WO2014015674A1 - Nano-ultrasonic vibrator - Google Patents

Nano-ultrasonic vibrator Download PDF

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Publication number
WO2014015674A1
WO2014015674A1 PCT/CN2013/072490 CN2013072490W WO2014015674A1 WO 2014015674 A1 WO2014015674 A1 WO 2014015674A1 CN 2013072490 W CN2013072490 W CN 2013072490W WO 2014015674 A1 WO2014015674 A1 WO 2014015674A1
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WO
WIPO (PCT)
Prior art keywords
carbon fiber
ultrasonic vibration
vibration machine
nano
oxidized
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PCT/CN2013/072490
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French (fr)
Chinese (zh)
Inventor
李泽堂
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纳米新能源（唐山）有限责任公司
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Publication of WO2014015674A1 publication Critical patent/WO2014015674A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/22—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for
    • A61B17/22004—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves
    • A61B17/22012—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves in direct contact with, or very close to, the obstruction or concrement
    • A61B17/2202—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves in direct contact with, or very close to, the obstruction or concrement the ultrasound transducer being inside patient's body at the distal end of the catheter
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/00234—Surgical instruments, devices or methods, e.g. tourniquets for minimally invasive surgery
    • A61B2017/00345—Micromachines, nanomachines, microsystems
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/22—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for
    • A61B17/22004—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves
    • A61B17/22012—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves in direct contact with, or very close to, the obstruction or concrement
    • A61B2017/22014—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves in direct contact with, or very close to, the obstruction or concrement the ultrasound transducer being outside patient's body; with an ultrasound transmission member; with a wave guide; with a vibrated guide wire
    • A61B2017/22015—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves in direct contact with, or very close to, the obstruction or concrement the ultrasound transducer being outside patient's body; with an ultrasound transmission member; with a wave guide; with a vibrated guide wire with details of the transmission member
    • A61B2017/22017—Implements for squeezing-off ulcers or the like on the inside of inner organs of the body; Implements for scraping-out cavities of body organs, e.g. bones; Calculus removers; Calculus smashing apparatus; Apparatus for removing obstructions in blood vessels, not otherwise provided for using mechanical vibrations, e.g. ultrasonic shock waves in direct contact with, or very close to, the obstruction or concrement the ultrasound transducer being outside patient's body; with an ultrasound transmission member; with a wave guide; with a vibrated guide wire with details of the transmission member the ultrasonic transmitting members being fibres

Definitions

  • the present invention relates to a nano-ultrasonic vibrating machine, and in particular to an ultrasonic vibrating machine using an oxidized nanowire. Background technique
  • a thrombus is a solid substance formed by precipitation, agglutination, and coagulation of blood components in a part of the heart or blood vessels. Thromboembolism can result in disruption of the supply of oxygen or nutrients to related tissues, resulting in structural metabolic disorders, associated tissue infarction, and the like.
  • Existing techniques for dissolving or removing thrombus fall into two categories. One is to use a thrombolytic agent or an anticoagulant to achieve thrombolysis or inhibit thrombus growth, but the drawback of this method is that the administration period is long, and in particular, it cannot be applied to intravascular formation. The other is to use a catheter-guided interventional approach to introduce a thrombectomy device into the blood vessel and use mechanical energy to remove the thrombus from the patient's body.
  • Chinese Patent Application No. 200680050755.6 discloses a device for removing thrombus, which uses a small lumen microcatheter to deliver a lesion to a lesion, and then punctures a thrombus, a flexible fiber hook and a thrombus, thereby scraping off the attached blood vessel.
  • the purpose of the wall is thrombus, but the device is more complicated and costly.
  • Chinese Patent Application No. 01127619.3 discloses a novel implantable thrombus filter which adheres to a thrombus through a filter to achieve thrombus removal, but which does not remove thrombus that has been attached to the vessel wall.
  • the oxidized nanowire is a known piezoelectric material, which is usually applied to a nanogenerator.
  • a piezoelectric potential is generated in the nanowire, and the corresponding transient current is in two. The end flows.
  • the object of the present invention is to provide a nano-ultrasonic vibrating machine capable of generating ultrasonic waves (ultrasonic vibration) under an applied voltage for driving foreign matter or thrombus in a body cavity and a blood vessel, in particular It is that the nano ultrasonic vibrating machine can be implanted into a blood vessel and promote thrombus dissolution on the blood vessel wall.
  • the ultrasonic vibrating machine of the present invention is capable of generating ultrasonic waves of different frequencies, for example, ultrasonic waves having a frequency of up to 10 MHz, which can be used to cause thrombus dissolution on the vessel wall.
  • the first technical solution provided by the present invention is a nano ultrasonic vibration machine
  • the ultrasonic vibration machine (electric energy-mechanical energy deformation conversion unit) includes carbon fiber, an oxidized nanowire array and a polymer insulation layer; carbon fiber
  • the surface includes an oxidized nanowire growth region and a dew region; in the oxidized nanowire growth region, the oxidized nanowire array is vertically grown on the surface of the carbon fiber to form a carbon fiber as a core, and the oxidized nanowire array is used as a cylindrical shell. a core-shell structure of the body; the oxidized nanowire array is covered with the polymer insulating layer.
  • the material used for the polymer insulating layer is polymethyl methacrylate or polydimethylsiloxane.
  • the ultrasonic vibration machine further includes a power source, and the power source includes two current output ends, wherein one current output end is connected to the exposed area of the carbon fiber, and the other current output end is connected to the receptor.
  • the receptor is electrically conductive, such as human skin, animal skin, and the like.
  • the ultrasonic vibration machine further includes a distributed electrode disposed on the polymer insulating layer; one current output end of the power source is connected to the exposed area of the carbon fiber, and the other current output end is connected Distributed electrode.
  • the distributed electrode material is any one of gold, platinum, titanium or nickel titanium alloy.
  • the oxidized nanowire growth region accounts for one quarter to four fifths of the length of the carbon fiber.
  • the power source is an alternating current
  • the power is between 5 and 100 W
  • the frequency is between ⁇ - ⁇ .
  • the oxidized nanowire can generate ultrasonic waves (ultrasonic vibration) for driving foreign matter or thrombus in the body cavity and the blood vessel.
  • the ultrasonic vibrating machine of the present invention is capable of generating ultrasonic waves of different frequencies depending on the field of application.
  • DRAWINGS BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a perspective view of a nano ultrasonic vibration machine of the present invention.
  • FIG. 2 is a diagram showing an example of application of the nanosonic vibration of the present invention in a blood vessel.
  • FIG. 3 is a schematic cross-sectional view of a nano ultrasonic vibration machine according to an embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing a nano ultrasonic vibration machine according to another embodiment of the present invention.
  • the nano-ultrasonic vibrating machine of the invention can generate ultrasonic waves (ultrasonic vibration) under the action of an electric field, and is used for driving foreign matter or thrombus in the body cavity and the blood vessel.
  • the nanosonic vibrators of the present invention are capable of generating ultrasonic waves of different frequencies.
  • the nano ultrasonic vibrating machine of the present invention has a diameter of 10 to 15 ⁇ m and can pass through other blood vessels other than the capillaries, and is used for driving a thrombus attached to the blood vessel wall and dissolving the thrombus.
  • the structure of the oxidized word can be described as a plurality of alternating planes composed of tetrahedral coordinated 0 2 - and Zn 2+ ions, which are stacked alternately along the c-axis.
  • the tetrahedral coordination in the oxidized word results in a non-centrosymmetric structure and thus a piezoelectric and thermoelectric phenomenon.
  • a nano ultrasonic vibration machine (electric energy-mechanical energy deformation conversion unit) includes: carbon fiber, an oxidized nanowire array and a polymer insulating layer; the surface of the carbon fiber includes an oxidized nanowire growth region. And the dew area; in the oxidation of the nanowire growth region, the oxidation
  • the rice noodle array is vertically grown on the surface of the carbon fiber to form a core-shell structure with carbon fiber as a core and an oxidized nanowire array as a cylindrical shell; the oxidized nanowire array is covered with the polymer insulating layer.
  • the ultrasonic vibration machine further includes a power source, and the power source includes two current output terminals, wherein one current output end is connected to the exposed area of the carbon fiber; and the other current output end is connected to the human body surface to be electrically connected to the body fluid of the human body.
  • the power source used in the present invention is preferably supplied with a high-frequency voltage having a voltage amplitude of 10 V or less and having no damage to the human body.
  • a conductive receptor such as animal skin can also be applied to the present invention for driving foreign bodies or blood clots in the body cavity and blood vessels of an animal.
  • the ultrasonic vibration machine further comprises a distributed electrode disposed on the high molecular insulating layer; one current output end of the power source is connected to the exposed area of the carbon fiber, and the other current output end is connected to the distributed electrode.
  • an electric field is formed between the carbon fiber and the human body or the carbon fiber and the distributed electrode, and the oxidized nanowire generates ultrasonic vibration under the electric field.
  • the skilled person in the art can adjust the current intensity of the external power source and the total area of the oxidized nanowire array according to the application field, so that the ultrasonic wave generated by the ultrasonic vibration machine of the present application has a suitable frequency, period and amplitude.
  • a medical carbon fiber having a resistance of less than 30 ⁇ / ⁇ and having a strength higher than T300 can be applied to the present invention, for example, medical polyacrylonitrile carbon fiber and medical asphalt carbon fiber, and preferred domestic medical CCF300, CCF500 carbon fiber can be applied to the present invention.
  • the present invention has no particular requirements on the specifications of carbon fibers.
  • the present invention preferably has carbon fibers having a diameter of 8 to 12 ⁇ m (more preferably ⁇ ⁇ ⁇ ).
  • the present invention has no special requirement for the length of the carbon fiber, and can satisfy the growth of the oxidized nanowire array and leave the exposed area.
  • the frequency and amplitude of the ultrasonic waves required to be applied in the field of application those skilled in the art can adjust the ratio of the oxidized nanowire growth region and the dew region on the surface of the carbon fiber, and the length of the oxidized nanowire is usually 300 nm-lum (preferably 500-800 nm). ).
  • a medical polymer material capable of insulating can be applied to the present invention, and medical polymethyl methacrylate (PMMA) or medical polydimethylsiloxane is preferred.
  • PMMA medical polymethyl methacrylate
  • the invention has no special requirement on the thickness of the polymer insulating layer, and can function as an insulation to form electricity between the carbon fiber and the distributed electrode.
  • the thickness of the polymer insulating layer of the field is within the protection range of the present invention, preferably 150-250 nm (more preferably 200)
  • the presence of the insulating layer provides an infinitely high barrier that prevents the electrons of the applied electric field from oxidizing and forming an electric field.
  • the polymer insulating layer forms a coating layer on the oxidized nanowire, and the covering layer is also coated on the top and the periphery of the nanowire array, and the stability of the nano ultrasonic vibration machine is improved when the oxidized nanowire is subjected to an electric field.
  • the distributed electrode material used in the present invention is a medical conductor material such as any one of gold, platinum, titanium or nickel-titanium alloy.
  • the present invention has no particular requirement for the thickness of the distributed electrode, and is preferably 100-250 nm.
  • the oxidized powder was mixed with the activated carbon powder in a ratio of 1-1:1-5 to obtain a mixture.
  • This mixture is the source of oxidation.
  • the mixture is subjected to coarse grinding and fine grinding for 15-60 min and then dried (50-100 ° C).
  • 0.5-5 g of the mixture obtained in step a is placed under the vertically placed carbon fiber, first vacuum to less than 0.05 Torr, then oxygen and argon are introduced, wherein the total flow of oxygen and argon is less than 100 ml/min, oxygen and argon.
  • the flow ratio is 1: 1-1: 5; according to the heating rate of 30 ° C / min, the mixture and carbon fiber are heated to 850 ° C, held for 10 minutes, and then at a rate of l - 10 ° C / min Heat to 960 ° C, keep warm for 30 minutes, then cool to room temperature.
  • the carbon fiber is removed from the surface of the carbon fiber by the method specified in Appendix A of GJB1982-94 before the step b, and then dried at 50-100 °C.
  • step b is carried out in a vacuum tube furnace.
  • the mixture obtained in the step a is placed at the bottom of the open quartz tube, and the carbon fiber is placed on the inner wall of the quartz tube.
  • the quartz tube is placed outward from the middle of the tube furnace, and the tube furnace is sealed, and the vacuum pump is used to evacuate to less than 0.05 Torr.
  • the step b preferably further comprises:
  • Bl photolithographic carbon fiber surface, a photoresist layer is disposed on the carbon fiber, and then a plurality of oxide nanowire growth regions are formed on the surface of the carbon fiber; B2 in the plurality of growth regions of the surface of the carbon fiber formed by the photoresist material, using the method of the above step b to grow the oxidized nanowire array, so that the oxidized nanowires are only grown on the surface of the exposed carbon fiber; b3. peeling off all remaining photoresist material.
  • the photoresist is covered on the carbon fiber, and a regular square window array is opened on the photoresist material by micro-processing lithography, and the inner surface of the square window is exposed with a carbon fiber surface as a growth region of the oxidized nanowire array.
  • a photoresist material in the gap between the square windows, so that the oxidized nanowires cannot grow.
  • the photoresist material is equivalent to a partitioned mold during the subsequent oxidation of the nanowires, so that the oxidized nanowires are only grown in the exposed regions, thereby realizing the subregional growth of the oxidized nanowire array.
  • the present invention has no special requirements for the photoresist material used, and a photoresist material conventionally used for substrate photolithography can be applied to the present invention, for example, including 5-60 mass% photosensitive resin (for example, epoxy resin modified), 5- 50 mass percent reactive diluent (e.g., polyethylene glycol dimethacrylate), 0.1-15 mass percent photoinitiator.
  • a photoresist material conventionally used for substrate photolithography can be applied to the present invention, for example, including 5-60 mass% photosensitive resin (for example, epoxy resin modified), 5- 50 mass percent reactive diluent (e.g., polyethylene glycol dimethacrylate), 0.1-15 mass percent photoinitiator.
  • the surface of one end of the carbon fiber is dissolved with a dilute alkali (preferably ⁇ 0.01 mol/L sodium hydroxide or potassium hydroxide solution) to obtain a carbon fiber exposed zone.
  • a dilute alkali preferably ⁇ 0.01 mol/L sodium hydroxide or potassium hydroxide solution
  • the present invention can control the oxidation of the nanowires to grow only on the surface of the carbon fiber, and omit the step c.
  • a polymer material (preferably polymethyl methacrylate) is coated on the oxidized word line array layer by spin coating to form a polymer insulating layer, thereby obtaining an electric energy-mechanical energy deformation converting unit.
  • the distributed electrode is disposed on the polymer insulating layer.
  • the method of disposing the distributed electrode on the polymer insulating layer is a conventional method in the art, for example, by using RF sputtering, any one of gold, platinum, titanium or nickel-titanium alloy is disposed on the polymer insulating layer.
  • the power source is an alternating voltage, and the power source frequency may be a single frequency power supply or a multiple frequency power supply.
  • the frequency and amplitude of the ultrasonic waves generated by the application field are easily determined by those skilled in the art. Select the type and frequency of the power supply.
  • the power source of the invention is a high frequency power source, the power is adjustable between 5 and 100 W, and the frequency is between ⁇ - ⁇ .
  • the application principle of the nano ultrasonic vibration machine of the present invention for removing thrombus in a blood vessel will be described in detail below with reference to FIG. Among them, 11 is carbon fiber, 12 is an oxidized nanowire array, and 13 is a polymer insulating layer.
  • the normal mean lumen diameter of the blood vessels is as follows: Elastic artery: 1.5 cm; Several meat arteries: About 6 mm; Arteriole: About 37 ⁇ m; Capillaries: About 9 ⁇ m; Vein: 20 ⁇ m; Vein: 5 mm.
  • the ultrasonic vibrating machine of the present invention has a diameter of 10 to 15 ⁇ m, and thus can pass through other blood vessels other than the capillaries.
  • the ultrasonic vibration machine of the present invention is transported to a target intravascular application site by using a conventional conventional delivery method, for example, using a small lumen microcatheter (as shown in Fig. 2). After reaching the application site, the ultrasonic vibration machine is released from the small lumen microcatheter, and then the power supply current of the ultrasonic vibration machine is controlled, two current output ends of the power source, one of which is connected to the exposed area of the carbon fiber of the ultrasonic vibration machine, and the other A current output terminal is connected to the distributed electrode of the human body or the ultrasonic vibration machine, so an electric field is formed between the carbon fiber of the ultrasonic vibration machine and the carbon fiber of the human skin and the distributed electrode, and the oxidation nanowire of the ultrasonic vibration machine generates the ultrasonic wave under the electric field.
  • a conventional conventional delivery method for example, using a small lumen microcatheter (as shown in Fig. 2).
  • the vibration which acts on the thrombus attached to the vessel wall, so that the thrombus attached to the vessel wall is removed; in addition, the ultrasonic vibration has an effect on the thrombus, and the thrombus is dissolved.
  • the ultrasonic vibrating machine of the present invention can be used in conjunction with a thrombus trapping device to remove large thrombotic debris from blood vessels.
  • the amplitude and period of the ultrasound can be selected to be used to remove thrombus attached to the vessel wall or to cause thrombus dissolution on the vessel wall. Selecting the appropriate ultrasonic wave, the ultrasonic wave blasts and vibrates in the blood, which can destroy the blood clot.
  • the nano ultrasonic vibration machine shown in FIG. Carbon fiber 11 uses domestic CCF300, its diameter 10 ⁇ ⁇ , length 1.5 m; oxidation of the carbon fiber surface
  • the nanowire growth region 111 accounts for four-fifths of the length of the carbon fiber 11.
  • the oxidized nanowire growth region 111 the oxidized nanowire array 12 is vertically grown on the surface of the carbon fiber 11, and the oxidized nanowire has a length of 500 nm.
  • Polymethyl methacrylate was used as the material of the polymer insulating layer 13, and a polymethyl methacrylate layer was spin-coated on the oxidized nanowire array 12 to have a thickness of 200 nm.
  • the high frequency power supply 3 is used, which is powered by an alternating voltage, the frequency is 80 kHz, and the power is adjustable between 5-100 W.
  • One current output of the power supply is connected to the carbon fiber dew area, and the other current output is connected to the human body surface.
  • the nano ultrasonic vibration machine is prepared as follows.
  • the lg oxidation powder (purity 99.9%) was mixed with 2 g of activated carbon powder, coarsely ground for 15 minutes, then agate finely ground for 30 minutes, and then dried at 50 °C.
  • Carbon fiber 11 is made of domestic CCF300 with a diameter of 10 ⁇ m and a length of 1.5 m.
  • the sizing agent on the surface of the carbon fiber was removed in accordance with the method specified in Appendix A of GJB1982-94, and then dried at 50 °C.
  • the mixture of the oxidized powder and the activated carbon powder was placed at the bottom of a quartz tube closed at one end, and the carbon fibers were placed on the inner wall of the quartz tube.
  • the assembled quartz tube is placed in the middle of the vacuum tube furnace, and the vacuum pump adjusts the valve to slowly draw vacuum to less than 0.05 Torr. Slowly pass 10 ml of oxygen and 30 ml of argon to adjust the vacuum to 2 Torr.
  • the vacuum tube furnace was heated and heated at a heating rate of 30 ° C / min.
  • the mixture and carbon fibers were heated to 850 ° C for 10 minutes, then heated to 960 ° C at a rate of 10 ° C / min for 30 minutes. Cool to room temperature and take it out.
  • the formed oxidized nanowire array 12 has an oxidized nanowire length of 500 nm.
  • the surface of one end of the carbon fiber was etched with a dilute alkali (0.01 mol/L sodium hydroxide solution) to obtain a carbon fiber dew region 112.
  • the oxidized nanowire growth region 111 on the surface of the carbon fiber accounts for four-fifths of the length of the carbon fiber 11.
  • Polymethyl methacrylate was coated on the oxidized nanowire array layer by a conventional spin coating method to form a polymer insulating layer 13 having a thickness of 200 nm.
  • the nano ultrasonic vibration machine of the embodiment has the same structure as that of the first embodiment, except that the nano ultrasonic vibration machine has a distributed electrode 2, and the types and thicknesses of the materials used in each layer of the nano ultrasonic vibration machine and the preparation process are slightly different.
  • the carbon fiber 11 uses CCF500, which has a diameter of 8 ⁇ m and a length of lm; the surface of the carbon fiber oxidized nanowire growth region 111 accounts for three-fifths of the length of the carbon fiber 11.
  • the oxidized nanowire array 12 is vertically grown on the surface of the carbon fiber 11, and the oxidized nanowire has a length of 300 nm.
  • Polymethyl methacrylate was used as the polymer insulating layer 13 material, and a polymethyl methacrylate layer was spin-coated on the oxidized quench line array 12 to have a thickness of 200 nm.
  • a nickel-titanium alloy having a thickness of 100 nm is used as the distributed electrode 2, and the distributed electrode 2 is disposed on the polymethyl methacrylate layer.
  • the high-frequency power supply 3 is used, which is an AC voltage supply, and the power is adjustable between 5 and 100 W, and the frequency is 2 MHz.
  • One current output of the power supply is connected to the carbon fiber dew area, and the other current output is connected to the distributed electrode 2.
  • the nano ultrasonic vibration machine is prepared as follows.
  • Carbon fiber 11 uses CCF500, which has a diameter of 8 ⁇ m and a length of lm.
  • the sizing agent on the surface of the carbon fiber was removed in accordance with the method specified in Appendix A of GJB1982-94, and then dried at 50 °C.
  • the mixture of the oxidized powder and the activated carbon powder was placed at the bottom of a quartz tube closed at one end, and the carbon fibers were placed on the inner wall of the quartz tube.
  • the assembled quartz tube is placed in the middle of the vacuum tube furnace, and the vacuum pump adjusts the valve to slowly draw vacuum to less than 0.05 Torr. Slowly pass 8 ml of oxygen and 32 ml of argon to adjust the vacuum to 2.4 Torr.
  • the vacuum tube furnace was heated and heated at a heating rate of 30 ° C / min.
  • the mixture and carbon fibers were heated to 850 ° C for 10 minutes, then heated to 960 ° C at a rate of 10 ° C / min for 30 minutes. Cool to room temperature and take it out.
  • the formed oxidized nanowire array 12 has an oxidized nanowire length of 300 nm.
  • the surface of one end of the carbon fiber was etched with a dilute alkali (0.01 mol/L sodium hydroxide solution) to obtain a carbon fiber dew zone 112.
  • the oxidation of the surface of the carbon fiber nanowire growth region 111 accounts for three-fifths of the length of the carbon fiber 11.
  • the polymethyl methacrylate is coated on the oxidized nanowire array layer by a conventional spin coating method.
  • the polymer insulating layer 13 having a thickness of 200 nm.
  • a nickel-titanium alloy having a thickness of 100 nm is placed on the polymer insulating layer 13 by RF sputtering to form a distributed electrode 2.
  • an electric field is formed between the carbon fiber 11 and the distributed electrode 2, and the oxidized nanowire array 12 generates ultrasonic vibration under the electric field, which is measured by an ultrasonic oscilloscope device, and the ultrasonic frequency is 2 MHz, and the voltage amplitude is It is 2V and can be used to dissolve thrombus in blood vessels.
  • the oxidized nanowire can generate ultrasonic waves (ultrasonic vibration) for driving foreign matter or thrombus in the body cavity and the blood vessel.
  • the ultrasonic vibratory machine of the present invention is capable of generating ultrasonic waves of different frequencies.
  • the ultrasonic vibrating machine of the present invention has a diameter of 10 to 15 ⁇ m and can pass through other blood vessels other than the capillaries to drive a thrombus attached to the blood vessel wall or to cause thrombus dissolution on the blood vessel wall.

Abstract

Disclosed is a nano-ultrasonic vibrator comprising a carbon fiber (11), a zinc oxide nanowire array (12) and a polymer insulating layer (13); the surface of the carbon fiber (11) comprises a zinc oxide nanowire-growing region (111) and a naked region (112); on the zinc oxide nanowire-growing region (111), the zinc oxide nanowire array (12) grows vertically on the surface of the carbon fiber (11), forming a core-shell structure with the carbon fiber (11) as a core and the zinc oxide nanowire array (12) as a cylinder shell; the polymer insulating layer (13) covers the zinc oxide nanowire array (12). Under the action of an electric field, the zinc oxide nanowire can produce ultrasonic waves for driving foreign bodies or thrombi in the body cavity and blood vessels.

Description

纳米超声振动机 技术领域  Nano ultrasonic vibration machine
本发明涉及一种纳米超声振动机， 具体的， 涉及一种利用氧化辞纳米线 的超声振动机。 背景技术  The present invention relates to a nano-ultrasonic vibrating machine, and in particular to an ultrasonic vibrating machine using an oxidized nanowire. Background technique
血栓是心脏或血管内某一部分因血液成分发生析出、 凝集和凝固所形成 的固体状物质。 血栓栓塞会导致氧气或营养物质向相关组织的供应中断， 从 而导致结构代谢障碍、 相关组织梗死等。 现有的溶解或去除血栓的技术分为 两类。 一种是采用血栓溶解剂或抗凝血剂， 用于实现血栓溶解或抑制血栓生 长， 但是该方法的缺陷是给药周期长， 特别不能应用于血管腔内形成术中。 另外一种是采用导管导引介入治疗方法， 将去除血栓装置导入血管中， 利用 机械能从患者的身体去除血栓。  A thrombus is a solid substance formed by precipitation, agglutination, and coagulation of blood components in a part of the heart or blood vessels. Thromboembolism can result in disruption of the supply of oxygen or nutrients to related tissues, resulting in structural metabolic disorders, associated tissue infarction, and the like. Existing techniques for dissolving or removing thrombus fall into two categories. One is to use a thrombolytic agent or an anticoagulant to achieve thrombolysis or inhibit thrombus growth, but the drawback of this method is that the administration period is long, and in particular, it cannot be applied to intravascular formation. The other is to use a catheter-guided interventional approach to introduce a thrombectomy device into the blood vessel and use mechanical energy to remove the thrombus from the patient's body.
专利申请号 200680050755.6的中国专利申请公开了一种用于去除血栓的 装置， 该装置利用小内腔微导管传送到病灶部位， 然后穿刺血栓， 挠性纤维 钩绊血栓， 从而达到刮去附到血管壁的血栓目的， 但是该装置较为复杂， 造 价成本高。 专利申请号 01127619.3的中国专利申请公开了一种新型植入式血 栓过滤器， 该装置通过过滤网附着血栓， 从而达到去除血栓的目的， 但是该 装置不能去除已经附到血管壁的血栓。  Chinese Patent Application No. 200680050755.6 discloses a device for removing thrombus, which uses a small lumen microcatheter to deliver a lesion to a lesion, and then punctures a thrombus, a flexible fiber hook and a thrombus, thereby scraping off the attached blood vessel. The purpose of the wall is thrombus, but the device is more complicated and costly. Chinese Patent Application No. 01127619.3 discloses a novel implantable thrombus filter which adheres to a thrombus through a filter to achieve thrombus removal, but which does not remove thrombus that has been attached to the vessel wall.
氧化辞纳米线是一种已知的压电材料， 通常将其应用于纳米发电机， 当 氧化辞纳米线在外力下动态拉伸时， 纳米线中生成压电电势， 相应瞬变电流 在两端流动。 目前， 没有在外加电压下氧化辞纳米线产生超声振动的构思。 发明内容  The oxidized nanowire is a known piezoelectric material, which is usually applied to a nanogenerator. When the oxidized nanowire is dynamically stretched under an external force, a piezoelectric potential is generated in the nanowire, and the corresponding transient current is in two. The end flows. At present, there is no idea of oxidizing nanowires to generate ultrasonic vibrations under an applied voltage. Summary of the invention
本发明的目的是提供一种纳米超声振动机， 氧化辞纳米线在外加电压作 用下能够产生超声波（超声振动）， 用于在体腔和血管内驱动异物或血栓， 尤 其是该纳米超声振动机可以植入血管中， 并促使血管壁上血栓溶解。 The object of the present invention is to provide a nano-ultrasonic vibrating machine capable of generating ultrasonic waves (ultrasonic vibration) under an applied voltage for driving foreign matter or thrombus in a body cavity and a blood vessel, in particular It is that the nano ultrasonic vibrating machine can be implanted into a blood vessel and promote thrombus dissolution on the blood vessel wall.
根据应用领域的不同， 本发明超声振动机能够产生不同频率的超声波， 例如频率为 ΙΚΗζ到 10MHz的超声波， 能够用于促使血管壁上血栓溶解。  Depending on the field of application, the ultrasonic vibrating machine of the present invention is capable of generating ultrasonic waves of different frequencies, for example, ultrasonic waves having a frequency of up to 10 MHz, which can be used to cause thrombus dissolution on the vessel wall.
为了解决上述技术问题， 本发明提供的第一技术方案是， 一种纳米超声 振动机， 该超声振动机（电能-机械能形变转换单元） 包括碳纤维， 氧化辞纳 米线阵列和高分子绝缘层；碳纤维的表面包括氧化辞纳米线生长区和棵露区； 在氧化辞纳米线生长区， 所述氧化辞纳米线阵列垂直生长在碳纤维表面上， 形成以碳纤维为核， 氧化辞纳米线阵列作为圓柱壳体的核壳结构； 所述氧化 辞纳米线阵列上覆盖有所述高分子绝缘层。  In order to solve the above technical problem, the first technical solution provided by the present invention is a nano ultrasonic vibration machine, the ultrasonic vibration machine (electric energy-mechanical energy deformation conversion unit) includes carbon fiber, an oxidized nanowire array and a polymer insulation layer; carbon fiber The surface includes an oxidized nanowire growth region and a dew region; in the oxidized nanowire growth region, the oxidized nanowire array is vertically grown on the surface of the carbon fiber to form a carbon fiber as a core, and the oxidized nanowire array is used as a cylindrical shell. a core-shell structure of the body; the oxidized nanowire array is covered with the polymer insulating layer.
前述的纳米超声振动机， 所述高分子绝缘层所用的材料是聚甲基丙烯酸 甲酯或聚二甲基硅氧烷。  In the above nano ultrasonic vibration machine, the material used for the polymer insulating layer is polymethyl methacrylate or polydimethylsiloxane.
前述的纳米超声振动机， 该超声振动机进一步包括电源， 所述电源包括 两个电流输出端， 其中一个电流输出端连接碳纤维的棵露区， 另一个电流输 出端连接受体。 所述受体是导电性的， 例如人体皮肤、 动物体皮肤等。  In the foregoing nano ultrasonic vibration machine, the ultrasonic vibration machine further includes a power source, and the power source includes two current output ends, wherein one current output end is connected to the exposed area of the carbon fiber, and the other current output end is connected to the receptor. The receptor is electrically conductive, such as human skin, animal skin, and the like.
前述的纳米超声振动机， 该超声振动机进一步包括分布式电极， 该分布 式电极设置在高分子绝缘层上； 所述电源的一个电流输出端连接碳纤维的棵 露区， 另一个电流输出端连接分布式电极。  In the foregoing nano ultrasonic vibration machine, the ultrasonic vibration machine further includes a distributed electrode disposed on the polymer insulating layer; one current output end of the power source is connected to the exposed area of the carbon fiber, and the other current output end is connected Distributed electrode.
前述的纳米超声振动机， 所述分布式电极材料为金、 铂、 钛或镍钛合金 中的任意一种。  In the aforementioned nano ultrasonic vibration machine, the distributed electrode material is any one of gold, platinum, titanium or nickel titanium alloy.
前述的纳米超声振动机， 所述氧化辞纳米线生长区域占碳纤维长度的四 分之一至五分之四。  In the aforementioned nano ultrasonic vibration machine, the oxidized nanowire growth region accounts for one quarter to four fifths of the length of the carbon fiber.
前述的纳米超声振动机， 所述电源是交流电， 功率在 5~100W之间， 频率 在 ΙΚΗζ-ΙΟΜΗζ之间。  In the aforementioned nano ultrasonic vibration machine, the power source is an alternating current, the power is between 5 and 100 W, and the frequency is between ΙΚΗζ-ΙΟΜΗζ.
本发明超声振动机， 在电场作用下， 氧化辞纳米线能够产生超声波（超 声振动）， 用于在体腔和血管内驱动异物或血栓。 根据应用领域的不同， 本发 明超声振动机能够产生不同频率的超声波。 附图说明 图 1是本发明纳米超声振动机立体图。 In the ultrasonic vibration machine of the present invention, under the action of an electric field, the oxidized nanowire can generate ultrasonic waves (ultrasonic vibration) for driving foreign matter or thrombus in the body cavity and the blood vessel. The ultrasonic vibrating machine of the present invention is capable of generating ultrasonic waves of different frequencies depending on the field of application. DRAWINGS BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a perspective view of a nano ultrasonic vibration machine of the present invention.
图 2是本发明纳米超声振动在血管中应用的示例图。  2 is a diagram showing an example of application of the nanosonic vibration of the present invention in a blood vessel.
图 3是本发明实施例纳米超声振动机剖面示意图。  3 is a schematic cross-sectional view of a nano ultrasonic vibration machine according to an embodiment of the present invention.
图 4是本发明另一实施例纳米超声振动机剖面示意图。  4 is a schematic cross-sectional view showing a nano ultrasonic vibration machine according to another embodiment of the present invention.
11-碳纤维； 12-氧化辞纳米线阵列； 11-carbon fiber; 12-oxidation nanowire array;
13-高分子绝 2-分布式电极；  13-polymer absolute 2-distributed electrode;
3-电源; 111-氧化辞纳米线生长区;  3-power; 111-oxidation nanowire growth zone;
112-棵露区 具体实施方式  112-bright dew area
为充分了解本发明之目的、 特征及功效， 借由下述具体的实施方式， 对 本发明做详细说明。  In order to fully understand the objects, features and advantages of the present invention, the invention will be described in detail.
本发明纳米超声振动机在电场作用下，氧化辞纳米线能够产生超声波（超 声振动）， 用于在体腔和血管内驱动异物或血栓。 根据应用领域的不同， 本发 明纳米超声振动机能够产生不同频率的超声波。 本发明纳米超声振动机直径 为 10~15微米， 可在除毛细血管外的其他血管通过， 用于驱动附到血管壁的 血栓以及溶解血栓。  The nano-ultrasonic vibrating machine of the invention can generate ultrasonic waves (ultrasonic vibration) under the action of an electric field, and is used for driving foreign matter or thrombus in the body cavity and the blood vessel. Depending on the field of application, the nanosonic vibrators of the present invention are capable of generating ultrasonic waves of different frequencies. The nano ultrasonic vibrating machine of the present invention has a diameter of 10 to 15 μm and can pass through other blood vessels other than the capillaries, and is used for driving a thrombus attached to the blood vessel wall and dissolving the thrombus.
本发明纳米超声振动机是应用氧化辞纳米线的反压电效应研制成功的。 具体的，从结构角度看，氧化辞是具有晶格常数 a=0.3296和 c=0.52065 nm 的 六边形结构（空间群 C6V )。氧化辞的结构可以筒单描述为若干由四面体配位 的 02-和 Zn2+离子组成的交替平面， 沿 c轴交互堆叠。 氧化辞中的四面体配位 导致非中心对称结构， 并从而导致压电和热电现象。 由于四面体配位沿 +c和 -C的非对称结构， 对于沿着 c轴生长的微米带， 当一个沿着氧化辞 a轴的电 场 E被应用时， 可以诱发氧化辞 a-c面的剪切应力。 The nano ultrasonic vibration machine of the invention is successfully developed by applying the anti-piezoelectric effect of the oxidized nanowire. Specifically, from a structural point of view, the oxidized word is a hexagonal structure (space group C6V) having a lattice constant of a=0.3296 and c=0.52065 nm. The structure of the oxidized word can be described as a plurality of alternating planes composed of tetrahedral coordinated 0 2 - and Zn 2+ ions, which are stacked alternately along the c-axis. The tetrahedral coordination in the oxidized word results in a non-centrosymmetric structure and thus a piezoelectric and thermoelectric phenomenon. Due to the asymmetrical structure of tetrahedral coordination along +c and -C, for the microstrip along the c-axis, when an electric field E along the a-axis of oxidation is applied, the shearing of the ac ac surface can be induced. stress.
如图 1所示， 一种纳米超声振动机， 该超声振动机（电能-机械能形变转 换单元） 包括： 碳纤维， 氧化辞纳米线阵列和高分子绝缘层； 碳纤维的表面 包括氧化辞纳米线生长区和棵露区； 在氧化辞纳米线生长区， 所述氧化辞纳 米线阵列垂直生长在碳纤维表面上， 形成以碳纤维为核， 氧化辞纳米线阵列 作为圓柱壳体的核壳结构； 所述氧化辞纳米线阵列上覆盖有所述高分子绝缘 层。 As shown in FIG. 1 , a nano ultrasonic vibration machine (electric energy-mechanical energy deformation conversion unit) includes: carbon fiber, an oxidized nanowire array and a polymer insulating layer; the surface of the carbon fiber includes an oxidized nanowire growth region. And the dew area; in the oxidation of the nanowire growth region, the oxidation The rice noodle array is vertically grown on the surface of the carbon fiber to form a core-shell structure with carbon fiber as a core and an oxidized nanowire array as a cylindrical shell; the oxidized nanowire array is covered with the polymer insulating layer.
该超声振动机进一步包括电源， 所述电源包括两个电流输出端， 其中一 个电流输出端连接碳纤维的棵露区； 另一个电流输出端和人体表面连接， 从 而与人体体液导电连接。 本发明所用电源优选高频电压供电， 该高频电压的 电压幅值在 10V以内， 对人体没有损害。 另外， 动物体皮肤等导电性的受体 也可以应用于本发明， 以用于动物体体腔和血管内驱动异物或血栓。  The ultrasonic vibration machine further includes a power source, and the power source includes two current output terminals, wherein one current output end is connected to the exposed area of the carbon fiber; and the other current output end is connected to the human body surface to be electrically connected to the body fluid of the human body. The power source used in the present invention is preferably supplied with a high-frequency voltage having a voltage amplitude of 10 V or less and having no damage to the human body. Further, a conductive receptor such as animal skin can also be applied to the present invention for driving foreign bodies or blood clots in the body cavity and blood vessels of an animal.
优选的， 该超声振动机进一步包括分布式电极， 该分布式电极设置在高 分子绝缘层上； 所述电源的一个电流输出端连接碳纤维的棵露区， 另一个电 流输出端连接分布式电极。  Preferably, the ultrasonic vibration machine further comprises a distributed electrode disposed on the high molecular insulating layer; one current output end of the power source is connected to the exposed area of the carbon fiber, and the other current output end is connected to the distributed electrode.
由于高分子绝缘层的绝缘作用， 在碳纤维与人体或碳纤维与分布式电极 之间形成电场， 氧化辞纳米线在该电场作用下产生超声振动。 本领域技术人 员根据应用领域的不同， 能够调整外电源的电流强度以及氧化辞纳米线阵列 的总面积， 使得本申请超声振动机产生的超声波具有适宜的频率、 周期和振 幅。  Due to the insulating effect of the polymer insulating layer, an electric field is formed between the carbon fiber and the human body or the carbon fiber and the distributed electrode, and the oxidized nanowire generates ultrasonic vibration under the electric field. The skilled person in the art can adjust the current intensity of the external power source and the total area of the oxidized nanowire array according to the application field, so that the ultrasonic wave generated by the ultrasonic vibration machine of the present application has a suitable frequency, period and amplitude.
电阻小于 30Ω/ιη, 强度大于 T300的具有导电性能的医用碳纤维均可应 用于本发明， 例如医用聚丙烯腈碳纤维和医用沥青碳纤维， 优选的国产医用 CCF300,CCF500碳纤维可以应用于本发明。  A medical carbon fiber having a resistance of less than 30 Ω/ιη and having a strength higher than T300 can be applied to the present invention, for example, medical polyacrylonitrile carbon fiber and medical asphalt carbon fiber, and preferred domestic medical CCF300, CCF500 carbon fiber can be applied to the present invention.
本发明对碳纤维的规格没有特殊要求， 为了能够应用于血管， 本发明优 选直径 8~12 μ ιη (更优选 ΙΟ μ ιη ) 的碳纤维。 本发明对碳纤维的长度没有特 殊要求， 能够满足氧化辞纳米线阵列生长并余留棵露区即可。 根据应用领域 需要产生的超声波的频率、 振幅， 本领域技术人员能够调整碳纤维表面的氧 化辞纳米线生长区和棵露区的比例， 通常氧化辞纳米线的长度为 300nm-lum (优选 500-800nm )。  The present invention has no particular requirements on the specifications of carbon fibers. In order to be applicable to blood vessels, the present invention preferably has carbon fibers having a diameter of 8 to 12 μm (more preferably ΙΟ μ ηη). The present invention has no special requirement for the length of the carbon fiber, and can satisfy the growth of the oxidized nanowire array and leave the exposed area. According to the frequency and amplitude of the ultrasonic waves required to be applied in the field of application, those skilled in the art can adjust the ratio of the oxidized nanowire growth region and the dew region on the surface of the carbon fiber, and the length of the oxidized nanowire is usually 300 nm-lum (preferably 500-800 nm). ).
能够起到绝缘作用的医用高分子材料均可应用于本发明， 优选医用聚甲 基丙烯酸甲酯 （PMMA )或医用聚二甲基硅氧烷。 本发明对高分子绝缘层的 厚度没有特殊要求， 能够起到绝缘作用以使碳纤维与分布式电极之间形成电 场的高分子绝缘层厚度均在本发明保护范围之内， 优选 150-250nm (更优选 200 A medical polymer material capable of insulating can be applied to the present invention, and medical polymethyl methacrylate (PMMA) or medical polydimethylsiloxane is preferred. The invention has no special requirement on the thickness of the polymer insulating layer, and can function as an insulation to form electricity between the carbon fiber and the distributed electrode. The thickness of the polymer insulating layer of the field is within the protection range of the present invention, preferably 150-250 nm (more preferably 200)
由于采用了高分子绝缘层， 绝缘层的存在提供了一个无限高的势垒， 阻 止外加电场的电子通过氧化辞， 而形成电场。 高分子绝缘层在氧化辞纳米线 上形成覆盖层， 同时覆盖层也包覆在纳米线阵列顶端和周围， 在氧化辞纳米 线承受电场作用时， 提高了纳米超声振动机的稳定性。  Due to the use of a polymer insulating layer, the presence of the insulating layer provides an infinitely high barrier that prevents the electrons of the applied electric field from oxidizing and forming an electric field. The polymer insulating layer forms a coating layer on the oxidized nanowire, and the covering layer is also coated on the top and the periphery of the nanowire array, and the stability of the nano ultrasonic vibration machine is improved when the oxidized nanowire is subjected to an electric field.
本发明所用分布式电极材料为医用导体材料， 例如金、 铂、 钛或镍钛合 金中的任意一种。 本发明对分布式电极的厚度没有特殊要求， 优选 100-250 nm。  The distributed electrode material used in the present invention is a medical conductor material such as any one of gold, platinum, titanium or nickel-titanium alloy. The present invention has no particular requirement for the thickness of the distributed electrode, and is preferably 100-250 nm.
下面详细说明本发明纳米超声振动机的制备方法。  The preparation method of the nano ultrasonic vibration machine of the present invention will be described in detail below.
a, 准备氧化辞纳米线生长源  a, preparing the oxidation source nanowire growth source
将氧化辞粉末与活性碳粉末按照 1-1 : 1-5的比例混合， 得到混合物。 该 混合物即为氧化辞生长源。 优选的， 将该混合物经过粗磨和精磨 15-60min, 然后烘干 ( 50-100 °C )。  The oxidized powder was mixed with the activated carbon powder in a ratio of 1-1:1-5 to obtain a mixture. This mixture is the source of oxidation. Preferably, the mixture is subjected to coarse grinding and fine grinding for 15-60 min and then dried (50-100 ° C).
b, 氧化辞纳米线生长  b, oxidation word nanowire growth
将 0.5-5g步骤 a所得混合物置于竖直放置的碳纤维下方， 先真空至小于 0.05托， 然后通入氧气和氩气， 其中氧气和氩气的总流量为小于 100ml/min, 氧气和氩气的流量比例为 1 : 1-1 : 5; 按照升温速率小于等于 30°C/min, 将所 述混合物和碳纤维加热到 850°C , 保温 10分钟， 然后以 l-10°C/min的速率加 热到 960 °C , 保温 30分钟后冷却到室温取出。  0.5-5 g of the mixture obtained in step a is placed under the vertically placed carbon fiber, first vacuum to less than 0.05 Torr, then oxygen and argon are introduced, wherein the total flow of oxygen and argon is less than 100 ml/min, oxygen and argon. The flow ratio is 1: 1-1: 5; according to the heating rate of 30 ° C / min, the mixture and carbon fiber are heated to 850 ° C, held for 10 minutes, and then at a rate of l - 10 ° C / min Heat to 960 ° C, keep warm for 30 minutes, then cool to room temperature.
具体的， 碳纤维在进行步骤 b前， 先按照 GJB1982-94附录 A规定的方 法去除碳纤维表面的上浆剂， 然后 50-100°C下烘干。  Specifically, the carbon fiber is removed from the surface of the carbon fiber by the method specified in Appendix A of GJB1982-94 before the step b, and then dried at 50-100 °C.
优选的， 在真空管式炉中进行步骤 b。 具体的， 将步骤 a所得混合物置于 一端开口的石英管底部， 碳纤维放置在石英管内壁。 石英管从管式炉中部向 外放置， 密封管式炉， 用真空泵抽真空至小于 0.05托。  Preferably, step b is carried out in a vacuum tube furnace. Specifically, the mixture obtained in the step a is placed at the bottom of the open quartz tube, and the carbon fiber is placed on the inner wall of the quartz tube. The quartz tube is placed outward from the middle of the tube furnace, and the tube furnace is sealed, and the vacuum pump is used to evacuate to less than 0.05 Torr.
所述步骤 b优选还包括：  The step b preferably further comprises:
bl. 光刻碳纤维表面， 在碳纤维上设置光阻材料层， 然后在碳纤维表面 形成多个氧化辞纳米线生长区域； b2在光阻材料形成的碳纤维表面的多个生长区域中， 采用如上述步骤 b 的方法生长氧化辞纳米线阵列，使氧化辞纳米线只生长在暴露的碳纤维表面； b3. 剥落所有剩余光阻材料。 Bl. photolithographic carbon fiber surface, a photoresist layer is disposed on the carbon fiber, and then a plurality of oxide nanowire growth regions are formed on the surface of the carbon fiber; B2 in the plurality of growth regions of the surface of the carbon fiber formed by the photoresist material, using the method of the above step b to grow the oxidized nanowire array, so that the oxidized nanowires are only grown on the surface of the exposed carbon fiber; b3. peeling off all remaining photoresist material.
具体的， 在碳纤维上覆盖光阻材料， 用微加工平板印刷法在光阻材料上 开一个个规则的方形窗阵列， 方形窗口内区域， 棵露有碳纤维表面， 作为氧 化辞纳米线阵列生长区域， 方形窗口间隙存在光阻材料而使氧化辞纳米线无 法生长。 光阻材料在随后的氧化辞纳米线生长过程中相当于一个分区模具， 使氧化辞纳米线只生长在暴露的区域， 从而实现氧化辞纳米线阵列的分区域 生长。  Specifically, the photoresist is covered on the carbon fiber, and a regular square window array is opened on the photoresist material by micro-processing lithography, and the inner surface of the square window is exposed with a carbon fiber surface as a growth region of the oxidized nanowire array. There is a photoresist material in the gap between the square windows, so that the oxidized nanowires cannot grow. The photoresist material is equivalent to a partitioned mold during the subsequent oxidation of the nanowires, so that the oxidized nanowires are only grown in the exposed regions, thereby realizing the subregional growth of the oxidized nanowire array.
本发明对所用光阻材料没有特殊要求， 常规用于基板光刻蚀的光阻材料 均可应用于本发明， 例如包括 5-60质量百分比感光树脂（例如环氧树脂改性 物 ) , 5-50质量百分比的反应性稀释剂（例如聚乙二醇二甲基丙烯酸酯 ) , 0.1-15 质量百分比的光引发剂。  The present invention has no special requirements for the photoresist material used, and a photoresist material conventionally used for substrate photolithography can be applied to the present invention, for example, including 5-60 mass% photosensitive resin (for example, epoxy resin modified), 5- 50 mass percent reactive diluent (e.g., polyethylene glycol dimethacrylate), 0.1-15 mass percent photoinitiator.
c, 溶独碳纤维棵露区  c, dissolved carbon fiber exposed area
用稀碱（优选 < 0.01mol/L氢氧化钠或氢氧化钾溶液）溶独碳纤维一端的 表面， 得到碳纤维棵露区。  The surface of one end of the carbon fiber is dissolved with a dilute alkali (preferably < 0.01 mol/L sodium hydroxide or potassium hydroxide solution) to obtain a carbon fiber exposed zone.
选择性的， 本发明在步骤 b氧化辞纳米线生长时， 可以控制氧化辞纳米 线仅生长在碳纤维表面的氧化辞纳米线生长区， 从而省略步骤 c。  Alternatively, in the step b of the oxidation of the nanowires, the present invention can control the oxidation of the nanowires to grow only on the surface of the carbon fiber, and omit the step c.
d, 通过旋涂法将高分子材料（优选聚甲基丙烯酸甲酯 )覆盖于氧化辞纳 米线阵列层上形成高分子绝缘层， 得到电能-机械能形变转换单元。  d, a polymer material (preferably polymethyl methacrylate) is coated on the oxidized word line array layer by spin coating to form a polymer insulating layer, thereby obtaining an electric energy-mechanical energy deformation converting unit.
可选择的， e, 将分布式电极设置在高分子绝缘层上。  Alternatively, e, the distributed electrode is disposed on the polymer insulating layer.
分布式电极设置在高分子绝缘层上的方法是本领域常规技术方法， 例如 利用射频溅镀， 将金、 铂、 钛或镍钛合金中的任意一种设置到高分子绝缘层 上。  The method of disposing the distributed electrode on the polymer insulating layer is a conventional method in the art, for example, by using RF sputtering, any one of gold, platinum, titanium or nickel-titanium alloy is disposed on the polymer insulating layer.
f, 将电源的其中一个电流输出端连接到碳纤维的棵露区， 另一个电流输 出端连接到人体表面或分布式电极。  f. Connect one of the current outputs of the power supply to the exposed area of the carbon fiber, and the other current output to the surface of the human body or to the distributed electrode.
所述电源是交流电压， 电源频率可以是单频率供电， 也可以是多频率供 电。 根据应用领域需要产生的超声波的频率、 振幅， 本领域技术人员很容易 选择电源的类型和频率。 优选的， 本发明电源是高频电源， 功率在 5~100W 之间可调， 频率在 ΙΚΗζ-ΙΟΜΗζ之间。 下面结合图 2, 详细说明本发明纳米超声振动机在血管内用于去除血栓 的应用原理。 其中， 11 为碳纤维， 12为氧化辞纳米线阵列， 13 为高分子绝 缘层。 The power source is an alternating voltage, and the power source frequency may be a single frequency power supply or a multiple frequency power supply. The frequency and amplitude of the ultrasonic waves generated by the application field are easily determined by those skilled in the art. Select the type and frequency of the power supply. Preferably, the power source of the invention is a high frequency power source, the power is adjustable between 5 and 100 W, and the frequency is between ΙΚΗζ-ΙΟΜΗζ. The application principle of the nano ultrasonic vibration machine of the present invention for removing thrombus in a blood vessel will be described in detail below with reference to FIG. Among them, 11 is carbon fiber, 12 is an oxidized nanowire array, and 13 is a polymer insulating layer.
通常血管的正常平均管腔直径如下： 弹性动脉： 1.5厘米； 几肉动脉： 约 6毫米； 小动脉： 约 37微米； 毛细血管： 约 9微米； 小静脉： 20微米； 静脉： 5毫米。 本发明超声振动机直径为 10~15微米， 因此可在除毛细血管外的其 他血管通过。  Usually the normal mean lumen diameter of the blood vessels is as follows: Elastic artery: 1.5 cm; Several meat arteries: About 6 mm; Arteriole: About 37 μm; Capillaries: About 9 μm; Vein: 20 μm; Vein: 5 mm. The ultrasonic vibrating machine of the present invention has a diameter of 10 to 15 μm, and thus can pass through other blood vessels other than the capillaries.
采用现有常规传送方法， 例如采用小内腔微导管将本发明超声振动机运 送到目标血管内应用部位（如图 2所示；)。 到达应用部位后超声振动机从小内 腔微导管中释放， 然后控制超声振动机的电源输送电流， 电源的两个电流输 出端， 其中一个电流输出端连接超声振动机的碳纤维的棵露区， 另一个电流 输出端连接人体或超声振动机的分布式电极， 因此在超声振动机的碳纤维与 人体皮肤碳纤维与分布式电极之间形成电场， 超声振动机的氧化辞纳米线在 该电场作用下产生超声振动， 该超声振动对附到血管壁的血栓产生作用， 因 此附到血管壁的血栓得以被清除下来； 另外， 该超声振动对血栓产生影响， 血栓会产生溶解。 本发明超声振动机可以结合血栓捕获装置一起使用， 将大 的血栓碎片从血管中清除。 根据血栓形成位置和大小， 通过调节氧化辞纳米 线的生长总面积和电源的类型和频率， 可以选择超声波的振幅和周期， 从而 应用于清除附到血管壁的血栓或者促使血管壁上血栓溶解。 选择适当的超声 波， 超声波在血液中空化***和振动， 从而能够破坏血栓。  The ultrasonic vibration machine of the present invention is transported to a target intravascular application site by using a conventional conventional delivery method, for example, using a small lumen microcatheter (as shown in Fig. 2). After reaching the application site, the ultrasonic vibration machine is released from the small lumen microcatheter, and then the power supply current of the ultrasonic vibration machine is controlled, two current output ends of the power source, one of which is connected to the exposed area of the carbon fiber of the ultrasonic vibration machine, and the other A current output terminal is connected to the distributed electrode of the human body or the ultrasonic vibration machine, so an electric field is formed between the carbon fiber of the ultrasonic vibration machine and the carbon fiber of the human skin and the distributed electrode, and the oxidation nanowire of the ultrasonic vibration machine generates the ultrasonic wave under the electric field. The vibration, which acts on the thrombus attached to the vessel wall, so that the thrombus attached to the vessel wall is removed; in addition, the ultrasonic vibration has an effect on the thrombus, and the thrombus is dissolved. The ultrasonic vibrating machine of the present invention can be used in conjunction with a thrombus trapping device to remove large thrombotic debris from blood vessels. Depending on the location and size of the thrombus, by adjusting the total area of growth of the oxidized nanowires and the type and frequency of the power source, the amplitude and period of the ultrasound can be selected to be used to remove thrombus attached to the vessel wall or to cause thrombus dissolution on the vessel wall. Selecting the appropriate ultrasonic wave, the ultrasonic wave blasts and vibrates in the blood, which can destroy the blood clot.
当理解的是， 这不应被理解为对本发明权利要求范围的限制。 It is understood that this should not be construed as limiting the scope of the claims.
实施例 1  Example 1
如图 3所示的纳米超声振动机。 碳纤维 11采用国产 CCF300, 其直径 10 μ ιη, 长度 1.5m; 碳纤维表面的氧化辞纳米线生长区 111占碳纤维 11长度的 五分之四。 在氧化辞纳米线生长区 111 , 氧化辞纳米线阵列 12垂直生长在碳 纤维 11表面上， 氧化辞纳米线长度 500nm。 采用聚甲基丙烯酸甲酯作为高分 子绝缘层 13材料， 聚甲基丙烯酸甲酯层旋涂在氧化辞纳米线阵列 12上， 厚 度为 200nm。 采用高频电源 3 , 其是交流电压供电， 频率为 80kHz, 功率在 5-100W之间可调。 该电源的一个电流输出端连接碳纤维棵露区， 另一个电 流输出端连接人体表面。 The nano ultrasonic vibration machine shown in FIG. Carbon fiber 11 uses domestic CCF300, its diameter 10 μ ιη, length 1.5 m; oxidation of the carbon fiber surface The nanowire growth region 111 accounts for four-fifths of the length of the carbon fiber 11. In the oxidized nanowire growth region 111, the oxidized nanowire array 12 is vertically grown on the surface of the carbon fiber 11, and the oxidized nanowire has a length of 500 nm. Polymethyl methacrylate was used as the material of the polymer insulating layer 13, and a polymethyl methacrylate layer was spin-coated on the oxidized nanowire array 12 to have a thickness of 200 nm. The high frequency power supply 3 is used, which is powered by an alternating voltage, the frequency is 80 kHz, and the power is adjustable between 5-100 W. One current output of the power supply is connected to the carbon fiber dew area, and the other current output is connected to the human body surface.
该纳米超声振动机得制备方法如下。  The nano ultrasonic vibration machine is prepared as follows.
将 lg氧化辞粉末（纯度 99.9% )与 2g活性碳粉末混合， 粗磨 15min, 然 后玛瑙精细研磨 30min, 接着 50°C下烘干。  The lg oxidation powder (purity 99.9%) was mixed with 2 g of activated carbon powder, coarsely ground for 15 minutes, then agate finely ground for 30 minutes, and then dried at 50 °C.
碳纤维 11采用国产 CCF300,其直径 10 μ ιη,长度 1.5m。按照 GJB1982-94 附录 A规定的方法去除碳纤维表面的上浆剂， 然后 50°C下烘干。  Carbon fiber 11 is made of domestic CCF300 with a diameter of 10 μm and a length of 1.5 m. The sizing agent on the surface of the carbon fiber was removed in accordance with the method specified in Appendix A of GJB1982-94, and then dried at 50 °C.
将氧化辞粉末与活性碳粉末混合物置于一端封闭的石英管底部， 将碳纤 维放置在石英管内壁。 装好后的石英管放置在真空管式炉的中部位置， 真空 泵调节气阀緩慢抽真空至小于 0.05托。 緩慢通入 10ml氧气和 30ml氩气， 调 节真空度为 2托。 真空管式炉升温加热， 升温速率为 30°C/min, 将所述混合 物和碳纤维加热到 850°C , 保温 10分钟， 然后以 10°C/min的速率加热到 960 °C , 保温 30分钟后冷却到室温取出。 形成的氧化辞纳米线阵列 12, 其氧化 辞纳米线长度为 500nm。  The mixture of the oxidized powder and the activated carbon powder was placed at the bottom of a quartz tube closed at one end, and the carbon fibers were placed on the inner wall of the quartz tube. The assembled quartz tube is placed in the middle of the vacuum tube furnace, and the vacuum pump adjusts the valve to slowly draw vacuum to less than 0.05 Torr. Slowly pass 10 ml of oxygen and 30 ml of argon to adjust the vacuum to 2 Torr. The vacuum tube furnace was heated and heated at a heating rate of 30 ° C / min. The mixture and carbon fibers were heated to 850 ° C for 10 minutes, then heated to 960 ° C at a rate of 10 ° C / min for 30 minutes. Cool to room temperature and take it out. The formed oxidized nanowire array 12 has an oxidized nanowire length of 500 nm.
用稀碱（ 0.01mol/L氢氧化钠溶液）溶蚀碳纤维一端的表面， 得到碳纤维 棵露区 112。 碳纤维表面的氧化辞纳米线生长区 111 占碳纤维 11长度的五分 之四。  The surface of one end of the carbon fiber was etched with a dilute alkali (0.01 mol/L sodium hydroxide solution) to obtain a carbon fiber dew region 112. The oxidized nanowire growth region 111 on the surface of the carbon fiber accounts for four-fifths of the length of the carbon fiber 11.
通过常规旋涂法将聚甲基丙烯酸甲酯覆盖于氧化辞纳米线阵列层上形成 厚度为 200nm的高分子绝缘层 13。  Polymethyl methacrylate was coated on the oxidized nanowire array layer by a conventional spin coating method to form a polymer insulating layer 13 having a thickness of 200 nm.
在高频电源作用下， 在碳纤维 11与人体皮肤之间形成电场， 氧化辞纳米 线阵列 12在该电场作用下产生超声振动， 采用超声波探头设备测得， 该超声 波频率为 80kHz, 振幅为 5V, 能够应用于血管中溶解血栓。 实施例 2 Under the action of the high-frequency power source, an electric field is formed between the carbon fiber 11 and the human skin, and the oxidized nanowire array 12 generates ultrasonic vibration under the electric field, which is measured by an ultrasonic probe device, and the ultrasonic frequency is 80 kHz, and the amplitude is 5V. It can be applied to dissolve blood clots in blood vessels. Example 2
如图 4所示的纳米超声振动机。 本实施例的纳米超声振动机， 其结构与 实施例 1基本相同， 区别在于该纳米超声振动机具有分布式电极 2, 且纳米 超声振动机各层所用材料的类型及厚度以及制备工艺略有不同。碳纤维 11采 用 CCF500, 其直径 8 μ ιη, 长度 lm; 碳纤维表面的氧化辞纳米线生长区 111 占碳纤维 11长度的五分之三。 在氧化辞纳米线生长区 111 , 氧化辞纳米线阵 列 12垂直生长在碳纤维 11表面上， 氧化辞纳米线长度 300nm。 采用聚甲基 丙烯酸甲酯作为高分子绝缘层 13材料，聚甲基丙烯酸甲酯层旋涂在氧化辞纳 米线阵列 12上， 厚度为 200nm。 采用厚度 lOOnm的镍钛合金作为分布式电 极 2, 分布式电极 2设置在聚甲基丙烯酸甲酯层上。 采用高频电源 3 , 其是交 流电压供电， 功率在 5~100W之间可调， 频率为 2MHz。 该电源的一个电流 输出端连接碳纤维棵露区， 另一个电流输出端连接分布式电极 2。  The nano ultrasonic vibrating machine shown in Fig. 4. The nano ultrasonic vibration machine of the embodiment has the same structure as that of the first embodiment, except that the nano ultrasonic vibration machine has a distributed electrode 2, and the types and thicknesses of the materials used in each layer of the nano ultrasonic vibration machine and the preparation process are slightly different. . The carbon fiber 11 uses CCF500, which has a diameter of 8 μm and a length of lm; the surface of the carbon fiber oxidized nanowire growth region 111 accounts for three-fifths of the length of the carbon fiber 11. In the oxidized nanowire growth region 111, the oxidized nanowire array 12 is vertically grown on the surface of the carbon fiber 11, and the oxidized nanowire has a length of 300 nm. Polymethyl methacrylate was used as the polymer insulating layer 13 material, and a polymethyl methacrylate layer was spin-coated on the oxidized quench line array 12 to have a thickness of 200 nm. A nickel-titanium alloy having a thickness of 100 nm is used as the distributed electrode 2, and the distributed electrode 2 is disposed on the polymethyl methacrylate layer. The high-frequency power supply 3 is used, which is an AC voltage supply, and the power is adjustable between 5 and 100 W, and the frequency is 2 MHz. One current output of the power supply is connected to the carbon fiber dew area, and the other current output is connected to the distributed electrode 2.
该纳米超声振动机得制备方法如下。  The nano ultrasonic vibration machine is prepared as follows.
将 2g氧化辞粉末（纯度 99.9% )与 2g活性碳粉末混合， 粗磨 15min, 然 后玛瑙精细研磨 30min, 接着 50°C下烘干。  2 g of oxidized powder (purity 99.9%) was mixed with 2 g of activated carbon powder, coarsely ground for 15 minutes, then agate was finely ground for 30 minutes, and then dried at 50 °C.
碳纤维 11采用 CCF500, 其直径 8 μ ιη, 长度 lm。 按照 GJB1982-94附 录 A规定的方法去除碳纤维表面的上浆剂， 然后 50°C下烘干。  Carbon fiber 11 uses CCF500, which has a diameter of 8 μm and a length of lm. The sizing agent on the surface of the carbon fiber was removed in accordance with the method specified in Appendix A of GJB1982-94, and then dried at 50 °C.
将氧化辞粉末与活性碳粉末混合物置于一端封闭的石英管底部， 将碳纤 维放置在石英管内壁。 装好后的石英管放置在真空管式炉的中部位置， 真空 泵调节气阀緩慢抽真空至小于 0.05托。 緩慢通入 8ml氧气和 32ml氩气， 调 节真空度为 2.4托。 真空管式炉升温加热， 升温速率为 30°C/min, 将所述混 合物和碳纤维加热到 850°C , 保温 10分钟， 然后以 10°C/min的速率加热到 960 °C , 保温 30分钟后冷却到室温取出。 形成的氧化辞纳米线阵列 12, 其氧 化辞纳米线长度为 300nm。  The mixture of the oxidized powder and the activated carbon powder was placed at the bottom of a quartz tube closed at one end, and the carbon fibers were placed on the inner wall of the quartz tube. The assembled quartz tube is placed in the middle of the vacuum tube furnace, and the vacuum pump adjusts the valve to slowly draw vacuum to less than 0.05 Torr. Slowly pass 8 ml of oxygen and 32 ml of argon to adjust the vacuum to 2.4 Torr. The vacuum tube furnace was heated and heated at a heating rate of 30 ° C / min. The mixture and carbon fibers were heated to 850 ° C for 10 minutes, then heated to 960 ° C at a rate of 10 ° C / min for 30 minutes. Cool to room temperature and take it out. The formed oxidized nanowire array 12 has an oxidized nanowire length of 300 nm.
用稀碱（ 0.01mol/L氢氧化钠溶液 )溶蚀碳纤维一端的表面， 得到碳纤维 棵露区 112。 碳纤维表面的氧化辞纳米线生长区 111 占碳纤维 11长度的五分 之三。  The surface of one end of the carbon fiber was etched with a dilute alkali (0.01 mol/L sodium hydroxide solution) to obtain a carbon fiber dew zone 112. The oxidation of the surface of the carbon fiber nanowire growth region 111 accounts for three-fifths of the length of the carbon fiber 11.
通过常规旋涂法将聚甲基丙烯酸甲酯覆盖于氧化辞纳米线阵列层上形成 厚度为 200nm的高分子绝缘层 13。 The polymethyl methacrylate is coated on the oxidized nanowire array layer by a conventional spin coating method. The polymer insulating layer 13 having a thickness of 200 nm.
利用射频溅镀， 将厚度 lOOnm的镍钛合金设置到高分子绝缘层 13上， 形成分布式电极 2。  A nickel-titanium alloy having a thickness of 100 nm is placed on the polymer insulating layer 13 by RF sputtering to form a distributed electrode 2.
在高频电源作用下， 在碳纤维 11与分布式电极 2之间形成电场， 氧化辞 纳米线阵列 12在该电场作用下产生超声振动， 采用超声示波器设备测得， 该 超声波频率为 2MHz, 电压振幅为 2V, 能够应用于血管中溶解血栓。  Under the action of the high-frequency power source, an electric field is formed between the carbon fiber 11 and the distributed electrode 2, and the oxidized nanowire array 12 generates ultrasonic vibration under the electric field, which is measured by an ultrasonic oscilloscope device, and the ultrasonic frequency is 2 MHz, and the voltage amplitude is It is 2V and can be used to dissolve thrombus in blood vessels.
本发明的超声振动机，在电场作用下，氧化辞纳米线能够产生超声波（超 声振动）， 用于在体腔和血管内驱动异物或血栓。 根据应用领域的不同， 本发 明超声振动机能够产生不同频率的超声波。 本发明超声振动机直径为 10~15 微米， 可在除毛细血管外的其他血管中通过， 用于驱动附到血管壁的血栓或 促使血管壁上血栓溶解。  In the ultrasonic vibration machine of the present invention, under the action of an electric field, the oxidized nanowire can generate ultrasonic waves (ultrasonic vibration) for driving foreign matter or thrombus in the body cavity and the blood vessel. Depending on the field of application, the ultrasonic vibratory machine of the present invention is capable of generating ultrasonic waves of different frequencies. The ultrasonic vibrating machine of the present invention has a diameter of 10 to 15 μm and can pass through other blood vessels other than the capillaries to drive a thrombus attached to the blood vessel wall or to cause thrombus dissolution on the blood vessel wall.

Claims

权 利 要 求 书 Claim
1. 一种纳米超声振动机， 其特征在于： 该超声振动机包括碳纤维， 氧化 辞纳米线阵列和高分子绝缘层； A nano ultrasonic vibration machine, characterized in that: the ultrasonic vibration machine comprises carbon fiber, an oxidized nanowire array and a polymer insulation layer;
其中， 碳纤维的表面包括氧化辞纳米线生长区和棵露区；  Wherein, the surface of the carbon fiber comprises an oxidized nanowire growth region and a dew region;
在氧化辞纳米线生长区， 所述氧化辞纳米线阵列垂直生长在碳纤维表面 上， 形成以碳纤维为核， 氧化辞纳米线阵列作为圓柱壳体的核壳结构；  In the oxidized nanowire growth region, the oxidized nanowire array is vertically grown on the surface of the carbon fiber to form a core-shell structure in which the carbon fiber is used as a core and the oxidized nanowire array is used as a cylindrical shell;
所述氧化辞纳米线阵列上覆盖有所述高分子绝缘层。  The oxidized nanowire array is covered with the polymer insulating layer.
2. 根据权利要求 1所述的纳米超声振动机， 其特征在于， 所述高分子绝 缘层所用的材料是聚甲基丙烯酸甲酯或聚二甲基硅氧烷。  The nano ultrasonic vibration machine according to claim 1, wherein the material for the polymer insulating layer is polymethyl methacrylate or polydimethylsiloxane.
3. 根据权利要求 1或 2所述的纳米超声振动机， 其特征在于， 该超声振 动机进一步包括电源， 所述电源包括两个电流输出端， 其中一个电流输出端 连接碳纤维的棵露区， 另一个电流输出端连接受体。  The nano ultrasonic vibration machine according to claim 1 or 2, wherein the ultrasonic vibration machine further comprises a power source, the power source comprises two current output ends, wherein one current output end is connected to the exposed area of the carbon fiber, Another current output is connected to the receptor.
4.根据权利要求 3所述的纳米超声振动机， 其特征在于， 该超声振动机 进一步包括分布式电极， 该分布式电极设置在高分子绝缘层上； 所述电源的 一个电流输出端连接碳纤维的棵露区， 另一个电流输出端连接分布式电极。  The nano ultrasonic vibration machine according to claim 3, wherein the ultrasonic vibration machine further comprises a distributed electrode, the distributed electrode is disposed on the polymer insulating layer; and a current output end of the power source is connected to the carbon fiber The exposed area, the other current output is connected to the distributed electrode.
5. 根据权利要求 4所述的纳米超声振动机， 其特征在于， 所述分布式电 极材料为金、 铂、 钛或镍钛合金中的任意一种。  The nano ultrasonic vibration machine according to claim 4, wherein the distributed electrode material is any one of gold, platinum, titanium or nickel titanium alloy.
6. 根据权利要求 1-5任一项所述的纳米超声振动机， 其特征在于， 所述 氧化辞纳米线生长区域占碳纤维长度的四分之一至五分之四。  The nano ultrasonic vibration machine according to any one of claims 1 to 5, wherein the oxidized nanowire growth region accounts for one quarter to four fifths of the length of the carbon fiber.
7. 根据权利要求 5所述的纳米超声振动机， 其特征在于， 所述电源是交 流电， 功率在 5~100W之间， 频率在 ΙΚΗζ-ΙΟΜΗζ之间。  The nano ultrasonic vibration machine according to claim 5, wherein the power source is AC, the power is between 5 and 100 W, and the frequency is between ΙΚΗζ-ΙΟΜΗζ.
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