WO2010147074A1 - 圧電体シート、ならびに圧電体シートの製造方法および製造装置 - Google Patents
圧電体シート、ならびに圧電体シートの製造方法および製造装置 Download PDFInfo
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- WO2010147074A1 WO2010147074A1 PCT/JP2010/060020 JP2010060020W WO2010147074A1 WO 2010147074 A1 WO2010147074 A1 WO 2010147074A1 JP 2010060020 W JP2010060020 W JP 2010060020W WO 2010147074 A1 WO2010147074 A1 WO 2010147074A1
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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
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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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
- 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
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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
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0855—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/42—Piezoelectric device making
Definitions
- the present invention relates to a piezoelectric sheet, and a piezoelectric sheet manufacturing method and manufacturing apparatus, and more particularly to a piezoelectric sheet made of polylactic acid, and a manufacturing method and manufacturing apparatus thereof.
- PLA Polylactic acid
- PLA has a molecular structure as shown in FIG.
- PLA is a dehydration condensation polymer and is obtained by ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid. Since lactic acid contains asymmetric carbon, it has chirality. Therefore, PLA has L-form and D-form, and the polymers are called L-type polylactic acid (PLLA) and D-type polylactic acid (PDLA), respectively.
- the main chain of PLLA has a left-handed spiral structure, and the main chain of PDLA has a right-handed spiral structure.
- Polylactic acid composed of lactic acid synthesized by the power of microorganisms is almost L-form, and PLA currently mass-produced and used is PLLA.
- a stretched PLA film exhibits piezoelectricity.
- point group of PLLA crystal is D 2
- the piezoelectric tensor with components such as shown in Figure 15 (a).
- PLLA is a helical polymer, and has a large dipole in the helical axis direction (C-axis direction).
- C-axis direction the helical axis direction
- the dipoles in the C-axis direction are erased from each other and become zero when viewed macroscopically. Therefore, as shown in FIG. 15B, if the PLLA sheet is stretched in the “3” axis direction, the piezoelectric tensor of the stretched uniaxially oriented PLLA sheet is, as a result, shown in FIG. It becomes a component like c).
- Piezoelectric phenomenon of a conventional piezoelectric PLLA for example, as described in Patent Documents 1 and 2, a principal by d 14 shown in FIG. 15 (c), the value is about 10 ⁇ 20 pC / N It is.
- the piezoelectric constant of PLLA is a remarkably high value among polymers.
- PZT is a material containing lead, and a lead-free piezoelectric material is desired in the market from the viewpoint of environmental protection.
- ceramics are mainly used for inorganic piezoelectric materials, and the manufacturing cost is high, and it is unavoidable to rely on processing such as landfill at the time of disposal. Therefore, a high-molecular piezoelectric material that is inexpensive to manufacture and easy to dispose of waste is desired, but it has not yet been found that there is a piezoelectric constant comparable to PZT.
- PVDF polyvinylidene fluoride
- PLLA polyvinylidene fluoride
- FIG. 14 contains only C, O, and H as constituent elements, and therefore does not cause harmful substances even when incinerated.
- PLLA is a biodegradable plastic that can be completely decomposed into water and CO 2 through a two-stage decomposition process of hydrolysis and microbial decomposition.
- the raw material is currently corn-derived starch, and the raw material itself does not use any petroleum.
- CO 2 resulting from energy used in the manufacturing process PLLA itself uses CO 2 in the air as the original material, and therefore does not increase CO 2 in the air after decomposition. This is the reason why it is called carbon neutral, and it is attracting a great deal of attention as an environmentally friendly material.
- the piezoelectric constant of the PLLA is at most 20 pC / N about at d 14, very small compared to the piezoelectric constant of PZT. Therefore, in order to use PLLA as an alternative material for PZT, it is necessary to increase the applied voltage during operation, and it has been difficult to replace with PLLA in the past.
- an object of the present invention is to provide a piezoelectric sheet having a high piezoelectric constant particularly in the thickness direction while using polylactic acid.
- Another object of the present invention is to provide a manufacturing method and a manufacturing apparatus for a piezoelectric sheet as described above.
- the present invention is first directed to a piezoelectric sheet made of polylactic acid, and in order to solve the above-described technical problem, at least a part of a polylactic acid molecule helical shaft is present so as to exhibit piezoelectricity in the thickness direction. Is relatively directed in the thickness direction.
- sheet and the term “film” may be used according to the thickness dimension, but in this specification, the term “sheet” is used regardless of the thickness dimension.
- the present invention is also directed to a method for manufacturing the above-described piezoelectric sheet.
- the method for manufacturing a piezoelectric sheet according to the present invention includes a step of preparing a polylactic acid sheet, a heating step of heating the polylactic acid sheet using a microwave, and a piezoelectric property in the thickness direction of the polylactic acid sheet. And a high voltage applying step of applying a high voltage in the thickness direction of the heated polylactic acid sheet to relatively orient the helical axes of at least some of the polylactic acid molecules in the thickness direction.
- the method for manufacturing a piezoelectric sheet according to the present invention preferably further includes a step of rapidly cooling the polylactic acid sheet after the high voltage application step.
- the high voltage application step is performed simultaneously with at least a part of the heating step.
- the present invention is further directed to an apparatus for manufacturing the above-described piezoelectric sheet.
- the piezoelectric sheet manufacturing apparatus applies a high voltage power source and a high voltage supplied from the high voltage power source in the thickness direction of the polylactic acid sheet to be processed.
- the piezoelectric sheet manufacturing apparatus applies a high voltage power source and a high voltage supplied from the high voltage power source in the thickness direction of the polylactic acid to be processed.
- a pair of high voltage applying conductors arranged so as to sandwich the sheet in the thickness direction, a microwave generator for generating microwaves, a coaxial line for transmitting microwaves from the microwave generator, and a connection to the coaxial line
- At least one stage of the semi-coaxial cavity filter, one of the high-voltage applying conductors is connected to the center conductor of the semi-coaxial cavity filter, and the other of the high-voltage applying conductors is the outer conductor of the semi-coaxial cavity filter
- one of the high-voltage applying conductors is composed of a plurality of pin-shaped conductors
- the other of the high-voltage applying conductors is composed of a planar conductor
- one and the other of the high voltage applying conductors may be composed of a plurality of pin-shaped conductors, and the plurality of pin-shaped conductors may be paired with each other without excess or deficiency.
- a plurality of types of microwaves having different frequencies are generated by the microwave generator.
- the above-mentioned plurality of types of microwaves are at least mainly those having a frequency effective for heating, those having a frequency suitable mainly for shaking the main chain of polylactic acid, and mainly bonding portions between polylactic acid molecules.
- the high voltage applying conductor is composed of a plurality of pin-shaped conductors
- the plurality of pin-shaped conductors are arranged in a plurality of rows
- the position of each conductor corresponds to a gap formed between each conductor in the adjacent row.
- the conductor has a square cross section, and the interval between adjacent conductors is equal to the length of one side of the square defining the cross section of each conductor.
- a cooling fluid outlet for rapidly cooling the polylactic acid sheet is provided in the vicinity of the high voltage applying conductor.
- a polylactic acid sheet in a bulk state (after being formed and in an untreated state) has a structure in which long helical molecules are entangled with each other. For example, even if a very large electric field is applied in the thickness direction, the polylactic acid sheet has piezoelectricity in the thickness direction. It does not occur.
- the piezoelectric sheet made of polylactic acid the entanglement of the helical molecules is loosened, and the helical axis is relatively oriented in the thickness direction for at least some of the helical molecules.
- the piezoelectric sheet shown can be obtained.
- the piezoelectric body can be oriented in the thickness direction of the piezoelectric sheet. If it can be oriented at a rate exceeding this, it can be a piezoelectric body that surpasses PZT. Even if the degree of orientation is 5%, the polymer piezoelectric body can have a surprisingly large piezoelectric constant.
- PZT which is often used for piezoelectric actuators and the like, is ceramic and contains lead, so that it is difficult to treat it as waste. If a piezoelectric constant comparable to PZT is obtained by PLLA, PZT can be replaced with PLLA.
- PLLA is a biopolymer with a simple composition that does not contain heavy metals, is biodegradable, and uses starch as a raw material, so it does not increase CO 2 in the air except for CO 2 generated during production. Furthermore, CO 2 at the time of manufacture is extremely small as compared with the case of manufacturing other organic polymers. Therefore, if PZT can be replaced with PLLA, there is a tremendous effect on reducing the environmental load.
- polylactic acid is a polymer and has higher flexibility than PZT, the displacement amount when applied to an actuator is larger than that of PZT.
- FIG. 2 is a more detailed diagram when the PLLA heating unit 17 on the block diagram shown in FIG. 2 is configured as a transmission line type, and shows the PLLA processing unit 30 including the PLLA heating unit 17, and FIG.
- the top view of the part 30 and (b) are front views of the PLLA processing part 30.
- FIG. 3A is a cross-sectional view taken along line AA in FIG. 3B, and FIG.
- FIG. 6A is a cross-sectional view taken along line BB in FIG. 6B
- FIG. 6B is a cross-sectional view taken along line AA in FIG.
- FIG. 5 shows the first embodiment relating to the arrangement of the pin conductors 36a shown in FIG.
- FIG. 4 shows a view showing the pin conductors 36a when the end surface of the front end portion 38a of the inner conductor 35a is viewed from the PLLA sheet 1 side.
- FIG. 5 shows a second embodiment relating to the arrangement of the pin conductors 36a shown in FIG. 4 and shows the pin conductors 36a when the end surface of the front end portion 38a of the inner conductor 35a is viewed from the PLLA sheet 1 side.
- FIG. 9 shows a third embodiment relating to the arrangement of the pin conductors 36a shown in FIG. 4 and shows the pin conductors 36a when the end surface of the front end portion 38a of the inner conductor 35a is viewed from the PLLA sheet 1 side.
- FIG. 4 shows a fourth embodiment relating to the arrangement of the pin conductors 36a shown in FIG. 4, and is a view showing the pin conductors 36a when the end surface of the front end portion 38a of the inner conductor 35a is viewed from the PLLA sheet 1 side.
- It is a molecular structure diagram of polylactic acid.
- (A) shows the piezoelectric tensor of PLLA crystal
- (b) is a figure for demonstrating the extending
- (c) shows the piezoelectric tensor of a uniaxially oriented PLLA sheet.
- FIG. 2 is a diagram schematically showing two lactic acid molecules bonded together.
- PLLA has a molecular structure as shown in FIG. 14 described above, but there are molecular groups that generate permanent dipoles such as C ⁇ O in the main chain. When viewed with a molecule in which two lactic acid molecules are bonded, an electric dipole as shown in FIG. 16 appears.
- polylactic acid includes PLLA that is L-form and PDLA that is D-form, and an active mixture thereof is also assumed, but in this section, for simplicity of explanation.
- PLLA that is L-form
- PDLA that is D-form
- a description will be given by taking PLLA as an example.
- the PLLA molecule has a 10/3 helix structure in which the molecule is spiraled three times with 10 monomers. If the molecular chain has a 10/3 helix structure based on the dipole in the PLLA molecule, the size of the dipole in the direction of the helical axis is 3.5 to 3.7 debye per period.
- the PLLA molecule has a molecular weight of about several hundreds of thousands and is composed of about 1000 to 3000 cycles. Hereinafter, in order to simplify the description, it is assumed that there are 2000 cycles. If this can be oriented as an extended chain, this length is about 100 nm (normal lamella thickness).
- the dipole sum of this molecule at this time is (3.5 to 3.7) ⁇ 2000, that is, 7000 to 7400 debye.
- this is assumed to be 7200 debye.
- the distance between the helical axes is estimated to be 0.4 to 0.8 nm.
- this value is assumed to be 0.4 nm for the sake of simplicity.
- the piezoelectric stress constant e of the macroscopic polymer is expressed by the following formula (1) using the polarizability Ps.
- ⁇ is a Poisson's ratio
- e ′ is a microscopic piezoelectric stress constant.
- e 31 e 31 '- ⁇ 21 e 32 ' - ⁇ 31 e 33 '+ (1- ⁇ 21 ) Ps (1)
- the three axes are in the C-axis direction.
- the first to third terms of the formula (1) are piezoelectric stress constants derived from the molecular structure itself and are very small.
- the fourth term depends on the polarizability Ps, and in the case of PLLA described here, Ps is very large. Therefore, the equation (1) can be approximated as the following equation (2).
- ⁇ 21 is usually about 0.2 to 0.5.
- e 31 0.7 Ps (3) It becomes.
- the piezoelectric constant of PLLA is as high as 1000 to 5000 pC / N in consideration of the numerical range. There are no examples of this yet.
- the spiral axis is oriented so as to be perpendicular to the thickness direction of the film, and about 10% of the potential of the original PLLA, that is, the state where the dipoles along the C axis are alternately packed can be broken by about 10%.
- a d 33 value of 100 to 500 pC / N (in this case, the thickness direction of the film is assumed to be three axes) is considered to be generated, and a value almost comparable to the piezoelectric constant of PZT is obtained.
- the PLLA sheet as described above can be manufactured as follows.
- a microwave is applied to a very narrow region 2 of, for example, about 0.01 to 1 mm 2 in an unprocessed PLLA sheet 1.
- the alternating electric field acts on the dipole to force the PLLA molecule to vibrate.
- the helical axis 3 of the PLLA molecule is schematically shown by an arrow, and the direction of the arrow indicates the direction of orientation.
- the PLLA molecules are heated and become easy to move, and a state in which the entanglement between the molecular chains is loosened by the microwave vibration is realized.
- the spiral axes 3 of all PLLA molecules are oriented in the thickness direction in a direction in which the dipole orientations do not cancel each other. You don't have to. It is sufficient if the helical axis 3 of only some PLLA molecules is oriented in the thickness direction. Further, the spiral axis 3 oriented in the thickness direction does not necessarily have to be oriented in a direction (90 degrees) perpendicular to the main surface direction of the PLLA sheet 1. The angle may be, for example, 5 to 10 degrees with respect to the main surface direction, and only needs to be relatively directed to the thickness direction.
- the region 2 of the PLLA sheet 1 is rapidly cooled to fix PLLA molecules.
- the above processing is repeated while shifting the position of the PLLA sheet 1 so that the processing is performed also in the region 4 adjacent to the region 2. In this way, a state in which the spiral axis 3 is relatively oriented in the thickness direction over a wide area of the PLLA sheet 1 is created, whereby a piezoelectric sheet having a high piezoelectric constant made of the PLLA sheet 1 is obtained. .
- the microwave applied is not limited to a single-frequency microwave, but has at least a frequency mainly effective for heating and a frequency mainly suitable for shaking the main chain.
- the region is a circle, the area is in the range of about 0.01 to 1 mm 2 .
- This size varies depending on the thickness of the PLLA sheet 1 and its molecular weight, and when the additive is dispersed in the PLLA sheet 1, its type and size.
- heating with a laser spot or the like can be considered.
- an electrode necessary for applying a strong electric field for orienting the helical axis of PLLA cannot be formed, or the laser spot is not irradiated at a predetermined position due to this electrode being an obstacle.
- the heating of the minute region by the microwave described here is very excellent in that the microwave irradiation and the application of the DC electric field can be performed simultaneously.
- FIG. 2 is a block diagram showing a piezoelectric sheet manufacturing apparatus 10 according to an embodiment of the present invention.
- a predetermined process is performed on the prepared PLLA sheet 1 in order to manufacture a piezoelectric sheet.
- the microwaves for vibrating the PLLA molecules constituting the PLLA sheet 1 are generated by the signal generators 11 and 12.
- FIG. 2 shows an example in which two signal generators 11 and 12 are used, the number may be appropriately changed according to the number of types of microwaves to be input.
- the frequency of the microwave to be generated is a frequency mainly for heating PLLA, a frequency mainly for loosening the entanglement of molecules, a frequency mainly for breaking bonds between molecules (partial crystallization), etc. . These frequencies vary depending on the molecular weight of the PLLA used as a raw material, the mixing ratio of D-form, crystallinity, orientation, filler blending amount, etc.
- the input level may be determined.
- the ratio of the input level of the microwaves having the respective frequencies is determined by the output levels of the signal generators 11 and 12.
- a plurality of types of microwaves having different frequencies generated from the signal generators 11 and 12 are mixed in the mixer 13 and then transmitted to the amplifier 14.
- the microwave amplified by the amplifier 14 passes through the circulator 15, then passes through the bias tee 16, and reaches the PLLA heating unit 17.
- the circulator 15 is provided to prevent the reflected power due to mismatch of the PLLA heating unit 17 from returning to the amplifier 14 and damaging the amplifier 14.
- the reflected power due to mismatching of the PLLA heating unit 17 is branched by the circulator 15, passes through the coupler 21, reaches the attenuator 22, and is consumed.
- a power meter 23 is connected to the coupler 21, and the reflected power is monitored.
- the PLLA heating unit 17 includes a portion where a capacitor is formed via the PLLA sheet 1 in a circuit in the electric power passage route. As the microwave passes through this part, part of it is converted to heat due to its dielectric loss.
- the dielectric loss tangent (tan ⁇ ) of PLLA is 0.01 to 0.012 (see, for example, Japanese Patent Laid-Open No. 2002-358829), and a capacitor using this as a dielectric always generates heat corresponding to tan ⁇ . . In addition, heat is generated due to friction caused by shaking the electric dipole.
- the microwave that has passed through the PLLA heating unit 17 passes through the bias tee 18, then passes through the coupler 24, reaches the attenuator 25, and is consumed.
- a power meter 26 is connected to the coupler 24 so as to monitor the passing power.
- the power consumed in the PLLA heating unit 17 can be indirectly grasped.
- the electric power consumed in the PLLA heating unit 17 is energy converted into heat in the PLLA sheet 1, and it is possible to roughly know how much temperature the PLLA sheet 1 is heated with this value.
- the temperature of the PLLA sheet 1 may be directly measured using an infrared non-contact thermometer or the like.
- the melting point of PLLA is around 170 ° C., it has been experimentally confirmed that about 140 ° C. to 150 ° C. is suitable for controlling molecular orientation. However, since this temperature depends on the molecular weight of PLLA, additives, and treatment of molecular end groups, it is appropriately selected according to the PLLA sheet 1 actually used.
- the high voltage DC power supply 20 and the switch 19 are connected to the bias tees 16 and 18. With the PLLA sheet 1 heated to a temperature suitable for orientation, the switch 19 is turned on and a high voltage is applied to the PLLA sheet 1. At least a part of the dipole swung by the microwave is relatively oriented in the thickness direction (direction of the electric field) by the electric field generated by the high voltage.
- the magnitude of the voltage and the application time are also appropriately selected according to the PLLA sheet 1 actually used because it depends on the molecular weight, the additive, and the treatment of the end groups of the molecule.
- the timing of cooling does not necessarily have to be immediately after the microwave and high voltage are stopped.
- the microwave and the high voltage may be stopped after the cooling is started, the cooling is started after the microwave is stopped, and then the high voltage is stopped.
- the order of stopping the voltage may be used.
- FIG. 3 is a more detailed diagram when the PLLA heating unit 17 on the block diagram shown in FIG. 2 is formed as a transmission line type, and shows the PLLA processing unit 30 including the PLLA heating unit 17.
- FIG. 3A is a plan view of the PLLA processing unit 30, and FIG. 3B is a front view of the PLLA processing unit 30.
- 4A is a cross-sectional view taken along line AA in FIG. 3B
- FIG. 4B is a cross-sectional view taken along line BB in FIG. 3A.
- the PLLA processing unit 30 has a housing 31, and the housing 31 is provided with holes 33 and 34 for inserting the PLLA sheet 1.
- the holes 33 and 34 are provided so as to penetrate the upper and lower wall portions of the casing 31 as well shown in FIG.
- the PLLA sheet 1 is processed in a state where the upper and lower holes 33 and 34 are inserted.
- the casing 31 is provided with a pair of guide rollers 32a and 32b and guide rollers 32c and 32d, and the PLLA sheet 1 is held by these guide rollers 32a to 32d.
- the PLLA sheet 1 can be moved in the vertical direction in FIGS. 3B and 4B.
- An arrow around each of the guide rollers 32a to 32d and an arrow above the PLLA sheet 1 shown in FIG. 4B indicate an example of the rotation direction of the guide rollers 32a to 32d and the moving direction of the PLLA sheet 1. . Note that the drive portions of the guide rollers 32a to 32d are not shown.
- the housing 31 is made of metal and constitutes an outer conductor of the coaxial line while forming a cavity inside. Copper, aluminum, brass, iron, stainless steel, and the like are suitable for the metal used to form the casing 31, and these are plated as necessary. In the case of using iron or stainless steel, the conductivity is not good, so it is preferable to perform copper plating or silver plating in consideration of transmission loss.
- inner conductors 35a and 35b as inner conductors (center conductors) of a coaxial line are arranged in a state of being held by insulators 37a and 37b.
- the inner conductors 35a and 35b do not show a cross section.
- the insulators 37a and 37b are made of a resin having a low dielectric constant, and polytetrafluoroethylene is a particularly preferable material.
- the inner conductors 35a and 35b have their respective tip portions 38a and 38b facing each other, and these tip portions 38a and 38b are wider than the other portions as well shown in FIG. 4 (a). It has a different shape.
- a plurality of pin conductors 36a and 36b as high-voltage applying conductors are provided so as to be paired with each other without excess or deficiency at the wide end portions 38a and 38b.
- the coaxial line composed of the casing 31 and the inner conductors 35a and 35b is formed with a characteristic impedance of 50 ⁇ except for the central part in the axial direction and the part where the cavity is widened. Matching is easy to take.
- the cavity of the casing 31 is enlarged while forming a taper in the center portion in the axial direction, and the inner conductors 35a and 35b are also tapered in accordance with the taper of the cavity, and the tip end 38a and Since 38b is wide, impedance conversion is performed smoothly, and power reflection due to impedance mismatching is hardly generated.
- the PLLA processing unit 30 is a transmission line type, the PLLA processing unit 30 can be applied to a very wide band frequency and is relatively easy to design and manufacture.
- Each of the pin conductors 36a and each of the pin conductors 36b are aligned so as to face each other and be located on the same axis.
- the PLLA sheet 1 is sandwiched between pin conductors 36a and 36b facing each other.
- a minute capacitor is formed between each pair of pin conductors 36a and 36b facing each other.
- Each of the pin conductors 36a and 36b has a diameter of about 0.1 mm to 1 mm, and an interval between adjacent pin conductors 36a and 36b is greater than or equal to the radius of each of the pin conductors 36a and 36b.
- the number of pin conductors 36a and 36b can be selected as appropriate. Since the diameter of each of the pin conductors 36a and 36b needs to be such that spherulites are not formed in the PLLA sheet 1, a smaller one is preferable.
- the pin conductors 36a and 36b sandwiching the PLLA sheet 1 are shown as a pair on both sides of the PLLA sheet 1, but one may be a pin conductor and the other may be a planar conductor. Such a shape is exemplified in the description of the PLLA processing unit 50 described later.
- the PLLA sheet 1 is suitable for heating in a minimum range.
- the advantage is that the assembly of the device is very simple.
- the inner conductors 35 a and 35 b and the pin conductors 36 a and 36 b are made of metal, like the casing 31.
- metal copper, aluminum, brass, iron, stainless steel, Invar, 42 alloy, etc. are suitable, and these are plated as necessary.
- iron, stainless steel, invar, or 42 alloy is used, the conductivity is not good, so it is preferable to perform copper plating or silver plating in consideration of transmission loss.
- the PLLA sheet 1 is heated by transmitting microwaves. However, if the thermal conductivity of the inner conductors 35a and 35b and the pin conductors 36a and 36b is high, the heat of the PLLA sheet 1 escapes.
- the inner conductors 35a and 35b and the pin conductors 36a and 36b are preferably made of a material having a relatively low thermal conductivity such as iron, stainless steel, invar, 42 alloy.
- the pin conductors 36a and 36b are preferably made of Invar or a 42 alloy alloy in consideration of thermal expansion.
- microwaves are input to locally heat the PLLA sheet 1, and a high voltage is applied to at least a part of the PLLA sheet.
- the PLLA molecule is fixed by rapidly cooling after orienting the helical axis of the molecule relatively in the thickness direction.
- a cooling gas is blown into the internal cavity of the casing 31.
- the passage for blowing the cooling gas is not shown in FIGS. 3 and 4, a passage through which the cooling gas flows is provided inside the inner conductors 35a and 35b, and in the vicinity of the pin conductors 36a and 36b at the time of cooling. It is preferable that the cooling gas is jetted directly toward the PLLA sheet 1 from the blow-out opening provided in. A specific example of the structure for cooling will be described later with reference to FIG.
- the inner conductors 35a and 35b can be moved in the directions indicated by arrows 39 and 40 in FIG. 4A, respectively. After the processing, the inner conductors 35a and 35b are moved to hold the PLLA sheet 1. Then, the guide rollers 32a to 32d are rotated to move the PLLA sheet 1 by a desired amount. After the PLLA sheet 1 is moved, the inner conductors 35a and 35b are moved again, the PLLA sheet 1 is held between the pin conductors 36a and 36b, and the above-described microwave heating, high voltage application, and rapid cooling processes are performed. By repeating this, a high piezoelectric constant PLLA sheet 1 in which the helical molecular axes are relatively oriented in the thickness direction over a wide range can be obtained.
- FIG. 5 is a cross-sectional view of one inner conductor 35a shown in FIG. 4, and shows one end portion of the transmission line portion composed of the casing 31 and the inner conductors 35a and 35b, which is not shown in FIG. It is shown.
- the inner conductor 35a is hollow inside, and a plurality of outlets 41 are provided in the vicinity of each position of the pin conductor 36a on the end face of the tip portion 38a where the pin conductor 36a is provided. ing. Since the microwave current flows through the surface layer of the inner conductor 35a due to the skin effect, the cavity inside the inner conductor 35a does not affect the microwave transmission current.
- the inner conductor 35a is electrically connected to another inner conductor 42 and transmits power transmitted from the inner conductor 42 side without reflection.
- the coaxial line where the inner conductor 42 is located also has a characteristic impedance of 50 ⁇ .
- a tube 43 made of, for example, polytetrafluoroethylene is inserted into the other end of the inner conductor 35a.
- the cooling gas is introduced into the tube 43 from the direction of the arrow 44, and then blown out from the outlet 41 in the direction of the arrow 45, thereby removing the pin conductor 36a and the PLLA sheet 1 (not shown in FIG. 5). Cooling.
- HCFC (-134a) or LPG is suitable.
- a liquid may be used instead of the cooling gas.
- the liquid for example, liquid nitrogen is preferably used. In this case, it is preferable that the liquid nitrogen is sprayed from the outlet 41.
- the cooling structure as described above may be provided only on the inner conductor 35a side, provided only on the other inner conductor 35b, or may be provided on both the inner conductors 35a and 35b. .
- the PLLA sheet 1 can be efficiently cooled, and the cooling gas or liquid can be used without waste.
- FIG. 6 is a more detailed diagram when the PLLA heating unit 17 on the block diagram shown in FIG. 2 is configured as a resonator type, and shows a PLLA processing unit 50 including the PLLA heating unit 17.
- 6A is a front view of the PLLA processing unit 50
- FIG. 6B is a side view of the PLLA processing unit 50.
- 7A is a cross-sectional view taken along the line BB in FIG. 6B
- FIG. 7B is a cross-sectional view taken along the line AA in FIG. 6A.
- the PLLA processing unit 50 has a casing 51, and the casing 51 is provided with holes 55 a and 55 b for inserting the PLLA sheet 1.
- the hole similar to the hole 55a is provided in the wall surface facing the wall surface in which the hole 55a was provided.
- a wall similar to the hole 55b is also provided on the wall facing the wall provided with the hole 55b.
- the PLLA sheet 1 is arranged so as to pass through the hole 55a and the hole facing the hole 55a, and so as to pass through the hole 55b and the hole facing the hole 55b.
- the guide rollers corresponding to the guide rollers 32a to 32d provided in the PLLA processing unit 30 shown in FIGS. 3 and 4 are not shown.
- the casing 51 is made of a metal having good conductivity.
- a metal to be used copper, aluminum, brass, iron, and stainless steel are preferable, and these are plated as necessary.
- iron or stainless steel is used, the conductivity is not good, and therefore it is preferable to perform copper plating or silver plating in consideration of insertion loss.
- the housing 51 plays a role of shielding electromagnetic waves, and an internal cavity becomes a resonance cavity.
- the PLLA processing unit 50 basically forms a semi-coaxial cavity filter.
- the casing 51 serves as an outer conductor of the semi-coaxial cavity filter. 6 and 7 constitute a two-stage bandpass filter.
- connectors 52a and 52b are provided as input / output units for supplying power to the filter. Since such a band-pass filter is basically symmetrical, either of the connectors 52a and 52b may be used as an input or an output.
- the connector 52a is described as the input side
- the connector 52b is described as the output side.
- the one end of an input lead 56a made of a metal wire is connected to the center conductor of the connector 52a, and the other end of the input lead 56a is connected to the center conductor 57a.
- a plurality of pin conductors 58a are provided at one end of the center conductor 57a.
- a base electrode 60a for providing a planar conductor is provided so as to face the tip of the pin conductor 58a. There is a slight gap between the tip of the pin conductor 58a and the base electrode 60a, and the PLLA sheet 1 is sandwiched here, and this portion forms a capacitor in an equivalent circuit.
- the other end of the center conductor 57a is opposed to the tip of the frequency adjusting screw 53a at a predetermined distance.
- the output lead 56b, the center conductor 57b, the pin conductor 58b, the base electrode 60b, and the frequency adjusting screw 53b provided in association with the connector 52b are apparent from FIG. 7B.
- the output lead 56a, the center conductor 57a, the pin conductor 58a, the base electrode 60a, and the frequency adjusting screw 53a are provided in association with the connector 52a described above.
- a coupling adjusting screw 54 is inserted in the vicinity of the middle between the center conductor 57a and the center conductor 57b.
- the PLLA sheet 1 is sandwiched between the pin conductor 58a and the base electrode 60a or the pin conductor 58b and the base electrode 60b.
- the pin conductors may be arranged in place of the base electrodes 60a and 60b so as to be paired with the pin conductors 58a and 58b. I do not care.
- the filter has desired characteristics within a range not departing from the original electrical design. Can be adjusted.
- the center conductors 57a and 57b, the frequency adjusting screws 53a and 53b, the coupling adjusting screw 54, the base electrodes 56a and 56b, and the pin conductors 58a and 58b are made of metal.
- copper, aluminum, brass, iron, and stainless steel are suitable as the metal used here, and these are plated as necessary.
- iron or stainless steel is used, the conductivity is not good, and therefore it is preferable to perform copper plating or silver plating in consideration of insertion loss.
- center conductors 57a and 57b are fixed to the casing 51 with an insulating material having a low dielectric constant.
- Polytetrafluoroethylene is preferred as the low dielectric constant material.
- the base electrodes 60a and 60b are formed with a recess (sinking portion) 61 having an opening facing outward, and the bottom wall 62 of the recess 61 is formed very thin. Specifically, the thickness of the bottom wall 62 is preferably about 0.3 to 0.8 mm.
- the base electrodes 60a and 60b are preferably formed of a metal having good thermal conductivity, and for example, aluminum and copper are suitable.
- the PLLA sheet 1 sandwiched between the pin conductors 58a and 58b and the base electrodes 60a and 60b is heated by inputting microwaves.
- the heated PLLA sheet 1 needs to be rapidly cooled after a high voltage is applied.
- the cooling gas By blowing the cooling gas directly onto the bottom wall 62 of the recess 61, the bottom wall 62 can be instantaneously cooled.
- the bottom wall 62 is made of a metal having good thermal conductivity and the thickness thereof is sufficiently thin, the PLLA sheet 1 is also cooled almost simultaneously.
- the cooling gas is the same as described above.
- this PLLA processing unit 50 is of a resonator type, the electric field strength applied to the PLLA sheet 1 is significantly higher than that of the transmission line type, and the filter designed with a center frequency of 2.4 GHz Is 100 times as large as the transmission line type.
- FIG. 8 shows the result of the finite element method simulation using the simplified model of the PLLA processing unit 50.
- an arrow indicates an electric field vector, and the magnitude indicates the strength of the electric field. It can be seen that there is a very large electric field vector at the position where the PLLA sheet 1 is inserted. Therefore, according to the PLLA processing unit 50, it is possible to reduce the output of the amplifier as compared with the transmission line type when heating by microwaves.
- the PLLA processing unit 50 shown in FIGS. 6 and 7 constitutes a two-stage bandpass filter. Although it can be used as a one-stage filter using only one semi-coaxial resonator, in this case, since it becomes a band-pass filter that passes only frequencies near the pole including the resonance frequency, it is very narrow band. The frequency that can be inserted is limited. Conversely, it is possible to increase the number of stages of the filter, and a filter having about 2 to 10 stages can be obtained as necessary. However, the number of stages of the filter is not limited, but it is preferable from experience that the number of stages is not more than 10 considering the labor of production. A filter having a specific bandwidth of about 4% can be manufactured relatively easily with the number of stages of about 4 to 8. If the center frequency of the passband at this time is 2 GHz, a bandpass filter with a bandwidth of 70 MHz can be obtained, and a device that can apply a plurality of frequencies simultaneously can be obtained.
- FIG. 9 shows an example in which the PLLA processing unit has a four-stage band pass.
- FIG. 9 is a diagram corresponding to FIG. In FIG. 9, elements corresponding to those shown in FIG. 7B are denoted by the same reference numerals, and redundant description is omitted.
- the PLLA processing unit 50a shown in FIG. 9 further includes center conductors 57c and 57d in addition to the center conductors 57a and 57b, and further includes frequency adjustment screws 53c and 53d in addition to the frequency adjustment screws 53a and 53b. .
- Three coupling adjusting screws 54a, 54b and 54c are provided.
- the microwave heating unit for the PLLA sheet 1 can always be provided in the input stage, the output stage, or both.
- a multi-stage band pass filter relatively large energy is accumulated in the input / output stage, and therefore, the electric field strength in this portion is large.
- the high voltage is applied via the bias tees 16 and 18 (see FIG. 2), it is easy to apply the high voltage at the input / output stage connected directly from the center conductor of the transmission line (connector) by the conductor. Can be done.
- an extremely wide band filter can be obtained by using an interdigital type. it can.
- FIGS. 10 to 13 are views showing the pin conductor 36a when the end surface of the tip end portion 38a of one inner conductor 35a shown in FIG. 4 is viewed from the PLLA sheet 1 side.
- illustration of the outlet 41 shown in FIG. 5 is omitted.
- the illustration and description of the other pin conductor 36b are omitted, but the other pin conductor 36b is substantially symmetrical to the illustrated pin conductor 36a.
- a plurality of pin conductors 36a are arranged in one row with a predetermined interval between each other.
- the PLLA sheet is shifted vertically by a predetermined distance, In this state, a series of processing for piezoelectric expression is performed again, and by repeating such operations, processing for piezoelectric expression is performed over a wide range of PLLA sheets.
- a plurality of pin conductors 36a are arranged in two rows with a predetermined interval between each other.
- the positions of the pin conductors 36a in each row correspond to the interval portions formed between the pin conductors 36a in the other rows.
- the PLLA sheet is shifted upward (or downward) by the distance d, and in this state, the series for piezoelectric expression is shifted.
- a process for expressing piezoelectricity is performed over a wide range of the PLLA sheet.
- a plurality of pin conductors 36a are arranged in four rows with a predetermined interval between each other.
- the positions of the pin conductors 36a in each row correspond to the interval portions formed between the pin conductors 36a in the adjacent rows.
- the PLLA sheet is shifted upward (or downward) by a distance d, and in this state, the series for piezoelectric expression is shifted.
- the PLLA sheet is shifted upward (or downward) by 3 times the distance d, and in this state, a series of processing for piezoelectric expression is performed again.
- the sheet is shifted upward (downward) by the distance d, and in this state, a series of processes for expressing piezoelectricity is performed again.
- the piezoelectricity is expressed over a wide range of the PLLA sheet. Processing for is performed.
- the embodiment shown in FIG. 12 is the most excellent and the next best is the embodiment shown in FIG. 11 in that the processing for expressing piezoelectricity can be performed collectively over a wider area.
- the dimensions of the inner conductors 35a and 35b and the number of pin conductors 36a and 36b arranged in the horizontal and vertical directions may be appropriately selected according to the design.
- the pin conductors 36a and 36b do not necessarily have a circular cross section, and may be an ellipse, an ellipse, a square, a polygon, or the like.
- FIG. 13 shows an example in which the pin conductor 36a has a square cross section.
- the arrangement of the pin conductors 36a shown in FIG. 13 is substantially the same as that shown in FIG. 12, but the interval between adjacent pin conductors 36a is equal to one side of the square that defines the cross section of each pin conductor 36a. It is equal to the length.
- the pin conductor 36a is shaded to make the position of the pin conductor 36a easier to understand.
- the same operation as in the embodiment shown in FIG. 12 is performed when performing the process for expressing the piezoelectricity on the PLLA sheet.
- the difference from the embodiment shown in FIG. 12 is that according to the embodiment shown in FIG. 13, a PLLA sheet having a high piezoelectric constant with fewer untreated parts can be obtained.
- pin conductors 36a and 36b described with reference to FIGS. 10 to 13 can also be employed in the arrangement of the pin conductors 58a and 58b shown in FIGS.
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Abstract
Description
(3.5~3.7)×2000、すなわち、7000~7400debyeとなる。以降、説明を簡単とするために、これを7200debyeと仮定する。
Ps=2.4×10-26×2/(0.4×10-9×0.4×10-9×100×10-9)=3.0C/m2
となる。
e31=e31′-ν21e32′-ν31e33′+(1-ν21)Ps …(1)
ここで、3軸はC軸方向とする。
e31≒(1-ν21)Ps …(2)
ポリマーの場合、通常ν21は0.2~0.5程度である。PLLAの場合、ν21≒0.3であるため、
e31=0.7Ps …(3)
となる。
e31=0.7×3.0=2.1C/m2
となる。
d31=e31・SE …(4)
と表される。PLLAの場合、未延伸フィルムの弾性定数はおよそ3.7GPa、4倍延伸フィルムの弾性定数はおよそ1.8GPaである。なお、延伸フィルムでは、C軸は延伸方向に配向する。
d31=2.1/1×109=2100pC/Nと見積もることができる。
d33=2100×2=4200pC/N
となる。
2 PLLA分子の螺旋軸
10 製造装置
11,12 シグナルジェネレータ
13 ミキサ
14 アンプ
16,18 バイアスティー
17 PLLA加熱部
20 高圧直流電源
30,50,50a PLLA処理部
31,51 筐体
35a,35b 内導体
36a,36b,58a,58b ピン導体
41 吹き出し口
57a,57b,57c,57d 中心導体
60a,60b ベース電極
Claims (13)
- ポリ乳酸からなる圧電体シートであって、厚み方向に圧電性を示すように、少なくとも一部のポリ乳酸分子の螺旋軸が相対的に厚み方向に向けられている、圧電体シート。
- ポリ乳酸シートを用意する工程と、
マイクロ波を用いて前記ポリ乳酸シートを加熱する、加熱工程と、
前記ポリ乳酸シートの厚み方向に圧電性を発現させるため、加熱された前記ポリ乳酸シートの厚み方向に高電圧を印加して、少なくとも一部のポリ乳酸分子の螺旋軸を相対的に厚み方向に向ける、高電圧印加工程と
を備える、圧電体シートの製造方法。 - 前記高電圧印加工程の後、前記ポリ乳酸シートを急冷する工程をさらに備える、請求項2に記載の圧電体シートの製造方法。
- 前記高電圧印加工程は、前記加熱工程の少なくとも一部と同時に実施される、請求項2または3に記載の圧電体シートの製造方法。
- 高電圧電源と、
前記高電圧電源から供給される高電圧を、処理されるべきポリ乳酸シートの厚み方向に印加するため、前記ポリ乳酸シートを厚み方向に挟むように配置される対をなす高電圧印加用導体と、
マイクロ波を発生するマイクロ波発生器と、
前記マイクロ波発生器からマイクロ波を伝送する同軸線路と
を備え、
前記高電圧印加用導体は、前記同軸線路の内導体に接続され、前記マイクロ波が、前記ポリ乳酸シートとそれを挟む前記高電圧印加用導体とによって構成されるコンデンサを通過するとき、誘電損失による熱を発生するようにされている、
圧電体シートの製造装置。 - 高電圧電源と、
前記高電圧電源から供給される高電圧を、処理されるべきポリ乳酸の厚み方向に印加するため、前記ポリ乳酸シートを厚み方向に挟むように配置される対をなす高電圧印加用導体と、
マイクロ波を発生するマイクロ波発生器と、
前記マイクロ波発生器からマイクロ波を伝送する同軸線路と、
前記同軸線路に接続される少なくとも1段の半同軸空洞フィルタと
を備え、
前記高電圧印加用導体の一方は、前記半同軸空洞フィルタの中心導体に接続され、
前記高電圧印加用導体の他方は、前記半同軸空洞フィルタの外導体に接続され、
前記マイクロ波が前記ポリ乳酸シートと前記高電圧印加用導体とによって構成されるコンデンサを通過するとき、誘電損失による熱を発生するようにされている、
圧電体シートの製造装置。 - 前記高電圧印加用導体の一方は、複数のピン状の導体から構成され、前記高電圧印加用導体の他方は、平面状の導体から構成されている、請求項6に記載の圧電体シートの製造装置。
- 前記高電圧印加用導体の一方および他方は、複数のピン状の導体から構成され、前記複数のピン状の導体は過不足なく互いに対をなすようにされている、請求項6または7に記載の圧電体シートの製造装置。
- 前記マイクロ波発生器によって、互いに異なる周波数を有する複数種類のマイクロ波が発生される、請求項5ないし8のいずれかに記載の圧電体シートの製造装置。
- 前記複数種類のマイクロ波は、少なくとも、主に加熱に有効な周波数のものと、主にポリ乳酸の主鎖を揺するのに適した周波数のものと、主にポリ乳酸の分子同士の結合部分を破壊するのに適した周波数のものとを含む、請求項9に記載の圧電体シートの製造装置。
- 前記高電圧印加用導体は、複数のピン状の導体から構成され、かつ、複数列をなすように配置され、各列の前記導体の各々の位置は、隣の列の前記導体の各々の間に形成される間隔部分に対応するようにされている、請求項7または8に記載の圧電体シートの製造装置。
- 前記導体は断面が正方形とされ、隣り合う前記導体間の間隔は、各導体の断面を規定する正方形の一辺の長さと等しくされる、請求項11に記載の圧電体シートの製造装置。
- 前記高電圧印加用導体の近傍に設けられる、前記ポリ乳酸シートを急冷するための冷却用流体の吹き出し口をさらに備える、請求項5なし12のいずれかに記載の圧電体シートの製造装置。
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CN102803357A (zh) | 2012-11-28 |
US20150280106A1 (en) | 2015-10-01 |
EP2444452A4 (en) | 2014-12-24 |
KR101431756B1 (ko) | 2014-08-20 |
US9537084B2 (en) | 2017-01-03 |
JPWO2010147074A1 (ja) | 2012-12-06 |
EP2444452A1 (en) | 2012-04-25 |
EP2444452B1 (en) | 2018-01-03 |
US20130228463A1 (en) | 2013-09-05 |
US9711710B2 (en) | 2017-07-18 |
JP5318203B2 (ja) | 2013-10-16 |
KR20120024697A (ko) | 2012-03-14 |
CN102803357B (zh) | 2014-07-09 |
US9048426B2 (en) | 2015-06-02 |
US20120108783A1 (en) | 2012-05-03 |
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