CN114953296A - Manufacturing method of polycrystalline phase polyvinylidene fluoride film and wearable device - Google Patents
Manufacturing method of polycrystalline phase polyvinylidene fluoride film and wearable device Download PDFInfo
- Publication number
- CN114953296A CN114953296A CN202210581109.3A CN202210581109A CN114953296A CN 114953296 A CN114953296 A CN 114953296A CN 202210581109 A CN202210581109 A CN 202210581109A CN 114953296 A CN114953296 A CN 114953296A
- Authority
- CN
- China
- Prior art keywords
- polyvinylidene fluoride
- fluoride film
- wearable device
- film
- phase
- 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.)
- Granted
Links
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 154
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000001523 electrospinning Methods 0.000 claims description 8
- 230000035790 physiological processes and functions Effects 0.000 claims description 8
- 230000036760 body temperature Effects 0.000 claims description 6
- 230000029058 respiratory gaseous exchange Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 230000036772 blood pressure Effects 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000010408 film Substances 0.000 description 76
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000010041 electrostatic spinning Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 210000000707 wrist Anatomy 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- BAAVRTJSLCSMNM-CMOCDZPBSA-N (2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-amino-3-(4-hydroxyphenyl)propanoyl]amino]-4-carboxybutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]pentanedioic acid Chemical compound C([C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=1C=CC(O)=CC=1)C(=O)N[C@@H](CCC(O)=O)C(O)=O)C1=CC=C(O)C=C1 BAAVRTJSLCSMNM-CMOCDZPBSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 108010032276 tyrosyl-glutamyl-tyrosyl-glutamic acid Proteins 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/30—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. moulding around inserts or for coating articles
-
- 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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/38—Moulds, cores or other substrates
-
- 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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/42—Removing articles from moulds, cores or other substrates
-
- 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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/52—Measuring, controlling or regulating
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a method for manufacturing a polycrystalline phase polyvinylidene fluoride film. The polycrystalline phase polyvinylidene fluoride film obtained by the manufacturing method of the invention has beta crystal phase and gamma crystal phase simultaneously, so the polycrystalline phase polyvinylidene fluoride film has good piezoelectric effect to sense pressure or tension in different directions. Meanwhile, the polycrystalline phase polyvinylidene fluoride film also has good pyroelectric effect for sensing the ambient temperature.
Description
Technical Field
The present invention relates to a method for manufacturing polyvinylidene fluoride (PVDF), and more particularly to a method for manufacturing a polycrystalline PVDF film.
Background
Polyvinylidene fluoride (PVDF) has good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance, radiation resistance, piezoelectric effect, pyroelectric effect and dielectric effect, and is widely applied to functional films such as piezoelectric films, solar back plate films, lithium battery diaphragms and the like. The piezoelectric effect means that when a piezoelectric crystal is deformed by an external force, charges of equal and opposite signs appear on some corresponding surfaces of the piezoelectric crystal. The pyroelectric effect is a phenomenon in which the electric polarization of a polar dielectric changes due to a change in temperature. The pyroelectric effect can be used for measuring the ambient temperature or the body temperature.
Compared with the traditional piezoelectric material (such as a ceramic piezoelectric plate), the polyvinylidene fluoride has the characteristics of wide frequency response, large dynamic range, high force point conversion sensitivity, good mechanical property, high mechanical strength, easy matching of acoustic impedance and the like, and has the advantages of light weight, softness, no brittleness, impact resistance, difficulty in being polluted by water and chemicals, easiness in manufacturing sheets or pipes with any shapes and different areas and the like. The method is widely applied to the technical fields of mechanics, acoustics, optics, electronics, measurement, infrared, safety alarm, medical care, military, traffic, information engineering, office automation, ocean development, geological exploration and the like.
The piezoelectric film formed by the polyvinylidene fluoride has the advantages of thin thickness, light weight, very flexibility, capability of working without a power supply and the like, so that the piezoelectric film is widely applied to devices such as medical sensors and the like. The piezoelectric film formed by polyvinylidene fluoride is used as a dynamic strain sensor, and is very suitable for being applied to the surface of human skin or implanted into the human body to monitor physiological states, such as respiration and heartbeat.
Polyvinylidene fluoride is a polycrystalline polymer, and polyvinylidene fluoride films with different crystal phases can be obtained by using different methods such as an additive and the like. The crystal phase mainly comprises alpha crystal phase, beta crystal phase and gamma crystal phase. The polyvinylidene fluoride of alpha crystal phase has high thermodynamic stability, and the molecular chain conformation of TGTG' in the crystal lattice causes the dipole polarity of the molecular chain to be opposite and not obvious in polarity. The polyvinylidene fluoride with the beta crystalline phase is in an all-trans conformation TTT of an orthorhombic system, has spontaneous polarity and excellent piezoelectric performance. The molecular conformation of the gamma crystalline phase polyvinylidene fluoride is TTTGTTTG', two molecular chains in the same unit cell are arranged in parallel, and the dipole moment direction is the same, so that the unit cell has polarity. Fig. 1, fig. 2 and fig. 3 respectively show the molecular structures of the polyvinylidene fluoride in the α crystal phase, the β crystal phase and the γ crystal phase, wherein C is a Carbon (Carbon) atom, F is a Fluorine (Fluorine) atom, and H is a Hydrogen (Hydrogen) atom.
The beta crystal phase and the gamma crystal phase of the polyvinylidene fluoride have higher spontaneous polarization intensity and are important crystal phase structures of the polyvinylidene fluoride. The polyvinylidene fluoride of the beta crystalline phase and the gamma crystalline phase has excellent ferroelectricity, pyroelectric property and piezoelectric property.
In recent years, polyvinylidene fluoride films have also begun to be used in wearable devices. However, the current pvdf film only uses a certain crystal phase, and has a single function, so that the application of the pvdf film to a wearable device with limited space is limited. Therefore, the invention provides a polycrystalline phase polyvinylidene fluoride film to provide multiple functions simultaneously.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for manufacturing a polycrystalline polyvinylidene fluoride film.
One of the objectives of the present invention is to provide a wearable device using a poly-phase polyvinylidene film.
According to the invention, the manufacturing method of the polycrystalline phase polyvinylidene fluoride film comprises the following steps: coating a polyvinylidene fluoride solution on a substrate to form a film shape, and heating the polyvinylidene fluoride solution on the substrate to be above the melting point of the polyvinylidene fluoride solution to generate a first polyvinylidene fluoride film; cooling the first polyvinylidene fluoride film to obtain a second polyvinylidene fluoride film in a semi-molten state; preparing a plurality of polyvinylidene fluoride fibers with beta crystalline phases by utilizing electrostatic spinning; arranging the polyvinylidene fluoride fibers on the second polyvinylidene fluoride film in parallel to obtain a third polyvinylidene fluoride film; and heating and annealing the third polyvinylidene fluoride film at a fixed temperature to change the alpha-phase crystal phase into the gamma-phase crystal, and finally obtaining the polycrystalline phase polyvinylidene fluoride film with the beta crystal phase and the gamma crystal phase.
In one embodiment, a polyvinylidene fluoride material may be dissolved in a solvent, such as but not limited to Dimethylformamide (DMF), to prepare a solution of the polyvinylidene fluoride material.
In an embodiment, the step of producing the first polyvinylidene fluoride film comprises heating the polyvinylidene fluoride solution on the substrate above a melting point (e.g., 200 ℃) to produce the first polyvinylidene fluoride film.
In one embodiment, the fixed temperature may be 160 ℃.
In an embodiment, the step of producing the plurality of polyvinylidene fluoride fibers comprises electrospinning a polyvinylidene fluoride material to produce the plurality of polyvinylidene fluoride fibers.
According to the present invention, a wearable device comprises a polycrystalline phase polyvinylidene fluoride film, a switching device and a processor. The polycrystalline phase polyvinylidene fluoride film has a beta crystal phase and a gamma crystal phase. The polycrystalline phase polyvinylidene fluoride film can sense temperature and pressure to generate a temperature sensing signal and a pressure sensing signal. The processor is coupled with the polycrystalline phase polyvinylidene fluoride film and the switch device, controls the switch device to start or close the wearable device according to the temperature sensing signal, and generates an electric signal according to the pressure sensing signal.
In one embodiment, when the polycrystalline phase polyvinylidene fluoride film senses the temperature of a human body, the processor starts the wearable device according to the temperature sensing signal.
In one embodiment, when the polycrystalline phase polyvinylidene fluoride thin film does not sense the temperature of the human body, the processor turns off the wearable device according to the temperature sensing signal.
In one embodiment, the electrical signal is used to determine a physiological state or generate related information.
In an embodiment, the physiological state comprises heart beat, blood pressure or respiration.
In one embodiment, the related information includes pressure, weight, or distance.
Drawings
Fig. 1 shows the molecular structure of polyvinylidene fluoride in the α -crystal phase.
Fig. 2 shows the molecular structure of the β crystal phase of polyvinylidene fluoride.
Fig. 3 shows the molecular structure of the gamma crystalline phase of polyvinylidene fluoride.
FIG. 4 shows a process for making polycrystalline phase polyvinylidene fluoride film according to the present invention.
FIG. 5 shows a wearable device using polycrystalline phase polyvinylidene fluoride films of the present invention.
Fig. 6 shows a first embodiment of the operation of the wearable device of fig. 5.
Fig. 7 shows a second embodiment of the operation of the wearable device of fig. 5.
Reference numerals:
S10
S14
S18
S22
S26
S29
Step s34
Carbon atom F
Hydrogen atom
Detailed Description
While the present invention has been described in considerable detail with reference to certain preferred versions and embodiments, it should be understood that the present invention is not limited to the precise forms disclosed. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The numerical values or ranges set forth herein are approximate unless expressly stated otherwise.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, and/or components.
Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In this document, numerous specific details are set forth in order to provide a thorough understanding of the following embodiments. However, embodiments of the invention may be practiced without these specific details. In other instances, well-known structures and devices are shown schematically in order to simplify the drawing.
In various embodiments, a feature, element, or circuit formed on, connected to, and/or coupled to another feature, element, or circuit may include an implementation in which the features, elements, or circuits are in contact with each other, or may include an implementation in which another feature, element, or circuit is in contact with and interposed between the features, elements, or circuits, so that the features, elements, or circuits may not be in direct contact with each other.
FIG. 4 shows a process for making polycrystalline phase polyvinylidene fluoride film according to the present invention. In step S10 of fig. 4, a polyvinylidene fluoride solution is prepared, coated on a substrate to form a film, and then heated to a temperature higher than the melting point of the polyvinylidene fluoride solution on the substrate to flatten the polyvinylidene fluoride solution into a first polyvinylidene fluoride film. The first polyvinylidene fluoride film produced in step S10 is a half melt film. The polyvinylidene fluoride solution is heated, and besides the first polyvinylidene fluoride film can be produced, the thermal history of a polyvinylidene fluoride material in the polyvinylidene fluoride solution can be eliminated, so that the subsequent crystallization is not influenced by the previous production conditions. Wherein the thermal history comprises the influence of temperature, shearing, stretching and the like on the polyvinylidene fluoride material before the polyvinylidene fluoride material is molded and leaves a factory. In one embodiment, the polyvinylidene fluoride solution on the substrate may be heated to about 200 ℃ to obtain the first polyvinylidene fluoride film. In one embodiment, the step of preparing the polyvinylidene fluoride solution comprises dissolving a polyvinylidene fluoride material in a corresponding solvent to obtain the polyvinylidene fluoride solution, wherein the solvent includes but is not limited to Dimethylformamide (DMF).
After the step S10 is completed to generate the first polyvinylidene fluoride film, step S12 of fig. 4 is performed. In step S12, the first polyvinylidene fluoride film is allowed to cool to form a semi-molten second polyvinylidene fluoride film. The second polyvinylidene fluoride film has an alpha crystalline phase. In one embodiment, the first polyvinylidene fluoride film is cooled from a temperature of about 200 ℃ to a temperature of about 160 ℃ to obtain the second polyvinylidene fluoride film. The cooling manner of step S12 includes, but is not limited to, natural cooling.
In step S14 of fig. 4, a polyvinylidene fluoride material is placed into an electrospinning apparatus for electrospinning to produce a plurality of polyvinylidene fluoride fibers having a β crystal phase. In the electrospinning process, the polyvinylidene fluoride material is melted to eliminate the thermal history of the polyvinylidene fluoride material, so as to avoid influencing subsequent crystallization. Electrostatic spinning is a technology for preparing fibers through a high electric field, and the beta crystalline phase of the polyvinylidene fluoride fibers prepared through electrostatic spinning is relatively stable and easy to prepare, mainly because the polyvinylidene fluoride materials are simultaneously stretched and solidified when being electrically polarized through electrostatic spinning. Electrospinning is a common technique, and therefore, the detailed operation and principle thereof will not be described herein. In the embodiment of fig. 4, electrospinning is used to produce a plurality of polyvinylidene fluoride fibers having a beta crystalline phase, but the invention is not limited thereto, and other ways of producing polyvinylidene fluoride fibers having a beta crystalline phase are also suitable for use in the invention.
In the embodiment of fig. 4, the steps S10 and S14 may be performed simultaneously, or one of the steps may be performed after the other step is completed. For example, steps S10 and S12 are performed first, and then step S14 is performed, or step S14 is performed first, and then steps S10 and S12 are performed.
In the embodiment of fig. 4, the polyvinylidene fluoride material in the polyvinylidene fluoride solution used in step S10 may be the same as or different from the polyvinylidene fluoride material used in step S14.
And performing step S16 after obtaining the second polyvinylidene fluoride film and the plurality of polyvinylidene fluoride fibers. In step S16, the second pvdf film is placed on a collection table, and the plurality of pvdf fibers are arranged in parallel on the second pvdf film, so as to obtain a third pvdf film having an α crystal phase and a β crystal phase. In an embodiment, the collection stage may be an electrospinning collection stage.
In one embodiment, after step S10 is completed to obtain the first polyvinylidene fluoride film, the first polyvinylidene fluoride film may be transferred to the collection stage, during which the first polyvinylidene fluoride film has sufficient time to cool naturally to form the second polyvinylidene fluoride film in a semi-molten state.
After the third polyvinylidene fluoride film is obtained, step S18 is performed. In step S18 of fig. 4, the third polyvinylidene fluoride film is placed on a heating table, and is annealed at a fixed temperature. In the heating annealing process of step S18, since the third polyvinylidene fluoride film has polyvinylidene fluoride fibers having a β crystal phase, α crystal phase in the third polyvinylidene fluoride film is changed into γ crystal phase, thereby producing a polycrystalline phase polyvinylidene fluoride film having a β crystal phase and a γ crystal phase. In one embodiment, the fixed temperature used in step S18 is about 160 ℃ and the duration of heating is about 48 hours.
The polycrystalline phase polyvinylidene fluoride film provided by the invention has a beta crystal phase and a gamma crystal phase at the same time, and the beta crystal phase and the gamma crystal phase are arranged to form an included angle of 90 ℃, so that the polycrystalline phase polyvinylidene fluoride film has good piezoelectric effect in different directions (such as d31 and d 33). In other words, when the polycrystalline phase polyvinylidene fluoride film of the present invention is applied to a ring-shaped wearable device, it can sense pressure or tension in various directions. In addition, the beta crystal phase and the gamma crystal phase have pyroelectric effect, so the polycrystalline phase polyvinylidene fluoride film of the invention can also achieve temperature sensing. In the wearable device, the temperature sensing function of the polycrystalline phase polyvinylidene fluoride film can be used for sensing the temperature of a human body, and when the polycrystalline phase polyvinylidene fluoride film senses the body temperature or the sensed temperature is higher than a preset value, the wearable device is started. Conversely, when the body temperature is not sensed or the sensed temperature is lower than a predetermined value, the wearable device is turned off. This automatic start and close function of wearing formula device can avoid the user to forget to close wearing formula device, leads to electric power extravagant, but also can prolong wearing formula device's life.
FIG. 5 shows a wearable device 10 using a polycrystalline phase polyvinylidene fluoride film 12 of the present invention. In the embodiment of fig. 5, wearable device 10 includes a polycrystalline phase polyvinylidene fluoride membrane 12, a processor 14, and a switching device 16. The polycrystalline phase polyvinylidene fluoride film 12 has both a β crystal phase and a γ crystal phase. The processor 14 is connected to the polycrystalline phase polyvinylidene fluoride film 12 and the switching device 16. The switch device 16 is used to control the on and off of the wearable device 10. The wearable device 10 may be, but is not limited to, a pulse sensor.
The processor 14 of FIG. 5 may be a machine utilizing hardware, firmware, and/or software and may be physically adapted via Boolean logic to operate on a plurality of logic gates forming certain physical circuits to perform certain tasks defined by executable machine instructions. Processors may utilize mechanical, pneumatic, hydraulic, electrical, magnetic, optical, information, chemical, and/or biological principles, mechanisms, adaptations, signals, inputs, and/or outputs to perform tasks. The processor may be a general purpose device such as a microcontroller and/or microprocessor. In some embodiments, the processor may be a special purpose device, such as an Application Specific Integrated Circuit (ASIC) or a Field Programmable Gate Array (FPGA).
The switching device 16 of fig. 5 is an on/off circuit for cutting off or conducting a current path. In one embodiment, the switching device 16 may be, but is not limited to, a switch formed by a transistor.
Fig. 6 shows a first embodiment of the operation of the wearable device 10 of fig. 5. As shown in steps S20 and S22 of fig. 6, when the user wears the wearable device 10 on the wrist, the poly-crystalline polyvinylidene fluoride film 12 of the wearable device 10 senses the body temperature of the user, and the poly-crystalline polyvinylidene fluoride film 12 outputs a temperature sensing signal to the processor 14. After the processor 14 receives the temperature sensing signal from the poly-phase polyvinylidene fluoride film 12, the processor 14 controls the switch device 16 to activate the wearable device 10, as shown in step S24 of fig. 6. When the user takes off the wearable device 10, the poly-crystalline phase polyvinylidene fluoride film 12 of the wearable device 10 cannot sense the body temperature of the user, and therefore the poly-crystalline phase polyvinylidene fluoride film 12 stops outputting the temperature sensing signal to the processor 14, as shown in steps S26 and S28 of fig. 6. After the polycrystalline-phase polyvinylidene fluoride film 12 stops outputting the temperature sensing signal, the processor 14 controls the switching device 16 to turn off the wearable device 10, as shown in step S29 of fig. 6.
Fig. 7 shows a second embodiment of the operation of the wearable device 10 of fig. 5. When the user wears the wearable device 10 on the wrist, the poly-vinylidene fluoride film 12 of the wearable device 10 can sense the pressure or tension on the wrist, as shown in step S30 of fig. 7. The pressure or strain on the wrist comes from the pulse or the arm's swing. Based on the sensed pressure or tension, the poly-phase polyvinylidene fluoride film 12 generates a pressure sensing signal to the processor 14. The processor 14 determines an electrical signal according to the pressure sensing signal, as shown in step S32. The wearable device 10 determines the physiological status of the user or generates related information according to the electrical signal. Finally, the wearable device 10 can feed back the obtained physiological status or related information to the user, as shown in step S34. The feedback to the user includes, but is not limited to, displaying the physiological status or related information on a display, wherein the display may be disposed on or external to the wearable device 10. Depending on the type of the wearable device 10, the physiological state of the wearable device 10 may be different, for example, when the wearable device 10 is a pulse sensor, the physiological state may be the heartbeat or blood pressure of the user. When the wearable device 10 is a respiration sensor, the physiological state may be the respiration of the user. Similarly, the related information obtained by the wearable device 10 can be, but is not limited to, pressure, weight or distance, depending on the type of the wearable device 10.
Although the present invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (11)
1. The method for manufacturing the polycrystalline phase polyvinylidene fluoride film is characterized by comprising the following steps:
coating a polyvinylidene fluoride solution on a substrate to form a film shape, and heating the polyvinylidene fluoride solution on the substrate to be above the melting point of the polyvinylidene fluoride solution to generate a first polyvinylidene fluoride film;
cooling the first polyvinylidene fluoride film to obtain a second polyvinylidene fluoride film in a semi-molten state;
producing a plurality of polyvinylidene fluoride fibers having a beta crystalline phase;
arranging the polyvinylidene fluoride fibers on the second polyvinylidene fluoride film in parallel to obtain a third polyvinylidene fluoride film with an alpha crystal phase and a beta crystal phase; and
and heating and annealing the third polyvinylidene fluoride film at a fixed temperature to generate the polycrystalline phase polyvinylidene fluoride film with a beta crystalline phase and a gamma crystalline phase.
2. The method of claim 1, further comprising dissolving a polyvinylidene fluoride material in a solvent to formulate the polyvinylidene fluoride solution.
3. The method of making of claim 1, wherein the step of producing the first polyvinylidene fluoride film comprises heating the polyvinylidene fluoride solution on the substrate to 200 ℃ to produce the first polyvinylidene fluoride film.
4. The method of claim 1, wherein the fixed temperature is 160 ℃.
5. The method of making of claim 1, wherein the step of producing the plurality of polyvinylidene fluoride fibers comprises electrospinning a polyvinylidene fluoride material to produce the plurality of polyvinylidene fluoride fibers.
6. A wearable device, comprising:
the polycrystalline phase polyvinylidene fluoride film is provided with a beta crystalline phase and a gamma crystalline phase, and the polycrystalline phase polyvinylidene fluoride film senses temperature and pressure to generate a temperature sensing signal and a pressure sensing signal;
a switching device; and
and the processor is coupled with the polycrystalline phase polyvinylidene fluoride film and the switch device, controls the switch device according to the temperature sensing signal to start or close the wearable device, and generates an electric signal according to the pressure sensing signal.
7. The wearable device of claim 6, wherein the processor activates the wearable device in response to the temperature sensing signal when the polycrystalline phase polyvinylidene fluoride film senses a temperature of a human body.
8. The wearable device of claim 6, wherein the processor turns off the wearable device in response to the temperature sensing signal when the polycrystalline phase polyvinylidene fluoride film does not sense human body temperature.
9. The wearable device of claim 6, wherein the electrical signal is used to determine a physiological state or to generate related information.
10. The wearable device of claim 9, wherein the physiological state comprises heartbeat, blood pressure, or respiration.
11. The wearable device of claim 9, wherein the related information comprises pressure, weight, or distance.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210581109.3A CN114953296B (en) | 2022-05-26 | 2022-05-26 | Manufacturing method of polycrystalline polyvinylidene fluoride film and wearable device |
| TW111120191A TWI828170B (en) | 2022-05-26 | 2022-05-31 | Fabrication method of polycrystalline phase polyvinylidene fluoride film and wearable device using polycrystalline phase polyvinylidene fluoride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210581109.3A CN114953296B (en) | 2022-05-26 | 2022-05-26 | Manufacturing method of polycrystalline polyvinylidene fluoride film and wearable device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114953296A true CN114953296A (en) | 2022-08-30 |
| CN114953296B CN114953296B (en) | 2023-08-29 |
Family
ID=82955622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210581109.3A Active CN114953296B (en) | 2022-05-26 | 2022-05-26 | Manufacturing method of polycrystalline polyvinylidene fluoride film and wearable device |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114953296B (en) |
| TW (1) | TWI828170B (en) |
Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308370A (en) * | 1979-04-26 | 1981-12-29 | Rikagauku Kenkyusho | Piezoelectric and pyroelectric polymer film and process for preparing same |
| ITMI972764A1 (en) * | 1997-12-15 | 1999-06-15 | Ausimont Spa | FLUORINATED THERMOPLASTIC ELASTOMERS |
| US5922493A (en) * | 1995-03-03 | 1999-07-13 | Elf Atochem North America, Inc. | Polymeric electrode and electrolyte article of manufacture |
| KR20090030827A (en) * | 2007-09-21 | 2009-03-25 | 경희대학교 산학협력단 | METHOD FOR PRODUCING POLY(VINYLIDENE FLUORIDE) NANOFIBER WEB WITH HIGH beta- TYPE CRYSTAL STRUCTURE |
| KR20090131313A (en) * | 2008-06-18 | 2009-12-29 | 연세대학교 산학협력단 | Spin cast ferroelectric beta poly(vinylidene fluoride) thin film via rapid thermal annealing |
| CN102805615A (en) * | 2012-07-26 | 2012-12-05 | 翁整 | Smart phone application-based life sign monitoring alarm |
| CN104291264A (en) * | 2014-10-17 | 2015-01-21 | 华中科技大学 | Nano-piezoelectric fiber based flexible energy-harvesting device and manufacturing method thereof |
| US20160016369A1 (en) * | 2014-05-21 | 2016-01-21 | University Of South Carolina | Novel Additive Manufacturing-Based Electric Poling Process of PVDF Polymer for Piezoelectric Device Applications |
| CN105385077A (en) * | 2015-12-21 | 2016-03-09 | 中国科学院长春应用化学研究所 | Polyvinylidene fluoride composite material, preparation method and applications thereof |
| CN105739612A (en) * | 2014-12-30 | 2016-07-06 | 意美森公司 | Deformable Haptic Wearables With Variable Physical Properties |
| CN105758452A (en) * | 2016-02-04 | 2016-07-13 | 歌尔声学股份有限公司 | Wearing state detection method and device of wearable equipment |
| US20160225775A1 (en) * | 2014-09-09 | 2016-08-04 | Sabic Global Technologies B.V. | Methods for producing a thin film ferroelectric device using a two-step temperature process |
| JP2016160307A (en) * | 2015-02-27 | 2016-09-05 | 公立大学法人大阪市立大学 | Method for producing polyvinylidene fluoride film |
| KR20160147446A (en) * | 2015-06-15 | 2016-12-23 | 서울시립대학교 산학협력단 | manufacture method of bulletproof glass using ferroelectrics |
| KR101840136B1 (en) * | 2016-11-10 | 2018-03-20 | 중앙대학교 산학협력단 | Manufacturing method for PVDF based film and fiber with an increased β-phase ratio |
| CN109686836A (en) * | 2018-11-27 | 2019-04-26 | 江苏大学 | A kind of preparation method of the 3D printing poly meta fluoroethylene piezoelectric film under uniform electric field |
| CN110752286A (en) * | 2019-10-25 | 2020-02-04 | 业成科技（成都）有限公司 | Piezoelectric film, preparation method thereof and piezoelectric film sensor |
| CN111166304A (en) * | 2019-12-31 | 2020-05-19 | 青岛理工大学 | Medical health flexible sensor detection system |
| CN112745519A (en) * | 2019-10-31 | 2021-05-04 | 北京化工大学 | Preparation method of polyvinylidene fluoride film |
| CN113336986A (en) * | 2021-06-03 | 2021-09-03 | 陕西科技大学 | Preparation method of oriented gamma-phase PVDF/CTAB composite film |
| CN214667279U (en) * | 2021-05-14 | 2021-11-09 | 深圳市三五智能科技有限公司 | Wearable intelligent body temperature monitoring device |
| JP2021176629A (en) * | 2020-05-01 | 2021-11-11 | 三菱ケミカル株式会社 | Resin composition manufacturing method, porous film manufacturing method, and porous film |
| CN113659069A (en) * | 2021-05-08 | 2021-11-16 | 西华大学 | High-performance PVDF (polyvinylidene fluoride) -based flexible piezoelectric device based on MXene and micro injection molding and preparation method thereof |
| CN113801413A (en) * | 2021-11-02 | 2021-12-17 | 北京航空航天大学 | Photosensitive ferroelectric polymer composite film, method for preparing the same, and ferroelectric device or piezoelectric device using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI614386B (en) * | 2015-03-11 | 2018-02-11 | National Taiwan University Of Science And Technology | Acoustic absorbing material |
| WO2021168750A1 (en) * | 2020-02-27 | 2021-09-02 | 南昌欧菲显示科技有限公司 | Piezoelectric film and preparation method therefor, and piezoelectric film sensor |
| CN113261841A (en) * | 2021-03-19 | 2021-08-17 | 武汉理工大学 | Noise reduction and power generation curtain based on flexible composite phonon structure |
-
2022
- 2022-05-26 CN CN202210581109.3A patent/CN114953296B/en active Active
- 2022-05-31 TW TW111120191A patent/TWI828170B/en active
Patent Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308370A (en) * | 1979-04-26 | 1981-12-29 | Rikagauku Kenkyusho | Piezoelectric and pyroelectric polymer film and process for preparing same |
| US5922493A (en) * | 1995-03-03 | 1999-07-13 | Elf Atochem North America, Inc. | Polymeric electrode and electrolyte article of manufacture |
| ITMI972764A1 (en) * | 1997-12-15 | 1999-06-15 | Ausimont Spa | FLUORINATED THERMOPLASTIC ELASTOMERS |
| KR20090030827A (en) * | 2007-09-21 | 2009-03-25 | 경희대학교 산학협력단 | METHOD FOR PRODUCING POLY(VINYLIDENE FLUORIDE) NANOFIBER WEB WITH HIGH beta- TYPE CRYSTAL STRUCTURE |
| KR20090131313A (en) * | 2008-06-18 | 2009-12-29 | 연세대학교 산학협력단 | Spin cast ferroelectric beta poly(vinylidene fluoride) thin film via rapid thermal annealing |
| CN102805615A (en) * | 2012-07-26 | 2012-12-05 | 翁整 | Smart phone application-based life sign monitoring alarm |
| US20160016369A1 (en) * | 2014-05-21 | 2016-01-21 | University Of South Carolina | Novel Additive Manufacturing-Based Electric Poling Process of PVDF Polymer for Piezoelectric Device Applications |
| US20160225775A1 (en) * | 2014-09-09 | 2016-08-04 | Sabic Global Technologies B.V. | Methods for producing a thin film ferroelectric device using a two-step temperature process |
| CN104291264A (en) * | 2014-10-17 | 2015-01-21 | 华中科技大学 | Nano-piezoelectric fiber based flexible energy-harvesting device and manufacturing method thereof |
| CN105739612A (en) * | 2014-12-30 | 2016-07-06 | 意美森公司 | Deformable Haptic Wearables With Variable Physical Properties |
| JP2016160307A (en) * | 2015-02-27 | 2016-09-05 | 公立大学法人大阪市立大学 | Method for producing polyvinylidene fluoride film |
| KR20160147446A (en) * | 2015-06-15 | 2016-12-23 | 서울시립대학교 산학협력단 | manufacture method of bulletproof glass using ferroelectrics |
| CN105385077A (en) * | 2015-12-21 | 2016-03-09 | 中国科学院长春应用化学研究所 | Polyvinylidene fluoride composite material, preparation method and applications thereof |
| CN105758452A (en) * | 2016-02-04 | 2016-07-13 | 歌尔声学股份有限公司 | Wearing state detection method and device of wearable equipment |
| KR101840136B1 (en) * | 2016-11-10 | 2018-03-20 | 중앙대학교 산학협력단 | Manufacturing method for PVDF based film and fiber with an increased β-phase ratio |
| CN109686836A (en) * | 2018-11-27 | 2019-04-26 | 江苏大学 | A kind of preparation method of the 3D printing poly meta fluoroethylene piezoelectric film under uniform electric field |
| CN110752286A (en) * | 2019-10-25 | 2020-02-04 | 业成科技（成都）有限公司 | Piezoelectric film, preparation method thereof and piezoelectric film sensor |
| CN112745519A (en) * | 2019-10-31 | 2021-05-04 | 北京化工大学 | Preparation method of polyvinylidene fluoride film |
| CN111166304A (en) * | 2019-12-31 | 2020-05-19 | 青岛理工大学 | Medical health flexible sensor detection system |
| JP2021176629A (en) * | 2020-05-01 | 2021-11-11 | 三菱ケミカル株式会社 | Resin composition manufacturing method, porous film manufacturing method, and porous film |
| CN113659069A (en) * | 2021-05-08 | 2021-11-16 | 西华大学 | High-performance PVDF (polyvinylidene fluoride) -based flexible piezoelectric device based on MXene and micro injection molding and preparation method thereof |
| CN214667279U (en) * | 2021-05-14 | 2021-11-09 | 深圳市三五智能科技有限公司 | Wearable intelligent body temperature monitoring device |
| CN113336986A (en) * | 2021-06-03 | 2021-09-03 | 陕西科技大学 | Preparation method of oriented gamma-phase PVDF/CTAB composite film |
| CN113801413A (en) * | 2021-11-02 | 2021-12-17 | 北京航空航天大学 | Photosensitive ferroelectric polymer composite film, method for preparing the same, and ferroelectric device or piezoelectric device using the same |
Non-Patent Citations (7)
| Title |
|---|
| LOVINGER, A.J.: "Flexoelectric and ferroelectric properties of quenched polyvinylidene fluoride (PVDF) homopolymer films", JOURNAL OF POLYMER SCIENCE, vol. 18, no. 4, pages 793 - 809 * |
| ZHAOLIANG CUI: "Crystalline polymorphism in poly(vinylidenefluoride) membranes", PROGRESS IN POLYMER SCIENCE, vol. 51, pages 94 - 126 * |
| 刘京强;崔巍巍;刘立柱;陆以杉;张娜;唐冬雁;: "不同溶剂配比对单轴共纺PVDF/PEI纤维薄膜性能影响的研究", 化工新型材料, no. 05 * |
| 张宇;王威;徐磊;: "浅谈聚偏氟乙烯压电薄膜的制备方法", 化工新型材料, no. 10 * |
| 张玲玲;国世上;: "铁电高分子PVDF及其共聚物研究进展", 物理学进展, no. 02 * |
| 梁爽;郑茂梅;孙平;汪忠兴;朱基亮;: "聚偏氟乙烯结晶结构及其β相制备方法的研究", 压电与声光, no. 05 * |
| 王威;马爽;韩都;徐磊;: "静电纺丝法制备服装用PVDF压电传感器", 仪表技术与传感器, no. 10 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114953296B (en) | 2023-08-29 |
| TWI828170B (en) | 2024-01-01 |
| TW202346437A (en) | 2023-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Flexible 3D architectured piezo/thermoelectric bimodal tactile sensor array for E‐skin application | |
| Gao et al. | A review of flexible perovskite oxide ferroelectric films and their application | |
| KR101302780B1 (en) | Piezoelectric polymer material, process for producing same, and piezoelectric element | |
| Yao et al. | Recent progress on the fabrication and applications of flexible ferroelectric devices | |
| Pan et al. | A self-powered vibration sensor based on electrospun poly (vinylidene fluoride) nanofibres with enhanced piezoelectric response | |
| US20190023817A1 (en) | Ferroelectric polymers from dehydrofluorinated PVDF | |
| US4204135A (en) | Piezoelectric elements of organic high molecular weight materials | |
| KR20160053079A (en) | A piezoelectric fiber, a preparation method thereof, and textile, clothing and a wearable piezoelectric sensor using the fiber | |
| CN114953296B (en) | Manufacturing method of polycrystalline polyvinylidene fluoride film and wearable device | |
| EP0047740A1 (en) | Vinylidene fluoride polymers | |
| Lei et al. | Short-term plasticity, multimodal memory, and logical responses mimicked in stretchable hydrogels | |
| Han et al. | Self-powered vision electronic-skin basing on piezo-photodetecting Ppy/PVDF pixel-patterned matrix for mimicking vision | |
| EP3583138B1 (en) | Ferroelectric polymers from dehydrofluorinated pvdf | |
| Lun et al. | Piezoelectric self-power supply driven by ferroelastic host–guest supramolecule with considerable electromechanical conversion capability | |
| GB2149204A (en) | Method of producing polymeric electret elements | |
| Karner‐Petritz et al. | Ultraflexible organic active matrix sensor sheet for tactile and biosignal monitoring | |
| CN111361302B (en) | Preparation method of flexible film resistant to stress stretching | |
| JP3470471B2 (en) | Polymer electret material and method for producing the same | |
| CN110464325A (en) | A kind of pulse inductive module and intelligent wearable device | |
| Huang et al. | Recent development of piezoelectric biosensors for physiological signal detection and machine learning assisted cardiovascular disease diagnosis | |
| Tao et al. | A multimodal ion electronic skin for decoupling temperature and strain | |
| Rokaya et al. | Motion energy harvesting and storage system including printed piezoelectric film and supercapacitor | |
| KR101840136B1 (en) | Manufacturing method for PVDF based film and fiber with an increased β-phase ratio | |
| Marcus | Polyvinylidene Fluoride for Piezoelectric and Pyroelectric Applications | |
| Batra et al. | Polyvinylidene fluoride-praseodymium oxide nanocomposite force sensors for monitoring human physiological and muscle motion signs |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240111 Address after: 518109, Building E4, 101, Foxconn Industrial Park, No. 2 East Ring 2nd Road, Fukang Community, Longhua Street, Longhua District, Shenzhen City, Guangdong Province (formerly Building 1, 1st Floor, G2 District), H3, H1, and H7 factories in K2 District, North Shenchao Optoelectronic Technology Park, Minqing Road, Guangdong Province Patentee after: INTERFACE OPTOELECTRONICS (SHENZHEN) Co.,Ltd. Patentee after: Interface Technology (Chengdu) Co., Ltd. Patentee after: GENERAL INTERFACE SOLUTION Ltd. Address before: No.689 Hezuo Road, West District, high tech Zone, Chengdu City, Sichuan Province Patentee before: Interface Technology (Chengdu) Co., Ltd. Patentee before: INTERFACE OPTOELECTRONICS (SHENZHEN) Co.,Ltd. Patentee before: Yicheng Photoelectric (Wuxi) Co.,Ltd. Patentee before: GENERAL INTERFACE SOLUTION Ltd. |
|
| TR01 | Transfer of patent right |