CN115477853A - Photo/thermal curing shape memory hybrid material, preparation method and application thereof - Google Patents
Photo/thermal curing shape memory hybrid material, preparation method and application thereof Download PDFInfo
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- CN115477853A CN115477853A CN202211039113.3A CN202211039113A CN115477853A CN 115477853 A CN115477853 A CN 115477853A CN 202211039113 A CN202211039113 A CN 202211039113A CN 115477853 A CN115477853 A CN 115477853A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
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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
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/264—Arrangements for irradiation
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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
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2475/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/12—Shape memory
Abstract
The invention discloses a light/heat cured shape memory hybrid material, a preparation method and application thereof, wherein the hybrid material comprises a light/heat cured elastic material and a phase-change material; the light/heat curing elastic material is cross-linked and cured after being blended with the phase-change material before curing to prepare the shape memory hybrid material; the light/heat-cured elastic material is light-cured elastic resin, heat-cured elastic resin or light-heat double-crosslinked elastic resin; the transition phase material may undergo melting/solidification or glass transition with temperature change, or may undergo hardness change by absorbing/volatilizing a solvent. The method can adjust the characteristics of the shape memory effect, the mechanical property and the like of the 3D printing shape memory structure; the produced material can be used for various 3D printing modes; the material can be used for printing an intelligent structure with a specific shape memory effect by a 3D printing technology, and the mechanical property, the shape memory property and the like of the material can be adjusted by selecting the combination and blending ratio of different materials.
Description
Technical Field
The invention relates to a shape memory material, a preparation method and application thereof, in particular to a light/heat cured shape memory hybrid material, a preparation method and application thereof.
Background
Shape Memory Effect (SME) refers to the property of fixing a temporary shape under certain external forces and environmental conditions and returning to its original shape under a specific external stimulus (e.g., heat, light, electricity, magnetism, etc.). Materials with a shape memory effect are referred to as shape memory materials. The shape memory polymer has the advantages of good biocompatibility and degradability, multi-stimulus response, good designability, large deformation, light weight and the like, and is widely applied to the fields of biomedical treatment, aerospace, intelligent manufacturing, footwear and clothing and the like. The traditional shape memory polymer needs to customize a specific mould for production during production and manufacturing, and can not be produced and processed in the face of some special customized products with complex shapes or fine shapes, so that the production efficiency is greatly reduced.
3D printing is a rapid prototyping technology, and can be divided into fused deposition modeling, three-dimensional light-cured modeling, selective laser sintering and the like according to different prototyping principles. Due to the characteristics of simple principle, convenient operation, low cost and the like, the 3D printing technology has important research significance and application value in the fields of industrial design, biomedical treatment, aerospace, civil engineering, automobile manufacturing, footwear and apparel and the like. In recent years, 4D printing technology has been developed based on 3D printing technology. By introducing the fourth dimension-time on the basis of 3D printing, the printed structure can be changed in shape or structure under external excitation (such as light, heat, electricity, magnetism, humidity and the like), the deformation design of the material and the structure is directly built in the material, the material manufacturing process from the design concept to the material object is simplified, the object can be automatically assembled and constructed, and the integration of product design, manufacturing and assembly is realized. Among them, the shape memory effect is the most common form in 4D printing. The shape memory polymer has the characteristics of low density, low cost, sensitivity to temperature and other stimuli, easiness in processing and the like, so that the 3D shape memory polymer has a huge application prospect in the intelligent manufacturing technology.
At present, some attempts have been made to use shape memory polymers as a 3D printing material to print an intelligent structure, and patent CN110093021A adopts a large amount of organic solvents to dissolve polymers, and controls the shape memory behavior of the material by adjusting the content ratio of polylactic acid and polyetheretherketone between different layers, and the process is tedious and not environment-friendly. Patent CN109878070A discloses a preparation method of a 3D printed thermotropic shape memory PLA composite material, which prepares a thermotropic shape memory polylactic acid composite material through extrusion type 3D printing, and does not well utilize the advantages of 3D printing technology to improve the shape memory characteristics of polylactic acid materials. Most of the shape memory materials used for 3D printing in the past only aim at fused deposition modeling materials, and cannot meet the requirements of modeling modes such as three-dimensional photocuring modeling and selective laser sintering for continuously improving 3D printing modeling technologies. Meanwhile, the mechanical properties, shape memory properties and the like of a 3D printed product can only be adjusted in a limited range, and various properties of the material, including the shape memory property, cannot be conveniently adjusted according to different application scenes, so that the development of a 3D printed shape memory structure is limited.
Disclosure of Invention
The purpose of the invention is as follows: the object of the present invention is to provide a light/heat curable shape memory hybrid material that can be 3D printed and can conveniently adjust the material properties;
the second object of the present invention is to provide a method for preparing the above-mentioned photo/thermal curing shape memory hybrid material;
it is a third object of the present invention to provide the use of the above-mentioned photo/thermal curable shape memory hybrid material.
The technical scheme is as follows: the light/heat cured shape memory hybrid material comprises a light/heat cured elastic material and a phase transition material; the light/heat curing elastic material is cross-linked and cured after being blended with the phase-change material before curing to prepare the shape memory hybrid material; the light/heat-cured elastic material is light-cured elastic resin, heat-cured elastic resin or light-heat double-crosslinked elastic resin; the transition phase material may undergo melting/solidification or glass transition with temperature change, or may undergo hardness change by absorbing/volatilizing a solvent.
Wherein the light/heat curable elastic material refers to a light curable elastic material or a heat curable elastic material. The thermoset elastomers are high viscosity and shear thinning prior to thermoset, useful for 3D printing, which can be achieved by pre-crosslinking.
The photo-and thermal-double-crosslinked elastic resin is preferably a photo-and thermal-double-crosslinked urethane acrylate; in particular to light and heat double-crosslinking polyurethane acrylate of Guangzhou Tianze new material technology limited company.
Wherein the volume ratio of the light/heat curable elastic material to the transition phase material is 9:1 to 4:6.
wherein the elastic modulus of the light/heat curing elastic material is 1MPa-10 GPa, and the elastic modulus of the conversion phase material is 10MPa-300 GPa.
Wherein the phase-change material is at least one of dry hydrogel, polycaprolactone, poly (butyl acrylate), polyurethane, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, polylactic acid, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyformaldehyde, polyamide, polycarbonate, polyethylene terephthalate, polyvinyl alcohol, polybutyl acrylate, polyethylene glycol, polyether ether ketone, polybutylene terephthalate, polyphenyl ether, polyphenylene sulfide and polytetrafluoroethylene.
Wherein, at least one of short carbon fiber, short glass fiber, carbon nano tube, graphene, nickel powder, iron oxide powder or attapulgite with the volume ratio of 0.1-10% is doped in the shape memory hybrid material; for increasing strength, conductivity, and magnetism.
Wherein, the shape memory hybrid material is doped with a foaming agent and is used for preparing a porous material.
The preparation method of the light/heat-cured shape memory hybrid material comprises the step of blending the light/heat-cured elastic material and the phase-change material, wherein the phase-change material is mixed with the light/heat-cured elastic material in a particle form, and the particle size of the phase-change material is 0.02-50 mu m.
Wherein, the blending mode comprises the following five modes: (1) Heating the phase-change material to melt and mixing with the liquid photo/thermal curing elastic material; (2) Mixing the liquid photo/thermal curing material and the phase change material at room temperature; (3) Dissolving the phase-change material in a chemical solvent, mixing with the liquid photo/thermal curing elastic material, and volatilizing the solvent; (4) Heating the phase-change material and the light/heat-cured elastic material to be molten and then mixing; (5) The phase-change material and the photo/thermal curing elastic material are respectively dissolved in the solvent and then mixed to volatilize the solvent.
The use of the above-described photo/thermal curable shape memory hybrid material in 3D printing.
Wherein, the light/heat-cured elastic material and the phase-change material are cured and crosslinked by UV light irradiation in printing or UV light irradiation or heating after printing and forming.
The shape memory hybrid material is preheated or heated when the shape memory hybrid material is extruded, so that the phase-change material is melted to a viscous state, UV light reflection or extrusion opening blockage of the phase-change material in the photocuring process is avoided, and the material matrix is ensured to be fully crosslinked.
The crosslinked photo/thermo-curable elastomeric material remains elastic in its application environment and during use. The material can be used for 3D printing of structures with specific shape memory effects, the original shape of the structure is formed through 3D printing, and the mechanical properties, the shape memory properties and the like of the structure, including elastic modulus, elongation at break, shape fixing temperature, shape fixing rate, shape recovery rate, shape fixing time, shape recovery temperature, shape recovery excitation mode and the like, can be adjusted by selecting the combination and blending ratio of different materials.
The shape memory hybrid material can customize the mechanical property and the shape memory property of a shape memory product according to the mechanism of the shape memory hybrid material and the specific application requirement; wherein the mechanical properties include modulus of elasticity, elongation at break; the shape memory characteristics include shape fixation temperature, shape fixation rate, shape recovery rate, shape fixation time, shape recovery activation mode, and shape recovery temperature.
The invention principle is as follows: shape memory hybrid materials are a new class of materials that are well mixed from two or more different materials. To achieve the shape memory effect of the hybridized materials, at least one material should be used as the elastic part and another material should be used as the transition part when mixing, wherein the elastic part is characterized by stable mechanical properties over a wide temperature range. The nature of the transition portion is reversed, and upon reaching certain conditions, such as temperature, a phase transition occurs, such as a glass transition or a melt transition, so that the mechanical strength thereof is significantly different before and after the transition. The hybrid material obtained by sufficiently blending the elastic portion and the transition portion is heated to a temperature higher than the phase transition temperature of the transition portion, and the mechanical strength of the transition portion is drastically reduced. At this time, the hybrid material is loaded, and the transition portion and the elastic portion are simultaneously deformed, but the elastic portion mainly receives an external force. The temperature is reduced to be lower than the phase transition temperature while the deformation is kept, the original mechanical strength is recovered by the transition part, the hybrid material is unloaded at the moment, the transition part can restrict the shape rebound of the elastic part, and the shape fixation of the deformed material is realized. When heated above the phase transition temperature again, the mechanical strength of the transition portion decreases again, resulting in its inability to limit the tendency of the elastic portion to rebound, and the hybrid material will return to its original shape prior to deformation. Compared with general chemical synthesis, the shape memory hybrid material has the characteristic that the elastic part and the transition part hardly have interaction, so that the shape memory characteristics and the mechanical characteristics of the material, such as the elasticity, the shape fixing temperature and time, the shape recovery driving mode, the driving temperature interval, the driving force, and the like of the material, can be conveniently adjusted by adjusting the proportion of the two parts or adopting different elastic part/transition part combinations.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) By controlling the types and the proportion of the blending materials, the characteristics of the shape memory effect, the mechanical property and the like of the 3D printing shape memory structure can be adjusted. (2) The material produced by the general preparation method can be used for fused deposition molding, direct writing printing and resin 3D printing, such as a plurality of 3D printing methods of stereolithography, digital photocuring, volume printing and the like, and the molding method of shape memory material printing is expanded. (3) The material can be used for printing an intelligent structure with a specific shape memory effect by a 3D printing technology, and the mechanical property, the shape memory property and the like of the material can be adjusted by selecting the combination and blending ratio of different materials.
Detailed Description
The present invention is described in further detail below.
Example 1
A light-cured shape memory hybrid material for 3D printing comprises light-cured elastic resin and a phase-change material; wherein the elastic modulus of the photo-curing elastic resin is 5MPa, the elongation at break is 50 percent, and the volume percentage is 90 percent; the phase-change material is polycaprolactone with the volume ratio of 10%.
The preparation method of the shape memory hybrid material comprises the following steps:
(1) Heating the photocuring elastic resin and polycaprolactone with corresponding volume fractions to 100 ℃ for melting and blending;
(2) Fully and uniformly mixing polycaprolactone with the photocuring elastic resin by high-speed stirring, wherein the particle size of the polycaprolactone is 0.1-50 mu m;
(3) And (3) standing and cooling the blended material to obtain the shape memory hybrid material for photocuring 3D printing.
The obtained shape memory hybrid material can be used for a resin type 3D printer, the material is preheated or heated during material extrusion to melt a transition phase in the material, UV light reflection or extrusion opening blockage of transition phase small particles in the material in a photocuring process is avoided, and sufficient crosslinking is ensured.
The shape recovery excitation mode of the shape memory structure printed by the photocuring 3D printing material obtained in the embodiment is thermal driving, the shape fixing rate reaches 70%, the shape recovery rate reaches 100%, the plastic hardening time at 25 ℃ is 10 minutes, the elastic modulus is 7.5MPa, and the tensile breaking elongation reaches 70%.
The printed part can be used for shaping at body temperature, and has excellent elasticity after shaping.
Example 2
A light-cured shape memory hybrid material for 3D printing comprises light-cured elastic resin and a phase-change material; wherein the elastic modulus of the photo-curing elastic resin is 20MPa, the elongation at break is 50 percent, and the volume percentage is 80 percent; the phase-change material is polycaprolactone with the volume ratio of 20%.
The manufacturing method and the 3D printing method are the same as in example 1.
The shape recovery excitation mode of the shape memory structure printed by the photocuring 3D printing material obtained in the embodiment is thermal driving, the shape fixing rate reaches 85%, the shape recovery rate reaches 100%, the plastic hardening time at 25 ℃ is 10 minutes, the elastic modulus is 75MPa, and the tensile breaking elongation reaches 90%.
Example 3
A light-cured shape memory hybrid material for 3D printing comprises light-cured elastic resin and a phase-change material; wherein the elastic modulus of the photo-curing elastic resin is 50MPa, the elongation at break is 50 percent, and the volume percentage is 70 percent; the phase-change material is polycaprolactone with the volume ratio of 30%.
The manufacturing method and the 3D printing method are the same as in example 1.
The shape recovery excitation mode of the shape memory structure printed by the photocuring 3D printing material obtained in the embodiment is thermal driving, the shape fixing rate reaches 95%, the shape recovery rate reaches 100%, the plastic hardening time at 25 ℃ is 10 minutes, the elastic modulus is 200MPa, and the tensile breaking elongation reaches 120%.
The printed part can be used for shaping at body temperature, has higher hardness after shaping, and can be used for splints and the like.
Example 4
A light-cured shape memory hybrid material for 3D printing comprises light-cured elastic resin and a phase-change material; wherein the elastic modulus of the photo-curing elastic resin is 100MPa, the elongation at break is 50 percent, and the volume percentage is 60 percent; the phase-change material is polycaprolactone with the volume ratio of 40%.
The manufacturing method and the 3D printing method are the same as in example 1.
The shape recovery excitation mode of the shape memory structure printed by the photocuring 3D printing material obtained in the embodiment is thermal driving, the shape fixing rate reaches 90%, the shape recovery rate reaches 100%, the plastic hardening time at 25 ℃ is 10 minutes, the elastic modulus is 50MPa, and the tensile breaking elongation reaches 200%.
Example 5
A light and heat curing shape memory hybrid material for 3D printing, wherein the 3D printing material in the composition is polyurethane acrylate which can be subjected to light and heat double crosslinking and is prepared by Guangzhou Tianze New Material technology Limited company, and the volume percentage is 90%; the phase-change material is polycaprolactone with the volume ratio of 10%.
The preparation method comprises the following steps: (1) Mixing polycaprolactone particles with the diameter of 10 mu m with liquid polyurethane acrylate; (2) After mixing, the mixture was moderately cross-linked with UV light to make the mixture viscous and shear-thinning.
When the obtained 3D printer and fused deposition modeling 3D printing equipment which can be used for the Sandraw are used for 3D printing, materials can be preheated or heated during material extrusion to enable a transformation phase in the materials to be melted and softened, and the phenomenon that the extrusion opening is blocked by transformation phase small particles in the materials during the printing extrusion process is avoided. After printing, photo/thermal crosslinking is carried out again.
The driving method of the shape memory structure printed by the embodiment is thermal driving or acetone driving, the shape fixing rate of the shape memory structure reaches 60%, the shape recovery rate reaches 100%, the plastic hardening time at 25 ℃ is 10 minutes, and the elastic modulus is 50MPa.
Example 6
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Limited company, and the volume ratio is 80%; the phase-change material is polycaprolactone, and the volume percentage is 20%.
The manufacturing method and the 3D printing method are the same as those of embodiment 5, and are not described again.
The driving method of the shape memory structure printed by the embodiment is thermal driving or acetone driving, the shape fixing rate of the shape memory structure reaches 75%, the shape recovery rate reaches 100%, the plastic hardening time at 25 ℃ is 10 minutes, and the elastic modulus is 100MPa.
Example 7
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Limited company, and the volume ratio is 70%; the phase-change material is polycaprolactone with the volume ratio of 30%.
The manufacturing method and the 3D printing method are the same as those of embodiment 5, and are not described again.
The shape memory structure printed in this example is driven by heat or acetone, and has a shape fixing rate of 85%, a shape recovery rate of 100%, a plastic hardening time of 10 minutes at 25 ℃, and an elastic modulus of 150MPa.
Example 8
A thermocuring shape memory hybrid material that can be used for 3D to print, 3D printing material chooses polyurethane acrylate that can be photo-and heat-double cross-linked of Guangzhou Tianze new material technology Limited company in the composition, the volume accounts for 60%; the phase-change material is polycaprolactone with the volume ratio of 40%.
The manufacturing method and the 3D printing method are the same as those of embodiment 5, and are not described again.
The shape memory structure printed in this example is driven by heat or acetone, and has a shape fixing rate of 95%, a shape recovery rate of 100%, a plastic hardening time of 10 minutes at 25 ℃, and an elastic modulus of 200MPa.
Example 9
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Limited company, and the volume ratio is 90%; the phase-change material is polyurethane with the volume percentage of 10%.
The manufacturing method and the 3D printing method are the same as those of embodiment 5, and are not described again.
The driving method of the shape memory structure printed by the embodiment is thermal driving, the shape fixing rate of the shape memory structure reaches 65%, the shape recovery rate reaches 100%, the plastic hardening time at 35 ℃ is 15 minutes, and the elastic modulus is 30MPa.
Example 10
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Limited company, and the volume ratio is 80%; the phase-change material is polyurethane with a volume ratio of 20%.
The manufacturing method and the 3D printing method are the same as those of embodiment 5, and are not described again.
The driving method of the shape memory structure printed by the embodiment is thermal driving, the shape fixing rate of the shape memory structure reaches 75%, the shape recovery rate reaches 100%, the plastic hardening time at 35 ℃ is 15 minutes, and the elastic modulus is 50MPa.
Example 11
A thermocuring shape memory hybrid material that can be used for 3D to print, 3D printing material chooses polyurethane acrylate that can be photo-and heat-double cross-linked of Guangzhou Tianze new material technology Limited company in the composition, the volume accounts for 70%; the phase-change material is polyurethane with a volume ratio of 30%.
The manufacturing method and the 3D printing method are the same as those of embodiment 5, and are not described again.
The driving method of the shape memory structure printed by the embodiment is thermal driving, the shape fixing rate of the shape memory structure reaches 80%, the shape recovery rate reaches 100%, the plastic hardening time at 35 ℃ is 15 minutes, and the elastic modulus is 60MPa.
Example 12
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Limited company, and the volume ratio is 60%; the phase-change material is polyurethane with a volume ratio of 40%.
The manufacturing method and the 3D printing method are the same as those of embodiment 5, and are not described again.
The driving method of the shape memory structure printed by the embodiment is thermal driving, the shape fixing rate of the shape memory structure reaches 85%, the shape recovery rate reaches 100%, the plastic hardening time at 35 ℃ is 15 minutes, and the elastic modulus is 80MPa.
Example 13
A light and heat curing shape memory hybrid material for 3D printing, wherein the 3D printing material in the composition is polyurethane acrylate which can be subjected to light and heat double crosslinking and is prepared by Guangzhou Tianze New Material technology Limited company, and the volume ratio is 62%; the phase-change material is prepared by selecting polycaprolactone particles with the diameter of 10 mu m, the volume ratio of the polycaprolactone particles is 28 percent, and adding the short carbon fibers as the additive component, and the volume ratio of the short carbon fibers is 10 percent.
The preparation method comprises the following steps: (1) mixing polycaprolactone with urethane acrylate; (2) Adding the short carbon fibers with the corresponding volume ratio, and fully mixing again; (3) The mixed material was irradiated with UV light to make it suitable for extrusion printing.
The obtained material can be used for 3D extrusion printing equipment used by Sandraw, when 3D printing is carried out, the material is preheated or heated when the material is extruded to enable a crystalline transformation phase in the material to be melted and softened, so that the phenomenon that the transformation phase small particles in the material block an extrusion opening in the process of printing and extruding is avoided, and after printing is finished, the material is heated again to enable the material to be fully crosslinked.
The shape memory structure printed by the 3D printing material obtained in the embodiment is driven by heat or acetone, has good conductivity, and has the shape fixing rate of 85 percent, the shape recovery rate of 100 percent, the plastic hardening time of 10 minutes at 25 ℃ and the elastic modulus of 150MPa.
Example 14
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Co., ltd, and the volume ratio is 62%; the phase-change material is prepared by selecting polycaprolactone particles with the diameter of 5 mu m, the volume ratio of the polycaprolactone particles is 28%, and adding the additive component graphene, wherein the volume ratio of the graphene is 10%.
The manufacturing method and the 3D printing method are the same as those of embodiment 13, and are not described again.
The shape memory structure printed by the 3D printed shape memory hybrid material obtained in the embodiment is driven by heat or acetone, has good conductivity and can be used for driving by energization and heating, the shape fixing rate of the shape memory structure reaches 90%, the shape recovery rate of the shape memory structure reaches 100%, the plastic hardening time at 25 ℃ is 10 minutes, and the elastic modulus of the shape memory structure is 30MPa.
Example 15
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Limited company, and the volume ratio is 60%; the transition phase material is polycaprolactone, the volume ratio of which is 30 percent, and particles with the diameter of 10 mu m are added, and the additive component of ferric oxide powder is added, and the volume ratio of which is 10 percent.
The manufacturing method and the 3D printing method are the same as those of embodiment 13, and are not described again.
The shape memory structure printed by the 3D printed shape memory hybrid material obtained in the embodiment is driven by heat, acetone or a magnetic field, the shape fixing rate of the shape memory structure reaches 90%, the shape recovery rate reaches 100%, the plastic hardening time is 10 minutes at 25 ℃, and the elastic modulus is 30MPa.
Example 16
A light and heat curing shape memory hybrid material for 3D printing, wherein the 3D printing material in the composition is polyurethane acrylate which can be subjected to light and heat double crosslinking and is prepared by Guangzhou Tianze New Material technology Limited company, and the volume ratio is 62%; the conversion phase material selects polyurethane particles with the diameter of 10 mu m, the volume ratio is 28%, and an additive foaming agent is added, and the volume ratio is 0.2%.
The preparation method comprises the following steps: (1) mixing polycaprolactone with urethane acrylate; (2) Adding the foaming agent with the corresponding volume ratio, and fully mixing again; (3) The mixed material was appropriately irradiated with UV light to make it suitable for extrusion printing.
The obtained mixed material can be used for extruding 3D printing equipment, when 3D printing is carried out, the material is preheated or heated when the material is extruded to melt and soften the crystalline transition phase in the material, and the phenomenon that the extrusion opening is blocked by the transition phase small particles in the material in the process of printing and extruding is avoided. Heating at high temperature to foam and fully crosslink after printing.
The shape memory structure obtained in this example is driven by heat or acetone, and has good compressibility, a shape fixing rate of 86% and a shape recovery rate of 100%, and a plastic hardening time of 10 minutes at 25 ℃ and an elastic modulus of 180MPa.
Example 17
A thermosetting shape memory hybrid material for 3D printing is disclosed, wherein the 3D printing material in the composition is polyurethane acrylate which can be photo-and thermally double-crosslinked and is prepared from Guangzhou Tianze New Material technology Limited company, and the volume ratio is 60%; the phase-change material is dry hydrogel with the volume ratio of 40%.
The preparation method comprises the following steps: (1) Mixing dry hydrogel particles with a diameter of 10 μm with liquid urethane acrylate; (2) After mixing, the mixture was moderately cross-linked with UV light to make the mixture viscous and shear-thinning.
When the obtained 3D printer and fused deposition modeling 3D printing equipment which can be used for the Sandraw are used for 3D printing, materials can be preheated or heated during material extrusion to enable a transformation phase in the materials to be melted and softened, and the phenomenon that the extrusion opening is blocked by transformation phase small particles in the materials during the printing extrusion process is avoided. After printing, photo/thermal crosslinking is carried out again.
The driving method of the printed shape memory structure in this embodiment is water driving, and the shape fixing rate reaches 80%, the shape recovery rate reaches 100%, and the elastic modulus is 50MPa.
Claims (10)
1. A light/heat curable shape memory hybrid material comprising a light/heat curable elastic material and a phase change material; the light/heat-cured elastic material is cross-linked and cured after being blended with a phase-change material before being cured to prepare the shape memory hybrid material; the light/heat-cured elastic material is light-cured elastic resin, heat-cured elastic resin or light-heat double-crosslinked elastic resin; the transition phase material may undergo melting/solidification or glass transition with temperature change, or may undergo hardness change by absorbing/volatilizing a solvent.
2. The light/heat-curable shape memory hybrid material according to claim 1, wherein the volume ratio of the light/heat-curable elastic material and the transition phase material is 9:1 to 4:6.
3. the photo/thermal curable shape memory hybrid material according to claim 1, wherein the elastic modulus of the photo/thermal curable elastic material is 100KPa to 10 GPa and the elastic modulus of the transition phase material is 1MPa to 300 GPa.
4. The photo/thermo-curable shape memory hybrid material according to claim 1, wherein the transition phase material is at least one of a dry hydrogel, polycaprolactone, poly (butyl acrylate), polyurethane, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, polylactic acid, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymethylmethacrylate, polyoxymethylene, polyamide, polycarbonate, polyethylene terephthalate, polyvinyl alcohol, polybutyl acrylate, polyethylene glycol, polyetheretherketone, polybutylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polytetrafluoroethylene.
5. The light/heat-curable shape memory hybrid material according to claim 1, wherein at least one of short carbon fiber, short glass fiber, carbon nanotube, graphene, nickel powder, iron oxide powder, or attapulgite is incorporated in the shape memory hybrid material in a volume ratio of 0.1 to 10%.
6. The photo/thermal curing shape memory hybrid material according to claim 1, wherein the shape memory hybrid material is incorporated with a foaming agent for preparing a porous material.
7. A method for preparing a light/heat curable shape memory hybrid material according to claim 1, wherein a light/heat curable elastic material and a transition phase material are blended, the transition phase material is mixed with the light/heat curable elastic material in the form of particles, and the particle size of the transition phase material is 0.02 to 50 μm.
8. The method for preparing a photo/thermal curable shape memory hybrid material according to claim 7, wherein the blending is performed by any one of the following methods:
heating the phase change material to melt and mixing with the liquid photo/thermal curing elastic material;
mixing the liquid photo/thermosetting material with the particulate phase change material at room temperature;
dissolving the phase-change material in a chemical solvent, mixing with the liquid photo/thermal curing elastic material, and volatilizing the solvent;
heating the phase-change material and the light/heat curing elastic material to be molten and then mixing;
the phase-change material and the photo/thermal curing elastic material are respectively dissolved in the solvent and then mixed to volatilize the solvent.
9. Use of a light/heat curable shape memory hybrid material according to claim 1 in 3D printing, wherein the curing crosslinking of the light/heat curable elastomer material with the phase change material is achieved by UV light irradiation during printing or by UV light irradiation or heating after print formation.
10. Use of the photo/thermal curable shape memory hybrid material according to claim 9 in 3D printing, wherein the shape memory hybrid material is preheated or heated during extrusion of the shape memory hybrid material to melt the phase change material to a viscous state, to avoid UV light reflection from the phase change material during photo curing or clogging of the extrusion orifice, to ensure sufficient cross-linking of the material matrix.
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