CN114015225A - Magnetic-drive shape memory material and preparation method and application thereof - Google Patents
Magnetic-drive shape memory material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114015225A CN114015225A CN202111164585.7A CN202111164585A CN114015225A CN 114015225 A CN114015225 A CN 114015225A CN 202111164585 A CN202111164585 A CN 202111164585A CN 114015225 A CN114015225 A CN 114015225A
- Authority
- CN
- China
- Prior art keywords
- shape memory
- particles
- magnetic
- memory polymer
- dimensional lattice
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012781 shape memory material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000431 shape-memory polymer Polymers 0.000 claims abstract description 88
- 230000005291 magnetic effect Effects 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 39
- 239000006249 magnetic particle Substances 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 238000010146 3D printing Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 230000009477 glass transition Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 10
- 239000004416 thermosoftening plastic Substances 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 31
- 238000003756 stirring Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000005284 excitation Effects 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 5
- 230000005294 ferromagnetic effect Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000001931 thermography Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000008672 reprogramming Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- B29C64/379—Handling of additively manufactured objects, e.g. using robots
-
- 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
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Robotics (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
Abstract
The invention provides a magnetic drive shape memory material and a preparation method and application thereof, wherein the magnetic drive shape memory material is prepared by the following steps: (a) uniformly mixing shape memory polymer particles with a solvent to obtain a shape memory polymer solution; (b) adding the magnetic particles into the shape memory polymer solution, and uniformly mixing to obtain the shape memory polymer solution with the magnetic particles; (c) and adding nano silicon dioxide into the shape memory polymer solution with the magnetic particles, and uniformly mixing to obtain the magnetic drive shape memory material. The invention provides a high-stretchability magnetic-drive shape-based polymer with a three-dimensional lattice structure, which has high stretchability, can be used for 3D printing, is simple and convenient in preparation method, and is easy to popularize and apply on a large scale.
Description
Technical Field
The invention relates to the technical field of mechanical metamaterials of three-dimensional lattice structures, in particular to a magnetic-drive shape memory material and a preparation method and application thereof.
Background
Soft materials with three-dimensional free structures and high stretchability are highly desirable in many engineering applications, from bumper modulators, soft robotics to stretchable electronics, however, the manufacturing process and basic mechanisms are largely elusive. By means of additive manufacturing technology, projection micro-stereolithography technology and post-processing, a microstructured metamaterial made of a highly stretchable elastomer is achieved. In sharp contrast to the power law of modulus of existing engineering materials. Under large strain compression, they exhibit tunable negative stiffness, thereby achieving ultra-high energy absorption efficiency. In order to take advantage of its extraordinary stretchability and microstructure.
Shape Memory Polymers (Shape Memory Polymers) are a new class of smart materials. Can be subjected to shape change under the action of external force at programmable temperature. Because of its advantages of small density, low cost, good biocompatibility, etc., the shape memory polymer is widely used in the fields of aerospace, biomedical, garment manufacturing, electronic instruments, etc. However, the inherent material deficiencies of shape memory polymers have limited their development and use in other areas. In order to improve the mechanical properties of shape memory polymer materials, researchers at home and abroad have paid more attention to the research on shape memory polymer composite materials and composite structures in recent years.
The shape memory mechanism of shape-based polymers is as follows: during the whole shape memory process, when the temperature is higher than the glass transition temperature of the material, the molecular chain segment is activated, the reversible phase is converted from a glass state to a rubber state, and the reversible phase can be greatly deformed by applying a load. On the basis, the temperature is suddenly reduced to be lower than the glass transition temperature while keeping the load unchanged, the reversible phase is converted into a glass state from a rubber state, and the internal polymer unit is fixed. The load is unloaded, and the deformed shape of the macromolecule is fixed due to the cross-linking action among the molecular chain segments. Therefore, when the temperature rises again, the reversible phase is converted into the rubber state again, the three-dimensional structure of the polymer is activated again, the internal consolidation stress is gradually released, the deformation of the polymer material is gradually recovered, and the polymer material is finally recovered to the initial form to realize the shape memory function.
The magnetic type shape memory polymer is a polymer which is added with magnetic particles to make the magnetic type shape memory polymer have magnetism, and the principle is that the magnetic particles in the material move according to the change of the external magnetic field condition under the drive of the external magnetic field and the electromagnetic field, and in the moving process, the particles collide to generate heat, and when the temperature is raised to the glass transition temperature of the shape memory polymer, the shape of the material is recovered. The patent application numbers are: 202110246270.0 discloses a shape memory recovery method of a thermo-adaptive shape memory polymer, which only realizes the self-unfolding/self-folding function under the condition of heating stimulation (higher than the glass transition temperature) and improves the application range of the shape memory polymer, but the deformation of the shape memory polymer is not controlled by the magnetic effect. The patent application numbers are: 201510623550.3 patent of invention-a transfer printing method with shape memory effect-utilizes shape memory polymer containing magnetic nanoparticles, functional units and a mold with a surface having a concave microstructure, and selectively transfers the functional units to a flexible substrate by applying steps of uniform pressure and radio frequency electric field to the shape memory polymer, belonging to the technical field of engineering materials, flexible electronic preparation and mechanical experimental equipment. It does not mention a shape memory polymer system with both magnetic particles and high tensile strength, its preparation process and application. At present, the conventional preparation method of the shape-based polymer containing the magnetic particles has the disadvantages of complex process, difficult product quality control, low tensile strength and difficult application to 3D printing, so that the development of a novel shape-based polymer material containing the magnetic particles is urgently needed.
Disclosure of Invention
The invention aims to provide a magnetic-drive shape memory material, a preparation method and application thereof, and aims to solve the problems that the existing material is complex in preparation process, unsatisfactory in tensile strength and difficult to prepare a three-dimensional lattice structure with high tensile property.
The technical scheme of the invention is as follows: a magnetically actuated shape memory material prepared by the method comprising:
(a) uniformly mixing shape memory polymer particles with a solvent to obtain a shape memory polymer solution;
(b) adding the magnetic particles into the shape memory polymer solution, and uniformly mixing to obtain the shape memory polymer solution with the magnetic particles;
(c) and adding nano silicon dioxide into the shape memory polymer solution with the magnetic particles, and uniformly mixing to obtain the magnetic drive shape memory material.
The shape memory polymer particles are at least one of epoxy-based shape memory polymers, cyanate-based shape memory polymers, polyimide-based shape memory polymers, styrene-based shape memory polymers, and ether block copolymer polyurethane thermoplastic shape memory polymers.
The solvent is at least one of N, N '-dimethylacetamide, N' -dimethylformamide and tetrahydrofuran.
The magnetic particles are at least one of ferroferric oxide particles and rubidium, iron and boron particles.
The mass ratio of the shape memory polymer particles to the solvent is 1: 4-6, wherein the mass ratio of the shape memory polymer particles, the magnetic particles and the nano silicon dioxide is 1: 0.25-2.1 g: 1.05-2.73. The nanosilica occupies 2% of the total mass of the material.
A preparation method of a magnetic drive shape memory material comprises the following steps:
(a) uniformly mixing shape memory polymer particles with a solvent to obtain a shape memory polymer solution;
(b) adding the magnetic particles into the shape memory polymer solution, and uniformly mixing to obtain the shape memory polymer solution with the magnetic particles;
(c) and adding nano silicon dioxide into the shape memory polymer solution with the magnetic particles, and uniformly mixing to obtain the magnetic drive shape memory material.
The shape memory polymer particles are at least one of epoxy-based shape memory polymers, cyanate-based shape memory polymers, polyimide-based shape memory polymers, styrene-based shape memory polymers and ether block copolymer polyurethane thermoplastic shape memory polymers; the solvent is at least one of N, N '-dimethylacetamide, N' -dimethylformamide and tetrahydrofuran; the magnetic particles are at least one of ferroferric oxide particles and rubidium, iron and boron particles; the mass ratio of the shape memory polymer particles to the solvent is 1: 4-6, wherein the mass ratio of the shape memory polymer particles, the magnetic particles and the nano silicon dioxide is 1: 0.25-2.1 g: 1.05-2.73.
The magnetic drive shape memory material is applied to 3D printing materials.
The application of the magnetic drive shape memory material in a three-dimensional lattice structure. Further, the magnetic drive shape memory material is used for manufacturing a telescopic three-dimensional lattice structural component.
A shape memory recovery method of a three-dimensional lattice structure comprises the following steps:
(a) 3D printing is carried out by utilizing the magnetic drive shape memory material to manufacture a three-dimensional lattice structural component; placing the component in an alternating magnetic field, enabling the component to reach a temperature higher than the glass transition temperature by utilizing the magnetocaloric effect, then applying a specific magnetic field to the three-dimensional lattice structural component to cause the structure of the component to deform, keeping the applied magnetic field to enable the three-dimensional lattice structural component to lock the shape above the glass transition temperature, and then cooling to room temperature to obtain the three-dimensional lattice structural component with a temporary shape;
(b) and continuously applying an alternating magnetic field to the three-dimensional lattice structural component with the temporary shape, heating to a temperature above the glass transition temperature, recovering the initial structure of the three-dimensional lattice structural component, and then cooling to room temperature.
The invention provides a magnetic drive shape-based polymer with a high-scalability three-dimensional lattice structure, which has the characteristics of integration, reprogramming, no tether, quickness, reversible driver and shape locking. The shape memory polymer is an amorphous shape memory polymer matrix composed of magnetic particles and nano silicon dioxide, has high stretchability, can be used for 3D printing, is simple and convenient in preparation method, and is easy to popularize and apply on a large scale.
The integrated multi-functional shape manipulation provided by the material of the present invention can be used in a wide range of new applications, including soft-grippers for reloading, reconfigurable deformable antennas and sequential logic circuits for digital computation. The flexible magnetic material is applied to a highly-telescopic three-dimensional lattice structure, the superstructure has multiple functions derived from complex shape changes due to magnetic effects, can be applied to jumping mechanical metamaterials, can further reconstruct soft electronic devices by considering program soft body deformation and rigid body rotation characteristics of the robot under different terrains, can be further made into a small robot which crawls, rolls, captures fast moving objects and transmits multi-modes of drug dosage, programs the robot, and is further applied to the fields of aerospace and biomedical science.
Drawings
FIG. 1 is a schematic representation of a homogeneous shape memory polymer liquid.
FIG. 2 is a homogeneous shape memory polymer solution containing magnetic particles and nanosilica.
FIG. 3 is a test piece prepared using the material of the present invention.
FIG. 4 is a schematic diagram of the lattice structure of the present invention.
FIG. 5 is a Lorentz field emission scanning electron micrograph of the test piece prepared in example 1: (a) amplifying by 1.00 Kv; (b) amplification of 10.00 kV.
FIG. 6 is a diagram showing a shape memory recovery process of the test piece prepared in example 1. (a) Preparing a test piece; (b) bending and stretching the test piece at high temperature and suddenly cooling to room temperature; (c) heating again to recover the shape of the test piece; (d) stretching the test piece at high temperature and suddenly cooling to room temperature; (e) the temperature was again raised to recover the shape of the test piece.
FIG. 7 is a graph of infrared thermal imaging of the material of the present invention: (a) a shape memory polymer; (b) an infrared thermal imaging graph of a shape memory polymer containing 15% ferroferric oxide; (c) and (3) infrared thermal imaging of the shape memory polymer containing 30% ferroferric oxide.
FIG. 8 is an experimental operating environment diagram of the apparatus for alternating magnetic field according to the present invention.
Fig. 9 is a printing process and equipment diagram of 3D direct write printing of the present invention.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
Example 1:
(a) 10g of the MM4520 material, 50g N, N' -dimethylacetamide solvent (DMAC) as ether block copolymer polyurethane thermoplastic shape memory polymer particles were mixed thoroughly at room temperature, sealed with a cling film, and left to stand for 48 hours. And uniformly stirring the solution after standing for 48 hours, then pouring the solution into a planetary stirrer, stirring the solution twice at the rotating speed of 2000r for 5 minutes, and removing bubbles for 1 minute. The stirred solution was examined until stirred to a uniform viscous liquid, as shown in fig. 1.
(b) Ferromagnetic tetraoxide particles (9 g) were added at a ratio of 15%, and stirring was continued for 2 minutes with a planetary stirrer, and defoaming was carried out for 1 minute. A uniform black shiny viscous liquid was obtained.
(c) 2% of nanosilica (99.5%, 15 ± 5nm, 1.38 g) was added on the basis of the total mass, and stirred manually for 1 minute. The mixture was stirred for 2 minutes by a planetary stirrer 2000r, and then defoamed for 1 minute as shown in FIG. 2. Preparing a test piece, placing the test piece on a glass plate, and baking the test piece for 24 hours in a constant-temperature drying box at 70 degrees, as shown in figure 3. And then preparing a high-telescopic three-dimensional lattice structure test piece by using a 3D printer.
Example 2:
(a) 10g of the MM4520 material, 50g N, N' -dimethylacetamide solvent (DMAC) as ether block copolymer polyurethane thermoplastic shape memory polymer particles were mixed thoroughly at room temperature, sealed with a cling film, and left to stand for 48 hours. And uniformly stirring the solution after standing for 48 hours, then pouring the solution into a planetary stirrer, stirring the solution twice at the rotating speed of 2000r for 5 minutes, and removing bubbles for 1 minute. The stirred solution was checked until stirred to a homogeneous viscous liquid.
(b) Ferroferric oxide magnetic particles (18 g) with the proportion of 30 percent are added, the mixture is stirred for 2 minutes by a planetary stirrer, and bubbles are removed for 1 minute. A uniform black shiny viscous liquid was obtained.
(c) 2% of nanosilica (99.5%, 15 ± 5nm, 1.56 g) was added on the basis of the total mass, and stirred manually for 1 minute. The mixture was stirred for 2 minutes by a planetary stirrer 2000r, and then defoamed for 1 minute. Preparing a test piece, putting the test piece into a glass plate, and baking for 24 hours in a constant-temperature drying box at 70 degrees. And then preparing a high-telescopic three-dimensional lattice structure test piece by using a 3D printer.
The prepared test piece was characterized, as shown in fig. 5 to 7, by placing the test piece in an alternating magnetic field coil, applying a current of 300.8A, and setting the frequency at 163 kHz. The temperature rise was measured by infrared thermal Imaging (IRT), and the present invention used a control test in which the temperature rise of the test pieces of examples 1 and 2 was compared with the shape memory polymer containing no magnetic particles.
Example 3
(a) 10g of the MM4520 material, 50g N, N' -dimethylacetamide solvent (DMAC) as ether block copolymer polyurethane thermoplastic shape memory polymer particles were mixed thoroughly at room temperature, sealed with a cling film, and left to stand for 48 hours. And uniformly stirring the solution after standing for 48 hours, then pouring the solution into a planetary stirrer, stirring the solution twice at the rotating speed of 2000r for 5 minutes, and removing bubbles for 1 minute. The stirred solution was checked until stirred to a homogeneous viscous liquid.
(b) Ferromagnetic tetraoxide particles (3 g) at a ratio of 5% were added, and stirring was continued for 2 minutes with a planetary stirrer, and defoaming was carried out for 1 minute. A uniform black shiny viscous liquid was obtained.
(c) 2% of nanosilica (99.5%, 15 ± 5nm, 1.26 g) was added on the basis of the total mass, and stirred manually for 1 minute. The mixture was stirred for 2 minutes by a planetary stirrer 2000r, and then defoamed for 1 minute. Preparing a test piece, putting the test piece into a glass plate, and baking for 24 hours in a constant-temperature drying box at 70 degrees. And then preparing a high-telescopic three-dimensional lattice structure test piece by using a 3D printer. It was tested to have similar properties to the material of example 1.
Example 4
(a) 10g of the ether block copolymer polyurethane thermoplastic shape memory polymer particles (MM 4520) material, 50g N, N' -dimethylacetamide solvent (DMAC) was mixed thoroughly at room temperature, sealed with a cling film, and allowed to stand for 48 hours. And uniformly stirring the solution after standing for 48 hours, then pouring the solution into a planetary stirrer, stirring the solution twice at the rotating speed of 2000r for 5 minutes, and removing bubbles for 1 minute. The stirred solution was checked until stirred to a homogeneous viscous liquid.
(b) Ferromagnetic tetraoxide particles (12 g) at a ratio of 20% were added, and stirring was continued for 2 minutes with a planetary stirrer, and defoaming was carried out for 1 minute. A uniform black shiny viscous liquid was obtained.
(c) On the basis of the total mass, 3% of nanosilica (99.5%, 15 ± 5nm, 2.16 g) was added and stirred manually for 1 minute. The mixture was stirred for 2 minutes by a planetary stirrer 2000r, and then defoamed for 1 minute. Preparing a test piece, putting the test piece into a glass plate, and baking for 24 hours in a constant-temperature drying box at 70 degrees. It was tested to have similar properties to the material of example 1.
Example 5
(a) 10g of the ether block copolymer polyurethane thermoplastic shape memory polymer particles (MM 4520) material, 50g N, N' -dimethylacetamide solvent (DMAC) was mixed thoroughly at room temperature, sealed with a cling film, and allowed to stand for 48 hours. And uniformly stirring the solution after standing for 48 hours, then pouring the solution into a planetary stirrer, stirring the solution twice at the rotating speed of 2000r for 5 minutes, and removing bubbles for 1 minute. The stirred solution was checked until stirred to a homogeneous viscous liquid.
(b) Ferromagnetic particles (9 g) at a ratio of 15% were added, and rubidium, iron and boron particles (2000 mesh, 3 g) at a ratio of 5% were added, and stirring was continued for 2 minutes by a planetary stirrer, and defoaming was carried out for 1 minute. A uniform black shiny viscous liquid was obtained.
(c) 2% of nanosilica (99.5%, 15 ± 5nm, 1.44 g) was added on the basis of the total mass, and stirred manually for 1 minute. The mixture was stirred for 2 minutes by a planetary stirrer 2000r, and then defoamed for 1 minute. Preparing a test piece, putting the test piece into a glass plate, and baking for 24 hours in a constant-temperature drying box at 70 degrees. It was tested to have similar properties to the material of example 1.
Example 6
(a) 10g of the ether block copolymer polyurethane thermoplastic shape memory polymer particles (MM 4520) material, 50g N, N' -Dimethylformamide (DMF) solvent were mixed thoroughly at room temperature, sealed with a cling film, and left to stand for 48 hours. And uniformly stirring the solution after standing for 48 hours, then pouring the solution into a planetary stirrer, stirring the solution twice at the rotating speed of 2000r for 5 minutes, and removing bubbles for 1 minute. The stirred solution was checked until stirred to a homogeneous viscous liquid.
(b) Ferromagnetic particles (9 g) at a ratio of 15% were added, and rubidium, iron and boron particles (2000 mesh, 3 g) at a ratio of 5% were added, and stirring was continued for 2 minutes by a planetary stirrer, and defoaming was carried out for 1 minute. A uniform black shiny viscous liquid was obtained.
(c) 2% of nanosilica (99.5%, 15 ± 5nm, 1.44 g) was added on the basis of the total mass, and stirred manually for 1 minute. The mixture was stirred for 2 minutes by a planetary stirrer 2000r, and then defoamed for 1 minute. Preparing a test piece, putting the test piece into a glass plate, and baking for 24 hours in a constant-temperature drying box at 70 degrees. It was tested to have similar properties to the material of example 1.
Example 7: a method of shape memory recovery of a magnetic material comprising the steps of:
(a) 3D printing is carried out on the magnetic drive shape memory material in the embodiment 1 to manufacture a magnetic material part; placing the component in an alternating magnetic field, the frequency of the applied alternating magnetic field being: 162-163 kH, the current is: 296.0A, magnetic field coil: 5 turns, about 0.1 meter in length, according to the formula H = N × I/Le, where H is the magnetic field strength in a/m; n is the number of turns of the excitation coil; i is the excitation current (measured value) in units of a; le is the effective magnetic path length of the test sample in m. The magnetic field strength is obtained by calculation as follows: 14800 the arrangement of the apparatus for alternating magnetic field is shown in FIG. 8.
(b) The method comprises the steps of utilizing a magnetocaloric effect to enable the three-dimensional lattice structural component to reach a temperature higher than a glass transition temperature, applying a specific magnetic field to the three-dimensional lattice structural component to cause structural deformation of the three-dimensional lattice structural component, keeping the applied magnetic field to enable the three-dimensional lattice structural component to lock the shape above the glass transition temperature, and then cooling to room temperature to obtain the three-dimensional lattice structural component with a temporary shape;
(c) and continuously applying an alternating magnetic field to the three-dimensional lattice structural component with the temporary shape, heating to a temperature above the glass transition temperature, recovering the initial structure of the three-dimensional lattice structural component, and then cooling to room temperature.
Example 8: a method of shape memory recovery of a magnetic material comprising the steps of:
(a) 3D printing is carried out on the magnetic drive shape memory material in the embodiment 1 to manufacture a manufactured film and manufacture a magnetic material part; placing the part in boiling water, maintaining the bend, tensile loading, the temperature of which has reached the glass transition temperature, allowing the temperature to drop suddenly and cool to room temperature, maintaining the bend, tensile loading, programming the material to a temporary shape memory material.
(b) And applying an alternating magnetic field to the temporary shape memory polymer material part, heating to a temperature higher than the glass transition temperature, recovering the initial structure of the three-dimensional lattice structure part, and then cooling to room temperature. The frequency of the applied alternating magnetic field is: 162-163 kH, the current is: 296.0A, magnetic field coil: 5 turns, about 0.1 meter in length, according to the formula H = N × I/Le, where H is the magnetic field strength in a/m; n is the number of turns of the excitation coil; i is the excitation current (measured value) in units of a; le is the effective magnetic path length of the test sample in m. The magnetic field strength is obtained by calculation as follows: 14800.
example 9: a shape memory recovery method for 3D direct write printing (DIW) of a magnetic structure comprises the following steps:
(a) using the magnetic-driven shape memory material of example 1 as ink, printing with a 3D direct write printer (DIW) to fabricate a single-layer part (shown in fig. 9) of magnetic material, air-drying after fabrication, taking off the material, and drying in a constant temperature drying oven at 45 ℃ for 8 hours; the part is placed in boiling water and held under bending or tensile loading, the temperature of which has reached the glass transition temperature, the temperature is allowed to cool down abruptly to room temperature, and the loading is maintained, so that the material is programmed as a temporary shape memory material.
(b) And applying an alternating magnetic field to the temporary shape memory polymer material part, heating to a temperature higher than the glass transition temperature, recovering the initial structure of the three-dimensional lattice structure part, and then cooling to room temperature. The frequency of the applied alternating magnetic field is: 162-163 kH, the current is: 296.0A, magnetic field coil: 5 turns, about 0.1 meter in length, according to the formula H = N × I/Le, where H is the magnetic field strength in a/m; n is the number of turns of the excitation coil; i is the excitation current (measured value) in units of a; le is the effective magnetic path length of the test sample in m. The magnetic field strength is obtained by calculation as follows: 14800.
Claims (10)
1. a magnetically actuated shape memory material, prepared by the following method:
(a) uniformly mixing shape memory polymer particles with a solvent to obtain a shape memory polymer solution;
(b) adding the magnetic particles into the shape memory polymer solution, and uniformly mixing to obtain the shape memory polymer solution with the magnetic particles;
(c) and adding nano silicon dioxide into the shape memory polymer solution with the magnetic particles, and uniformly mixing to obtain the magnetic drive shape memory material.
2. The magnetically actuated shape memory material of claim 1, wherein said shape memory polymer particles are at least one of epoxy-based shape memory polymers, cyanate-based shape memory polymers, polyimide-based shape memory polymers, styrene-based shape memory polymers, ether block copolymer polyurethane thermoplastic shape memory polymers.
3. The magnetically actuated shape memory material of claim 1, wherein said solvent is at least one of N, N '-dimethylacetamide, N' -dimethylformamide, tetrahydrofuran; the magnetic particles are at least one of ferroferric oxide particles and rubidium, iron and boron particles.
4. The magnetically actuated shape memory material of claim 1, wherein the mass ratio of the shape memory polymer particles to the solvent is 1: 4-6, wherein the mass ratio of the shape memory polymer particles to the magnetic particles to the nano silicon dioxide is 1: 0.25-2.1: 1.05-2.73.
5. A preparation method of a magnetic drive shape memory material is characterized by comprising the following steps:
(a) uniformly mixing shape memory polymer particles with a solvent to obtain a shape memory polymer solution;
(b) adding the magnetic particles into the shape memory polymer solution, and uniformly mixing to obtain the shape memory polymer solution with the magnetic particles;
(c) and adding nano silicon dioxide into the shape memory polymer solution with the magnetic particles, and uniformly mixing to obtain the magnetic drive shape memory material.
6. The method of claim 5, wherein the shape memory polymer particles are at least one of epoxy-based shape memory polymers, cyanate-based shape memory polymers, polyimide-based shape memory polymers, styrene-based shape memory polymers, ether block copolymer polyurethane thermoplastic shape memory polymers; the solvent is at least one of N, N '-dimethylacetamide, N' -dimethylformamide and tetrahydrofuran; the magnetic particles are at least one of ferroferric oxide particles and rubidium, iron and boron particles; the mass ratio of the shape memory polymer particles to the solvent is 1: 4-6, wherein the mass ratio of the shape memory polymer particles to the magnetic particles to the nano silicon dioxide is 1: 0.25-2.1: 1.05-2.73.
7. Use of a magnetically actuated shape memory material according to any of claims 1 to 4 in 3D printing material.
8. Use of a magnetically actuated shape memory material according to any of claims 1 to 4 in a three-dimensional lattice structure.
9. Use according to claim 8, wherein the magnetically actuated shape memory material is used to make a scalable three-dimensional lattice structure component.
10. A shape memory recovery method of a three-dimensional lattice structure is characterized by comprising the following steps:
(a) 3D printing the magnetic drive shape memory material of any one of claims 1 to 4 to manufacture a three-dimensional lattice structural component; placing the component in an alternating magnetic field, enabling the component to reach a temperature higher than the glass transition temperature by utilizing the magnetocaloric effect, then applying a specific magnetic field to the three-dimensional lattice structural component to cause the structure of the component to deform, keeping the applied magnetic field to enable the three-dimensional lattice structural component to lock the shape above the glass transition temperature, and then cooling to room temperature to obtain the three-dimensional lattice structural component with a temporary shape;
(b) and continuously applying an alternating magnetic field to the three-dimensional lattice structural component with the temporary shape, heating to a temperature above the glass transition temperature, recovering the initial structure of the three-dimensional lattice structural component, and then cooling to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111164585.7A CN114015225A (en) | 2021-09-30 | 2021-09-30 | Magnetic-drive shape memory material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111164585.7A CN114015225A (en) | 2021-09-30 | 2021-09-30 | Magnetic-drive shape memory material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114015225A true CN114015225A (en) | 2022-02-08 |
Family
ID=80055202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111164585.7A Pending CN114015225A (en) | 2021-09-30 | 2021-09-30 | Magnetic-drive shape memory material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114015225A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115029575A (en) * | 2022-07-06 | 2022-09-09 | 河北大学 | In-situ preparation method of gradient porous composite material |
| CN115625694A (en) * | 2022-11-10 | 2023-01-20 | 厦门大学 | Temperature sensing integrated electric/magnetic field hybrid driving software driver and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02116102A (en) * | 1988-10-26 | 1990-04-27 | Mitsubishi Heavy Ind Ltd | Magnet with shape memory properties |
| US6388043B1 (en) * | 1998-02-23 | 2002-05-14 | Mnemoscience Gmbh | Shape memory polymers |
| JP2008013631A (en) * | 2006-07-04 | 2008-01-24 | Bando Chem Ind Ltd | Magnetic responsive material |
| CN104744922A (en) * | 2015-03-27 | 2015-07-01 | 同济大学 | Method for preparing magneto type biodegradable shape-memory-polymer nano composite material |
| CN107803983A (en) * | 2017-11-02 | 2018-03-16 | 哈尔滨工业大学 | Preparation method and application method for the compound 4D print wires of shape-memory polymer of fusion sediment printing |
| CN107987518A (en) * | 2017-12-11 | 2018-05-04 | 大连理工大学 | A kind of magnetic base organic composite shaping phase-change material and preparation method thereof |
| CN108219105A (en) * | 2018-02-11 | 2018-06-29 | 中国工程物理研究院激光聚变研究中心 | For the preparation method of the molding polyfunctionality cladodification polyurethane slurry of photocuring direct write |
| CN108384219A (en) * | 2018-03-25 | 2018-08-10 | 桂林理工大学 | A kind of preparation method and applications of TPU bases magnetic response 4D printing consumables |
| US20190152133A1 (en) * | 2017-10-16 | 2019-05-23 | Voxel8, Inc. | 3d-printing using reactive precursors |
| US20190263060A1 (en) * | 2015-12-07 | 2019-08-29 | Northeastern University | Direct Write Three-Dimensional Printing of Aligned Composite Materials |
| US20190338079A1 (en) * | 2016-12-30 | 2019-11-07 | Jf Polymers (Suzhou) Co., Ltd. | Biological ink |
| CN112492864A (en) * | 2020-11-26 | 2021-03-12 | 华中科技大学 | Controllable electromagnetic shielding component and preparation method thereof |
| CN112980165A (en) * | 2021-02-25 | 2021-06-18 | 四川大学 | Self-repairing shape memory composite material with photo-magnetic response and preparation and application thereof |
-
2021
- 2021-09-30 CN CN202111164585.7A patent/CN114015225A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02116102A (en) * | 1988-10-26 | 1990-04-27 | Mitsubishi Heavy Ind Ltd | Magnet with shape memory properties |
| US6388043B1 (en) * | 1998-02-23 | 2002-05-14 | Mnemoscience Gmbh | Shape memory polymers |
| JP2008013631A (en) * | 2006-07-04 | 2008-01-24 | Bando Chem Ind Ltd | Magnetic responsive material |
| CN104744922A (en) * | 2015-03-27 | 2015-07-01 | 同济大学 | Method for preparing magneto type biodegradable shape-memory-polymer nano composite material |
| US20190263060A1 (en) * | 2015-12-07 | 2019-08-29 | Northeastern University | Direct Write Three-Dimensional Printing of Aligned Composite Materials |
| US20190338079A1 (en) * | 2016-12-30 | 2019-11-07 | Jf Polymers (Suzhou) Co., Ltd. | Biological ink |
| US20190152133A1 (en) * | 2017-10-16 | 2019-05-23 | Voxel8, Inc. | 3d-printing using reactive precursors |
| CN107803983A (en) * | 2017-11-02 | 2018-03-16 | 哈尔滨工业大学 | Preparation method and application method for the compound 4D print wires of shape-memory polymer of fusion sediment printing |
| CN107987518A (en) * | 2017-12-11 | 2018-05-04 | 大连理工大学 | A kind of magnetic base organic composite shaping phase-change material and preparation method thereof |
| CN108219105A (en) * | 2018-02-11 | 2018-06-29 | 中国工程物理研究院激光聚变研究中心 | For the preparation method of the molding polyfunctionality cladodification polyurethane slurry of photocuring direct write |
| CN108384219A (en) * | 2018-03-25 | 2018-08-10 | 桂林理工大学 | A kind of preparation method and applications of TPU bases magnetic response 4D printing consumables |
| CN112492864A (en) * | 2020-11-26 | 2021-03-12 | 华中科技大学 | Controllable electromagnetic shielding component and preparation method thereof |
| CN112980165A (en) * | 2021-02-25 | 2021-06-18 | 四川大学 | Self-repairing shape memory composite material with photo-magnetic response and preparation and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| JOHN CARRELL ET AL.: "Shape Memory Polymer Nanocomposites for Application of Multiple-Field Active Disassembly: Experiment and Simulation", 《ENVIRON. SCI. TECHNOL.》 * |
| M. HEUCHEL ET AL.: "Modeling the heat transfer in magneto-sensitive shape-memory polymer nanocomposites with dynamically changing surface area to volume ratios", 《POLYMER》 * |
| 张大伟: "苯乙烯形状记忆聚合物及其光、磁驱动特性的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 汪多仁: "《绿色纳米化学品》", 科学技术文献出版社 * |
| 王国全: "《聚合物共混改性原理与应用》", 31 January 2007, 中国轻工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115029575A (en) * | 2022-07-06 | 2022-09-09 | 河北大学 | In-situ preparation method of gradient porous composite material |
| CN115625694A (en) * | 2022-11-10 | 2023-01-20 | 厦门大学 | Temperature sensing integrated electric/magnetic field hybrid driving software driver and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | 3D printing of thermoreversible polyurethanes with targeted shape memory and precise in situ self-healing properties | |
| CN114015225A (en) | Magnetic-drive shape memory material and preparation method and application thereof | |
| Chen et al. | Light-and magnetic-responsive synergy controlled reconfiguration of polymer nanocomposites with shape memory assisted self-healing performance for soft robotics | |
| Fang et al. | Shape-memory polymer composites selectively triggered by near-infrared light of two certain wavelengths and their applications at macro-/microscale | |
| Liu et al. | Stimulus methods of multi-functional shape memory polymer nanocomposites: A review | |
| Zhang et al. | Highly stretchable, bionic self-healing waterborne polyurethane elastic film enabled by multiple hydrogen bonds for flexible strain sensors | |
| Ma et al. | 4D printing of PLA/PCL shape memory composites with controllable sequential deformation | |
| Gong et al. | Remotely actuated shape memory effect of electrospun composite nanofibers | |
| Zhang et al. | Electrically/infrared actuated shape memory composites based on a bio-based polyester blend and graphene nanoplatelets and their excellent self-driven ability | |
| CN109880294B (en) | Epoxy nanocomposite of tannic acid modified graphene oxide | |
| Xiao et al. | Stereolithography (SLA) 3D printing of carbon fiber-graphene oxide (CF-GO) reinforced polymer lattices | |
| WO2015139517A1 (en) | Barrier anti-static tpu composite material film and preparation method therefor | |
| US20130082423A1 (en) | Method for making electrostrictive composite | |
| CN108102121B (en) | Anisotropic magnetic polymer composite film material and preparation method thereof | |
| Zeng et al. | Recent progress in 3D printing piezoelectric materials for biomedical applications | |
| Park et al. | Infrared light actuated shape memory effects in crystalline polyurethane/graphene chemical hybrids | |
| Liu et al. | Fabrication and properties of BaTiO3 ceramics via digital light processing for piezoelectric energy harvesters | |
| Li et al. | 3D printing of mechanically robust MXene-encapsulated polyurethane elastomer | |
| CN111349257A (en) | Method for constructing 3D shape memory material through optical programming, obtained product and application | |
| Mauriello et al. | 3D/4D printing of polyurethanes by vat photopolymerization | |
| Guo et al. | Ultra-tough and stress-free two-way shape memory polyurethane induced by polymer segment “spring” | |
| Khasraghi et al. | Efficient inductively heated shape memory polyurethane acrylate network with silane modified nanodiamond@ Fe3O4 superparamagnetic nanohybrid | |
| Xie et al. | Thermo-and near infrared light-induced reversible multi-shape memory materials for actuators and sensors | |
| Han et al. | Nanowire enhanced dimensional accuracy in acrylate resin-based 3D printing | |
| Chen et al. | A Multiple Remotely Controlled Platform from Recyclable Polyurethane Composite Network with Shape‐Memory Effect and Self‐Healing Ability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220208 |
|
| RJ01 | Rejection of invention patent application after publication |