CN113635554A - Suspension photocuring 3D printing device for manufacturing hydrogel optical fiber and printing method thereof - Google Patents
Suspension photocuring 3D printing device for manufacturing hydrogel optical fiber and printing method thereof Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/188—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control
- B29C64/194—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control during lay-up
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/264—Arrangements for irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/56—Acrylamide; Methacrylamide
Abstract
The invention discloses a suspension photocuring 3D printing device for manufacturing hydrogel optical fibers and a printing method thereof, and provides a suspension photocuring 3D printing device which is based on a suspension photocrosslinking control technology and can simultaneously regulate and control a geometric structure and a crosslinking degree aiming at the requirements of preparing low-loss and high-signal-to-noise ratio hydrogel optical fibers, and a printing method based on the device. The 3D printing method provided by the invention has incomparable advantages in the manufacturing of the continuous microstructure of the hydrogel material, and provides a novel sensing and wave guide device for the fields of biomedicine and the like.
Description
Technical Field
The invention belongs to the field of advanced material manufacturing, and particularly relates to a suspension photocuring 3D printing device for manufacturing a hydrogel optical fiber and a printing method thereof.
Background
The hydrogel optical fiber is considered as an ideal optical waveguide device of the next generation in the fields of optogenetics, photochemical sensing and the like because of biocompatibility, flexibility and plasticity. However, hydrogel optical fibers generally have high transmission loss, which directly affects its signal-to-noise performance and sensing sensitivity. Moreover, the current main manufacturing method includes that a mold gelling method or an extrusion type 3D printing method is limited by mechanical precision, and the geometric structure and chemical parameters of the hydrogel optical fiber cannot be flexibly modulated, while the existing projection type 3D printing method cannot manufacture the hydrogel optical fiber with axial continuity and uniformity requirements due to a layer-by-layer stacked printing mode, so that nonlinear propagation of an optical field is easily caused. Therefore, an advanced preparation method for a high-efficiency hydrogel optical fiber, which can meet the axial continuous and uniform requirements of the fiber, can simultaneously modulate the fiber diameter, the core cladding structure and the refractive index distribution of the hydrogel optical fiber, and provides a new sensing and wave-guiding device for the fields of biomedicine and the like, is urgently needed.
Disclosure of Invention
The invention aims to provide a suspension photocuring 3D printing device for manufacturing hydrogel optical fibers and a printing method thereof, which can realize axial continuous and uniform 3D printing of the hydrogel optical fibers, have the function of simultaneously modulating the geometric structure and the crosslinking degree of the hydrogel optical fibers, realize the preparation of high-efficiency hydrogel optical fibers, and have the advantages of one-time molding, simultaneous multi-parameter regulation and control, rapid preparation and the like.
The technical solution for realizing the purpose of the invention is as follows: a suspension photocuring 3D printing device for manufacturing hydrogel optical fibers adopts a top-down projection structure and comprises a DLP (digital light processing) module, an optical micro-projection module, a crosslinking reaction monitoring module and an electric axial printing module; the DLP provides projection light with photocureable image information, and the photocureable image is used for simultaneously regulating and controlling the geometric structure and the crosslinking degree of the hydrogel optical fiber; the optical miniature projection module comprises a first tube lens, a transflective lens and a microscope objective, projection light enters the first tube lens, enters the transflective lens after passing through the first tube lens, enters the microscope objective through the transflective lens, is reduced by the microscope objective with the multiplying power of the microscope objective to obtain a micron-sized photocured image, and is projected to the liquid level of the printing tank, namely a printing surface; the cross-linking reaction monitoring module is positioned on a conjugate light path of the miniature projection module, the cross-linking reaction monitoring module comprises a second tube lens and a CCD (charge coupled device), reflected light of the printing surface is transmitted to the second tube lens through the transflective lens and is converged on the CCD through the second tube lens, the cross-linking reaction degree of the printing surface is observed in real time, and the hydrogel optical fiber printing quality is regulated and controlled by matching with a suspended light cross-linking control technology; electronic axial printing module is including printing the groove, quartz fiber and electronic translation platform, print the groove and take the cask of through wires hole for the bottom, print the interior packing of groove and be used for printing the prefabricated liquid of blocking of aquogel optic fibre, quartz fiber penetrates through the through wires hole and prints the groove, quartz fiber prints the basement as the photocrosslinking at the terminal surface of printing the inslot, the other end is fixed in electronic translation bench, electronic translation platform provides the pull at the uniform velocity and makes the motion of photocrosslinking basement from top to bottom, the continuous even axial of aquogel optic fibre is printed in cooperation suspension photocrosslinking control technique realization.
A blocking type prefabricated liquid for printing hydrogel optical fibers comprises 30-40% of acrylamide monomer compounds, 1-2% of N, N' -methylenebisacrylamide, 0.01-0.03% of lithium phenyl-2, 4, 6-trimethylbenzoyl phosphite, 0.01-0.05% of lemon yellow and 57.92-68.98% of deionized water in percentage by volume, and the total volume is 100%; wherein the acrylamide monomer compound is used for forming a high-molecular hydrogel polymer; n, N' -methylene-bisacrylamide, which provides unsaturated double bonds or a plurality of functional groups for the crosslinking monomers to be connected into a polymer network; lithium phenyl-2, 4, 6-trimethylbenzoylphosphite for absorbing photon energy to generate free radical to initiate the cross-linking reaction of monomer compound; the lemon yellow is used for a suspension photocuring control technology, limits photocrosslinking reaction outside a reaction surface, and improves the axial printing precision and resolution; deionized water as solvent, dissolving the above materials and proportioning the total prefabricated liquid to 100% volume.
A printing method of a suspension photocuring 3D printing device based on hydrogel optical fiber manufacturing comprises the following steps:
the first step is as follows: penetrate the printing groove with quartz optical fiber from the through wires hole, print the groove this moment and form seal structure naturally, pour into the formula of blocking prefabricated liquid that is used for printing aquogel optic fibre again to printing the inslot, prefabricated liquid level flushes as the terminal surface of printing the basement with quartz optical fiber to it eliminates liquid and rocks to stew.
The second step is that: and projecting the photocuring image with the hydrogel optical fiber cross section regulation information at a gas-liquid junction through DLP.
The third step: the gas-liquid junction begins to generate a crosslinking reaction and form a hydrogel optical fiber, and the hydrogel optical fiber and the quartz optical fiber form a coupling structure by utilizing the light-induced coupling technology;
the fourth step: and pulling the quartz optical fiber downwards at a constant speed, further continuously pulling the crosslinked hydrogel optical fiber to move downwards, and continuously generating photocuring crosslinking reaction at the junction by using a suspended photocrosslinking control technology to obtain the axially continuous and uniform hydrogel optical fiber.
The fifth step: and after the manufactured hydrogel optical fiber is taken out from the printing tank, soaking the hydrogel optical fiber in deionized water or distilled water for at least 30 minutes to separate out a light absorbing agent and other unreacted residual liquid.
Compared with the prior art, the invention has the remarkable advantages that:
(1) compared with the existing hydrogel fiber, the high-efficiency hydrogel fiber has higher signal-to-noise performance and sensing sensitivity, and can be used as a stable low-loss optical waveguide device for in-vivo and in-vitro optical transmission and optical sensing applications of organisms.
(2) The existing methods (such as a mold method and an extrusion type 3D printing method) are generally limited by the mechanical precision of a mold, are not flexible enough in selecting a geometric structure and a crosslinking degree in the preparation of a hydrogel optical fiber, and are difficult to improve the optical transmission efficiency of the hydrogel optical fiber.
(3) The existing method (projection type 3D printing method) is generally based on layer-stack type printing, namely a mode of covering a layer after curing, the mode will lead to axial fault of hydrogel optical fiber, influence the continuity of optical waveguide, and further cause the nonlinear transmission of optical field, and the suspension light crosslinking control technology adopted by the method ensures that the printed hydrogel optical fiber has axial continuity and uniformity, ensures the high-quality linear transmission of optical field therein, further improves the optical waveguide conduction efficiency, and makes up the defects of the existing projection type 3D method.
(4) The blocking type prefabricated liquid is simple in components, the light absorbent with proper dosage is introduced, the axial printing resolution of 3D printing is improved, the axial fidelity of a suspension photo-crosslinking control technology is guaranteed, and the printed hydrogel optical fiber is more uniform in axial direction and higher in transverse reduction degree.
(5) The coupling structure formed by the hydrogel optical fiber and the quartz optical fiber enables the hydrogel optical fiber and the traditional optical fiber to form a composite functional optical fiber, the networking capability of the quartz optical fiber is utilized, the large-scale optical transmission and optical sensing application can be realized, and meanwhile, due to the good biocompatibility of the hydrogel, the multi-material composite optical fiber formed by the hydrogel optical fiber and the quartz optical fiber fills the blank that the traditional optical fiber cannot be applied in vivo for a long time.
Drawings
Fig. 1 is a schematic view of a suspension photocuring 3D printing apparatus for manufacturing a hydrogel optical fiber according to the present invention.
Fig. 2 is a schematic diagram of a printing effect of a suspension photocrosslinking control technology of the suspension photocuring 3D printing apparatus for manufacturing a hydrogel optical fiber according to the present invention.
Detailed Description
The invention is further described with reference to the following figures and detailed description. It should be understood that the embodiments and methods described herein are illustrative and explanatory only and are not restrictive of the embodiments as claimed.
Aiming at the requirements of preparing hydrogel optical fibers with low loss and high signal-to-noise ratio, the invention provides a suspension photocuring 3D printing device which is based on a suspension photocrosslinking control technology and can simultaneously regulate and control a geometric structure and a crosslinking degree, and a printing method based on the device. The 3D printing method provided by the invention has incomparable advantages in the manufacturing of the continuous microstructure of the hydrogel material, and provides a novel sensing and wave guide device for the fields of biomedicine and the like.
With reference to fig. 1, the suspension photocuring 3D printing method for manufacturing the hydrogel optical fiber is implemented based on the suspension photocuring 3D printing device provided by the invention, and the device adopts a top-down projection structure and comprises a DLP, an optical micro-projection module, a crosslinking reaction monitoring module and an electric axial printing module. Among them, the DLP provides a projection light with information of a photo-cured image for simultaneously controlling the geometry and the degree of crosslinking of the hydrogel optical fiber. The optical miniature projection module comprises a first tube lens, a transflective lens and a microscope objective, projection light enters the first tube lens, enters the transflective lens after passing through the first tube lens, enters the microscope objective through the transflective lens, is reduced by the microscope objective with the multiplying power of the microscope objective to obtain a micron-sized photocured image, and is projected to the liquid level of the printing tank, namely a printing surface. The cross-linking reaction monitoring module is positioned on a conjugate light path of the miniature projection module and comprises a second tube lens and a CCD (charge coupled device), reflected light of the printing surface is transmitted to the second tube lens through the transflective lens and is converged on the CCD through the second tube lens, the cross-linking reaction degree of the printing surface is observed in real time, and the hydrogel optical fiber printing quality is regulated and controlled by matching with a suspended light cross-linking control technology. Electronic axial printing module is including printing the groove, quartz fiber and electronic translation platform, print the groove and take the cask of through wires hole for the bottom, print the interior packing of groove and be used for printing the prefabricated liquid of formula of blocking of aquogel optic fibre, quartz fiber penetrates through the through wires hole and prints the groove, quartz fiber prints the basement as the photocrosslinking at a terminal surface of printing the inslot, the other end is fixed in electronic translation bench, electronic translation platform provides the pull at the uniform velocity and makes the motion of photocrosslinking basement from the top down, the continuous even axial of aquogel optic fibre is printed in cooperation suspension photocrosslinking control technique realization.
The invention provides a suspension photocuring 3D printing method for manufacturing a hydrogel optical fiber, which aims at the requirement of the hydrogel optical fiber on linear propagation of an optical field of the hydrogel optical fiber and requires that the axial distribution in the optical fiber has the characteristics of continuity and uniformity. The suspension photo-crosslinking control technology utilizes the control photo-curing image of the crosslinking reaction monitoring module to project at the liquid level of the printing tank, namely the photo-curing crosslinking reaction area is controlled to be always maintained at the junction of the hydrogel prefabricated liquid and the air, the surface energy of the junction is low, and the hydrogel release capacity is high; meanwhile, the micro-scale hydrogel optical fiber diameter is limited by using an optical micro-projection module, and under the micro printing area with the micro-scale size, the full backflow of the prefabricated liquid can be ensured by matching with a proper printing stretching speed, so that the printing surface continuously generates a photocuring crosslinking reaction; in addition, by means of the optical high-resistance characteristic of the hydrogel optical fiber blocking type prefabricated liquid, the effective photocuring area is only arranged at the junction, the axial resolution of photocuring printing is ensured, and further the linear hydrogel optical fiber with axial continuity and uniformity is manufactured. The characteristics are as follows:
1) the focal plane and the liquid level are always superposed by the crosslinking reaction control module, namely, the projected photocured image is always clearly imaged on the liquid level.
2) By utilizing the characteristic of low gas-liquid interfacial surface energy, the crosslinked hydrogel is easy to separate in the printing process.
3) The blocking type prefabricated liquid for printing the hydrogel optical fiber contains a light absorbing agent, has a remarkable absorption effect on cross-linked light, can inhibit the propagation of a focused light beam, enables a printing area to be only arranged on a focal plane, namely the liquid level position, is used for improving the axial resolution of photocuring printing, and further ensures the axial uniformity and the transverse reduction degree of the hydrogel optical fiber.
4) The diameter of the prepared hydrogel optical fiber is micrometer to millimeter magnitude, and the small-size diameter realizes timely and sufficient backflow filling effect of the printing surface prefabricated liquid at a proper printing stretching speed.
The invention can simultaneously regulate and control the geometric structure and the polymerization degree of the hydrogel optical fiber so as to improve the optical transmission efficiency of the hydrogel optical fiber. Based on the micron-sized programmable photocuring projection image provided by the suspension photocuring 3D printing device, the cross section of the manufactured hydrogel optical fiber is determined by photocuring image parameters, wherein the size of the photocuring image determines the diameter size of the cross section of the hydrogel optical fiber; the shape of the photocured image determines the cross-sectional geometry of the hydrogel optical fiber; the light intensity distribution of the photo-cured image determines the cross-sectional free radical crosslinking degree distribution, namely the refractive index distribution, of the hydrogel optical fiber. For example, when the photocured image is concentric and the intensity of the inner circle is greater than that of the outer circle, the hydrogel optical fiber forms a step-type core-cladding configuration with a core refractive index greater than that of the cladding.
The blocking type hydrogel prefabricating liquid for the suspended light-curing 3D printing device comprises:
1) the monomer compound participating in the crosslinking reaction is acrylamide with the volume percentage of 30-40% and is used for forming the high-molecular hydrogel polymer.
2) The cross-linking agent for initiating the cross-linking reaction is N, N' -methylene bisacrylamide with the volume percentage of 1-2 percent, and provides unsaturated double bonds or a plurality of functional group cross-linking monomers to be connected into a polymer network.
3) The photoinitiator for the photocuring reaction is 0.01-0.03 volume percent of lithium phenyl-2, 4, 6-trimethylbenzoyl phosphite, and photon-absorbing energy generates free radicals to initiate a monomer compound to perform a crosslinking reaction.
4) The light absorbent for the suspension photocuring control technology is 0.01-0.05 volume percent of lemon yellow, limits the photocrosslinking reaction except a reaction surface (a focal surface), and improves the axial printing precision and resolution.
5) 57.92-68.98% of deionized water for dissolving the reagents, wherein the total volume is 100%.
Example of preformulation:
the blocking type prefabricated liquid for printing the hydrogel optical fiber is prepared by using 30 volume percent of acrylamide monomer compound, 1 volume percent of N, N' -methylene bisacrylamide, 0.01 volume percent of lithium phenyl-2, 4, 6-trimethylbenzoyl phosphite, 0.01 volume percent of lemon yellow and 68.98 volume percent of deionized water, and the hydrogel optical fiber is soft in mechanical property and slow in photocuring rate and is suitable for printing the flexible hydrogel optical fiber. If the concentration of the monomer compound or the concentration of the cross-linking agent is increased, the mechanical property of the optical fiber is gradually hardened, and the volume percentage of the components of the blocking type prefabricated liquid is adjusted according to the application requirement of the hydrogel optical fiber.
With reference to fig. 1 and fig. 2, the printing method based on the suspension photocuring 3D printing apparatus for manufacturing the hydrogel optical fiber includes the following steps:
the first step is as follows: penetrate the printing groove with quartz optical fiber from the through wires hole, print the groove this moment and form seal structure naturally, pour into the formula of blocking prefabricated liquid that is used for printing aquogel optic fibre again to printing the inslot, prefabricated liquid level flushes as the terminal surface of printing the basement with quartz optical fiber to it eliminates liquid and rocks to stew.
The second step is that: and projecting the photocuring image with the hydrogel optical fiber cross section regulation information at a gas-liquid junction through DLP.
The third step: and (3) performing a crosslinking reaction at a gas-liquid junction, namely a printing surface, to start forming the hydrogel optical fiber, and forming a coupling structure between the hydrogel optical fiber and the quartz optical fiber by using a light-induced coupling technology.
The fourth step: and pulling the quartz optical fiber downwards at a constant speed, further continuously pulling the crosslinked hydrogel optical fiber to move downwards, and continuously generating photocuring crosslinking reaction at the junction by using a suspended photocrosslinking control technology to obtain the axially continuous and uniform hydrogel optical fiber.
The fifth step: and after the manufactured hydrogel optical fiber is taken out from the printing tank, soaking the hydrogel optical fiber in deionized water or distilled water for at least 30 minutes to separate out a light absorbing agent and other unreacted residual liquid.
The light-induced coupling technology is specifically as follows: the used quartz optical fiber is directly used as a printing substrate on the end face of a printing groove, the quartz optical fiber is placed in a gas-liquid interface and stands before printing is started, a crosslinking reaction monitoring module is used for observing clear images of projected photocured images on the printing substrate (namely the quartz optical fiber), the printing is started, the images are kept still within a period of time after the crosslinking reaction is started until hydrogel colloid is stably formed on the printing end face of the quartz optical fiber and completely wraps the tail section of the quartz optical fiber, and then the drawing printing of the hydrogel optical fiber is started, at the moment, a tight and stable coupling connection structure is formed between the hydrogel optical fiber and the quartz optical fiber, so that the optical coupling and optical fiber networking application of the hydrogel optical fiber are facilitated.
Claims (7)
1. The utility model provides a suspension photocuring 3D printing device of preparation aquogel optic fibre which characterized in that: a top-down projection structure is adopted, and comprises a DLP (digital light processing), an optical miniature projection module, a crosslinking reaction monitoring module and an electric axial printing module; the DLP provides projection light with photocureable image information, and the photocureable image is used for simultaneously regulating and controlling the geometric structure and the crosslinking degree of the hydrogel optical fiber; the optical miniature projection module comprises a first tube lens, a transflective lens and a microscope objective, projection light enters the first tube lens, enters the transflective lens after passing through the first tube lens, enters the microscope objective through the transflective lens, is reduced by the microscope objective with the multiplying power of the microscope objective to obtain a micron-sized photocured image, and is projected to the liquid level of the printing tank, namely a printing surface; the cross-linking reaction monitoring module is positioned on a conjugate light path of the miniature projection module, the cross-linking reaction monitoring module comprises a second tube lens and a CCD (charge coupled device), reflected light of the printing surface is transmitted to the second tube lens through the transflective lens and is converged on the CCD through the second tube lens, the cross-linking reaction degree of the printing surface is observed in real time, and the hydrogel optical fiber printing quality is regulated and controlled by matching with a suspended light cross-linking control technology; electronic axial printing module is including printing the groove, quartz fiber and electronic translation platform, print the groove and take the cask of through wires hole for the bottom, print the interior packing of groove and be used for printing the prefabricated liquid of blocking of aquogel optic fibre, quartz fiber penetrates through the through wires hole and prints the groove, quartz fiber prints the basement as the photocrosslinking at the terminal surface of printing the inslot, the other end is fixed in electronic translation bench, electronic translation platform is at the uniform velocity pulling photocrosslinking basement and is carried out from top to bottom motion, the continuous even axial of aquogel optic fibre is printed in cooperation suspension photocrosslinking control technique realization.
2. The suspended photocuring 3D printing device for making hydrogel optical fibers according to claim 1, wherein: the suspended photocrosslinking control technology can realize continuous occurrence of photocuring crosslinking reaction and only occurs on a printing surface, and specifically comprises the following steps: the cross-linking reaction monitoring module is used for controlling the projection of the photocured image on the liquid level of the printing tank, namely the photocuring cross-linking reaction of the printing surface always occurs at the junction of the hydrogel prefabricated liquid and air, the surface energy of the junction is low, and the hydrogel release capacity is high; meanwhile, the fiber diameter of the micron-sized hydrogel optical fiber limited by the optical miniature projection module is matched with a proper printing stretching speed to ensure the full backflow of the prefabricated liquid, so that the printing surface continuously generates a photocuring crosslinking reaction; in addition, by means of the optical high-resistance characteristic of the hydrogel optical fiber blocking type prefabricated liquid, the effective photocuring area is only generated on the printing surface, the axial resolution of photocuring printing is ensured, and further the linear hydrogel optical fiber with axial continuity and uniformity is manufactured.
3. The suspended photocuring 3D printing device for making hydrogel optical fibers according to claim 1, wherein: the method can simultaneously regulate and control the geometric structure and the crosslinking degree of the hydrogel optical fiber, and specifically comprises the following steps: the cross section of the manufactured hydrogel optical fiber is determined by the information of the photocured image, wherein the size of the photocured image determines the diameter size of the cross section of the hydrogel optical fiber; the shape of the photocured image determines the cross-sectional geometry of the hydrogel optical fiber; the light intensity distribution of the photo-cured image determines the cross-sectional free radical crosslinking degree distribution, namely the refractive index distribution, of the hydrogel optical fiber.
4. The suspended photocuring 3D printing device for making hydrogel optical fibers according to claim 1, wherein: the blocking type prefabricated liquid for printing the hydrogel optical fiber is specifically as follows: the composite material comprises 30-40% of acrylamide monomer compound, 1-2% of N, N' -methylene bisacrylamide, 0.01-0.03% of phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite, 0.01-0.05% of lemon yellow and 57.92-68.98% of deionized water in percentage by volume, and the total volume is 100%;
the acrylamide monomer compound is used for forming a high-molecular hydrogel polymer;
n, N' -methylene-bisacrylamide, which provides unsaturated double bonds or a plurality of functional groups for the crosslinking monomers to be connected into a polymer network;
lithium phenyl-2, 4, 6-trimethylbenzoylphosphite for absorbing photon energy to generate free radical to initiate the cross-linking reaction of monomer compound;
the lemon yellow is used for a suspension photocuring control technology, limits photocrosslinking reaction outside a reaction surface, and improves the axial printing precision and resolution;
deionized water as solvent, dissolving the above materials and proportioning the total prefabricated liquid to 100% volume.
5. A block formula prefabricated liquid for printing aquogel optic fibre which characterized in that: the composite material comprises 30-40% of acrylamide monomer compound, 1-2% of N, N' -methylene bisacrylamide, 0.01-0.03% of phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite, 0.01-0.05% of lemon yellow and 57.92-68.98% of deionized water in percentage by volume, and the total volume is 100%;
the acrylamide monomer compound is used for forming a high-molecular hydrogel polymer;
n, N' -methylene-bisacrylamide, which provides unsaturated double bonds or a plurality of functional groups for the crosslinking monomers to be connected into a polymer network;
lithium phenyl-2, 4, 6-trimethylbenzoylphosphite for absorbing photon energy to generate free radical to initiate polymerization reaction of monomer compound;
the lemon yellow is used for a suspension photocuring control technology, limits photocrosslinking reaction outside a reaction surface, and improves the axial printing precision and resolution;
deionized water as solvent, dissolving the above materials and proportioning the total prefabricated liquid to 100% volume.
6. A printing method of a suspension photocuring 3D printing device based on hydrogel optical fiber manufacturing is characterized by comprising the following steps:
the first step is as follows: penetrating the quartz optical fiber into the printing groove from the threading hole, wherein the printing groove naturally forms a sealing structure, pouring blocking type prefabricated liquid for printing the hydrogel optical fiber into the printing groove, wherein the liquid level of the prefabricated liquid is flush with the printing substrate of the quartz optical fiber, and standing to eliminate liquid shaking;
the second step is that: projecting a photocuring image with hydrogel optical fiber cross section regulation information at a gas-liquid junction through a DLP (digital light processing);
the third step: the gas-liquid junction begins to generate a crosslinking reaction and form a hydrogel optical fiber, and the hydrogel optical fiber and the quartz optical fiber form a coupling structure by utilizing the light-induced coupling technology;
the fourth step: pulling the quartz optical fiber downwards at a constant speed, further continuously pulling the crosslinked hydrogel optical fiber to move downwards, and continuously generating photocuring crosslinking reaction at a junction by using a suspended photocrosslinking control technology to obtain an axially continuous and uniform hydrogel optical fiber;
the fifth step: and after the manufactured hydrogel optical fiber is taken out from the printing tank, soaking the hydrogel optical fiber in deionized water or distilled water for at least 30 minutes to separate out a light absorbing agent and other unreacted residual liquid.
7. The printing method of the suspension photocuring 3D printing device based on the hydrogel optical fiber manufacturing process according to claim 6, wherein the light-induced coupling technology is as follows: the end face of the used quartz optical fiber in the printing groove is used as a printing substrate, the quartz optical fiber is placed in a gas-liquid interface and stands before printing is started, a crosslinking reaction monitoring module is used for observing that a projected photocured image is clearly imaged on the quartz optical fiber, the printing is started, the quartz optical fiber is kept still within a period of time after the crosslinking reaction is started until hydrogel colloid is stably formed on the printing end face of the quartz optical fiber and completely wraps the tail section of the quartz optical fiber, and then the drawing printing of the hydrogel optical fiber is started, at the moment, a tight and stable coupling connection structure is formed between the hydrogel optical fiber and the quartz optical fiber, so that the optical coupling and optical fiber networking application of the hydrogel optical fiber are facilitated.
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