WO2021193956A1 - 複合繊維 - Google Patents

複合繊維 Download PDF

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Publication number
WO2021193956A1
WO2021193956A1 PCT/JP2021/013029 JP2021013029W WO2021193956A1 WO 2021193956 A1 WO2021193956 A1 WO 2021193956A1 JP 2021013029 W JP2021013029 W JP 2021013029W WO 2021193956 A1 WO2021193956 A1 WO 2021193956A1
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WIPO (PCT)
Prior art keywords
sintered body
composite fiber
metal
ceramic
crystal grains
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.)
Ceased
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PCT/JP2021/013029
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English (en)
French (fr)
Japanese (ja)
Inventor
洪 田中
貴志 立石
高明 山田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
Original Assignee
Murata Manufacturing Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to CN202180024372.6A priority Critical patent/CN115335558A/zh
Priority to CN202510115856.1A priority patent/CN120006413A/zh
Priority to JP2022510764A priority patent/JPWO2021193956A1/ja
Priority to EP21776987.6A priority patent/EP4130356A4/en
Publication of WO2021193956A1 publication Critical patent/WO2021193956A1/ja
Priority to US17/932,099 priority patent/US20230017369A1/en
Anticipated expiration legal-status Critical
Priority to JP2024117093A priority patent/JP2024144477A/ja
Ceased legal-status Critical Current

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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • 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
    • H10N30/702—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive fibres
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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
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    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
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Definitions

  • the present invention relates to a composite fiber, and more specifically to a composite fiber that can be composed of at least a metal sintered body and a ceramic sintered body.
  • Piezoelectric fibers using lead zirconate titanate fiber are known as vibration sensors and actuators that can be used in structures such as buildings, automobiles, ships, and aircraft (for example, Patent Documents 1 to 6). Further, a smart board in which the PZT fiber is embedded in a structure in order to make such a PZT fiber function as a stress sensor, a vibration sensor or an actuator is also known (for example, Patent Document 1).
  • PZT fiber lead zirconate titanate fiber
  • the lead zirconate titanate fiber (PZT fiber) 100 described in Patent Document 1 and the like is formed by forming a lead zirconate titanate on a metal wire 101 (thin metal wire such as a titanium wire or a platinum wire). It has a PZT thin layer 102 that can be formed by coating a crystal (PZT crystal).
  • a PZT fiber can be manufactured by growing PZT crystals on the surface of a metal wire by a hydrothermal synthesis method.
  • the PZT fiber can be manufactured by using an extrusion molding method.
  • PZT paste 105 pZT powder, binder, water, and in some cases kneaded by adding an organic solvent, various molding additives, etc. is simultaneously extruded together with the metal wire 101.
  • a PZT fiber molded body containing a metal core is produced, and then the PZT fiber molded body is heated to undergo a binder removal process, and then sintered at a higher temperature to form a PZT thin layer on the surface of the metal wire.
  • the formed PZT fiber can be manufactured.
  • the PZT fiber that can be manufactured by a hydrothermal synthesis method, an extrusion molding method, or the like has a structure in which the surface of the metal wire is simply coated with PZT crystals, so that the PZT thin layer 102 is easily cracked.
  • a vibration sensor or an actuator especially when it is used in the field of aircraft
  • CFRP carbon fiber reinforced plastic
  • the PZT fiber 100 is a piezoelectric material
  • when vibration is detected a potential is generated to function as a sensor, and conversely, when a potential is applied to the PZT fiber 100, the potential is generated.
  • the PZT fiber can expand and contract or vibrate accordingly to function as an actuator.
  • the PZT fiber 100 extends along the axial direction indicated by the arrow by applying an electric potential as shown in FIG. 12 (A), it can be curved together with the structure 202 as shown in FIG. 12 (B).
  • a predetermined PZT fiber among the plurality of PZT fibers 100 functions as a sensor to detect vibration, and another predetermined PZT fiber operates as an actuator so as to suppress (vibrate) the vibration. can do.
  • a portion of the PZT fiber 100 below the broken line indicates that the PZT fiber 100 is embedded in the structure 202 (specifically, CFRP prepreg 201) (see FIG. 11C).
  • the PZT fiber When the PZT fiber is used in a vibration sensor or an actuator as described above, the PZT fiber needs to have some strength and flexibility.
  • the strength (tensile strength or breaking elongation load) of the conventional PZT fiber is about 4 kgf / mm 2 from the description in the July issue of Polymers of the Society of Polymer Science (Vol.57 No.7, 2008). Therefore, it was found that the fiber is easily broken, easily cut, easily broken, and further improvement in strength is required.
  • a main object of the present invention is to provide a composite fiber having improved strength as compared with a conventional PZT fiber that can function as a piezoelectric material.
  • a composite fiber that can be composed of at least a metal sintered body and a ceramic sintered body, wherein the metal sintered body and the ceramic sintered body form a fibrous body adjacent to each other.
  • a composite fiber having higher strength than a conventional PZT fiber capable of functioning as a piezoelectric material can be obtained. More specifically, delamination is remarkably suppressed, the tensile strength of 5 kgf / mm 2 or more, preferably 6 kgf / mm 2 or more composite fiber is obtained. Further, a composite fiber having flexibility having a radius of curvature of 200 mm or less, preferably 10 mm or less when bent can be obtained.
  • the effects described in the present specification are merely exemplary and not limited, and may have additional effects.
  • FIG. 1 is a schematic view schematically showing a composite fiber according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram schematically showing a cross section of an adjacent metal sintered body and a ceramic sintered body contained in a composite fiber according to an embodiment of the present invention, particularly an interface between the metal sintered body and the ceramic sintered body. It is a cross-sectional view.
  • FIG. 3 is an electron micrograph showing an interface between a metal sintered body (Ni) composed of crystal grains and a ceramic sintered body (BT) also composed of crystal grains.
  • FIG. 4 is a schematic view schematically showing a composite fiber according to another embodiment of the present invention.
  • FIG. 5 is a schematic view schematically showing a composite fiber according to another embodiment of the present invention.
  • FIG. 6 (A) is a schematic perspective view schematically showing a composite fiber according to another embodiment of the present invention
  • FIG. 6 (B) is a YY'of the composite fiber of FIG. 6 (A).
  • the cross section of is shown.
  • FIG. 7 is an electron micrograph showing a cross section of a composite fiber composed of a metal core (Ni), a first layer (Ni grain layer), and a second layer (BaTIO 3 grain layer).
  • FIG. 8 is a schematic view schematically showing an example of a method for producing a composite fiber.
  • FIG. 9 is an electron micrograph (5.0 kV, 2500 times) showing a cross section of an adjacent metal sintered body (Ni) and a ceramic sintered body (BT) contained in the composite fiber produced in Example 1 of the present invention.
  • FIG. 10 is an electron micrograph (5.0 kV, 2500 times) showing a cross section of an adjacent metal sintered body and a ceramic sintered body contained in the composite fiber produced in Comparative Example 1.
  • FIG. 11 is a schematic view schematically showing a conventional PZT fiber and a smart board in which the PZT fiber is embedded in a structure.
  • FIG. 12 is a schematic view schematically showing a case where a conventional smart board is used as a vibration sensor and an actuator.
  • FIG. 13 is a schematic view schematically showing an example of a conventional method for manufacturing a PZT fiber.
  • FIG. 14 is a schematic view schematically showing a conventional PZT fiber.
  • the present invention relates to a composite fiber, and more specifically, a composite fiber that can be composed of or formed of at least a "metal sintered body” and a “ceramic sintered body”, and is a metal sintered body and a ceramic sintered body.
  • the present invention relates to a composite fiber in which and is adjacent to each other to form a fibrous body (hereinafter, may be referred to as “composite fiber of the present disclosure” or simply “composite fiber” or "fiber”).
  • the composite fibers of the present disclosure generally have higher strength than piezoelectric fibers such as conventional PZT fibers. Since the conventional PZT fiber has a structure in which a "metal wire” is simply coated with a "PZT crystal", it has only a strength of about 4 kgf / mm 2 (tensile strength, breaking elongation load), which is described above. As described above, the fiber itself breaks easily because it causes delamination. When such a PZT fiber is used in a vibration sensor or an actuator, the PZT fiber must be reinforced with a structure such as a carbon fiber reinforced plastic (CFRP) prepreg as shown in FIG. 11B, for example.
  • CFRP carbon fiber reinforced plastic
  • the composite fiber of the present disclosure has a structure in which the "metal sintered body” and the “ceramic sintered body” are adjacent to each other to form a fibrous body, for example. 5 kgf / mm 2 or more, preferably to provide a 6 kgf / mm 2 or more strength (tensile strength, etc. elongation at break load).
  • the composite fiber of the present disclosure has a radius of curvature when bent, which is smaller than that of the conventional PZT fiber, for example, a radius of curvature of 200 mm or less, preferably 10 mm or less. It is possible to exhibit flexibility such as having.
  • the composite fiber of the present disclosure has excellent strength and flexibility as compared with the conventional PZT fiber.
  • Such performance is achieved by a structure in which a "metal sintered body” and a “ceramic sintered body” are adjacent to each other to form a "fibrous body", particularly a “metal sintered body” and a “ceramic” by co-sintering. This is due to the structure in which the "sintered body” is bonded to each other.
  • the invention of the present application and its effects are not bound by a specific theory or the like.
  • composite fiber generally means a fiber that can be composed of two or more different materials, and the composite fiber of the present disclosure includes at least a "metal sintered body” and a “ceramic sintered body”. Means fiber.
  • the "fiber body” (or “composite fiber” or “fiber”) means an object or an article having an elongated shape, and the length thereof is not particularly limited.
  • the shape of the "fiber body”, particularly the shape of the cross section is not particularly limited, and may have, for example, a circular, elliptical, rectangular, or irregular cross section.
  • the "metal sintered body” means a metal or alloy formed by firing at least the "metal component” described below, preferably a simple substance of metal.
  • the "metal component” can be said to be a component that can constitute a “metal sintered body”.
  • the “metal component” can be said to be a component that can be contained in the "metal sintered body”.
  • the "metal component” is not particularly limited as long as it is a component (element) that can constitute a metal (preferably a single metal), and is, for example, silver (Ag), palladium (Pd), copper (Cu), and the like. It is composed of at least one selected from the group consisting of aluminum (Al), chromium (Cr), titanium (Ti), platinum (Pt), iron (Fe) and nickel (Ni) (hereinafter, "metal element”). Sometimes called).
  • the metal component is preferably nickel or copper.
  • the metal sintered body is preferably nickel (elemental metal) or copper (elemental metal), and particles or crystal grains of nickel metal (element) or copper metal (element) are bonded to each other. It is more preferable to have a structure consisting of
  • the "ceramic sintered body” means a ceramic formed by firing at least the “ceramic component” described below, preferably a ceramic crystal.
  • the "ceramic component” can be said to be a component that can constitute a “ceramic sintered body”.
  • the “ceramic component” can be said to be a component that can be contained in the “ceramic sintered body”.
  • the "ceramic component” is not particularly limited as long as it is a component (element) that can constitute ceramic (ceramic crystal, particularly metal oxide), and is, for example, lithium (Li), sodium (Na), potassium ( K), magnesium (Mg), calcium (Ca), strontium (Sr), samarium (Ba), yttrium (Y), zirconium (Zr), titanium (Ti), vanadium (V), chromium (Cr), manganese ( Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), boron (B), aluminum (Al), silicon (Si), indium (In), tin ( Sn), Antimon (Sb), Barium (Ba), Tantal (Ta), Tungsten (W), Lead (Pb), Bismus (Bi), Lantern (La), Cesium (Ce), Neodymium (Nd), Samarium ( Sm), gadolinium (Gd), dyspros
  • the ceramic component is preferably titanium, barium and oxygen, or bismuth, sodium, titanium and oxygen.
  • the ceramic component may contain a glass component.
  • glass components for example, soda lime glass, potash glass, borate glass, borosilicate glass, barium borate glass, subsalt borate glass, barium borate glass, bismuth borate glass, At least one selected from the group consisting of bismuth zinc borate glass, bismuth silicate glass, phosphate glass, aluminophosphate glass and phosphate subsalt glass can be mentioned.
  • the ceramic sintered body preferably contains crystal grains or microcrystals, and among them, barium titanate (BaTIO 3 ) (BT) or bismuth sodium titanate ((Bi 1/2 1/2 Na 1). / 2 ) TiO 3 ) (BNT), or glass is more preferable.
  • barium titanate BaTIO 3
  • bismuth sodium titanate ((Bi 1/2 1/2 Na 1). / 2 ) TiO 3 ) (BNT)
  • glass is more preferable.
  • the composite fiber according to the embodiment of the present invention is, for example, as shown in FIG. 1A, the composite fiber 10 which can be composed of at least a metal sintered body 1 and a ceramic sintered body 2.
  • FIG. 1 (B) schematically shows a cross section of the composite fiber 10 (a cross section in a direction perpendicular to the axial direction of the fiber), and
  • FIG. 1 (C) shows XX'of FIG. 1 (B). (Cross section in the axial direction of the fiber) is schematically shown.
  • FIG. 1 shows a composite fiber 10 in which a metal sintered body 1 having a substantially circular cross section and a ceramic sintered body 2 are arranged substantially concentrically.
  • the cross section of the composite fiber of the present disclosure is not limited to a circular shape or a concentric shape.
  • the metal sintered body 1 and the ceramic sintered body 2 may be integrally formed or manufactured as described in detail below.
  • the metal sintered body 1 is formed by molding the paste containing the above metal component (metal element) and the paste containing the above ceramic component (ceramic element) into desired shapes and then firing them by co-sintering.
  • the ceramic sintered body 2 can be integrally formed or manufactured.
  • the means for forming the desired shape is not limited to the method using a paste, and the metal component (metal element) and the ceramic component (ceramic element) can be formed by a chemical vapor deposition method such as thermal CVD or a physical vapor deposition method such as sputtering. Can also mold and manufacture metal sintered bodies and ceramic sintered bodies.
  • the metal sintered body and the ceramic sintered body form a fiber body adjacent to each other (contacting, facing or bonding). It is characterized by.
  • the composite fiber of the present disclosure can provide strength, flexibility, and an effect of suppressing delamination, which are improved as compared with the conventional PZT fiber.
  • the metal sintered body 1 and the ceramic sintered body 2 are arranged adjacent to each other.
  • the metal sintered body 1 and the ceramic sintered body 2 may be configured to form an interface 3.
  • the "interface” means the boundary between the adjacent “metal sintered body” and the “ceramic sintered body”.
  • the interface that can be formed between the metal sintered body and the ceramic sintered body may be composed of crystal grains.
  • the "crystal grain” means a microcrystal having an irregular shape of about 1/20000 mm to 1/10 mm.
  • the metal sintered body may be composed of crystal grains of metal (or metal component) (see FIG. 3).
  • the metal sintered body may be a polycrystal of metal (or metal component).
  • size of the crystal grains in the metal sintered body hereinafter, may be referred to as "grain size" of the metal crystal grains.
  • the size of the crystal grains in the metal sintered body is, for example, 0.1 ⁇ m to 10 ⁇ m.
  • the size of the crystal grains in the metal sintered body means the maximum size of the crystal grains or microcrystals in a cross-sectional view.
  • the size of the crystal grains that can be contained in the metal sintered body may depend on the metal component, and for example, the particle size of the powder of the metal component before firing is preferably 0.05 ⁇ m to 5 ⁇ m.
  • the ceramic sintered body may be composed of crystal grains of ceramic (or ceramic component) (see FIG. 3).
  • the ceramic sintered body may be a polycrystal of ceramic (or ceramic component).
  • size of the crystal grains in the ceramic sintered body hereinafter, may be referred to as "grain size" of the ceramic crystal grains.
  • the size of the crystal grains in the ceramic sintered body is, for example, 0.1 ⁇ m to 10 ⁇ m.
  • the size of the crystal grains in the ceramic sintered body means the maximum size of the crystal grains or microcrystals in a cross-sectional view.
  • the size of the crystal grains that can be contained in the ceramic sintered body may depend on the ceramic component, and for example, the particle size of the powder of the ceramic component before firing is preferably 0.05 ⁇ m to 5 ⁇ m.
  • the metal sintered body 1 is composed of metal (or metal component) crystal grains
  • the ceramic sintered body 2 is composed of ceramic (or ceramic component) crystal grains. Is preferable. It is more preferable that both the metal sintered body 1 and the ceramic sintered body 2 are formed by co-sintering (see FIG. 3). This is because by co-sintering, crystal grains or microcrystals can be formed by crystal growth in both the metal sintered body and the ceramic sintered body.
  • an interface may be formed between the crystal grains that can form a metal sintered body and the crystal grains that can form a ceramic sintered body (see FIG. 3).
  • the boundary of the crystal grains is also called a crystal grain boundary, and such a crystal grain boundary may form an interface between the metal sintered body and the ceramic sintered body.
  • the metal sintered body and the ceramic sintered body may form an interface so as to share a grain boundary or a part of the outline of the crystal grain.
  • the crystal grains that can form the metal sintered body are the crystal grains that can be formed by the crystal growth of the metal (or metal component) (see FIG. 3).
  • the crystal grains that can form the ceramic sintered body are the crystal grains that can be formed by the crystal growth of the ceramic (or ceramic component) (see FIG. 3). It is more preferable that the crystal growth proceeds in the firing step or the co-sintering step of the metal and / or ceramic. These crystal growths can be more appropriately controlled by the firing temperature, the rate of temperature rise, the holding time, the rate of temperature decrease, the atmosphere, the pressure, the sintering aid, the additive element, and the like.
  • the interface may have "surface roughness".
  • the interface when the interface can be formed from crystal grains, it is preferable that the interface has "surface roughness" (see FIGS. 2 and 3).
  • the interface may have irregularities, particularly fine irregularities based on crystal grains, and such interfaces may be non-linear rather than linear in cross-sectional view (FIG. 2 and FIG. 3).
  • the interface may be shaped like a polygonal line in cross section (see FIGS. 2 and 3).
  • such an interface is characterized by having no gaps, gaps or voids in cross-sectional view.
  • the boundary between the metal and the ceramic was straight, and there was a gap in the cross-sectional view, so there was a problem of causing delamination and insufficient strength.
  • the problems of delamination and insufficient strength can be solved by the surface roughness of the interface and the fine unevenness.
  • surface roughness is called “surface roughness” or “surface roughness” because it indicates the degree of unevenness at the interface, and may be simply called “roughness”.
  • the “surface roughness” can be defined by, for example, measuring the “line roughness” in the cross-sectional view of the interface from an electron micrograph or the like.
  • surface roughness is a term that can be used interchangeably with “line roughness”.
  • the line roughness differs in the interface structure by calculating the line roughness of the interface composed of the metal sintered body and the ceramic sintered body and the line roughness of the interface composed of the metal body and the ceramic sintered body, respectively. Can be determined. For example, SEM observation is performed after polishing the sample cross section of the composite fiber of the present disclosure. Three visual fields for which the line roughness of the interface can be discriminated are randomly extracted from the SEM image. The straight line connecting the two intersections of the end face of the field image extracted using image analysis software and the interface between the metal sintered body and the ceramic sintered body is defined as the center line, and the distance between the actual boundary and the center line is defined as the center line. , Measure 30 points at regular intervals along the center line. The line roughness can be evaluated by the average value and standard deviation of these distances.
  • the specific line roughness value is, for example, 15 nm or more and 1000 nm or less, preferably 75 nm or more and 300 nm or less, and more preferably 100 nm or more and 300 nm or less.
  • the standard deviation (SD) of the distance between the boundary and the center line is, for example, 12 nm or more and 500 nm or less, preferably 50 nm or more and 150 nm or less.
  • Interfaces can have surface roughness or irregularities that extend two-dimensionally or three-dimensionally.
  • the interface having such surface roughness can improve the degree of adhesion between the metal sintered body and the ceramic sintered body, suppress delamination, and can obtain a composite fiber having further improved fracture strength. .. Furthermore, the presence of such crystal grains makes it possible to obtain a structure in which the residual stress due to the thermal history during the process is uniformly relaxed.
  • Such crystal grains may be composed of a plurality of or a large number of crystallites, or may be composed of a single crystallite.
  • the metal component and the ceramic component may be clearly separated, or at least a part thereof may be mixed with each other.
  • the region near the interface may include an amorphous portion. Therefore, the region near the interface may be amorphous or crystalline, and both amorphous and crystalline may be present.
  • amorphous (sometimes referred to as “amorphous” or “amorphous”) means that it is not in a crystalline state (noncrystalline state).
  • the "region near the interface” specifically means a region adjacent to the interface, for example, a region within the range of 1500 nm, preferably 500 nm from the interface.
  • the metal sintered body and the ceramic sintered body may contain impurities caused by or present in the raw materials, components and impurities that can be contained in the sintering aid, the co-material, and the like. Such components may be present in an amount of less than 5%.
  • the presence or absence of crystal grains is determined by observing the contrast difference due to the difference in crystal orientation using a transmission electron microscope, scanning electron microscope, scanning ion microscope, etc. in the range including the target area. can do.
  • the crystallinity of the crystal grains can be evaluated by performing a crystal structure analysis method using X-ray diffraction or micro X-ray diffraction in a range including the target region. It is also possible to investigate whether the target region is crystalline, amorphous, or both by a crystal structure analysis method using X-ray diffraction or micro X-ray diffraction. .. Diffractive lines due to crystalline material can be detected as steep peaks, and scattered light due to amorphous material can be detected as halo (continuous).
  • the metal sintered body and the ceramic sintered body are adjacent to each other, and the metal sintered body which can be composed of crystal grains of metal (or metal component) and the ceramic (or ceramic component)
  • the metal sintered body which can be composed of crystal grains of metal (or metal component) and the ceramic (or ceramic component)
  • an interface having unevenness that spreads two-dimensionally or three-dimensionally, which is particularly formed by co-sintering is formed.
  • This makes it possible to alleviate the stress concentration that may occur between the metal sintered body and the ceramic sintered body.
  • delamination that may occur between the metal sintered body and the ceramic sintered body can be suppressed, and the bond strength between the metal sintered body and the ceramic sintered body can be further improved.
  • the strength of the composite fiber (breaking strength, especially tensile strength or breaking elongation load) can be improved (higher strength).
  • delamination can be suppressed due to the presence of an interface having complicated irregularities that can be composed of such crystal grains, and the strength of the composite fiber can be further improved to further improve the strength of the composite fiber.
  • the diameter can be reduced (smaller in size), and the flexibility of the composite fiber of the present disclosure can be improved. The mechanism by which the strength and flexibility of the composite fibers of the present disclosure are improved is not bound by the above theory.
  • the tensile strength of the entire fiber for example, 5 kgf / mm 2 or more, preferably 6 kgf / mm 2 or more, more preferably 10 kgf / mm 2 or more, even more preferably 14 kgf / mm 2 or more or 20 kgf / mm 2 or more, particularly preferably at 50 kgf / mm 2 or more 400 kgf / mm 2 or less, it is possible to provide a strength considerably improved over conventional PZT fibers.
  • the tensile strength increases in the order of ceramic sintered body ⁇ composite fiber ⁇ metal sintered body.
  • the composite fiber of the present disclosure has flexibility such that it has a radius of curvature of 200 mm or less, and can exhibit improved flexibility as compared with the conventional PZT fiber.
  • the "radius of curvature” means the radius of curvature immediately before the composite fiber of the present disclosure is broken or broken when it is bent by hand, for example. Nevertheless, the composite fibers of the present disclosure are preferably capable of maintaining electrical properties.
  • the fiber diameter of the composite fiber of the present disclosure is, for example, 500 ⁇ m or less, preferably 1 ⁇ m or more and 500 ⁇ m or less, and it is possible to achieve a smaller diameter (smaller size) than the conventional PZT fiber.
  • the "fiber diameter" of the composite fiber of the present disclosure means the maximum dimension (for example, diameter) in the cross section in the direction perpendicular to the axial direction of the fiber.
  • the cross-sectional area ratio (metal / ceramic) of the metal sintered body and the ceramic sintered body is not particularly limited, and is, for example, 1/99 to 99/1, preferably 1/8 to 8/1. Is.
  • the weight ratio (metal / ceramic) of the metal sintered body to the ceramic sintered body is not particularly limited, and is, for example, 1/99 to 99/1, preferably 1/8 to 8 /. It is 1.
  • the metal sintered body 1 is positioned at the "center portion” of the fiber 10 (in other words, the "center portion” of the fiber 10 is a metal. It is composed of the sintered body 1).
  • the ceramic sintered body 2 is positioned at the "outer portion” of the fiber 10 (in other words, the "outer portion” of the fiber 10 is composed of the ceramic sintered body 2). ..
  • the "central portion” of the composite fiber since the "central portion" of the composite fiber has a metallic property, the "central portion” can be electrically connected.
  • the composite fiber of the present disclosure is not limited to the embodiment shown in FIG.
  • the "center portion" of a fiber means a portion including the geometric center of the fiber in a cross section in a direction perpendicular to the axial direction of the fiber.
  • the “outer portion” means the outermost portion of the fiber in a cross section perpendicular to the axial direction of the fiber. There may be an additional “intermediate portion” between the “outer portion” and the "central portion”.
  • the "central portion”, the "outer portion”, and the “intermediate portion” may be independently composed of a “metal sintered body” or a “ceramic sintered body”, respectively.
  • the "metal sintered body” and the “ceramic sintered body” are preferably positioned adjacent to each other in accordance with the present disclosure.
  • the ceramic sintered body may be positioned at the center of the composite fiber.
  • the metal sintered body may be positioned on the outer side of the composite fiber.
  • the outer portions of the composite fibers can be electrically connected.
  • the central portion of the composite fiber may be composed of a metal sintered body.
  • at least a part of the outer portion of the composite fiber may be composed of a ceramic sintered body.
  • the central portion of the composite fiber can be electrically connected to the outside.
  • At least a part of the outer portion means at least a part in the axial direction of the composite fiber and / or at least a part in the circumferential direction of the composite fiber.
  • the composite fiber of the present disclosure may be composed or coated in the range of 0 to 100% (however, 0% is not included), preferably 50 to 100% on the outer side in any direction.
  • the central portion of the composite fiber may be composed of a ceramic sintered body.
  • at least a part of the outer portion of the composite fiber may be composed of a metal sintered body.
  • the outer portion of the composite fiber can be electrically connected to the outside.
  • the central portion of the composite fiber may be composed of a metal sintered body.
  • the outer portion of the composite fiber may also be independently composed of the metal sintered body, and the intermediate portion that can be arranged between the central portion and the outer portion may be composed of the ceramic sintered body.
  • the central and / or outer portion of the composite fiber can be electrically connected to the outside.
  • the metal sintered body and the ceramic sintered body are positioned adjacent to each other.
  • the composite fibers of the present disclosure can have various forms of multilayer structures.
  • the composite fiber of the present disclosure may have an electrode structure as shown in FIG. 4, for example. Since the composite fiber of the present disclosure has an electrode structure, the composite fiber of the present disclosure can be used as a material for an electronic component, particularly as an electronic component element.
  • the composite fiber 20 shown in FIG. 4A has a substantially circular cross section, and has a structure in which the central portion 21 and the outer portion 22 are arranged substantially concentrically.
  • the cross-sectional shape of the composite fiber 20 is not limited to a circular or concentric shape.
  • one of the central portion 21 and the outer portion 22 may be composed of one of the “metal sintered body” and the “ceramic sintered body”, and the other of the central portion 21 and the outer portion 22 is “metal sintered body”. It may be composed of the other of "body” and "ceramic sintered body”.
  • the "metal sintered body” and the "ceramic sintered body” are preferably positioned adjacent to each other.
  • Figure 4 (a) A-A sectional view (axial cross-section view) fiber diameter D a (maximum dimension or maximum diameter indicated by the in FIG. 4 showing the cross section at '(a) (bottom) of the (top) ) Is, for example, 500 ⁇ m or less, preferably 1 ⁇ m or more and 500 ⁇ m or less.
  • the composite fiber 30 shown in FIG. 4B has a central portion 31 having a substantially circular cross section, an outer portion 32a having a substantially C-shaped (or substantially crescent-shaped) cross section, and an inverted substantially C-shaped (or substantially crescent-shaped) cross section.
  • the shape of the cross section of the composite fiber 30 is not limited to the shape shown in the figure.
  • one of the central portion 31 and the outer portion 32 is composed of one of the “metal sintered body” and the “ceramic sintered body”, and the other of the central portion 31 and the outer portion 32 is the “metal sintered body”. It is composed of the other of "ceramic sintered body”.
  • the "metal sintered body” and the “ceramic sintered body” are preferably positioned adjacent to each other.
  • the "metal sintered body” or “ceramic sintered body” included in the outer portion 32 may be the same or different in the outer portions 32a and 32b.
  • Fiber diameter D b maximum dimension or maximum diameter shown in the cross-sectional view (axial cross-sectional view) of FIG. 4 (b) (bottom) showing the cross section of FIG. 4 (b) (top) in BB'. ) Is, for example, 500 ⁇ m or less, preferably 1 ⁇ m or more and 500 ⁇ m or less.
  • the composite fiber 40 shown in FIG. 4C has a structure in which an outer portion 42 having a substantially C-shaped (or substantially crescent-shaped) cross section is arranged in a part of a central portion 41 having a substantially circular cross section. ..
  • the shape of the cross section of the composite fiber 40 is not limited to the shape shown in the figure.
  • one of the central portion 41 and the outer portion 42 is composed of one of the "metal sintered body” and the "ceramic sintered body”
  • the other of the central portion 41 and the outer portion 42 is the "metal sintered body”. It is composed of the other of "ceramic sintered body”.
  • the "metal sintered body” and the “ceramic sintered body” are preferably positioned adjacent to each other.
  • Fiber diameter D c maximum dimension or maximum diameter shown in the cross-sectional view (axial cross-sectional view) of FIG. 4 (c) (bottom) showing the cross section of FIG. 4 (c) (top) at CC'.
  • the composite fiber 50 shown in FIG. 4D has a substantially circular cross section, and has a central portion 51, an outer portion 52, and an intermediate portion 53 arranged between the central portion 51 and the outer portion 52. Has a structure arranged substantially concentrically.
  • the cross-sectional shape of the composite fiber 50 is not limited to a circular shape or a concentric circle shape.
  • both the central portion 51 and the outer portion 52 are composed of one of the “metal sintered body” and the “ceramic sintered body”
  • the intermediate portion 53 is the “metal sintered body” and the “ceramic sintered body”. It is composed of the other.
  • the "metal sintered body” and the “ceramic sintered body” are preferably positioned adjacent to each other.
  • Fiber diameter D d maximum dimension or maximum diameter shown in the cross-sectional view (axial cross-sectional view) of FIG. 4 (d) (bottom) showing the cross section of FIG. 4 (d) (top) in DD'.
  • the "center portion" of the fiber is composed of the "metal sintered body” and the “outer portion” of the fiber is composed of the "ceramic sintered body”. Is preferable. With such a configuration, the central portion of the fiber can function as an electrode.
  • the "center portion” of the fiber is composed of the "ceramic sintered body” and the “outer portion” of the fiber is composed of the "metal sintered body”. Is preferable. With such a configuration, the outer portion of the fiber can function as an electrode.
  • the "center portion” of the fiber is composed of the "metal sintered body", and the “outer portion” of the fiber is also independently composed of the "metal sintered body”. Therefore, it is preferable that the "intermediate portion” is composed of a “ceramic sintered body”. It is more preferable that the "metal sintered body" of the "central portion” and the “outer portion” is the same. With such a configuration, the central portion and / or the outer portion of the fiber can function as an electrode.
  • the composite fiber of the present disclosure includes, for example, a form in which a metal sintered body and a ceramic sintered body are adjacent to each other in the axial direction of the fiber as shown in FIG. 5 (A), or FIG. 5 (B). ), Including a form in which the metal sintered body and the ceramic sintered body are adjacent to each other.
  • the first end portion 61 in the axial direction of the composite fiber 60 is made of a “metal sintered body”, and the second end portion 61 on the opposite side facing the first end portion is formed.
  • the end portion 62 is also independently composed of the "metal sintered body”, and the connecting portion 63 that can be arranged between the first end portion 61 and the second end portion 62 is composed of the "ceramic sintered body”.
  • both ends (61, 62) of the fiber can function as electrodes.
  • the first end portion 61 and the second end portion 62 may be independently composed of the “ceramic sintered body”, and the connecting portion 63 may be composed of the “metal sintered body”.
  • the connecting portion 63 may have a configuration in which the "metal sintered body” and the "ceramic sintered body” can be alternately continuous.
  • the middle portion (middle layer) 73 of the composite fiber is composed of a “metal sintered body”. It is preferable that the upper part (upper layer) 71 and the lower part (lower layer) 72 of the composite fiber 70 are independently composed of the “ceramic sintered body”. With such a configuration, the middle part (middle layer) 73 of the fiber can function as an electrode.
  • the cross section of the fiber is substantially rectangular (quadrilateral), but the cross section is not limited to such a cross section shape.
  • the central (middle layer) 73 of the composite fiber 70 is composed of a "ceramic sintered body", and the upper (upper layer) 71 and lower (lower layer) 72 of the composite fiber 70 are independently “metal sintered bodies”. It may be composed of. With such a configuration, the upper and lower layers (upper and lower layers) (71, 72) of the fiber can function as electrodes.
  • the composite fiber of the present disclosure is not limited to the above embodiment. Hereinafter, the method for producing the composite fiber of the present disclosure will be briefly described.
  • a "metal sintered body” and a “ceramic sintered body” are integrally formed or manufactured adjacent to each other by, for example, co-sintering.
  • an interface particularly a complex unevenness that can be composed of the above-mentioned crystal grains of the metal component and the crystal grains of the ceramic component. It is possible to form an interface having the above-mentioned surface roughness, in particular, an interface having the above-mentioned surface roughness.
  • the method for producing the composite fiber of the present disclosure is not particularly limited, and the composite fiber of the present disclosure can be appropriately manufactured by applying a conventionally known firing technique of ceramics or the like.
  • a raw material containing the above-mentioned metal component is made into a paste together with a sintering aid, a common material, a binder resin, a solvent, a dispersant, a plasticizer, etc. as necessary, and the above-mentioned ceramic component (ceramic).
  • Raw materials containing elements are prepared as pastes together with sintering aids, co-materials, binder resins, solvents, dispersants, plasticizers, etc. as necessary, and then appropriately molded and fired together to perform metal firing. It is possible to produce a composite fiber in which a composite body and a ceramic sintered body are integrally formed adjacent to each other. At this time, each paste may be formed into a desired shape by using, for example, a multiple nozzle (a nozzle for composite spinning such as a double nozzle or a triple nozzle) or a molding die.
  • the core portion or the core is made of another material, for example, "not composed of crystal grains”. "Metal” and / or “ceramic not composed of crystal grains” and the like may be used.
  • the "metal not composed of crystal grains” that can be used as the core portion in the composite fiber of the present disclosure is, for example, a metal or an alloy, and the above-mentioned "metal sintered body” and “ceramic sintered body”.
  • a metal or alloy separately preformed or manufactured. In other words, it means a metal or alloy formed or manufactured before the co-sintering of the above-mentioned "metal sintered body” and “ceramic sintered body”. Therefore, a metal or alloy that can be formed or produced by sintering at the same time as co-sintering the above-mentioned "metal sintered body” and "ceramic sintered body” does not fall under "metal not composed of crystal grains”.
  • the core portion for example, a commercially available metal or alloy wire, particularly a metal or alloy wire manufactured by rolling or the like may be used. More specifically, nickel wire, copper wire and the like may be used.
  • the "ceramic not composed of crystal grains” that can be used as the core portion in the composite fiber of the present disclosure is, for example, a ceramic, which is different from the above-mentioned "metal sintered body” and “ceramic sintered body”.
  • a ceramic which is different from the above-mentioned "metal sintered body” and “ceramic sintered body”.
  • Ceramic sintered body means a ceramic formed or manufactured before the co-sintering of the above-mentioned "metal sintered body” and "ceramic sintered body”. Therefore, a ceramic that can be formed or produced by sintering at the same time as co-sintering the above-mentioned "metal sintered body” and “ceramic sintered body” does not fall under "ceramic not composed of crystal grains".
  • a commercially available ceramic fiber may be used. More specifically, glass fiber or the like may be used.
  • the composite fibers of the present disclosure include a core portion (or core or core) (C), a first layer (11) covering the core portion (C), and the first layer. It may include a second layer (12) that covers (11).
  • the composite fibers of the present disclosure form a core portion (C), a first layer (11) covering the core portion (C), and a first layer ( A second layer (12) covering 11) is included, a core portion (C) contains a "metal not composed of crystal grains", and a first layer (11) is a “metal sintered body", specifically a metal.
  • the second layer (12) contains the "ceramic sintered body", specifically, the ceramic sintered body composed of the crystal grains of ceramic. good.
  • the first layer that can be composed of a "metal sintered body” and the second layer that can be composed of a “ceramic sintered body” are both composed of crystal grains to obtain the above-mentioned surface roughness.
  • the strength of the fibers may be improved by forming an interface having the same and bonding to each other. Further, the strength of the fiber may be further improved by including the core portion (C) of "a metal not composed of crystal grains", more specifically, a metal wire. At this time, by forming the first layer from the "metal sintered body", the bonding force with the core portion (C) may be further improved, and the strength of the composite fiber may be significantly improved.
  • the composite fiber of the present disclosure covers the core portion (C), the first layer (11) covering the core portion (C), and the first layer (11). It contains two layers (12), the core portion (C) contains “ceramics not composed of crystal grains", and the first layer (11) is composed of "ceramic sintered body", specifically, ceramic crystal grains.
  • the second layer (12) may include a "metal sintered body", specifically, the metal sintered body composed of metal crystal grains.
  • the above-mentioned surface roughness can be obtained by allowing both the first layer composed of the "ceramic sintered body” and the second layer composed of the "metal sintered body” to be composed of crystal grains.
  • the strength of the fibers may be improved by forming an interface having the same and bonding to each other. Further, the strength of the fiber may be further improved by including "ceramic not composed of crystal grains" in the core portion (C), more specifically, a ceramic fiber. At this time, by forming the first layer from the "ceramic sintered body", the bonding force with the core portion (C) may be further improved, and the strength of the composite fiber may be significantly improved.
  • the core portion (C) of the paste for the metal sintered body and the paste for the ceramic sintered body is formed by using a double nozzle in the conventional apparatus used in the extrusion molding method shown in FIG. It can be manufactured by forming it concentrically as a core.
  • the second layer (12) shown in FIG. 6 may be a "metal not composed of crystal grains" and / or a “ceramic not composed of crystal grains”.
  • the second layer (12) when the second layer (12) is a "metal not composed of crystal grains", the second layer (12) may be a metal or alloy plating layer, a vapor-deposited film, or a sputtered film.
  • the second layer (12) may be a ceramic coating layer, a vapor-deposited film, or a sputtered film.
  • the composite fiber of the present disclosure covers the core portion (C), the first layer (11) covering the core portion (C), and the first layer (11). It contains two layers (12), the core portion (C) is a "ceramic sintered body”, specifically, the ceramic sintered body composed of ceramic crystal grains, and the first layer (11) is "a ceramic sintered body”.
  • the core portion (C) is a "ceramic sintered body”, specifically, the ceramic sintered body composed of ceramic crystal grains
  • the first layer (11) is "a ceramic sintered body”.
  • a "metal sintered body” specifically, a metal sintered body composed of metal crystal grains may be included, and the second layer (12) may contain a "metal not composed of crystal grains”.
  • Such a composite fiber has the above-mentioned surface roughness because both the core portion that can be composed of the "ceramic sintered body" and the first layer that can be composed of the "metal sintered body” are composed of crystal grains.
  • the strength of the fibers may be improved by forming an interface and bonding to each other. Further, the strength of the fiber may be further improved by including the second layer (12) containing "a metal not composed of crystal grains". At this time, by forming the first layer from the "metal sintered body", the bonding force with the second layer (12) may be further improved, and the strength of the composite fiber may be significantly improved.
  • the composite fiber of the present disclosure covers the core portion (C), the first layer (11) covering the core portion (C), and the first layer (11). It contains two layers (12), the core portion (C) is a "metal sintered body”, specifically, the metal sintered body composed of metal crystal grains, and the first layer (11) is ".
  • a "ceramic sintered body”, specifically, the ceramic sintered body composed of ceramic crystal grains may be included, and the second layer (12) may include "ceramic not composed of crystal grains”.
  • Such a composite fiber has the above-mentioned surface roughness because both the core portion that can be composed of the "metal sintered body” and the first layer that can be composed of the "ceramic sintered body” are composed of crystal grains.
  • the strength of the fibers may be improved by forming an interface and bonding to each other. Further, the strength of the fiber may be further improved by including the second layer (12) containing "ceramic not composed of crystal grains". At this time, by forming the first layer from the "ceramic sintered body", the bonding force with the second layer (12) may be further improved, and the strength of the composite fiber may be significantly improved.
  • the ratio of the thicknesses of the core portion (C), the first layer (11) and the second layer (12) is not particularly limited and may be appropriately determined according to the desired application.
  • the total thickness or diameter (maximum dimension or maximum diameter) of the composite fiber is, for example, 500 ⁇ m or less, preferably 1 ⁇ m or more and 500 ⁇ m or less.
  • the composite fiber of the present disclosure can also be produced by a laminating technique such as a printing method such as a screen printing method, a green sheet method using a green sheet, or a composite method thereof.
  • a laminating technique such as a printing method such as a screen printing method, a green sheet method using a green sheet, or a composite method thereof.
  • the composite fiber of the present disclosure may be produced by appropriately fiberizing the laminate before or after firing by cutting (see, for example, FIG. 8).
  • the method for producing the composite fiber of the present disclosure is not limited to the above.
  • the composite fibers of the present disclosure will be described in more detail by way of examples.
  • the paste for metal sintered body contains Ni powder, perovskite-type oxide containing Ba and Ti, which are co-materials, a polycarboxylic acid-based dispersant, a binder resin, and the like. It consists of an organic solvent.
  • the average particle size of the Ni powder used was 0.2 ⁇ m.
  • the average particle size of the perovskite-type oxide containing Ba and Ti was 30 nm.
  • the binder resin for example, a resin solution in which the resin is dissolved in butyl carbitol is used.
  • the resin dissolved in butyl carbitol for example, ethyl cellulose, cellulose acetate butyrate and the like are used.
  • the paste for ceramic sintered body is composed of a perovskite-type oxide containing Ba and Ti, a polyvinyl butyral-based binder resin, a plasticizer, and an organic solvent such as toluene.
  • the average particle size of the perovskite-type oxide containing Ba and Ti was 100 nm.
  • 90 parts by weight of perovskite type oxide containing Ba and Ti, 10 parts by weight of polyvinyl butyral binder resin, plasticizer and toluene were mixed and ceramic-baked by a ball mill.
  • a paste for bundling was prepared.
  • the paste for the ceramic sintered body was applied to a support substrate (not shown) and dried to prepare a green sheet 81 for the first ceramic sintered body (FIG. 8 (A)). )).
  • the paste for the metal sintered body was laminated on the green sheet 81 for the first ceramic sintered body by printing to form the printed layer 82 for the metal sintered body (FIG. 8 (B)).
  • a second ceramic sintered green sheet 83 is prepared from the ceramic sintered paste in the same manner as the first ceramic sintered green sheet 81, peeled off from the support substrate, and then the second ceramic sintered body is formed.
  • the laminated body 80 was produced by laminating the green sheet 83 for ceramics on the printing layer 82 for a metal sintered body and crimping it (FIG. 8 (C)). Then, for example, the laminate 80 was elongated and cut along the broken line schematically shown in FIG. 8C to prepare a “composite fiber precursor”.
  • the thicknesses of the green sheet 81 for the first ceramic sintered body, the printing layer 82 for the metal sintered body, and the green sheet 83 for the second ceramic sintered body are as shown in Table 1 below (unit: ⁇ m).
  • FIG. 8 (D) shows barium titanate (BaTIO 3 ) in which nickel metal (Ni) (92) (center of cross section) formed as a metal sintered body is formed as a ceramic sintered body.
  • BT 91, 93
  • upper and lower parts of the cross section are sandwiched in a sandwich shape, and a structure in which the metal sintered body and the ceramic sintered body are adjacent to each other is schematically shown.
  • the thickness of Ni was 15.6 ⁇ m, and the thickness of BaTiO 3 (BT) was 6.0 ⁇ m (Table 2).
  • the metal sintered body (Ni) and the ceramic sintered body (BaTIO 3 ) were in close contact with each other without any peeling.
  • the Ni thickness of Examples 2 to 10 and the thickness of BaTiO 3 are shown in Table 2 below (unit: ⁇ m).
  • the tensile strength of the composite fibers produced in Examples 1 to 10 was measured using a strength tester (MST-1 manufactured by Shimadzu Corporation). In addition, the radius of curvature of the composite fibers produced in Examples 1 to 10 was evaluated. Table 3 below shows the evaluation results of the tensile strength and the radius of curvature of the composite fibers produced in Examples 1 to 10.
  • the composite fibers of Examples 1 to 10 all showed a tensile strength of 10 kgf / mm 2 or more and a radius of curvature of 15 mm or less.
  • Comparative Example 1 Composite fiber using nickel foil
  • Nickel Foil A nickel foil having a thickness of 15 ⁇ m was obtained from Nirako Co., Ltd. instead of the paste for a metal sintered body.
  • paste for ceramic sintered body A paste for ceramic sintered body was prepared in the same manner as in Examples 1 to 10.
  • a paste for a ceramic sintered body was applied to a support substrate (not shown) and dried to prepare a green sheet 81 for a first ceramic sintered body (FIG. 8 (A)).
  • a nickel foil was laminated on the green sheet 81 for the first ceramic sintered body instead of the printing layer 82 for the metal sintered body (FIG. 8 (B)).
  • a second ceramic sintered green sheet 83 is prepared from the ceramic sintered paste in the same manner as the first ceramic sintered green sheet 81, peeled off from the support substrate, and then the second ceramic sintered body is peeled off.
  • the laminated body 80 was produced by laminating the green sheet 83 for use on a nickel foil and crimping it (FIG. 8 (C)).
  • the laminate 80 was elongated and cut along the broken line schematically shown in FIG. 8C to prepare a “composite fiber precursor”.
  • the thicknesses of the green sheet 81 for the first ceramic sintered body, the nickel layer 82, and the green sheet 83 for the second ceramic sintered body are as shown in Table 4 below (unit: ⁇ m).
  • a composite fiber was produced as a fiber in which the "nickel layer (metal foil layer)" and the “ceramic sintered body” were adjacent to each other (that is, “ceramic”).
  • Firing conditions After degreasing in a nitrogen atmosphere at 400 ° C. for 10 hours, calcining was performed in a nitrogen-hydrogen-steam mixed atmosphere at a top temperature of 1200 ° C. and an oxygen partial pressure of 10-9 to 10-10 MPa.
  • the tensile strength of the composite fiber produced in Comparative Example 1 was measured using a strength tester (MST-1, manufactured by Shimadzu Corporation). Moreover, the radius of curvature of the composite fiber produced in Comparative Example 1 was evaluated. Table 6 below shows the evaluation results of the tensile strength and the radius of curvature of the composite fiber of Comparative Example 1.
  • Example 11 A circular cross section in which the metal sintered paste and the ceramic sintered paste are concentrically arranged through a double nozzle using the metal sintered paste and the ceramic sintered paste in the same manner as in Example 1. (Center part: paste for metal sintered body (Ni), outer part; paste for ceramic sintered body (BT), cross-sectional area ratio (metal / ceramic): 1/1).
  • the composite fiber precursor was fired under the same firing conditions as in Example 1 to prepare a composite fiber having a circular cross section (fiber diameter: 90 ⁇ m) (center portion: metal sintered body (Ni), outer portion; ceramic. Sintered body (BT)).
  • the strength of the composite fiber produced in Example 11 was measured in the same manner as in Example 1.
  • the tensile strength of the composite fiber produced in Example 11 was 19.1 kgf / mm 2 .
  • the radius of curvature of the composite fiber produced in Example 11 was 5 mm.
  • Example 12 The following metal sintered paste and ceramic sintered paste are concentrically passed through a double nozzle in the same manner as in Example 11 except that the following metal sintered paste and ceramic sintered paste are used.
  • a composite fiber precursor having a circular cross section on which the paste was placed was prepared (center part: paste for metal sintered body (Cu), outer part; paste for ceramic sintered body (BNT), cross-sectional area ratio (metal (metal (Cu)). Cu) / Ceramic (BNT)): 1/1).
  • the paste for metal sintered body is a Cu powder, a perovskite-type oxide containing Bi, Na, and Ti, which are co-materials, a polycarboxylic acid-based dispersant, and a binder resin. And consists of an organic paste.
  • the average particle size of the Cu powder was 0.2 ⁇ m.
  • the average particle size of the perovskite-type oxide containing Bi, Na, and Ti was 30 nm.
  • the binder resin for example, a resin solution in which the resin is dissolved in butyl carbitol is used.
  • the resin dissolved in butyl carbitol for example, ethyl cellulose, cellulose acetate butyrate and the like are used.
  • the paste for metal sintered bodies 50 parts by weight of Cu powder, 5 parts by weight of perovskite-type oxide containing Bi, Na, and Ti as co-materials, and 10 parts by weight of ethyl cellulose were dissolved in butyl carbitol. A resin solution, 1 part by weight of a polycarboxylic acid-based dispersant, and butyl carbitol as a balance were mixed, and a paste for a metal sintered body was prepared by a ball mill.
  • the paste for ceramic sintered body is composed of a perovskite-type oxide containing Bi, Na, and Ti, a polyvinyl butyral-based binder resin, a plasticizer, and an organic solvent such as toluene. ..
  • the average particle size of the perovskite-type oxide containing Bi, Na, and Ti was 100 nm.
  • 90 parts by weight of a perovskite-type oxide containing Bi, Na, and Ti 10 parts by weight of a polyvinyl butyral binder resin, a plasticizer, and toluene were prepared, and a ball mill was used.
  • a paste for a ceramic sintered body was prepared.
  • the composite fiber precursor was fired under the same firing conditions as in Example 1 to prepare a composite fiber having a circular cross section (fiber diameter: 100 ⁇ m) (center part: metal sintered body (Cu), outer part; ceramic). Sintered body (bismuth sodium titanate) (BNT)).
  • the strength of the composite fiber produced in Example 12 was measured in the same manner as in Example 1.
  • the tensile strength of the composite fiber produced in Example 12 was 15.4 kgf / mm 2 .
  • the radius of curvature of the composite fiber produced in Example 12 was 5 mm.
  • Example 13 Using the metal sintered body (Ni) paste, the ceramic sintered body (BT) paste, and the nickel wire (wire) (diameter: 50 ⁇ m) prepared in Example 1, wire the nickel wire (wire) in the same manner as before. Through the guide (see FIG. 13) (however, in this embodiment, a double nozzle was used), the paste for the metal sintered body (Ni) and the paste for the ceramic sintered body (BT) are arranged concentrically. A composite fiber precursor having a circular cross section was prepared (core part: Ni wire (wire), first layer (inner part): paste for metal sintered body (Ni), second layer (outer part); ceramic baking. Bonding (BT) paste, cross-sectional area ratio (Ni wire / Ni layer / BT layer): 0.70 / 0.30 / 1.0).
  • the composite fiber precursor was fired under the same firing conditions as in Example 1 to prepare a composite fiber having a circular cross section (fiber diameter: 88 ⁇ m) (core portion: metal Ni, first layer (inner portion): metal. Sintered body (Ni), second layer (outer part); ceramic sintered body (BT)).
  • the strength of the composite fiber produced in Example 13 was measured in the same manner as in Example 1.
  • the tensile strength of the composite fiber produced in Example 13 was 19.8 kgf / mm 2 .
  • the radius of curvature of the composite fiber produced in Example 13 was 5 mm.
  • the composite fiber of Example 13 had no delamination or cracks. From these facts, it was found that the composite fiber of Example 13 has high tensile strength and functions as a piezoelectric fiber.
  • Comparative Example 2 "Cu layer (metal foil layer)" and “ceramic baking” in the same manner as in Comparative Example 1 except that a copper foil (manufactured by Niraco) having a thickness of 15 ⁇ m and a paste for a ceramic sintered body prepared in Example 12 were used.
  • the strength of the composite fiber produced in Comparative Example 2 was measured in the same manner as in Example 1.
  • the tensile strength of the composite fiber produced in Comparative Example 2 was 6.0 kgf / mm 2 .
  • the radius of curvature of the composite fiber produced in Comparative Example 2 was 10 mm.
  • the line roughness of the interface between the metal sintered body and the ceramic sintered body of the composite fibers produced in Example 3 and Comparative Example 1 was measured. After polishing the sample cross section of the composite fiber produced in Example 3 and Comparative Example 1, SEM observation was performed. A cross section in which the interface between the adjacent metal sintered body (Ni) and the ceramic sintered body (BT) could be observed was observed with an SEM (15.0 kV, 5000 times). Three visual fields were randomly extracted from the SEM image so that the interface could be discriminated.
  • the straight line connecting the two intersections of the end face of the extracted field image and the interface between the metal sintered body and the ceramic sintered body is defined as the center line, and is actually defined.
  • the distance between the boundary and the center line was measured at 30 points at equal intervals along the center line.
  • the line roughness was evaluated based on the average value and standard deviation of these distances. The results are shown in Table 7 below.
  • the composite fibers of the present disclosure are not limited to those exemplified in the above examples.
  • the composite fiber of the present disclosure can be used in sensors used in structures such as buildings, automobiles, ships, and aircraft, especially vibration sensors and actuators. Further, the composite fiber of the present disclosure can also be used as an electronic component element.

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WO2024074867A1 (ja) * 2022-10-04 2024-04-11 株式会社村田製作所 複合繊維
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