CN115891135A - Shape memory composite material and preparation method and application thereof - Google Patents
Shape memory composite material and preparation method and application thereof Download PDFInfo
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- 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
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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
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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
- B29C64/321—Feeding
- B29C64/336—Feeding of two or more materials
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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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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
- B29C64/171—Processes of additive manufacturing specially adapted for manufacturing multiple 3D objects
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a shape memory composite material and a preparation method and application thereof, wherein the shape memory composite material comprises a polymer matrix and a bracket structure arranged in the polymer matrix; the support structure is provided with a truss lattice structure, and the material of the support structure is a first polymer; the material of the polymer matrix is a second polymer; the glass transition temperature of the first polymer is larger than that of the second polymer, and the difference between the glass transition temperature of the first polymer and the glass transition temperature of the second polymer is larger than or equal to 40 ℃. According to the invention, the support structure with the truss lattice structure is embedded into the matrix as the reinforcing phase, and through the design of the support structure and the design and compounding of two polymers, the interface bonding force between the matrix and the reinforcing phase is good, the modulus of the shape memory composite material is obviously improved, the shape memory composite material has an excellent shape memory function and can bear large-degree deformation, and thus the wide application of the 4D printing technology based on the shape memory material in engineering is greatly expanded.
Description
Technical Field
The invention belongs to the technical field of 4D printing materials, and particularly relates to a shape memory composite material and a preparation method and application thereof.
Background
The 4D printing is the characteristic that the shape of a material/structure printed by 3D changes along with time under the stimulation of an external environment, and due to the fact that one dimension (time) is added, the shape of a 4D printing part is not static any more, but is presented in a controllable dynamic form, and the shape can be converted into a new shape in an expected mode under the excitation of the environment to meet new requirements. In other words, 4D printing is based on 3D printing, and is intelligently implanted into a part, so that the application prospect is very wide.
Most of the current 4D printing is realized based on the principle of polymer shape memory effect, i.e. mechanical deformation is performed on a polymer material at a high temperature (the polymer is in a rubbery state), cooling is performed under the condition of maintaining the constraint on deformation, the temperature of the polymer material is reduced (the polymer is in a glassy state), and the deformation of the material is substantially maintained after the constraint on the release; by reheating, the material releases the stress, achieving a recovery of the shape. Thus, the polymeric material is a natural shape memory material.
However, the current 4D printed shape memory polymer materials have a natural drawback that the elastic modulus of the polymer materials is very small at temperatures above their own glass transition temperature, and thus it is difficult to apply the polymer materials to a strong and stable structure. Therefore, it is an important research subject in the field of materials to improve the modulus of 4D printed shape memory polymer materials.
To overcome the natural drawback of low modulus of shape memory polymers, researchers have attempted to increase their modulus by means of composite materials. For example, CN109897375A discloses a high-strength flexible epoxy resin modified cyanate ester resin/carbon fiber composite shape memory material, which is formed by compounding a carbon fiber material reinforcing phase and a modified cyanate ester resin matrix, wherein the modified cyanate ester resin matrix comprises the following components: 2-4 parts of carboxyl-terminated liquid nitrile rubber, 2-5 parts of flexible epoxy resin and 8-12 parts of cyanate resin; wherein, the cyanate resin is matrix resin, the carboxyl-terminated liquid nitrile rubber and the flexible epoxy resin are toughening agents, the carbon fiber material is a reinforcing phase, and the carbon fiber material is formed by vacuum heating and curing, and accounts for 40-60% of the total mass of the shape memory material; the shape memory material has smooth surface, no obvious defect, high tensile strength, high tensile modulus, high shearing strength and high bending strength. CN111171520A discloses a modified carbon nanotube reinforced shape memory epoxy resin composite material, which is prepared by heating epoxy resin, a modified carbon nanotube and a curing agent under the vacuum condition in the presence of a catalyst; wherein the modified carbon nanotube is carbon nanotube powder with surface modified epoxy groups, and the addition amount is 0.05-1.5wt.%; the modified carbon nanotube reinforced shape memory epoxy resin composite material has good mechanical strength, toughness and shape memory performance. CN103897337A discloses a nano graphite sheet reinforced shape memory composite material, which comprises thermosetting resin, flake nano graphite reinforced material and curing agent, wherein the weight ratio of the thermosetting resin to the flake nano graphite reinforced material is 100 (0.5-4), and the weight ratio of the thermosetting resin to the curing agent is 100 (10-20); the shape memory composite material has an extremely wide temperature regulation range and shows good practical performance in the aspects of tensile strength, elastic modulus, shape memory performance and the like.
In general, a more common mode of modulus enhancement is to add a second phase with ultra-high modulus, such as carbon fiber, carbon nanotube, graphene, carbon black, ceramic sheet, etc., to the shape memory polymer. However, the reinforced phases and the polymer matrix have large differences in material properties and basically belong to different material categories, and the bonding force of the materials belongs to different categories, so that the interface bonding force between the materials is poor, the deformation of the composite material cannot be too large, or the falling of the reinforced phases is easy to occur; on the other hand, the reinforcing phase material is distributed in the matrix in a random mode, so that the shape memory performance of the shape memory polymer material is reduced, and the performance requirement of 4D printing is difficult to meet.
Therefore, the development of a material with good shape memory performance, high modulus and large deformation tolerance is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a shape memory composite material and a preparation method and application thereof, wherein the shape memory composite material has high modulus and excellent shape memory characteristics by introducing a support structure with a truss lattice structure and by the material design of the support structure and a polymer matrix, can bear large-degree deformation, and greatly expands the application of a 4D printing technology based on the shape memory material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a shape memory composite comprising a polymer matrix and a scaffold structure disposed in the polymer matrix; the support structure is provided with a truss lattice structure, and the material of the support structure is a first polymer; the material of the polymer matrix is a second polymer; the glass transition temperature of the first polymer is larger than that of the second polymer, and the difference between the glass transition temperature of the first polymer and the glass transition temperature of the second polymer is larger than or equal to 40 ℃.
In the shape memory composite material provided by the invention, the support structure with a truss lattice structure and high glass transition temperature is used as a reinforcing phase and embedded into the polymer matrix with low glass transition temperature, so that the modulus of the shape memory composite material is obviously improved; meanwhile, the reinforcing phase has a regular truss lattice structure, so that the shape memory composite material has excellent shape memory characteristics; moreover, the support structure and the polymer matrix are both polymer materials, and the interface bonding force between the matrix and the reinforcing phase is good, so that the shape memory composite material can bear large deformation. Therefore, the shape memory composite material has high modulus and excellent shape memory function and can deform to a large extent through the design of the support structure and the design and compounding of the two polymers, so that the wide application of the 4D printing technology based on the shape memory material in engineering is greatly expanded.
In the present invention, the material of the scaffold is a first polymer having a high glass transition temperature, preferably a glassy polymer having a high modulus at the temperature of use (e.g., room temperature). The material of the polymer matrix is a second polymer having a relatively low glass transition temperature, preferably rubbery at the use temperature (e.g., room temperature). Based on the screening and design of the first polymer and the second polymer with specific glass transition temperatures, the high-modulus glassy polymer is integrally embedded into the low-modulus rubbery polymer in a high-modulus and light-weight truss lattice structure, the formed shape memory composite can bear large deformation, the interfacial bonding force between the matrix and the reinforcing phase is high, and the support structure basically only elastically deforms in the deformation range set by the shape memory composite, so that the shape memory characteristic of the polymer matrix is not influenced, and the shape memory function of the shape memory composite is excellent.
In the present invention, the glass transition temperature (T) of the first polymer g1 ) Glass transition temperature (T) with a second polymer g2 ) The difference of (a) is not less than 40 ℃, for example, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃ or 140 ℃, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
Therefore, the shape memory composite material has a wider temperature regulation range and a wider deformation range, and the stent structure basically only deforms elastically in the deformation range, so that the shape memory function of the polymer matrix is not influenced/reduced, and the shape memory composite material has excellent shape memory characteristics. In particular, the shape memory composite material is at T g2 To T g1 The temperature range of (A) is in a rubber state, has excellent shape programming and memory capabilities and simultaneously hasAnd high modulus.
In the present invention, the term "modulus" refers to "elastic modulus" and "storage modulus" and, unless otherwise specified, refers to the modulus at room temperature (25 ℃ C.).
Preferably, the lattice structure is an octet-tress lattice structure.
Preferably, the cell members of the octet-tress truss lattice structure have a diameter of 0.2-2mm, such as 0.3mm, 0.5mm, 0.8mm, 1mm, 1.1mm, 1.3mm, 1.5mm, 1.7mm or 1.9mm, and specific values therebetween are not exhaustive, and for brevity and conciseness, the invention is not intended to be limited to the specific values included in the range, and more preferably 0.6-1.8mm.
Preferably, the volume percentage of the scaffold structure in the shape memory composite material is 3-30%, for example, 4%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 27% or 29%, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range, and more preferably 5-28%.
As a preferred technical scheme of the invention, the truss lattice structure is an octat-tress truss lattice structure (octagonal truss lattice structure), the size of the rod piece of the unit cell is determined by mechanical simulation calculation based on the mechanical property of the material, and the preferred diameter is 0.2-2mm, and further preferred is 0.6-1.8mm. Based on the geometric dimension design of the lattice structure of the truss (the dimension of the rod piece, the pore inside the unit cell; if the dimension of the rod piece is large, the pore inside the unit cell is reduced), the volume percentage of the support structure in the shape memory composite material can be adjusted, and then the shape memory composite material with different mechanical properties, deformation sizes and moduli is obtained.
In a preferred technical scheme, the support structure with the lattice structure of the octet-tress truss is designed and manufactured digitally by a computer, so that the geometric dimension of the support structure can be accurately controlled; because the scaffold structure and the polymer matrix form a solid structure with 100% of the volume, namely the shape memory composite material, after the scaffold structure is designed, boolean operation is carried out on the scaffold structure, and the rest structure after the scaffold structure is removed is the structure of the polymer matrix. According to the invention, the high-precision complex composite material structure (the structure of the support structure and the polymer matrix) designed based on a computer is prepared in a lossless manner by a 3D printing technology and is obtained after design, so that the shape memory composite material is precise and controllable in structure and can be customized in a differentiation manner according to actual requirements.
Preferably, the difference in glass transition temperature of the first polymer and the second polymer is from 40 to 130 ℃, further preferably from 50 to 100 ℃.
Preferably, the glass transition temperature of the first polymer is 40 to 190 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, and specific values therebetween, for reasons of space and brevity, the present invention is not exhaustive of the specific values included in the ranges, and more preferably 50 to 160 ℃.
Preferably, the first polymer includes any one of an acrylate polymer, an epoxy polymer, polysulfone, polycarbonate, and polyvinyl chloride, or a combination of at least two thereof, and is more preferably an acrylate polymer.
Preferably, the first polymer is a photo-curable acrylate polymer.
Preferably, the first polymer is a photo-curing acrylate polymer with a glass transition temperature of 50-60 ℃.
The first polymer is commercially available, and preferably, the first polymer is a photocurable polymer to facilitate 3D printing. Illustratively, the first polymer is Veroblue, is pale blue in color, has a glass transition temperature of about 58 ℃, is in a glassy state at room temperature, and has a relatively high modulus (elastic/storage modulus)
Preferably, the second polymer has a glass transition temperature of-10 ℃ to 80 ℃, for example, -5 ℃, 0 ℃, 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 75 ℃, and specific values therebetween, for reasons of space and brevity, the present invention is not exhaustive of the specific values included in the ranges, and further preferably-5 ℃ to 65 ℃.
Preferably, the second polymer comprises any one of acrylate polymer, polylactic acid, polystyrene and polyvinyl acetate or a combination of at least two of the above polymers, and is further preferably acrylate polymer.
Preferably, the second polymer is a photocurable acrylate polymer.
Preferably, the second polymer is a photocurable acrylate polymer having a glass transition temperature of-5 ℃ to 5 ℃.
The second polymer is commercially available, and preferably, the second polymer is a photocurable polymer, which facilitates 3D printing. Illustratively, the second polymer is Tangoblack +, black in color, has a glass transition temperature of about-0.5 ℃, is rubbery at room temperature, and has a low modulus (elastic modulus/storage modulus).
In a preferable technical scheme, the first polymer is a light-cured acrylate polymer Veroblue, the second polymer is a light-cured acrylate polymer Tangoblack +, the two polymers can be randomly distributed in space, and the interface bonding force between a support structure prepared from the two polymers and a polymeric matrix is good, so that the shape memory composite material has high modulus and excellent shape memory function, can bear large deformation, and expands the application of a 4D printing technology based on the shape memory material.
In another embodiment, the first polymer may be Polysulfone (PSF) having a glass transition temperature of about 190 ℃ and the second polymer may be polylactic acid having a glass transition temperature of about 60 ℃; the two polymers are compounded to be respectively used as a support structure and a polymer matrix, so that the shape memory composite material is in a rubbery state within the temperature range of 60-190 ℃, has excellent shape editing and memory functions, and has remarkably improved rubbery modulus.
In another embodiment, the first polymer may be polycarbonate having a glass transition temperature of about 120 ℃ and the second polymer may be polylactic acid having a glass transition temperature of about 60 ℃; the two polymers are compounded to be respectively used as a support structure and a polymer matrix, so that the shape memory composite material is in a rubbery state within the temperature range of 60-120 ℃, has excellent shape editing and memory functions, and has remarkably improved rubbery modulus.
Preferably, the elastic modulus of the first polymer > the elastic modulus of the second polymer.
Preferably, the elastic modulus of the first polymer is 500MPa or more, and may be 600MPa, 800MPa, 1000MPa, 1200MPa, 1500MPa, 1800MPa, 2000MPa, 2200MPa, 2500MPa, 2800MPa, 3000MPa, 3200MPa or 3500MPa, for example, and the specific values therebetween are not exhaustive, and for the sake of brevity and brevity, the invention is not intended to be exhaustive of the specific values included in the ranges, and more preferably 800 to 3000MPa.
Preferably, the elastic modulus of the second polymer is 100MPa or less, and may be, for example, 0.5MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa or 90MPa, and specific values therebetween are limited for the sake of brevity and brevity, and the invention is not exhaustive list of specific values included in the range, and more preferably 10MPa or less.
In a second aspect, the present invention provides a method of making a shape memory composite as described in the first aspect, the method comprising: and 3D printing the first polymer material and the second polymer material to obtain the shape memory composite material.
Preferably, the method of 3D printing is inkjet 3D printing.
Preferably, the preparation method specifically comprises: and respectively placing the first polymer material and the second polymer material in different printing channels, and carrying out ink-jet 3D printing on the basis of a preset graph structure to obtain the shape memory composite material.
The first polymer material may be understood as the starting material of the first polymer forming the scaffold structure and the second polymer material may be understood as the starting material of the second polymer forming the polymer matrix.
The method comprises the steps of placing a first polymer material and a second polymer material in different printing channels of a 3D printer, automatically slicing a 3D model and distributing spraying positions of different materials by printing software of the 3D printer based on an introduced 3D graph structure (a pre-designed support structure and a polymer matrix structure), moving a printer nozzle in a horizontal direction and spraying the polymer materials in the printing process, simultaneously carrying out curing (for example, carrying out photocuring by ultraviolet rays and the like), and printing, curing and stacking layer by layer in such a way until the printing design height is up to stop to obtain the shape memory composite material.
It should be noted that the shape memory composite material provided by the present invention is not limited to be prepared by the aforementioned preparation method.
Illustratively, the preparation method of the shape memory composite material further comprises the following steps: the shape memory composite material is obtained by first preparing (e.g., 3D printing preparation) a polymer matrix, then injecting a first polymer material into the internal voids of the polymer matrix and curing.
Illustratively, the preparation method of the shape memory composite material further comprises the following steps: the shape memory composite is obtained by first preparing (e.g., 3D printing) a scaffold, and then placing the scaffold in a second polymeric material and curing.
Preferably, the method of curing comprises photo-curing and/or thermal curing.
In a third aspect, the present invention provides a use of a shape memory composite material as described in the first aspect in a 4D printed material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the shape memory composite material provided by the invention, the support structure with the truss lattice structure is used as a reinforcing phase to be embedded into the matrix, and through the design of the support structure and the design and compounding of two polymers, the interface bonding force between the matrix and the reinforcing phase is good, the modulus of the shape memory composite material is obviously improved, the shape memory composite material has an excellent shape memory function and can bear large-degree deformation, and thus the wide application of the 4D printing technology based on the shape memory material in engineering is greatly expanded.
(2) According to the invention, through size design and optimization of the lattice structure of the truss, the volume percentage of the support structure in the shape memory composite material can be adjusted, so that the shape memory composite material with different mechanical properties, deformation sizes and moduli is obtained, the elastic modulus of the shape memory composite material is designed and customized within the range of 22.4-54.1MPa, and the requirement on differentiated mechanical properties is met.
Drawings
FIG. 1 is a graph of loss tangent versus temperature for a first polymer and a second polymer in one embodiment;
FIG. 2 is a graph of storage modulus versus temperature for a first polymer and a second polymer in one embodiment;
FIG. 3 is a schematic structural view of a stent structure according to an embodiment;
FIG. 4 is a schematic diagram of the structure of a polymer matrix in one embodiment;
FIG. 5 is a schematic diagram of the structure of a shape memory composite in one embodiment;
FIG. 6 is a pictorial view of the shape memory composite provided in example 1;
FIG. 7 is a stress-strain plot of the shape memory material provided in comparative example 1;
FIG. 8 is a stress-strain plot of the shape memory composite provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
"optionally" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
In the present invention, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features for distinguishing between descriptive features, non-sequential, non-trivial and non-trivial. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
Reference throughout this specification to "one embodiment," "some embodiments," "exemplary," "specific examples" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this document, schematic representations of the above terms are not necessarily intended to refer to the same embodiment or example.
In one embodiment, the first polymer is a photocurable acrylate polymer, veroblue, with a light blue color, and the second polymer is a photocurable acrylate polymer, tangoblack +, with a black color.
Dynamic thermo-mechanical analysis (DMA, Q800, TA) was performed on Veroblue and Tangoblack + first polymer to obtain a loss tangent-temperature curve as shown in FIG. 1, and it can be seen from FIG. 1 that Veroblue has a glass transition temperature of about 58 ℃ and is in a glassy state at room temperature; the glass transition temperature of Tangoblack + is about-0.5 deg.C, which is rubbery at room temperature.
Dynamic thermomechanical analysis (DMA) is carried out on the Veroblue polymer and the Tangoblack + polymer to obtain a storage modulus-temperature curve graph as shown in figure 2, and the Veroblue has a modulus of nearly 1000MPa at room temperature as can be seen from figure 2; tangoblack + has a modulus at room temperature of less than 1MPa.
In the following embodiments of the invention, the first polymer used is Veroblue and the second polymer is Tangoblack +.
In one embodiment, the scaffold structure in the shape memory composite material is an octet-tress truss lattice structure, the structural diagram of which is shown in fig. 3, and the unit cell geometric parameters (the size of the rods) of the octet-tress truss lattice structure are determined by mechanical simulation calculation based on the mechanical properties of the material.
In one embodiment, the shape memory composite material is a cubic structure, wherein the embedded scaffold structure is an octet-truss lattice structure shown in fig. 3, and boolean operations are performed on the cubic structure, and the remaining structure after the scaffold structure is removed is the structure of the polymer matrix, and a schematic structural diagram of the structure is shown in fig. 4. The lattice structure of the octet-tress truss shown in FIG. 3 is combined with the polymer matrix shown in FIG. 4 to form a 100% solid cube, which constitutes the shape memory composite of the present invention, and the schematic structure thereof is shown in FIG. 5.
In the following embodiments of the present invention, the scaffold structures have the lattice structure of the octet-tress truss shown in fig. 3, and the volume percentage of the scaffold structure in the shape memory composite material is adjusted by designing the diameters of the unit cell rods (the diameter of the rod is increased, the pores inside the unit cell are reduced, and the volume percentage of the scaffold structure is increased).
In one embodiment, the shape memory composite material is prepared by an inkjet 3D printing method, and specifically comprises: designing a support structure and a polymer matrix structure through computer drawing software to generate an stl format file; importing stl format files into printing software of a 3D printer, then giving material attributes of each component, automatically slicing a three-dimensional model by the software, distributing the spraying positions of each polymer material, moving a printer nozzle in the horizontal direction to spray the polymer materials in the printing process, simultaneously carrying out photocuring by ultraviolet rays, and printing photocuring and stacking layer by layer according to the mode until the designed height is printed.
Example 1
A shape memory composite material and a preparation method thereof, the structure schematic diagram of the shape memory composite material is shown in figure 5, the shape memory composite material comprises a polymer matrix and a bracket structure arranged in the polymer matrix, and the structure schematic diagrams of the polymer matrix and the bracket structure are respectively shown in figure 4 and figure 3; the support structure is an octet-tress truss lattice structure, and the diameter of the unit cell rod piece is 1mm; the volume percentage content of the support structure in the shape memory composite material is 11.4%. The material of the scaffold structure is a first polymer Veroblue, and the material of the polymer matrix is a second polymer Tangoblack +.
The preparation method of the shape memory composite material comprises the following steps:
the preparation was carried out by inkjet 3D printing using a 3D printer (Connex 350 from Stratasys corporation), simultaneously printing the two above mentioned polymeric materials in one piece, specifically: the Veroblue material and the Tangoblack + material are respectively arranged in different printing channels of a 3D printer, based on a leading-in preset 3D graph structure, printing software automatically slices a 3D model and distributes the spraying positions of different materials, a printer nozzle moves in the horizontal direction to spray a polymer material in the printing process, ultraviolet light curing is carried out simultaneously, printing, curing and stacking are carried out layer by layer until the height of the printed design is stopped, and the shape memory composite material is obtained.
The physical diagram of the shape memory composite material provided in this example is shown in fig. 6, where the dark region is the polymer matrix (second polymer Tangoblack +), and the light region is the externally shown scaffold (first polymer Veroblue).
Comparative example 1
A shape memory material which differs from example 1 only in that it does not contain a scaffold structure, i.e. is only a shape memory material consisting of the second polymer Tangoblack +.
The mechanical properties of the shape memory composite materials provided in example 1 and comparative example 1 were examined by the following specific methods:
the stress-strain curve of the material to be tested is tested by adopting a Zwick/Roell Z020 universal material testing machine, the stress-strain curve graph of the shape memory material in the comparative example 1 is shown in figure 7, the stress-strain curve is a stress-strain curve of a second polymer Tangoblack + at room temperature (25 ℃), and the elastic modulus of the material at the room temperature is 0.37MPa according to the slope of the curve.
The stress-strain curve of the shape memory composite provided in example 1 is shown in fig. 8, where different curves in fig. 8 represent the total amount of strain loaded in different experiments, and the total strain increases sequentially when multiple experiments are performed on the same composite sample at room temperature (25 ℃), with cyclic loading-unloading. From FIG. 8, it can be calculated that the elastic modulus of the shape memory composite material at room temperature is 26.6MPa, which is about 70 times the elastic modulus of the Tangoblack + material at room temperature.
Meanwhile, the curves in fig. 8 all have a horizontal portion at the end of the unloading section, coinciding with the X-axis. This is due to the viscoelasticity of the first polymer, veroblue, as a scaffold structure. Due to the visco-elastic property, the Veroblue polymer material has a hysteresis effect in deformation, and the horizontal segment of the curve coincident with the X axis is not caused by plasticity. The residual deformation can be quickly eliminated only by increasing the temperature, and particularly, the residual deformation of the material can be eliminated instantly by heating the temperature of the shape memory composite material to be higher than the glass transition temperature of the Veroblue material, so that the shape memory composite material can be quickly recovered to the initial size without remaining permanent residual deformation.
Therefore, the shape memory composite material provided by the invention is wholly in a rubber state at room temperature (25 ℃), and has the characteristic of high elasticity; meanwhile, the elastic modulus is far higher than that of a matrix material Tangoblack +, so that the application space of the matrix material Tangoblack + at room temperature (rubber state) is greatly expanded.
Since the volume percentage of the scaffold structure in the shape memory composite material provided in example 1 is only 11.4%, the volume percentage is low, therefore, the original characteristics of the polymer matrix Tangoblack + material can be well preserved, and the shape memory composite material is in a rubbery state at room temperature and has high elasticity and shape programming capability. Meanwhile, the shape memory composite material can realize the effect of enhancing the elastic modulus of the original matrix phase Tangoblack + by 70 times at room temperature with extremely low volume fraction of the enhanced phase.
In addition, the shape memory composite material structure can obtain shape fixation below 0 ℃ after being deformed at room temperature, once the temperature is raised to the room temperature again, the 4D printed shape memory composite material structure can be restored to the original shape, and the rubber state modulus is ultrahigh, so that the shape memory composite material structure can be widely applied to application scenes with certain constrained deformation.
Examples 2 to 5
A shape memory composite material, which is different from example 1 only in that the unit cell rods of the lattice structure of the octet-tress truss as a scaffold structure have different diameters, thereby making the volume percentage of the scaffold structure in the shape memory composite material different, as shown in table 1; other structures, materials and preparation methods are the same as those of example 1. The shape memory composite materials provided in examples 2 to 5 were subjected to modulus test in the same manner as in example 1, and the data are shown in Table 1.
TABLE 1
| Rod diameter (mm) | Percent volume of scaffold (%) | Modulus of elasticity (MPa) |
| 0.8 | 7.5 | 22.4 |
| 1 | 11.4 | 26.6 |
| 1.2 | 15.9 | 32.6 |
| 1.4 | 20.8 | 41.6 |
| 1.6 | 26.2 | 54.1 |
The performance test results of the embodiments 1 to 5 show that the shape memory composite material with a specific structure is formed by using two polymer materials, namely Veroblue and Tangoblack + by a 3D printing method, and the novel shape memory composite material has higher mechanical properties such as modulus, hardness and the like in a rubber state (at normal temperature), and simultaneously has excellent properties such as high elasticity, shape programmability and the like when the polymer is in the rubber state. Meanwhile, through the geometric parameter design of the lattice structure of the octet-tress truss in the support structure, the shape memory composite material with different reinforced phase volume fractions can be obtained, so that the mechanical properties of the shape memory composite material, such as modulus and the like, can be regulated and controlled, the elastic modulus is 22.4-54.1MPa, and the performance requirements on the 4D printing material under different application scenes are met.
The applicant states that the present invention is illustrated by the above examples of the shape memory composite material of the present invention and the preparation method and application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A shape memory composite, comprising a polymer matrix and a scaffold structure disposed in the polymer matrix;
the support structure is provided with a truss lattice structure, and the material of the support structure is a first polymer;
the material of the polymer matrix is a second polymer;
the glass transition temperature of the first polymer is larger than that of the second polymer, and the difference between the glass transition temperature of the first polymer and the glass transition temperature of the second polymer is larger than or equal to 40 ℃.
2. The shape memory composite of claim 1, wherein the truss lattice structure is an octet-tress truss lattice structure;
preferably, the unit cell rods of the octet-tress truss lattice structure have a diameter of 0.2 to 2mm, more preferably 0.6 to 1.8mm.
3. Shape memory composite material according to claim 1 or 2, characterized in that the volume percentage of the scaffold structure in the shape memory composite material is 3-30%, preferably 5-28%.
4. Shape memory composite material according to any of claims 1 to 3, characterized in that the difference in glass transition temperature of the first polymer and the second polymer is 40-130 ℃, preferably 50-100 ℃.
5. Shape memory composite material according to any of claims 1 to 4, characterized in that the first polymer has a glass transition temperature of 40 to 190 ℃, preferably 50 to 160 ℃;
preferably, the first polymer comprises any one or a combination of at least two of acrylate polymer, epoxy polymer, polysulfone, polycarbonate and polyvinyl chloride, and is preferably acrylate polymer;
preferably, the first polymer is a photo-curable acrylate polymer;
preferably, the first polymer is a light-cured acrylate polymer, and the glass transition temperature of the light-cured acrylate polymer is 50-60 ℃.
6. Shape memory composite material according to any of claims 1 to 5, characterized in that the second polymer has a glass transition temperature of-10 ℃ to 80 ℃, preferably-5 ℃ to 65 ℃;
preferably, the second polymer comprises any one of or a combination of at least two of acrylate polymer, polylactic acid, polystyrene and polyvinyl acetate, and is preferably acrylate polymer;
preferably, the second polymer is a photocurable acrylate polymer;
preferably, the second polymer is a photocurable acrylate polymer having a glass transition temperature of-5 ℃ to 5 ℃.
7. The shape memory composite of any one of claims 1-6, wherein the elastic modulus of the first polymer > the elastic modulus of the second polymer;
preferably, the elastic modulus of the first polymer is more than or equal to 500MPa, and further preferably 800-3000MPa;
preferably, the elastic modulus of the second polymer is equal to or less than 100MPa, and more preferably equal to or less than 10MPa.
8. A method of preparing a shape memory composite as claimed in any one of claims 1 to 7, wherein the method of preparation comprises: and 3D printing the first polymer material and the second polymer material to obtain the shape memory composite material.
9. The method of manufacturing according to claim 8, wherein the method of 3D printing is inkjet 3D printing;
preferably, the preparation method specifically comprises: and respectively placing the first polymer material and the second polymer material in different printing channels, and carrying out ink-jet 3D printing on the basis of a preset graph structure to obtain the shape memory composite material.
10. Use of a shape memory composite according to any one of claims 1 to 7 in a 4D printed material.
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| CN117087287A (en) * | 2023-07-28 | 2023-11-21 | 西北工业大学 | 4D printing reusable composite material energy absorption structure and preparation and reuse method |
| WO2024109838A1 (en) * | 2022-11-24 | 2024-05-30 | 中国科学院深圳先进技术研究院 | Shape memory composite material, preparation method therefor and use thereof |
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| CN113143536B (en) * | 2016-05-16 | 2022-08-30 | 万能医药公司 | Opening support |
| US11059948B2 (en) * | 2019-05-24 | 2021-07-13 | The Florida International University Board Of Trustees | Shape memory-based self-healing polymer composite reinforced with graphene foam |
| CN115891135A (en) * | 2022-11-24 | 2023-04-04 | 中国科学院深圳先进技术研究院 | Shape memory composite material and preparation method and application thereof |
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| WO2024109838A1 (en) * | 2022-11-24 | 2024-05-30 | 中国科学院深圳先进技术研究院 | Shape memory composite material, preparation method therefor and use thereof |
| CN117087287A (en) * | 2023-07-28 | 2023-11-21 | 西北工业大学 | 4D printing reusable composite material energy absorption structure and preparation and reuse method |
| CN117087287B (en) * | 2023-07-28 | 2024-06-11 | 西北工业大学 | 4D printing reusable composite material energy absorption structure and preparation and reuse method |
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