generated microvoid spaces after each displacement of the build elevator away from the build surface.

[0157] 51. The system of any one of clauses 33-50, wherein the memory includes instructions for continuously polymerizing the polymerizable composition while displacing the build elevator away from the build surface.

[0158] 52. The system of clause 51, wherein the memory includes instructions for continuously contacting the non-reactive composition with the generated microvoid spaces while displacing the build elevator away from the build surface.

[0159] 53. The system of any one of clauses 33-52, wherein the memory includes instructions for removing the non-polymerizable composition from the generated microvoid spaces of the polymer structure.

[0160] 54. A micro-digital light projection system, an optical beam generator component; and 54. The system of any one of clauses 30 to 53, comprising an optical projection monitoring component.

[0161] 55. A light beam generator component light source, Tube lenses, and 55. The system of clause 54, comprising one or more projection lenses.

[0162] 56. A system according to clause 54 or 55, wherein the light beam generator component comprises two projection lenses.

[0163] 57. The system according to clause 56, wherein the projection lens is a magnifying lens.

[0164] 58. The system of clause 57, wherein the projection lens provides a magnification of between 2x and 10x.

[0165] 59. A system according to any one of clauses 54 to 58, wherein the optical projection monitoring component comprises a photodetector.

[0166] 60. The system of clause 59, wherein the photodetector comprises a charge-coupled device (CCD).

[0167] 61. The system of any one of clauses 30-60, wherein the polymerizable composition comprises a polymerizable material selected from the group consisting of polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-ene, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl ester, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof.

[0168] 62. The system of clause 61, wherein the polymerizable composition comprises polyethylene glycol dimethacrylate (PEGDMA).

[0169] 63. The system of clause 61 or 62, wherein the polymerizable material comprises carbon nanotubes.

[0170] 64. The system of clause 63, wherein the polymerizable material comprises one or more of single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs).

[0171] 65. A polymeric structure comprising resolved microvoid spaces containing a non-polymerizable composition located therein.

[0172] 66. The polymer structure of clause 65, wherein the non-polymerizable composition fills at least a portion of the void volume of the microvoid space.

[0173] 67. The polymer structure of clause 66, wherein the non-polymerizable composition fills 5% or more of the void volume of the microvoid space.

[0174] 68. The polymer structure of any one of clauses 65-67, wherein the non-polymerizable composition is non-reactive with the polymer structure.

[0175] 69. The polymer structure of any one of clauses 65 to 68, wherein the microvoid spaces comprise microchannels within the polymer structure.

[0176] 70. The polymer structure of clause 69, wherein the microchannels extend through the polymer structure.

[0177] 71. A polymer structure according to any one of clauses 65 to 70, wherein the polymer structure comprises a plurality of microvoid spaces.

[0178] 72. The polymer structure of any one of clauses 65-71, wherein the non-polymerizable composition is selected from the group consisting of a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electric field-responsive liquid, and a gas.

[0179] 73. The polymeric structure of any one of clauses 65-72, formed from a polymerizable material selected from the group consisting of polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-enes, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl esters, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof.

[0180] 74. The polymer structure according to clause 73, formed from polyethylene glycol dimethacrylate (PEGDMA).

[0181] 75. A polymer structure according to any one of clauses 73-74, wherein the polymerizable material comprises carbon nanotubes.

[0182] 76. The polymer structure of clause 75, wherein the polymerizable material comprises one or more of single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs).

[0183] 77. Polymer structures containing resolved microvoid spaces.

[0184] 78. The polymer structure of clause 77, wherein the microvoid spaces comprise microchannels within the polymer structure.

[0185] 79. The polymer structure of clause 78, wherein the microchannels extend through the polymer structure.

[0186] 80. The polymer structure of any one of clauses 77-79, wherein the polymer structure comprises a plurality of microvoid spaces.

[0187] 81. The polymeric structure of any one of clauses 77 to 80, formed from a polymerizable material selected from the group consisting of polycaprolactone, polyglycolic acid, polylactic acid, polylactic-co-glycolic acid, polyethylene glycol, polyethylene glycol dimethacrylate (PEGDMA), thiol-enes, anhydrides, polyacrylic acid, polymethyl methacrylate, trimethylolpropane triacrylate (TMPTA) monomer, polyvinyl alcohol, polyvinylpyrrolidone, vinyl carbonate, vinyl esters, acrylamide, hyaluronic acid, chitosan, collagen, gelatin, carboxymethylcellulose, and blends or copolymers thereof.

[0188] 82. The polymer structure according to clause 81, formed from polyethylene glycol dimethacrylate (PEGDMA).

[0189] 83. The polymer structure of clause 81 or 82, wherein the polymerizable material comprises carbon nanotubes.

[0190] 84. The polymer structure of clause 83, wherein the polymerizable material comprises one or more of single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs).

[0191] experiment The following examples are offered by way of illustration and not by way of limitation. Specifically, the following examples are examples of specific embodiments for carrying out the present disclosure. The examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure in any way. Efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperatures, etc.), but some experimental error and deviation should be allowed for.

[0192] High-resolution stereolithography - negative space enabled by controlled fluid dynamics In this example, a method for fabricating polymer structures with microvoid spaces (e.g., high-resolution injection CLIP (iCLIP)) is used, achieving micrometer X, Y, and Z resolution using synergistic control of high-resolution optics and fluid dynamics. Conventional digital light projection (e.g., CLIP) uses ultraviolet (UV) light projection to cure layers of photopolymerizable resin layer by layer. These processes utilize the regeneration of resin at the build surface through the formation of a continuous liquid interface (dead zone). Resin is drawn into the gap by suction forces formed as the cured portion gradually pulls away from the window (Figure 2A). The dead zone is formed and maintained by a constant supply of oxygen (a polymerization inhibitor) delivered through a highly oxygen-permeable window at the bottom of the resin reservoir. Light delivery is controlled by high-resolution optics that can precisely guide the UV light path and cure a single layer of resin in the XY plane with high resolution. As shown in Figure 2A, light attenuates exponentially beyond the intended layer, causing over-curing in the negative space or loss of part resolution due to print-through (Figure 2A). Specifically, the penetration depth of a resin represents the characteristic length over which exponential decay occurs within the resin. Print-through limits the ability of stereolithography processes to resolve negative spaces compared to the characteristic penetration depth.

[0193] In certain embodiments of the disclosed method, a stream of fresh polymerizable resin is continuously fed through the build platform, displacing trapped resin to maintain the designed negative space and eliminate print-through (Figure 2B). The methods described herein therefore enable the fabrication of channels with significantly smaller heights / diameters than previously achievable, achieving channel resolution that matches or exceeds resin penetration depths (Figure 2C). Fabrication of high-resolution negative spaces using a wider variety of materials enables the 3D printing of high-resolution microsystem devices such as vascular beds and microfluidic backside microneedles (examples shown in Figure 2D and Figures 6A-6F).

[0194] Print-through modeling In all DLP-based processes, including CLIP, the XY resolution is limited by the projected pixel size, and the Z resolution is affected by the penetration depth of the resin. A greater penetration depth results in a buildup of more UV light in the resin, which can result in unintentional print-through. The Beer-Lambert law, E N was used to determine the cumulative UV exposure energy per area after N exposure during part fabrication. N The formula is as follows:

number

[0195] E N Resin D, which determines the depth to which UV energy can penetrate and accumulate in the negative space. p The disclosed system, according to certain embodiments, displaces trapped resin with fresh resin, resulting in a final E in the microchannel. N Minimize resin D to maintain constant turnover and improve Z-axis resolutionp Eliminates the need to reduce

[0196] Equation 1 can be used to predict UV dose accumulation within an entire 3D-printed microstructure. When the critical energy of trapped resin is exceeded, print-through occurs (shown by the blue shading in Figure 3A). Figure 3 shows dose accumulation in a serpentine microchannel during fabrication to generate a polymerized structure with (iCLIP) and without (CLIP) injection of a polymerizable composition through the microchannel. Under CLIP conditions with no resin turnover, the accumulation model predicts print-through, which blocks the microfluidic channel (Figure 3A). The model is supported by the resulting CLIP print (Figure 3B). Conversely, a continuous flow of fresh resin through the microchannel displaces trapped resin before it reaches the critical threshold, preserving the serpentine microchannel and mitigating the print-through effect (Figure 3C). This is supported by the resulting iCLIP print (Figure 3D).

[0197] Maintaining the microchannel To maintain negative space resolution in various geometric configurations and channel resolution, we investigated the ability to generate polymer structures by injecting a polymerizable composition through microchannels during fabrication (iCLIP). First, to evaluate the performance of iCLIP in resolving various microfluidic geometries, we designed 200 µm diameter microchannels and varied the pitch angle from 0° to 90° (Figure 4A). The 0° pitch channel, which serves as a control, is least susceptible to print-through because it is not exposed to UV light below the fabricated channel. In contrast, the 90° pitch channel faces the highest risk of channel blockage as the vertical z-axis channel height decreases. Optical microscope images of the cross-sectional profiles of printed microchannels demonstrate that injecting fresh resin through microchannels during fabrication (iCLIP) consistently achieves accurate resolution of channels, regardless of their pitch (Figure 4A and Figure 4C). The 90° pitch is fully resolved near the injection port, while channels further from the injection source have smaller diameters. We speculate that this is due to insufficient resin flow before the channel becomes blocked. To further evaluate the ability of iCLIP to maintain high-resolution negative spaces, we designed and printed branched microfluidic networks with a 30° pitch, varying channel diameters from 50 μm to 200 μm. Optical microscope images of the cross-sectional profiles of the printed microchannels confirm the precise microchannel resolution achieved by iCLIP (Figures 4B and 4D).

[0198] Process Characterization To further evaluate the generation of polymeric structures by injecting a polymerizable composition through microchannels during fabrication (iCLIP), we determined the effect of the infusion rate of fresh polymerizable resin on channel resolution. The dimensionless turnover number (Tu) represents the ratio of the infusion rate to the negative space fabrication rate (the rate at which the microchannel volume is printed). For a given set of printing parameters, Tu quantifies the number of printed layers cleared by fresh resin before subsequent UV light exposure. For example, if the infusion rate is zero, simulating conventional CLIP printing, Tu = 0. If the infusion rate matches the fabrication rate, Tu = 1. If the infusion rate exceeds the fabrication rate, Tu > 1. The dimensionless channel diameter is defined as d / D, where d is the resulting channel diameter measured by optical microscopy after printing, and D is the design channel diameter.

[0199] Figure 5 evaluates microchannel resolution in relation to resin turnover when generating polymeric structures with microchannels, according to certain embodiments. Under conditions where no polymerizable composition (i.e., fresh resin) is injected through the forming microchannels (CLIP) (Tu=0), unresolved channels result from print-through. As Tu increases, d / D approaches 1, indicating the minimum Tu required to resolve a given microfluidic structure. In particular, in this case, D p For resins with a diameter of 237 μm, achieving a Tu greater than 17.5 was found to be essential for accurate microchannel resolution (Figure 5A). To further explore the impact of Tu, the influence of channel design and geometry on minimum Tu was determined. First, the minimum Tu required to resolve microfluidic channels with diameters ranging from 100 μm to 300 μm at a 30° pitch was determined (Figure 5B). Subsequently, the minimum Tu required to resolve microchannels with a fixed diameter of 200 μm was determined at various pitch angles, including 30°, 45°, and 60° (Figure 5C). Across the variation in channel diameter and pitch, a D of 237 μm was achieved. p The minimum Tu for resins with 100% T showed minimal variation and were consistently within 15% of each other.

[0200] D for minimum Tu p The effect of D on the viscosity of various resins was investigated. p We demonstrate how the Tu required to achieve precise negative features is affected by the Tu. To perform this study, the effect of varying Tu on the ability to resolve 100 μm branching microchannels at a 30° pitch was investigated. Various D values ​​ranging from 65 μm to 237 μm were used. p For different resins with different values, the corresponding minimum Tu for accurate resolution is higher D p It increased with the value of D p Increasing T allows the UV light to penetrate deeper into the printed part, requiring a greater amount of resin displacement with each fabricated layer. In certain embodiments, accurate channel resolution may involve replacing the resin in the channel before printing each subsequent layer if the original resin has accumulated a dose above a critical threshold, denoted as E*. By following a derivation process similar to Jacobs' standard curve, the relationship between T and the threshold dose is expressed as shown in Equation 2.

number

number

[0201] High-resolution polymer structures and applications Methods for preparing polymeric structures according to the present disclosure (e.g., iCLIP) can be utilized to fabricate freeform structures with micrometer-scale feature resolution in the X, Y, and Z coordinates. Using this process control framework, a variety of microsystems have been constructed, ranging from personalized medical technologies to microelectromechanical systems (Figure 6).

[0202] Advances in bioengineering and materials science have led to the development of personalized medical technologies that enable "point-of-person" disease diagnosis and therapeutic delivery. Among these technologies, microneedles are a promising solution for transdermal drug delivery due to their minimally invasive nature. Microfluidic elements using microneedle technology have been shown to offer new fluid management capabilities for transdermal drug delivery and unique filling and finishing opportunities for such devices (Figures 6A and 6B). An example of a microelectromechanical system fabricated with a freeform design is shown in Figure 6C, where a microfluidic inductor is embedded with a gallium metal conductive element. Furthermore, the methods described herein can be used to fabricate interlocking vascular perfusion networks for molecular blood transport systems, as shown in Figure 6E. The disclosed system also demonstrates the ability to print porous perfusion networks to perform improved separation (Figure 6F).

[0203] conclusion The disclosed method enables freeform fabrication of microsystems using fluid control methodologies rather than the use of optical dyes. This approach, according to certain embodiments, breaks the relationship between resin penetration depth and negative feature resolution and can resolve microscale negative spaces. This allows for printing high-resolution microsystems in materials and designs that were previously impossible, overcoming resolution limitations. In certain cases, the method involves injecting different classes of displacement agents, including non-polymerizable fluids such as water and air, to enable the resolution of negative spaces.

[0204] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be readily apparent to those skilled in the art, in light of the teachings of this invention, that certain changes and modifications can be made thereto without departing from the spirit or scope of the appended claims.

[0205] Accordingly, the foregoing merely illustrates the principles of the present invention. It will be appreciated that those skilled in the art will be able to devise various arrangements, not explicitly described or shown herein, which embody the principles of the present invention and are within its spirit and scope. Furthermore, all examples and conditional language recited herein are intended primarily to aid the reader in understanding the principles of the present invention and the concepts contributed by the inventors to further advance the art, and should not be construed as being limited to such specifically recited examples and conditions. Furthermore, all statements herein describing principles, aspects, and embodiments of the present invention, as well as specific examples thereof, are intended to encompass both structural and functional equivalents thereof. Additionally, such equivalents are intended to include both currently known equivalents and future-developed equivalents, i.e., any elements developed to perform the same function, regardless of structure. Furthermore, nothing disclosed herein is intended to be dedicated to the public, regardless of whether such disclosure is expressly recited in the claims.

[0206] Accordingly, the scope of the present invention is not intended to be limited to the exemplary embodiments shown and described herein. Rather, the scope and spirit of the present invention is embodied by the appended claims. In the claims, 35 U.S.C. 112(f) or 35 U.S.C. 112(6) is expressly defined as being invoked for a limitation in a claim only when the precise phrase "means for" or the precise phrase "step for" is recited at the beginning of such limitation in the claim; if such precise phrases are not used in the limitation in the claim, 35 U.S.C. 112(f) or 35 U.S.C. 112(6) is not invoked.

[0207] CROSS-REFERENCE TO RELATED APPLICATIONS Pursuant to 35 U.S.C. §119(e), this application claims priority to the filing date of U.S. Provisional Patent Application No. 63 / 416,789, filed October 17, 2022, the entire disclosure of which is incorporated herein by reference. This application is related to U.S. Provisional Patent Application No. 63 / 321,052, filed March 17, 2022, the disclosure of which is incorporated herein by reference.

Claims

1. 1. A method for making a polymer structure containing microvoid spaces, comprising: a) irradiating a polymerizable composition positioned between a build elevator of a liquid interface-generating module and a build surface to generate a polymerizable composition comprising polymerized regions of the polymerizable composition that include microvoid spaces in contact with the build elevator and unpolymerized regions of the polymerizable composition in contact with the build surface; b) displacing the build elevator away from the build surface; c) contacting the created microvoid spaces with a non-reactive composition; d) repeating steps a) through c) in a manner sufficient to produce a polymer structure having resolved microvoid spaces.

2. The method of claim 1 , wherein the microvoid space created comprises one or more microchannels within the polymer structure extending through the polymer structure.

3. 3. The method of claim 1 or 2, comprising conveying a quantity of the polymerizable composition through the created microvoid spaces in a manner sufficient to displace polymerized material within the microvoid spaces.

4. 3. The method of claim 1 or 2, comprising contacting the created microvoid spaces with a non-polymerizable composition.

5. The method of claim 4 , wherein the non-polymerizable composition continuously contacts the microvoid spaces while producing the polymeric structure.

6. The method of claim 4 or 5, wherein the non-polymerizable composition is non-reactive with the polymerizable composition of the polymer structure.

7. 7. The method of claim 6, wherein the non-polymerizable composition is selected from the group consisting of water, a Newtonian liquid, a shear-thinning liquid, a shear-thickening liquid, a magnetorheological liquid, an electro-responsive liquid, and a gas.

8. The method of any one of claims 1 to 7, further comprising applying a polymerizable composition to the build surface after each displacement of the build elevator away from the build surface.

9. 9. The method of claim 8, further comprising contacting the created microvoid spaces with the non-reactive composition after each displacement of the build elevator away from the build surface.

10. 1. A system for fabricating polymer structures containing microvoid spaces, comprising: A light source and a light interface polymerization module configured to generate a polymer structure having resolved microvoid spaces therein from a polymerizable composition positioned between a build elevator and a build surface.

11. The system of claim 10 , wherein the optical interface polymerization module is configured to produce a polymer structure having one or more microchannels within the polymer structure.

12. The system further comprises a processor comprising a memory, the memory operatively coupled to the processor, the memory comprising instructions stored therein, the instructions, when executed by the processor, causing the processor to: a) irradiating a polymerizable composition positioned between a build elevator and a build surface to produce a polymerizable composition comprising polymerized regions of the polymerizable composition that include microvoid spaces in contact with the build elevator and unpolymerized regions of the polymerizable composition in contact with the build surface; b) displacing the build elevator away from the build surface; c) contacting the created microvoid spaces with a non-reactive composition; d) repeating steps a) through c) in a manner sufficient to produce a polymer structure having resolved microvoid spaces.

13. 13. The system of claim 12, wherein the memory includes instructions for conveying a quantity of the polymerizable composition through the created microvoid space in a manner sufficient to displace polymerized material within the microvoid space.

14. The system of any one of claims 10 to 12, wherein the memory includes instructions for contacting the created microvoid spaces with a non-polymerizable composition.

15. A polymeric structure comprising resolved microvoid spaces containing a non-polymerizable composition located therein.

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