WO2013020410A1 - 聚四氟乙烯机电能量转换功能膜的连续化生产工艺 - Google Patents

聚四氟乙烯机电能量转换功能膜的连续化生产工艺 Download PDF

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Publication number
WO2013020410A1
WO2013020410A1 PCT/CN2012/076329 CN2012076329W WO2013020410A1 WO 2013020410 A1 WO2013020410 A1 WO 2013020410A1 CN 2012076329 W CN2012076329 W CN 2012076329W WO 2013020410 A1 WO2013020410 A1 WO 2013020410A1
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Prior art keywords
film
polytetrafluoroethylene
composite film
corona
composite
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PCT/CN2012/076329
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English (en)
French (fr)
Inventor
宫香山
张晓青
宫继业
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上海大宫新材料有限公司
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Priority claimed from CN201110227833.8A external-priority patent/CN102350850B/zh
Application filed by 上海大宫新材料有限公司 filed Critical 上海大宫新材料有限公司
Priority to US14/359,470 priority Critical patent/US20140318703A1/en
Priority to EP12822691.7A priority patent/EP2756951B1/en
Publication of WO2013020410A1 publication Critical patent/WO2013020410A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
    • H10N30/045—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning by polarising
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/098—Forming organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/14—Velocity, e.g. feed speeds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • B32B2327/18—PTFE, i.e. polytetrafluoroethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Definitions

  • the invention relates to a preparation method of a polymer-based functional film, in particular to a continuous production process of a polytetrafluoroethylene electromechanical energy conversion functional film.
  • Piezoelectrets are space-charged electret materials with piezoelectric effects (ie, electromechanical energy conversion effects) whose piezoelectric effect originates from long-term storage of matrix electret materials.
  • piezoelectric effects ie, electromechanical energy conversion effects
  • Figure 1 is a schematic diagram of the microstructure of the piezoelectric electret material, the space charge distribution, and the piezoelectric effect.
  • Piezoelectric electrets are a new class of piezoelectric functional materials that appeared just around 1990. They concentrate the piezoelectric effect of piezoelectric ceramics and the flexibility of polymer ferroelectric materials such as polyvinylidene fluoride piezoelectric films. As a result, such materials have broad application prospects in various fields such as electroacoustic sensors, pressure sensors, ultrasonic sensors, vibration energy harvesters, and medical care.
  • piezoelectric electret material is polypropylene (PP) piezoelectric electret film. Its manufacturer is EMFit Company of Finland. In other countries and in China, there is no enterprise capable of producing such products. Therefore, The current applications of piezoelectric electrets are based on commercial PP piezoelectric electret films.
  • the operating temperature of the PP piezoelectric electret film generally cannot exceed 60 ° C.
  • the piezoelectric effect of the PP piezoelectric electret film is higher than the working temperature. It will be sharply weakened or even completely lost.
  • the technical problem to be solved by the present invention is to provide a continuous production process of a polytetrafluoroethylene electromechanical energy conversion functional film, which has a large-scale and continuous operation suitable in a factory, and thermal stability and piezoelectricity of the product.
  • the properties are significantly better than those of the PP piezoelectric electret film.
  • Another technical problem to be solved by the present invention is to provide a polytetrafluoroethylene electromechanical energy conversion functional film product obtained by the above production method.
  • the technical solution adopted by the present invention to solve the above technical problems is: a continuous production process of a polytetrafluoroethylene electromechanical energy conversion functional film, including a thermal bonding step of a microporous composite film and a charging of a composite film
  • the electrical step is two parts, wherein the thermal bonding step of the microporous composite film is: at least two layers of dense polytetrafluoroethylene film, and a layer between each adjacent two-layer polytetrafluoroethylene film
  • the porous polytetrafluoroethylene film is alternately laminated and then introduced into the composite film by hot press bonding between the upper and lower hot press rolls; and then the composite film is charged to obtain a polytetrafluoroethylene piezoelectric electret film.
  • the PTFE film refers to a dense structure PTFE film prepared by various processes, such as a turning film (orienting film), a cast film, a blown film, and the like.
  • the porous PTFE film refers to a porous structure PTFE film obtained by various processes.
  • the charging step of the composite film is: the composite film enters between the electrode roller and the corona electrode for corona polarization, and the corona polarization treated polytetrafluoroethylene composite film is obtained and rolled up. volume.
  • the charging step of the composite film is: the composite film enters the electroplating zone and the electrode is attached to the upper and lower surfaces of the film, and enters the contact charging zone to obtain a corona-polarized polytetrafluoroethylene composite film. Roll up on the roll.
  • the polytetrafluoroethylene composite film derived from the upper and lower hot pressing rolls is pressed against the surface of the electrode roller through the corona polarization zone, and then wound up by the winding roller to complete the PTFE piezoelectric station. Production of polar film.
  • a porous polytetrafluoroethylene film having a thickness of 2 to 40 ⁇ m and a layer of expanded porous polytetrafluoroethylene film having a thickness of 2 to 400 ⁇ m are used to expand the porous polytetrafluoroethylene.
  • the film is sandwiched between two layers of dense polytetrafluoroethylene film to form a film system.
  • the two embossings on the surface of the upper and lower hot press rolls are 150 mm, and the embossing on the surface of the hot press roll 9 is a cross pattern.
  • the temperature of the film is 0. 1 ⁇ 20m/min, after hot pressing, the temperature of the film is 0. 1 ⁇ 20m/min.
  • the distance between the corona electrode and the electrode roller is 0. 1 ⁇ 50cm, and the corona voltage is 20kV, the distance between the corona electrode and the electrode roller is 0. 1 ⁇ 50cm,
  • the temperature of the corona zone is -40 to 380 ° C, and after corona treatment, a polytetrafluoroethylene piezoelectric electret film is obtained.
  • a film surface plating system and a contact charging system are disposed between the upper and lower hot pressing rolls and the winding roller, and the polytetrafluoroethylene composite film derived from the upper and lower hot pressing rolls first enters the electroplating.
  • the system attaches a well-conductive electrode to the upper and lower surfaces of the film, and then the PTFE composite film with electrodes on both sides enters the contact charging system under the action of the winding roller, and the high-voltage direct current is directly applied to the PTFE composite film.
  • the electrodeposition step of the polytetrafluoroethylene composite film is completed, and finally, the winding roller is wound up.
  • a finished product of a polytetrafluoroethylene piezoelectric electret film is disposed between the upper and lower hot pressing rolls and the winding roller, and the polytetrafluoroethylene composite film derived from the upper and lower hot pressing rolls first enters the electroplating.
  • the system attaches a well-conductive electrode to the upper and lower surfaces of
  • a porous polytetrafluoroethylene film having a thickness of 20 to 200 ⁇ m and a layer of expanded porous polytetrafluoroethylene film having a thickness of 20 to 1000 ⁇ m are used to expand the porous polytetrafluoroethylene.
  • the film is sandwiched between two layers of dense polytetrafluoroethylene film to form a film system.
  • the two embossing surfaces of the surface of one or two hot pressing rolls are cross-shaped by two upper and lower hot pressing rolls with a diameter of 150 mm. 5 ⁇ 60 ⁇ / ⁇ , The film is passed through the upper and lower hot press rolls at a speed of 0.
  • the film system is After hot pressing, a microporous structure polytetrafluoroethylene composite film is prepared, and then the composite film enters the electroplating system, and a metal aluminum electrode of 2 to 1000 nm thick is vapor-deposited on the upper and lower surfaces of the composite film, and then a DC voltage of 100 to 20000 V is applied thereto.
  • the set temperature of the contact charging system is -40 to 380 ° C, and the polytetrafluoroethylene piezoelectric electret film is obtained by the contact charging treatment.
  • the polytetrafluoroethylene electromechanical energy conversion functional film obtained by the above continuous production process having at least two layers of dense polytetrafluoroethylene film and being disposed between each adjacent two-layer polytetrafluoroethylene film A layer of porous polytetrafluoroethylene film is sandwiched to form an alternately laminated film structure.
  • the functional film product comprises a porous fluoroplastic piezoelectric functional film formed by laminating a porous polytetrafluoroethylene film with a porous polytetrafluoroethylene film, wherein the porous polytetrafluoroethylene film is an n layer, ⁇ 1,
  • the dense PTFE film is n+1 layer.
  • a layer of porous PTFE film sandwiched between two layers of dense PTFE film formed by a polytetrafluoroethylene voltage electret functional film two layers of porous PTFE film stack sandwiched between three layers of dense PTFE film formed of polytetrafluoroethylene Voltage electret functional film, etc.
  • the production process of the invention has continuity, high production efficiency, and the polytetrafluoroethylene electromechanical energy conversion function film product has excellent piezoelectric performance and high thermal temperature.
  • Fig. 1 is a schematic diagram showing the microstructure, space charge distribution, and piezoelectric effect of the piezoelectric electret material of the present invention.
  • FIG. 2 is a schematic view showing a process for producing a PTFE piezoelectric electret film by corona polarization according to the present invention.
  • Fig. 3 is a schematic view showing the process of producing a PTFE piezoelectric electret film by contact charging according to the present invention.
  • 4 is a graph showing the pressure characteristic curve of the piezoelectric coefficient t 33 of the PTFE piezoelectric electret film according to Example 1 of the present invention.
  • 5 is an isothermal decay of a piezoelectric coefficient of a PTFE piezoelectric electret film according to Embodiment 1 of the present invention at 120 ° C. Decrease the graph.
  • Fig. 6 is a graph showing the isothermal decay curve of the piezoelectric coefficient ⁇ of the PTFE piezoelectric electret film at 200 ° C according to Example 1 of the present invention.
  • FIG. 7 is a schematic structural view of a polytetrafluoroethylene piezoelectric electret functional film of the present invention.
  • 16 contact charging system (15 is high voltage DC power supply, 16 is the electrode).
  • FIG. 1 is a schematic diagram showing the microstructure, space charge distribution, and piezoelectric effect of a piezoelectric electret material according to the present invention, and a continuous production process of a polytetrafluoroethylene electromechanical energy conversion functional film, including micro a thermal bonding step of the pore structure composite film and a charging step of the composite film, wherein
  • the thermal bonding step of the microporous composite film is as follows: using a dense layer of 5 ⁇ thick dense PTFE film 6, 8 and a 5 ⁇ m thick expanded porous PTFE film 7, the expanded porous PTFE film 7 is sandwiched between two layers of dense PTFE membranes 6, 8 to form a membrane system, and then introduced two upper and lower hot press rolls 9, 10 having a diameter of 150 mm for thermocompression bonding, upper and lower hot press rolls 9, 10 surface
  • the embossing is a cross pattern, the temperature is 150 ° C, the pressure applied by the upper and lower hot pressing rolls 9 and 10 on the film system is 1 MPa, and the speed at which the film is traveling between the upper and lower hot pressing rolls 9 and 10 is 0.
  • FIG. 2 is a schematic view showing a process for producing a PTFE piezoelectric electret film by corona polarization according to the present invention
  • the corona polarization step of the charging or composite film is: the composite film enters the electrode roller 12 and the corona electrode 11 (corona polarization region) to perform corona polarization, the corona voltage is 20 kV, and the corona electrode (11) and The distance between the electrode rolls (12) is 4 cm, and the temperature in the corona area is 25 ° C.
  • PTFE composite film treatment is to obtain a piezoelectric PTFE electret film, wound on a take-up reel 13.
  • FIG. 4 is a pressure coefficient of a piezoelectric coefficient of a PTFE piezoelectric electret film according to Embodiment 1 of the present invention.
  • the piezoelectric coefficient of the film prepared in Example 1 can be as high as SOOpC/N, which is much higher than that of the commercial PP piezoelectric electret film (0S01 model: 25pC/N; HS01 model) : 230 pC/N), and maintains good stability over a pressure range of l-6 kPa.
  • Example 5 is a graph showing the isothermal decay curve of the piezoelectric coefficient of a PTFE piezoelectric electret film according to Embodiment 1 of the present invention at 120 ° C.
  • the film prepared in Example 1 is in the early stage of heat aging (3 hours). Inside), the value decreased; after 3 hours of heat aging treatment, the value was stable in the range of 200-400 pC/N.
  • the thermal stability of the PTFE piezoelectric electret film is significantly better than that of the commercial PP piezoelectric electret film (the operating temperature of the PP piezoelectric electret film is lower than 60 ° C, at 120 ° C, PP piezoelectric The electret film is strongly contracted and deformed, and the piezoelectric effect is lost).
  • the film of the first embodiment is a PTFE piezoelectric electret film.
  • a PTFE piezoelectric electret film having a high piezoelectric effect (for example, 100 pC/N) which can operate under an extreme temperature (for example, 200 ° C).
  • a film surface plating system 14 and a contact charging system 15, 16 are disposed between the upper and lower heat pressing rolls 9, 10 and the take-up roll 13.
  • a continuous production process of a polytetrafluoroethylene electromechanical energy conversion functional film comprising a thermal bonding step of a microporous composite film and a charging step of a composite film, wherein
  • the thermal bonding step of the microporous composite film is: sandwiching the expanded porous PTFE film on the second layer by using two layers of a dense PTFE film having a thickness of 20 ⁇ m and a layer of a 400 ⁇ m thick expanded porous PTFE film.
  • the dense PTFE film forms a film system between two upper and lower hot press rolls 9, 10 having a diameter of 150 mm, wherein the embossing of the surface of the upper heat press roll 9 is a cross pattern, and the temperature is 420 ° C.
  • the pressure of the lower hot press rolls 9, 10 applied to the film system is 200 MPa, and the film travels at a speed of 32 m/min between the upper and lower hot press rolls 9, 10, and the film system is subjected to hot pressing to obtain a microporous structure PTFE.
  • FIG. 3 a schematic diagram of a process for producing a PTFE piezoelectric electret film by contact charging according to the present invention is shown.
  • the charging process of the composite film that is, the contact charging method of the composite film is: the composite film enters the plating system 14 (plating area) ), depositing a 100 nm thick metal aluminum electrode on the upper and lower surfaces of the composite film, and then applying a DC voltage of 8000 V between the upper and lower metal aluminum electrodes of the PTFE composite film, the contact charging system 15, 16 (contact charging area)
  • the set temperature is 25 °C, and the PTFE pressure is obtained after the contact method is charged.
  • the electric electret film is wound up on the take-up roll 13.
  • the product prepared by the process of the embodiment of the invention comprises a porous fluoroplastic piezoelectric functional film formed by laminating a porous PTFE film with a porous PTFE film, wherein the porous PTFE film is n layer, n ⁇ l
  • the dense PTFE film is n+1 layer.
  • Example 3 The piezoelectric coefficient ⁇ of the film prepared in Example 2 at a pressure of 3. 2 kPa was 1362 pC/N, indicating that a higher piezoelectric effect PTFE piezoelectric electret film can be obtained by optimizing the electrodeization parameters.
  • Example 3 The piezoelectric coefficient ⁇ of the film prepared in Example 2 at a pressure of 3. 2 kPa was 1362 pC/N, indicating that a higher piezoelectric effect PTFE piezoelectric electret film can be obtained by optimizing the electrodeization parameters.
  • a two-layer 50 ⁇ m thick turned PTFE film 6, 8 and a 2 ⁇ m thick expanded porous PTFE film 7 are used to sandwich the expanded porous PTFE film 7 between two layers of dense PTFE film 6 and 8 to form a film.
  • two upper and lower hot press rolls 9, 10 having a diameter of 150 mm are introduced for hot press bonding, and the embossing of the upper and lower hot press rolls 9, 10 is a cross pattern, and the temperature is 150 ° C.
  • the lower pressing roller 9, 10 applies a pressure of 200 MPa on the film system, and the film travels at a speed of 10 m/min between the upper and lower hot pressing rolls 9, 10, and the microporous structure PTFE composite is obtained by hot pressing.
  • FIG. 2 is a schematic view showing a process for producing a PTFE piezoelectric electret film by corona polarization according to the present invention.
  • the charging process of the composite film that is, the corona polarization step of the composite film is: the composite film enters the electrode roller 12 and Corona polarization is performed between the corona electrode 11 (corona polarization region), the corona voltage is 20 kV, the distance between the corona electrode (11) and the electrode roller (12) is 4 cm, and the temperature in the corona region is 25 At °C, a corona-polarized PTFE composite film was obtained, and a PTFE piezoelectric electret film was obtained, which was wound up on a winding roller 13.
  • Example 4 The test result of the piezoelectric coefficient ⁇ at a pressure of 3. 2 kPa of the film obtained in Example 3 was 998.
  • a two-layer 200 ⁇ m thick dense PTFE film 6, 8 and a 1000 ⁇ m thick expanded porous PTFE film 7 are used to sandwich the expanded porous PTFE film 7 between two layers of dense PTFE films 6, 8 to form a film.
  • two upper and lower hot press rolls 9, 10 having a diameter of 150 mm are introduced for hot press bonding, and the embossing of the upper and lower hot press rolls 9, 10 is a cross pattern, and the temperature is 550 ° C
  • the pressure applied by the lower hot press rolls 9, 10 on the film system is 400 MPa, and the film speed is 60 m/min between the upper and lower hot press rolls 9, 10, and the microporous structure PTFE composite is obtained by hot pressing. membrane.
  • FIG. 2 is a schematic view showing a process for producing a PTFE piezoelectric electret film by corona polarization according to the present invention.
  • the charging process of the composite film that is, the corona polarization step of the composite film is: the composite film enters the electrode roller 12 and Corona polarization is performed between the corona electrode 11 (corona polarization region), the corona voltage is 20 kV, the distance between the corona electrode (11) and the electrode roller (12) is 4 cm, and the temperature in the corona region is 25 At °C, a corona-polarized PTFE composite film was obtained, and a PTFE piezoelectric electret film was obtained, which was wound up on a winding roller 13.
  • the piezoelectric modulus of the film prepared in Example 4 at a pressure of 3.2 kPa was 1928 pC/N 0
  • a two-layer 40 ⁇ m thick dense PTFE film 6, 8 and a 500 ⁇ m thick expanded porous PTFE film 7 are used to sandwich the expanded porous PTFE film 7 between two layers of dense PTFE films 6 and 8.
  • two upper and lower hot press rolls 9, 10 having a diameter of 150 mm are introduced for hot press bonding, and the embossing of the upper and lower hot press rolls 9, 10 is a cross pattern, and the temperature is 450 ° C.
  • the micro-porous structure is obtained by hot pressing after the hot pressing of the film is carried out at a pressure of 200 MPa, and the film is fed between the upper and lower hot-pressing rolls 9, 10 at a speed of 0.5 m/min.
  • PTFE composite film is obtained by hot pressing after the hot pressing of the film is carried out at a pressure of 200 MPa, and the film is fed between the upper and lower hot-pressing rolls 9, 10 at a speed of 0.5 m/min.
  • FIG. 2 is a schematic view showing a process for producing a PTFE piezoelectric electret film by corona polarization according to the present invention.
  • the charging process of the composite film that is, the corona polarization step of the composite film is: the composite film enters the electrode roller 12 and Corona polarization is performed between the corona electrode 11 (corona polarization region), the corona voltage is 20 kV, the distance between the corona electrode (11) and the electrode roller (12) is 4 cm, and the temperature in the corona region is 25 At °C, a corona-polarized PTFE composite film was obtained, and a PTFE piezoelectric electret film was obtained, which was wound up on a winding roller 13.
  • the piezoelectric coefficient of the film prepared in Example 5 at a pressure of 3.2 kPa was tested at 2446 pC/N 0 .

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  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Fluid Mechanics (AREA)
  • General Electrical Machinery Utilizing Piezoelectricity, Electrostriction Or Magnetostriction (AREA)
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Abstract

本发明涉及聚四氟乙烯机电能量转换功能膜的连续化生产工艺，包括微孔结构复合膜的热粘合步骤以及复合膜的充电步骤两部分，其中，所述的微孔结构复合膜的热粘合步骤为：至少有二层致密聚四氟乙烯薄膜，且在每相邻的二层聚四氟乙烯薄膜间夹有一层多孔聚四氟乙烯薄膜交替层叠后导入上、下热压辊之间进行热压粘合，制成复合膜；然后将复合膜进行充电，得到聚四氟乙烯压电驻极体薄膜。复合膜的充电步骤为：复合膜进入电极辊与电晕电极间进行电晕极化，或者，复合膜进入电镀区在薄膜上下表面附着电极，在进入接触法充电区。优点是：本发明的生产工艺具有连续性，生产效率高，聚四氟乙烯机电能量转换功能膜产品具有优异的压电性能和高热温度性。

Description

聚四氟乙烯机电能量转换功能膜的连续化生产工艺
技术领域
本发明涉及高分子基功能薄膜的制备方法，尤其涉及聚四氟乙烯机电能量转 换功能膜的连续化生产工艺。
背景技术
压电驻极体 piezoelectrets (或称为铁电驻极体 ferroelectrets 是指具 有压电效应（即机电能量转换效应）的空间电荷驻极体材料， 其压电效应源于基 体驻极体材料长期储存空间电荷的能力和材料特殊的微孔结构。图 1是压电驻极 体材料微观结构、 空间电荷分布， 以及压电效应产生的原理图。
压电驻极体是 1990年前后刚刚出现的新一类压电功能材料， 它集中了压电 陶瓷的强压电效应和聚合物铁电材料（例如聚偏氟乙烯压电薄膜）的柔韧性于一 身， 因此， 这类材料在各类电声传感器、 压力传感器、 超声波传感器、 振动能量 采集器、 医疗护理等领域有广阔的应用前景。
目前唯一商品化的压电驻极体材料是聚丙烯（PP)压电驻极体薄膜， 其生产 商为芬兰的 EMFit公司，其它国家和我国国内尚无企业有能力生产该类产品， 因 此， 当前应用压电驻极体的产品均是基于商品 PP压电驻极体薄膜。 但是受限于 PP材料自身较低的空间电荷储存稳定性， PP压电驻极体薄膜的工作温度一般不 能超过 60°C， 高于工作温度时 PP压电驻极体薄膜的压电效应便会急剧减弱、 甚 至完全丧失。基于此，许多相关领域的科研工作者努力研制高热稳定性的压电驻 极体新材料， 并出现了一些具有高热稳定性的实验室样品。但是目前还没有关于 高热稳定性压电驻极体薄膜规模化、 连续化生产工艺的报道。
发明内容
本发明所要解决的技术问题在于提供一种聚四氟乙烯机电能量转换功能膜 的连续化生产工艺， 该生产工艺具有适合在工厂中大规模、连续化作业， 并且产 品的热稳定性和压电性均显著优于 PP压电驻极体薄膜的特点。
本发明所要解决的另一技术问题在于提供利用上述制备方法获得的聚四氟 乙烯机电能量转换功能膜产品。
本发明解决上述技术问题所采取的技术方案是：一种聚四氟乙烯机电能量转 换功能膜的连续化生产工艺，包括微孔结构复合膜的热粘合步骤以及复合膜的充 电步骤两部分， 其中， 所述的微孔结构复合膜的热粘合步骤为： 至少有二层致密 聚四氟乙烯薄膜，且在每相邻的二层聚四氟乙烯薄膜间夹有一层多孔聚四氟乙烯 薄膜交替层叠后导入上、下热压辊之间进行热压粘合， 制成复合膜； 然后将复合 膜进行充电， 得到聚四氟乙烯压电驻极体薄膜。
所述的 PTFE薄膜是指采用各种工艺制备的致密结构 PTFE薄膜，例如车削膜 (定向膜）、流延膜、 吹塑膜等等。所述的多孔 PTFE薄膜是指用各类工艺制备获 得的多孔结构 PTFE薄膜。
在上述方案的基础上，所述的复合膜的充电步骤为： 复合膜进入电极辊与电 暈电极间进行电暈极化， 得到电暈极化处理的聚四氟乙烯复合薄膜并辊上收卷。
在上述方案的基础上，所述的复合膜的充电步骤为： 复合膜进入电镀区在薄 膜上下表面附着电极，在进入接触法充电区，得到电暈极化处理的聚四氟乙烯复 合薄膜并辊上收卷。
在上述方案的基础上， 由上、下热压辊间导出的聚四氟乙烯复合膜紧贴电极 辊表面经过电暈极化区，然后由收卷辊收卷完成聚四氟乙烯压电驻极体薄膜的生 产。
在上述方案的基础上， 采用二层 2〜40 μ πι厚度的致密聚四氟乙烯薄膜和一 层 2〜400 μ πι厚度的膨体多孔聚四氟乙烯薄膜，将膨体多孔聚四氟乙烯薄膜夹在 二层致密聚四氟乙烯薄膜之间构成膜系， 经两个直径为 150mm的上、 下热压辊， 上、 热压辊 9表面的压花为十字图案， 上、 下热压辊的温度为 100〜450°C， 施 加在膜系上的压力为 0. l〜200MPa， 膜系在上、 下热压辊间行进的速度为 0. 1〜 20m/min, 经热压后制得微孔结构聚四氟乙烯复合膜， 然后复合膜经过电暈极化 区进行电暈充电处理，电暈电压为 20kV， 电暈电极与电极辊之间的距离为 0. 1〜 50cm, 电暈区的温度为 -40〜380°C， 经过电暈处理后制得聚四氟乙烯压电驻极体 薄膜。
在上述方案的基础上，在上、下热压辊和收卷辊之间设置一薄膜表面电镀系 统和接触法充电系统， 由上、下热压辊导出的聚四氟乙烯复合膜首先进入电镀系 统使薄膜上下表面附着导电性良好的电极，然后双面带有电极的聚四氟乙烯复合 膜在收卷辊的牵动下进入接触法充电系统，高压直流电直接施加在聚四氟乙烯复 合膜的上下电极间， 完成聚四氟乙烯复合膜的电极化步骤， 最后由收卷辊收卷， 制成聚四氟乙烯压电驻极体薄膜的成品。
在上述方案的基础上， 采用二层 20〜200 μ πι厚度的致密聚四氟乙烯薄膜和 一层 20〜1000 μ πι厚度的膨体多孔聚四氟乙烯薄膜，将膨体多孔聚四氟乙烯薄膜 夹在二层致密聚四氟乙烯薄膜之间构成膜系， 经两个直径为 150mm的上、下热压 辊， 其中一个或两个热压辊的表面的压花为十字图案， 上、 下热压辊的温度为 150〜550°C， 施加在膜系上的压力为 2〜400MPa， 膜系在上、 下热压辊间行进的 速度为 0. 5〜60m/min， 膜系经热压后制得微孔结构聚四氟乙烯复合膜， 然后复 合膜进入电镀系统，在复合膜上下两表面蒸镀 2〜1000nm厚的金属铝电极，随后， 将 100〜20000V的直流电压加在聚四氟乙烯复合膜的上下两金属铝电极之间，接 触法充电系统的设定温度为 -40〜380°C，经接触法充电处理后制得聚四氟乙烯压 电驻极体薄膜。
利用上述的连续化生产工艺制得的聚四氟乙烯机电能量转换功能膜，所述的 功能膜至少有二层致密聚四氟乙烯薄膜，且在每相邻的二层聚四氟乙烯薄膜间夹 有一层多孔聚四氟乙烯薄膜构成交替层叠的膜系结构。
具体的， 功能膜产品包括以多孔聚四氟乙烯薄膜作为夹层， 与致密聚四氟乙 烯薄膜复合形成的多孔氟塑料压电功能薄膜， 其中， 多孔聚四氟乙烯薄膜为 n 层， η 1， 致密 PTFE薄膜为 n+1层。如： 一层多孔 PTFE薄膜夹在二层致密 PTFE 薄膜之间形成的聚四氟乙烯电压驻极体功能薄膜， 二层多孔 PTFE薄膜叠夹在三 层致密 PTFE薄膜之间形成的聚四氟乙烯电压驻极体功能薄膜， 等。
本发明的优越性在于：
本发明的生产工艺具有连续性， 生产效率高，聚四氟乙烯机电能量转换功能 膜产品具有优异的压电性能和高热温度性。
附图说明
图 1为本发明压电驻极体材料微观结构、空间电荷分布， 以及压电效应产生的原 理图。
图 2为本发明采用电暈极化生产 PTFE压电驻极体薄膜的工艺示意图。
图 3为本发明采用接触法充电生产 PTFE压电驻极体薄膜的工艺示意图。
图 4为本发明实施例 1的 PTFE压电驻极体薄膜压电系数 t33的压强特性曲线。 图 5为本发明实施例 1的 PTFE压电驻极体薄膜压电系数 ^在 120°C下的等温衰 减曲线图。
图 6为本发明实施例 1的 PTFE压电驻极体薄膜压电系数 ^在 200°C下的等温衰 减曲线图。
图 7为本发明聚四氟乙烯压电驻极体功能薄膜的结构示意图。
附图中标号说明
1一电极 2—基体驻极体 3—正极性空间电荷
4一气体孔洞 5—负极性空间电荷 6—致密 PTFE薄膜
7—多孔 PTFE薄膜 8—致密 PTFE薄膜 9一上热压辊
10—下热压辊 11一电暈电极 12—电极辊
13—收卷辊 14一电镀系统
15、 16接触法充电系统 （其中 15为高压直流电源， 16为电极）。
具体实施方式
实施例 1
请参阅图 1为本发明压电驻极体材料微观结构、空间电荷分布， 以及压电效 应产生的原理图所示， 一种聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 包括微孔结构复合膜的热粘合步骤以及复合膜的充电步骤两部分， 其中，
所述的微孔结构复合膜的热粘合步骤为： 采用二层 5 μ πι厚度的致密 PTFE 薄膜 6、 8和一层 5 μ m厚度的膨体多孔 PTFE薄膜 7， 将膨体多孔 PTFE薄膜 7夹 在二层致密 PTFE薄膜 6、 8之间构成膜系， 然后导入两个直径为 150mm的上、下 热压辊 9、 10进行热压粘合， 上、 下热压辊 9、 10表面的压花为十字图案， 温度 均为 150°C， 上、 下热压辊 9、 10施加在膜系上的压力为 lMPa， 膜系在上、 下热 压辊 9、 10间行进的速度为 0. 5m/min, 经热压后制得微孔结构 PTFE复合膜； 请参阅图 2为本发明采用电暈极化生产 PTFE压电驻极体薄膜的工艺示意图 所示， 所述复合膜的充电即复合膜的电暈极化步骤为： 复合膜进入电极辊 12与 电暈电极 11 (电暈极化区） 间进行电暈极化， 电暈电压为 20kV， 电暈电极（11 ) 与电极辊（12 )之间的距离为 4cm， 电暈区的温度为 25°C， 得到电暈极化处理的 PTFE复合薄膜， 得到 PTFE压电驻极体薄膜， 在收卷辊 13上收卷。
对上述微孔结构 PTFE压电驻极体膜的测试结果为：
请参阅图 4为本发明实施例 1的 PTFE压电驻极体薄膜压电系数 ^的压强特 性曲线所示， 实施例 1制得的薄膜的压电系数 ^的数值可高达 SOOpC/N左右， 这一数值远高于商品 PP压电驻极体膜（0S01型号： 25pC/N ; HS01型号： 230 pC/N), 并且在 l-6kPa的压强范围内保持较好的稳定性。
请参阅图 5为本发明实施例 1的 PTFE压电驻极体薄膜压电系数 ^在 120 °C 下的等温衰减曲线图所示， 实施例 1制得的薄膜在热老化的前期 （3小时内）， 数值有所下降； 热老化处理 3小时后， 数值稳定在 200-400pC/N的范围内。说明 该 PTFE压电驻极体膜的热稳定性显著优于商品 PP压电驻极体膜 （PP压电驻极 体膜的工作温度低于 60°C， 在 120°C下， PP压电驻极体膜强烈收缩变形， 压电效 应丧失）。
请参阅图 6为本发明实施例 1的 PTFE压电驻极体薄膜压电系数 ^在 200 °C 下的等温衰减曲线图所示， 实施例 1制得的薄膜对 PTFE压电驻极体膜进行适当 的预老化处理， 能够获得可以工作在极端温度 （例如 200°C) 环境下的具有较高 压电效应 （例如 100pC/N) 的 PTFE压电驻极体薄膜。
实施例 2
在上、下热压辊 9、 10和收卷辊 13之间设置一薄膜表面电镀系统 14和接触 法充电系统 15、 16。
一种聚四氟乙烯机电能量转换功能膜的连续化生产工艺，包括微孔结构复合 膜的热粘合步骤以及复合膜的充电步骤两部分， 其中，
所述的微孔结构复合膜的热粘合步骤为： 采用二层 20 μ πι厚度的致密 PTFE 薄膜和一层 400 μ m厚度的膨体多孔 PTFE薄膜， 将膨体多孔 PTFE薄膜夹在二层 致密 PTFE薄膜之间构成膜系， 经两个直径为 150mm的上、 下热压辊 9、 10， 其 中上热压辊 9的表面的压花为十字图案， 温度均为 420°C， 上、 下热压辊 9、 10 施加在膜系上的压力为 200MPa， 膜系在上、 下热压辊 9、 10 间行进的速度为 32m/min, 膜系经热压后制得微孔结构 PTFE复合膜；
请参阅图 3为本发明采用接触法充电生产 PTFE压电驻极体薄膜的工艺示意 图所示，所述复合膜的充电即复合膜的接触法充电步骤为： 复合膜进入电镀系统 14 (电镀区）， 在复合膜上下两表面蒸镀 lOOnm厚的金属铝电极， 随后， 将 8000V 的直流电压加在 PTFE复合膜的上下两金属铝电极之间， 接触法充电系统 15、 16 (接触法充电区） 的设定温度为 25 °C， 经接触法充电处理后制得聚四氟乙烯压 电驻极体薄膜， 在收卷辊 13上收卷。
通过本发明实施例中的工艺制成的产品， 包括以多孔 PTFE薄膜作为夹层， 与致密 PTFE薄膜复合形成的多孔氟塑料压电功能薄膜， 其中， 其中， 多孔 PTFE 薄膜为 n层， n^ l， 致密 PTFE薄膜为 n+1层。 如： 一层多孔 PTFE薄膜夹在二层 致密 PTFE薄膜之间形成的多孔氟塑料电压功能薄膜，二层多孔 PTFE薄膜叠夹在 三层致密 PTFE薄膜之间形成的多孔氟塑料电压功能薄膜， 等。
由实施例 2制得的薄膜在 3. 2kPa压强下的压电系数 ^的测试结果为 1362 pC/N,说明通过优化电极化参数可以获得更高压电效应的 PTFE压电驻极体薄膜。 实施例 3
采用二层 50 μ m厚度的车削 PTFE薄膜 6、8和一层 2 μ m厚度的膨体多孔 PTFE 薄膜 7， 将膨体多孔 PTFE薄膜 7夹在二层致密 PTFE薄膜 6、 8之间构成膜系， 然后导入两个直径为 150mm的上、 下热压辊 9、 10进行热压粘合， 上、 下热压辊 9、 10表面的压花为十字图案， 温度均为 150°C， 上、 下热压辊 9、 10施加在膜 系上的压力为 200MPa， 膜系在上、 下热压辊 9、 10间行进的速度为 10m/min， 经 热压后制得微孔结构 PTFE复合膜；
请参阅图 2为本发明采用电暈极化生产 PTFE压电驻极体薄膜的工艺示意图 所示， 所述复合膜的充电即复合膜的电暈极化步骤为： 复合膜进入电极辊 12与 电暈电极 11 (电暈极化区） 间进行电暈极化， 电暈电压为 20kV， 电暈电极（11 ) 与电极辊（12 )之间的距离为 4cm， 电暈区的温度为 25°C， 得到电暈极化处理的 PTFE复合薄膜， 得到 PTFE压电驻极体薄膜， 在收卷辊 13上收卷。
由实施例 3制得的薄膜在 3. 2kPa压强下的压电系数 ^的测试结果为 998 实施例 4
采用二层 200 μ m厚度的致密 PTFE薄膜 6、 8和一层 1000 μ m厚度的膨体多 孔 PTFE薄膜 7， 将膨体多孔 PTFE薄膜 7夹在二层致密 PTFE薄膜 6、 8之间构成 膜系， 然后导入两个直径为 150mm的上、 下热压辊 9、 10进行热压粘合， 上、 下 热压辊 9、 10表面的压花为十字图案， 温度均为 550°C， 上、 下热压辊 9、 10施 加在膜系上的压力为 400MPa，膜系在上、下热压辊 9、 10间行进的速度为 60m/min， 经热压后制得微孔结构 PTFE复合膜。 请参阅图 2为本发明采用电暈极化生产 PTFE压电驻极体薄膜的工艺示意图 所示， 所述复合膜的充电即复合膜的电暈极化步骤为： 复合膜进入电极辊 12与 电暈电极 11 (电暈极化区） 间进行电暈极化， 电暈电压为 20kV， 电暈电极（11 ) 与电极辊（12 )之间的距离为 4cm， 电暈区的温度为 25°C， 得到电暈极化处理的 PTFE复合薄膜， 得到 PTFE压电驻极体薄膜， 在收卷辊 13上收卷。
由实施例 4 制得的薄膜在 3. 2kPa 压强下的压电系数 ^的测试结果为 1928pC/N0
实例 5
采用二层 40 μ m厚度的致密 PTFE薄膜 6、 8和一层 500 μ m厚度的膨体多孔 PTFE薄膜 7， 将膨体多孔 PTFE薄膜 7夹在二层致密 PTFE薄膜 6、 8之间构成膜 系， 然后导入两个直径为 150mm的上、 下热压辊 9、 10进行热压粘合， 上、 下热 压辊 9、 10表面的压花为十字图案， 温度均为 450°C， 上、 下热压辊 9、 10施加 在膜系上的压力为 200MPa，膜系在上、下热压辊 9、 10间行进的速度为 0. 5m/min, 经热压后制得微孔结构 PTFE复合膜。
请参阅图 2为本发明采用电暈极化生产 PTFE压电驻极体薄膜的工艺示意图 所示， 所述复合膜的充电即复合膜的电暈极化步骤为： 复合膜进入电极辊 12与 电暈电极 11 (电暈极化区） 间进行电暈极化， 电暈电压为 20kV， 电暈电极（11 ) 与电极辊（12 )之间的距离为 4cm， 电暈区的温度为 25°C， 得到电暈极化处理的 PTFE复合薄膜， 得到 PTFE压电驻极体薄膜， 在收卷辊 13上收卷。
由实施例 5 制得的薄膜在 3. 2kPa 压强下的压电系数 ^的测试结果为 2446pC/N0

Claims

权 利 要 求
1、 一种聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 包括微孔结构复合 膜的热粘合步骤以及复合膜的充电步骤两部分，其特征在于： 所述的微孔结构复 合膜的热粘合步骤为： 至少有二层致密聚四氟乙烯薄膜 （6、 8)， 且在每相邻的 二层聚四氟乙烯薄膜间夹有一层多孔聚四氟乙烯薄膜 （7 ) 交替层叠后导入上、 下热压辊 （9、 10 ) 之间进行热压粘合， 制成复合膜； 然后将复合膜进行充电， 得到聚四氟乙烯压电驻极体薄膜。
2、 根据权利要求 1所述的聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 其特征在于： 所述的复合膜的充电步骤为： 复合膜进入电极辊与电暈电极间进行 电暈极化， 得到电暈极化处理的聚四氟乙烯复合薄膜并上辊收卷。
3、 根据权利要求 1所述的聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 其特征在于： 所述的复合膜的充电步骤为： 复合膜进入电镀区在薄膜上下表面附 着电极，在进入接触法充电区，得到电暈极化处理的聚四氟乙烯复合薄膜并上辊 收卷。
4、 根据权利要求 2所述的聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 其特征在于： 由上、 下热压辊 （9、 10 ) 间导出的聚四氟乙烯复合膜紧贴电极辊 表面经过电暈极化区， 然后由收卷辊收卷完成聚四氟乙烯压电驻极体薄膜的生 产。
5、 根据权利要求 4所述的聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 其特征在于： 采用二层 2〜40 μ πι厚度的致密聚四氟乙烯薄膜和一层 2〜400 μ πι 厚度的膨体多孔聚四氟乙烯薄膜，将膨体多孔聚四氟乙烯薄膜夹在二层致密聚四 氟乙烯薄膜之间构成膜系， 经两个直径为 150mm的上、 下热压辊 （9、 10)， 上、 下热压辊 （9、 10 ) 表面的压花为十字图案， 温度均为 100〜450°C， 上、 下热压 辊（9、 10 )施加在膜系上的压力为 0. l〜200MPa， 膜系在上、 下热压辊（9、 10 ) 间行进的速度为 0. l〜20m/min， 经热压后制得微孔结构聚四氟乙烯复合膜， 然 后复合膜经过电暈极化区进行电暈充电处理， 电暈电压为 l〜200kV， 电暈电极
( 11 ) 与电极辊 （12 ) 之间的距离为 0. l〜50cm， 电暈区的温度为 _40〜380°C， 经过电暈处理后制得聚四氟乙烯压电驻极体薄膜。
6、 根据权利要求 3所述的聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 其特征在于： 在上、 下热压辊 （9、 10 ) 和收卷辊 （13 ) 之间设置一薄膜表面电 镀系统 （14)和接触法充电系统 （15、 16)， 由上、 下热压辊 （9、 10 ) 导出的聚 四氟乙烯复合膜首先进入电镀系统（14)使薄膜上下表面附着导电性良好的电极， 然后双面带有电极的聚四氟乙烯复合膜在收卷辊（13 )的牵动下进入接触法充电 系统 （15、 16)， 高压直流电直接施加在聚四氟乙烯复合膜的上下电极间， 完成 聚四氟乙烯复合膜的电极化步骤，最后由收卷辊收卷， 制成聚四氟乙烯压电驻极 体薄膜的成品。
7、 根据权利要求 6所述的聚四氟乙烯机电能量转换功能膜的连续化生产工艺， 其特征在于： 采用二层 20〜200 μ m厚度的致密聚四氟乙烯薄膜和一层 20〜1000 μ πι厚度的膨体多孔聚四氟乙烯薄膜， 将膨体多孔聚四氟乙烯薄膜夹在二层致密 聚四氟乙烯薄膜之间构成膜系， 经两个直径为 150mm的上、 下热压辊 （9、 10)， 其中一个热压辊的表面的压花为十字图案， 温度均为 150〜550°C， 上、 下热压 辊 （9、 10 ) 施加在膜系上的压力为 2〜400MPa， 膜系在上、 下热压辊 （9、 10 ) 间行进的速度为 0. 5〜60m/min， 膜系经热压后制得微孔结构聚四氟乙烯复合膜， 然后复合膜进入电镀系统 （14)， 在复合膜上下两表面蒸镀 lOOnm厚的金属铝电 极， 随后，将 100〜20000V的直流电压加在聚四氟乙烯复合膜的上下两金属铝电 极之间， 接触法充电系统（15、 16 ) 的设定温度为 -40〜380°C， 经接触法充电处 理后制得聚四氟乙烯压电驻极体薄膜。
8、 利用权利要求 1至 7之一所述的连续化生产工艺制得的聚四氟乙烯机电能量 转换功能膜， 其特征在于： 所述的功能膜至少有二层致密聚四氟乙烯薄膜， 且在 每相邻的二层聚四氟乙烯薄膜间夹有一层多孔聚四氟乙烯薄膜构成交替层叠的 膜系结构。
PCT/CN2012/076329 2011-08-10 2012-05-31 聚四氟乙烯机电能量转换功能膜的连续化生产工艺 WO2013020410A1 (zh)

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