CN111710778B - Stretchable magnetoelectric electret and preparation method thereof - Google Patents
Stretchable magnetoelectric electret and preparation method thereof Download PDFInfo
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- CN111710778B CN111710778B CN202010729068.9A CN202010729068A CN111710778B CN 111710778 B CN111710778 B CN 111710778B CN 202010729068 A CN202010729068 A CN 202010729068A CN 111710778 B CN111710778 B CN 111710778B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 239000011159 matrix material Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims description 36
- -1 polydimethylsiloxane Polymers 0.000 claims description 18
- 239000006249 magnetic particle Substances 0.000 claims description 17
- 229920002379 silicone rubber Polymers 0.000 claims description 13
- 230000005415 magnetization Effects 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 6
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 6
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000004945 silicone rubber Substances 0.000 claims description 6
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 5
- 229920005839 ecoflex® Polymers 0.000 claims description 5
- 230000010287 polarization Effects 0.000 claims description 4
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 claims description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005459 micromachining Methods 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 230000001846 repelling effect Effects 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 210000003205 muscle Anatomy 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
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- 238000005859 coupling reaction Methods 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- 239000007767 bonding agent Substances 0.000 description 1
- 238000010367 cloning Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N50/00—Galvanomagnetic devices
- H10N50/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N50/00—Galvanomagnetic devices
- H10N50/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N50/00—Galvanomagnetic devices
- H10N50/80—Constructional details
- H10N50/85—Magnetic active materials
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Abstract
The invention discloses a stretchable magnetoelectric electret and a preparation method thereof, wherein the magnetoelectric electret consists of an upper part and a lower part which form a continuous arched hole structure, and the upper wall and the lower wall of the hole structure carry opposite charges; the upper half part is sequentially provided with a magnetically active polymer matrix, an electrode and a polymer matrix with surface charges from top to bottom, and the lower half part is sequentially provided with a polymer matrix with surface charges, an electrode and a magnetically active polymer matrix from top to bottom. The invention also discloses a preparation method of the magnetoelectric electret, which has the advantages of simplicity, low manufacturing cost and easy large-scale production and can be used in the fields of energy capture, flexible sensors, artificial skin, artificial muscle, self-powered equipment and the like.
Description
Technical Field
The invention belongs to the field of functional materials, and mainly relates to a stretchable magnetoelectric electret and a preparation method thereof.
Background
The magnetoelectric effect means that the material can generate electric polarization under the action of a magnetic field and can generate magnetic polarization under the action of an electric field. Due to the natural coupling effect, the material has a plurality of application prospects, such as the fields of energy capture, sensing, data storage, drug transmission and the like.
In addition, new requirements are also placed on the performance of the device in order to pursue a comfortable and convenient lifestyle, and flexibility (large deformation that can occur) is one of the important properties. Research on flexible electronic devices is receiving attention from various researchers. Such as: the American journal of science and electronic technology lists the progress of organic electronic technology as one of ten scientific and technological achievements in the world in 2000, and parallels with important findings of human genome draft, biological cloning technology and the like. Meanwhile, developed countries in the western world make major research plans for flexible electronics, such as the FDCASU plan in the United states and the TRADIM plan in Japan. If a magnetoelectric material is flexible and has stretchability, the magnetoelectric material has wide application prospect in the fields of flexible electronics, biomedicine and the like.
However, the current magnetoelectric materials are hard materials which are difficult to deform under the action of external force. Therefore, it is difficult to be compatible with the living body, and the patient feels a great foreign body sensation in practical use. Therefore, the preparation of the soft and stretchable electret with obvious magnetoelectric effect has important significance for solving the problem that the current magnetoelectric material is difficult to deform, and the application of a magnetoelectric coupling device is greatly promoted.
The invention content is as follows:
in order to overcome the problems of the prior art, the invention provides a stretchable electret with a remarkable magnetoelectric effect and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a stretchable magnetoelectric electret is composed of an upper part and a lower part, wherein the upper part and the lower part form a continuous arched hole structure, and the upper wall and the lower wall of the hole structure carry opposite charges; the upper half part is provided with a magnetically active polymer matrix 1, an electrode 2 and a polymer matrix 3 with surface charges from top to bottom in sequence, and the lower half part is provided with the polymer matrix 3 with surface charges, the electrode 2 and the magnetically active polymer matrix 1 from top to bottom in sequence.
The magnetically active polymer matrix 1 is formed by doping hard magnetic particles with high remanent magnetization into a silicon rubber material, and the contents of the hard magnetic particles in the magnetically active polymer matrix in the upper part and the lower part are different.
The silicon rubber material is polydimethylsiloxane PDMS or platinum-catalyzed silicon rubber ECOFLEX; the hard magnetic particles with high remanent magnetization are any one of neodymium iron boron (NdFeB), rare earth cobalt magnet and samarium cobalt alloy.
The magnetically active polymer matrix 1 contains hard magnetic particles with high remanent magnetization, and in the preparation process, the unmagnetized hard magnetic particles are doped into the silica gel material, and are magnetized after being solidified, wherein the thickness of the magnetically active polymer matrix 1 is 1 mu m-1 mm.
The polymer matrix 3 with the surface charge is made of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), Polyethylene (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), fluorinated ethylene propylene copolymer (FEP) or Cyclic Olefin Copolymer (COC), and the thickness of the polymer matrix 3 with the surface charge is 1 mu m-1 mm.
The hole structure is formed by micro-processing or mutual repulsion of magnetic fields in the upper and lower layers of magnetically active polymer matrixes.
Firstly, doping hard magnetic particles in the silicon rubber in the preparation process, curing and forming, and putting a cured and formed sample into a pulse direct current magnetic field to be magnetized along the thickness to form a magnetically active polymer matrix 1; then plating an electrode on one surface of the polymer film, and carrying charges on the other surface by adopting polarization treatment to enable the polymer film to carry surface charges to form a polymer matrix 3 with the surface charges; then, using uniformly mixed but not solidified silicon rubber as bonding liquid, bonding the magnetically active polymer matrix 1 on one side of an electrode of the polymer matrix 3 with surface charges to obtain a first material for bonding the magnetically active polymer matrix and the polymer matrix with surface charges; through the same operation, a second material is obtained, wherein the magnetically active polymer matrix and the polymer matrix with surface charges are bonded, but the charges on the two polymer matrices with surface charges in the second material and the first material are different; and finally, coating adhesives on the two obtained materials with charge carrying surfaces oppositely and equidistantly to obtain the stretchable magnetoelectric electret.
The direction of the direct current pulse magnetic field applied to the magnetically active polymer in the second material and the direction of the direct current pulse magnetic field applied to the magnetically active polymer in the first material in the magnetizing process are the same, so that the magnetic fields in the upper and lower layers of magnetically active polymer matrixes are mutually repulsive, and the amplitude of the magnetic field is 1T-4T.
When two charge-carrying surfaces of the materials are oppositely bonded, the adhesive is partially coated, and the distance between two bonding areas is 1 mm-10 cm.
The invention has the following advantages:
1. has considerable magnetoelectric coupling effect, and the working temperature is at room temperature.
2. The materials used in the invention are all green and nontoxic.
3. The preparation method is simple and easy to implement.
4. The stretchable magnetoelectric electret has good capability of active and passive deformation and good biocompatibility.
5. In the aspect of realizing magnetoelectric coupling, the material used by the invention is cheaper and the material selection is more common.
6. The magnetoelectric electret film prepared by the invention can be applied to the fields of energy capture, flexible sensors, artificial skin, soft robots and the like.
Drawings
Fig. 1 is a structural view of a magnetoelectric electret according to the present invention.
FIG. 2 is a flow chart of a method for preparing a magnetoelectric electret according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific examples, but the present invention is not limited thereto.
As shown in fig. 1, the present invention relates to a stretchable magnetoelectric electret, which is composed of an upper part and a lower part, wherein the upper part and the lower part form a continuous arched hole structure, and the upper wall and the lower wall of the hole structure carry opposite charges; the upper half part is provided with a magnetically active polymer matrix 1, an electrode 2 and a polymer matrix 3 with surface charges from top to bottom in sequence, and the lower half part is provided with the polymer matrix 3 with surface charges, the electrode 2 and the magnetically active polymer matrix 1 from top to bottom in sequence.
As a preferred embodiment of the present invention, the magnetically active polymer matrix 1 is formed by doping hard magnetic particles having high remanent magnetization into a silicone rubber material, and the contents of the hard magnetic particles in the magnetically active polymer matrix in the upper and lower portions are different.
As a preferred embodiment of the present invention, the silicone rubber material is polydimethylsiloxane PDMS or platinum-catalyzed silicone rubber ECOFLEX; the hard magnetic particles with high remanent magnetization are any one of neodymium iron boron (NdFeB), rare earth cobalt magnet and samarium cobalt alloy.
As a preferred embodiment of the present invention, the magnetically active polymer matrix 1 contains hard magnetic particles with high remanent magnetization, and during the preparation process, the unmagnetized hard magnetic particles are doped into the silica gel material, and then magnetized after being solidified, and the thickness of the magnetically active polymer matrix 1 is 1 μm-1 mm.
As a preferred embodiment of the present invention, the material of the surface charge polymer matrix 3 is polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF, polypropylene PP, polyethylene PE, polyethylene terephthalate PET, polyethylene naphthalate PEN, fluorinated ethylene propylene copolymer FEP or cyclic olefin copolymer COC, and the thickness of the surface charge polymer matrix 3 is 1 μm to 1 mm.
As a preferred embodiment of the invention, the hole structure is formed by micromachining or formed by mutually repelling magnetic fields in the upper and lower layers of magnetically active polymer matrixes.
The sample shown on the left in step 1 of fig. 2 was formed by cutting polytetrafluoroethylene into a regular rectangle and coating a silver electrode on one side thereof by a spin coater, as shown in step 1 of fig. 2. Mixing the Ecoflex-0010A solution and the B solution in equal mass, adding a proper amount of unmagnetized neodymium iron boron powder, and uniformly stirring. And carrying out spin coating on the uniformly mixed solution by using a spin coater, and curing in a constant temperature box (at 70 ℃). Repeating the steps until the thickness of the finally solidified film exceeds 300um, and cutting the film into a rectangle with the same length and width as the polytetrafluoroethylene to obtain the magnetic polymer shown in the right diagram in the step 1 of the figure 2.
The solutions of Ecoflex 0010A and B, which are uniformly mixed and not yet solidified, are used as a binder to bind the ptfe and the magnetic polymer, forming a sandwich structure of ptfe and magnetic polymer sandwiched electrodes, as shown in sample 1 on the left in step 2 of fig. 2. The above procedure was repeated to prepare sample 2 shown in the right panel of step 1. The content of neodymium iron boron in the magnetically active polymer was different in sample 1 and sample 2.
As shown in step 3 in fig. 2, the two samples obtained in step 2 are placed in a magnetic field for magnetization (the amplitude of the magnetic field is 1T to 4T), and the directions of the applied magnetic fields of the two samples during magnetization are the same.
Both samples were charged by means of corona, as shown in step 4 of figure 2. The electrodes of both samples obtained in step 3 were first grounded. In addition, the needle point of one sample is connected with positive 10kV high voltage in the corona process, and the needle point of the other sample is connected with negative 10kV high voltage in the corona process.
As shown in step 5 in fig. 2, the two samples obtained in step 4 were bonded and cured with the uniform mixture of solutions Ecoflex 0010A and B that had not yet solidified as a bonding agent, with a bonding distance of 5 mm.
Due to the mutual repulsion between the two magnetically active polymers, the solidified sample can obtain the dome shape as shown in step 6 of fig. 2.
Claims (8)
1. A stretchable magnetoelectric electret is characterized by comprising an upper part and a lower part, wherein the upper part and the lower part form a continuous arched hole structure, and the upper wall and the lower wall of the hole structure carry opposite charges; the upper half part is sequentially provided with a magnetically active polymer matrix (1), an electrode (2) and a polymer matrix (3) with surface charges from top to bottom, and the lower half part is sequentially provided with the polymer matrix (3) with surface charges, the electrode (2) and the magnetically active polymer matrix (1) from top to bottom.
2. The stretchable magnetoelectric electret according to claim 1, wherein the magnetically active polymer matrix (1) is formed by doping hard magnetic particles with high remanent magnetization into silicone rubber material, and the content of the hard magnetic particles in the magnetically active polymer matrix in the upper and lower portions is different.
3. The stretchable magnetoelectric electret according to claim 2, wherein the silicone rubber material is polydimethylsiloxane PDMS or platinum catalyzed silicone rubber ECOFLEX; the hard magnetic particles with high remanent magnetization are any one of neodymium iron boron (NdFeB), rare earth cobalt magnet and samarium cobalt alloy.
4. The stretchable magnetoelectric electret according to claim 2, wherein the magnetically active polymer matrix (1) contains hard magnetic particles with high remanent magnetization, and the hard magnetic particles which are not magnetized are doped into the silica gel material during the preparation process, and then are magnetized after being cured, and the thickness of the magnetically active polymer matrix (1) is 1 μm-1 mm.
5. The stretchable magnetoelectric electret according to claim 1, wherein the material of the surface-charged polymer matrix (3) is Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), Polyethylene (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), fluorinated ethylene propylene copolymer (FEP) or Cyclic Olefin Copolymer (COC), and the thickness of the surface-charged polymer matrix (3) is 1 μm to 1 mm.
6. The stretchable magnetoelectric electret according to claim 1, wherein the hole structure is formed by micromachining or by repelling magnetic fields in two layers of magnetically active polymer matrices.
7. The method for preparing a stretchable magnetoelectric electret according to any one of claims 1 to 6, characterized in that, firstly, the silicon rubber is doped with hard magnetic particles in the preparation process, and is solidified and formed, and the solidified and formed sample is put into a pulse direct current magnetic field to be magnetized along the thickness to form a magnetically active polymer matrix (1); then plating an electrode on one surface of the polymer film, and carrying charges on the other surface by adopting polarization treatment to enable the polymer film to carry surface charges to form a polymer matrix (3) with the surface charges; then, using uniformly mixed but not solidified silicon rubber as bonding liquid, bonding the magnetically active polymer matrix (1) on one side of an electrode of the polymer matrix (3) with surface charges to obtain a first material bonding the magnetically active polymer matrix and the polymer matrix with surface charges; through the same operation, a second material is obtained, wherein the magnetically active polymer matrix and the polymer matrix with surface charges are bonded, but the charges on the two polymer matrices with surface charges in the second material and the first material are different; finally, oppositely adhering the two obtained charge-carrying surfaces of the two materials, partially coating the adhesive, and setting the distance between the two adhesion areas to be 1-10 cm to obtain the stretchable magnetoelectric electret;
8. the method for preparing a stretchable magnetoelectric electret according to claim 7, wherein the direction of the applied direct current pulse magnetic field of the magnetically active polymers in the second material and the first material is the same during magnetization, so that the magnetic fields in the upper and lower layers of magnetically active polymer matrixes repel each other, and the amplitude of the magnetic field is 1T-4T.
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| CA2037942A1 (en) * | 1990-03-12 | 1991-09-13 | Satoshi Matsuura | Process for producing an electret, a film electret, and an electret filter |
| CN102569641A (en) * | 2012-01-10 | 2012-07-11 | 同济大学 | Method for producing piezoelectric electret functional films with piezoelectric coefficient d31 |
| CN103531706B (en) * | 2013-10-22 | 2016-05-25 | 深圳市豪恩声学股份有限公司 | Piezo-electric electret material and preparation method thereof |
| CN106291408B (en) * | 2016-10-11 | 2023-06-09 | 中国计量大学 | Magneto-electric converter based on magnetostrictors and electrets |
| CN108347198B (en) * | 2017-01-25 | 2020-06-16 | 北京纳米能源与系统研究所 | Electret self-generating device and electret self-generating intelligent shoe |
| CN108613688A (en) * | 2018-07-23 | 2018-10-02 | 中国计量大学 | Multi-functional set sensing device based on magnetic electric compound material and electret |
| CN109950045B (en) * | 2019-03-19 | 2020-08-14 | 西安交通大学 | Flexoelectric electret with adjustable and controllable flexoelectric effect and preparation method thereof |
| CN110993784B (en) * | 2019-11-29 | 2022-05-06 | 西安交通大学 | Magnetoelectric electret with adjustable magnetoelectric effect and preparation method thereof |
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