WO2022186804A1 - Artificial tympana of graphene-magnetic nano-particle composite structure - Google Patents

Artificial tympana of graphene-magnetic nano-particle composite structure Download PDF

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Publication number
WO2022186804A1
WO2022186804A1 PCT/TR2022/050182 TR2022050182W WO2022186804A1 WO 2022186804 A1 WO2022186804 A1 WO 2022186804A1 TR 2022050182 W TR2022050182 W TR 2022050182W WO 2022186804 A1 WO2022186804 A1 WO 2022186804A1
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WIPO (PCT)
Prior art keywords
graphene
membrane
magnetic
magnetic nanoparticle
feec
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PCT/TR2022/050182
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French (fr)
Inventor
Cumhur Gökhan ÜNLÜ
Aleyna AKÇAY
Elif GÖKOĞLAN
Hatice Nur KOYUN
Sinem KARATEKİN
Çiğdem YENER
Hatice Dilay YAZICI
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Pamukkale Üni̇versi̇tesi̇
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Priority claimed from TR2021/004168 external-priority patent/TR2021004168A2/en
Application filed by Pamukkale Üni̇versi̇tesi̇ filed Critical Pamukkale Üni̇versi̇tesi̇
Publication of WO2022186804A1 publication Critical patent/WO2022186804A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/18—Internal ear or nose parts, e.g. ear-drums
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/443—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with carbon fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/18—Internal ear or nose parts, e.g. ear-drums
    • A61F2002/183—Ear parts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/14—Materials or treatment for tissue regeneration for ear reconstruction or ear implants, e.g. implantable hearing aids

Definitions

  • Invention relates to artificial Tympana comprising a graphene magnetic nano-particle composite membrane embodiment.
  • Invention particularly relates to an artificial Tympana comprising a graphene /polymetylmetacrrylate polymer nano-composite membrane reinforced by magnetite nano particles and a production method.
  • Hearing aids or implants are used in various forms and various functions to provide hearing ability to persons suffering from full and partial hearing loss. Hearing aids used today are described below.
  • Such hearing aids are convenient for light-medium hearing loss and combination of “behind the ear” and “receiver in ear” aids.
  • these strong hearing aids are convenient for those suffering high hearing loss.
  • hearing aids are placed into ear. They are formed specifically to fit into ear and almost not visible and range from "Completely in the Canal” (CIC) model to strong In the Ear (ITE).
  • CIC Completely in the Canal
  • ITE strong In the Ear
  • Bio-nano-technology helps in aiding display of combining biological studies with various fields of nano-technology.
  • concepts developed by means of nano-technology are nano circuits, nano particulates and nano scaled parts available nano-technology discipline. This technical approach to biology allows design and creation of systems that can be used for biological studies by scientists. Use of nanomaterials may allow tracking, treatment and recreation of biological systems in human in molecular size in medicine.
  • EP3087761 B1 relates to hearing aid and hearing aid system that can be placed in hearing path.
  • the invention discloses a hearing aid that can be placed into hearing path of patient and comprising an actuator providing activation of ear membrane mechanically.
  • Actuator comprises an inner surface connected to ear membrane and an outer surface connected to hearing path and is formed in surface disk actuator shape. Deformation thereof warns ear membrane.
  • a membrane disk is placed onto outer surface of actuator in intervals and limiting space with outer surface in lens form.
  • the present invention relates to an artificial ear membrane meeting the needs mentioned above, eliminating all disadvantages and providing some additional advantages.
  • Primary purpose of the invention is to develop an artificial ear working as ear membrane in order to eliminate hearing loss of individuals having damages arising from all stages from ear membrane to hearing nerves.
  • Another purpose of the invention is to provide production of a nano-technological membrane which takes ear membrane as model to provide hearing functions and can be integrated to micro-electronic systems for artificial ear design developed for patients having hearing disability.
  • a further purpose of the invention is to prevent bio-compatibility problems that can occur in body due to device .by means of using PMMA and graphene which are biocompatible materials instead of chemical binding. Also the method applied hereunder provides reduction in costs commercially.
  • Another purpose of the invention is to realise immobilization of nano-particulates onto graphene surface without use of any chemicals.
  • the invention developed in order to achieve above mentioned purposes is an artificial ear membrane and comprises graphene magnetic nano-particulate composite membrane embodiment.
  • Applications of the invention preferably comprise a graphene/polymethylmethacrylate polymer nanocomposite membrane embodiment reinforced by magnetite ( FeeC ) and/or magnetic nano-particulate and/or graphene/poly methyl methacrylate polymer nanocomposite membrane embodiment having sensitive ear membrane nature reinforced by magnetite ( FeeC ) nano-particulates.
  • Invention developed to achieve above mentioned purposes is a method for producing artificial ear membrane and comprises following process steps: i. production of graphene in one single layer on a copper surface by use of chemical steam collection method, ii. Forming graphene/PMMA nanocomposite membrane embodiment by coating produced graphene by polymethylmethacrylate polymer by spin coating method, iii. Application of chemical etching on copper surface in iron (III) nitrate (Fe(NC> 3 ) 3 ) solution, iv. Synthesising magnetite (FeeC ) nano-particles by sol-gel method, v. Adding FeeC nanoparticles of magnetic feature onto single layer graphene by dripping -distribution method, vi.
  • Forming sandwich structure by adding a second single layer graphene structure onto graphene/magnetic nanoparticle composite membrane vii.
  • Figure 1 is a figurative view of graphene/magnetic nanocomposite membrane structured device.
  • Figure 2 is an optic microscope view of copper surface before production (a) and after production (b).
  • Figure 3 is a figurative view of production stages of graphene/magnetic nanoparticle composite structured device.
  • Figure 4 is a scanned electron microscope (SEM) view of Fe nanoparticles (a) and Fe nanoparticles (b) composed by CVD graphene.
  • the invention is an artificial ear membrane comprising graphene-magnetic nanoparticle composite membrane.
  • a preferred application of the invention comprises magnetite (FeeC ) providing sound transmission of nature similar to ear membrane structure as membrane structure magnetic nanoparticle.
  • Artificial membrane of the invention comprises a graphene/ polymethylmethacrylate polymer nanocomposite membrane having sensitive ear membrane nature with preferably magnetic particle reinforcement.
  • Artificial membrane of the invention comprises a graphene/ polymethylmethacrylate polymer nanocomposite membrane reinforced with preferably magnetite (FeeC ) nanoparticles.
  • Manufacture method of artificial ear membrane of the invention comprises following process steps: i. production of graphene in one single layer on a copper surface by use of chemical steam collection method, ii. Forming graphene/PMMA nanocomposite membrane embodiment by coating produced graphene by polymethylmethacrylate polymer by spin coating method, iii. Application of chemical etching on copper surface in iron (III) nitrate (Fe(NC> 3 ) 3 ) solution, iv. Synthesising magnetite (FeeC ) nano-particles by sol-gel method, v. Adding FeeC nanoparticles of magnetic feature onto single layer graphene by dripping -distribution method, vi.
  • Forming sandwich structure by adding a second single layer graphene structure onto graphene/magnetic nanoparticle composite membrane vii.
  • Electromagnetic induction forms an electrical current due to varying magnetic field.
  • This case is released by Michael Faraday’s experimental studies and James Clerk Maxwell's mathematical 4 Maxwell Equations.
  • the equations respectively indicate Gauss Rule indicating that electric field is formed by electric loads, Gauss rule for magnetism, varying magnetic field producing electric field (Faraday’s Induction Rule), loads and varying electric fields produce magnetic field (Ampere-Maxwell Rule).
  • Faraday Induction Rule is taken as basis in this invention.
  • Faraday describes it with an experiment.
  • Faraday Induction Law experiment, Faraday takes a magnet and a coil and connects a galvanometer across the coil. When the magnet is moved towards the coil, the needle of the galvanometer deflects in one direction. Current is produced with movement of magnet in the coil if the magnet is held stationary, the galvanometer needle does not move.
  • Faraday concluded that whenever there is relative motion between a conductor and a changing magnetic field, there is a flux linkage with a coil changes Current generated by induced voltage is called induction current.
  • a device where an electrical signal can be generated specifically from different sound waves by use of nanotechnology similar to Faraday's experiment ( Figure 1).
  • Figure 1 For magnet to perform its function, it is planned to produce a magnetic nanoparticle above 100nm dimensionally having magnetizing function. It is because magnetic nanoparticles of ferromagnetic feature lose their ferromagnetic features but display super paramagnetic features when reduced into sizes under 100 nm in general. Thus as the intensity of magnetic nanoparticles obtained at nanometre level dimensionally will be bigger, total obtained magnetic flux change will be proportionally more.
  • Ferromagnetic materials are materials having non-doubled magnetic moments, too high sensitivity and reacting in the same direction as applied outer magnetic field. Even when placed inside a poor magnetic field they will move parallel to one another and having too strong magnetization and frequently used materials ( Figure 2).
  • Reason for such strong magnetization features is the magnetic moments directed in the same directions as one another in groups inside areas called domain in internal structures.
  • Inner structures such as ferromagnetic have materials containing magnetic arrangements. They are called ferromagnetic materials and move in the same direction as area of ferromagnetic.
  • ferromagnetic definition is made for magnetite (FeeC ) nanoparticles which are magnetic materials frequently used in biomedical applications.
  • Super paramagnetic materials act as material containing one single domain because of their sizes. Therefore, each nanoparticle becomes a single domain. When outer magnetic field is applied, field returns to field direction and when field is removed, it moves randomly and total magnetizations reset. Because of such features, hysteris behaviour seen in ferromagnetic are not observed in super paramagnetic particles. Despite having high saturation magnetization values, permanent magnetization and coercivity values are zero. Some magnetic features vary depending on coercivity and magnet grain size in particular. When reducing under 30 nm in coercivity change depending on grain size for magnetite, super paramagnetic feature is displayed.
  • nanoparticles used in the invention act like permanent magnets at room temperature, nanoparticles displaying ferromagnetic feature instead of super paramagnetic feature at sizes above 40 nm will be produced by method of sol-gel ( Figure 4).
  • another reason for use of FeeC nanoparticles is that they show biocompatible feature.
  • Such nanoparticles are already used in biomedical applications such as hyperthermia for cancer treatment. It is intended to use sol-gel method for production of FesC nanoparticles above 100 nm.
  • Sol-gel method consists of stages of hydrolysis and intensifying of initial material. As initial material, alkoxide, inorganic and organic salts can be used.
  • sol-gel process a reactive metal such as metal alkoxide is hydrolysed with an initial material water and hydrolysed derivatives are allowed to concentrate with one another to form metal oxide nanoparticle sedimentations. Sedimentation is then washed and dried. At the next stage, crystal metal oxide is calcinated at high temperature for formation of nanoparticles.
  • Graphene is a carbon allotrope and is of plane structure having single atom thickness where carbon atoms tied with covalent bonding are packed tightly inside honey comb crystal cage structure ( Figure 5)
  • graphene have superior natures such as high electronic motion ( ⁇ 250.000 cm 2 .V 1 .s 1 ), high optic permeability ( ⁇ % 97,7), high electrical and thermal conductivity (above 3000 W.rrr 1 .K _1 )
  • Graphene is also of high mechanical hardness, resistance (-130 GPa) and flexibility (-1.0 TPa) Ultra low mass of graphene, its elasticity and high resistant features makes it considerably attractive material for sound transmission applications.
  • the graphene used in this invention is also produced by CVD method.
  • Poly-Methyl- Methacrylate (PMMA) intended to be used as graphene support material is thermoplastic polymer having amorph structure, linear chain and low manufacture cost. Combination of graphene and PMMA enhances micro structure and viscoelastic features of polymer considerably. Because of biocompatibility feature of PMMA, it is used as lens material in biomedical applications. Single layer graphene surface obtained on copper surface is coated with biocompatible PMMA polymer and membrane is formed. The formed graphene/PMMA composite structure provides hardness, resistant, size and thermal balance of graphene.
  • Graphene part of copper where 1 hollow is formed is added by dropping Fe 3 0 4 nanoparticles of magnetic feature produced by sol-gel method by means of drop-casting method. After fixing Fe 3 0 4 nanoparticles onto graphene, non-graphene parts of second copper foil having hollow thereon are combined to have non-graphene parts are on one another and thus a sandwich structure is formed. After this stage remaining part is cut and removed by laser controlled cutting in order to obtain a circle away from 1 .25 cm diameter from centre. 2 pieces of copper wire contacts are made to read current occurring as a result of voltage generated on terminals. Thus sandwich type ear membrane design for artificial ear is produced (Figure 7). SEM views of nanoparticles reinforced onto graphene in preliminary studies are shown in Figure 4.
  • FeaC nanoparticles having magnetic features are added between two graphene layers called sandwich type graphene and composite structure is formed.
  • Hearing function is provided by sending signal to hearing nerves by help of sending electric current signal produced by means of induction to be provided by help of graphene acoustic features and magnetic nanoparticle vibrations by help of micro electronic system.
  • n Number of magnetic moments in unit volume.
  • m magnetic permeability of medium.
  • B magnetization will be found out from hysterisis curve of magnetic nanoparticles obtained as a result of experiment to be obtained at around room temperature.
  • membrane When sound wave hits membrane functioning as diaphragm, membrane will be vibrated subject to change in pressure and frequency of sound and thus a mechanic vibration will be generated.
  • the vibration also means vibration of magnetic nanoparticles within current circle.
  • magnetic flux equation created in a surface of nanoparticles having M magnetization and acting as a magnet
  • This formula indicates that current flux change generated in current circle by nanoparticles having M magnetization as a result of sound wave generates a voltage between current circle ends.
  • the voltage to be generated is subject to speed and frequency of vibration of nanoparticles.
  • FeaC nanoparticles of magnetic feature synthesized by sol-gel method are reinforced between sandwich graphene layers produced by CVD method. No inter-linker bond molecule is used for grasp of the nanoparticles to graphene surface, instead particles are covered by a second graphene layer to immobilize nanoparticles.
  • strength is also increase as graphene supported by PMMA is double folded.
  • Product design of the invention is an original design.
  • literature and market there is no similar method and similar product that can be implanted into system having graphene magnetic nanoparticle composite structure developed by use of method of the invention for use in ear.
  • Sol-gel method suggested for production of particles is seen as a multi directional and economic method. It is possible to produce nano-materials having various shapes, dimensions and structures by use of the method.
  • Single layer or multi-layer high quality graphene can be easily produced by CVD method.
  • Graphene having very broad surface area can be easily synthesised.
  • Produced graphene can easily be transferred to other surfaces for next processes for chemical etching of metal catalyst.
  • Catalyser type of method have several various experimental parameters such as pressure, raw material, carrying gas types, temperature etc.
  • Features of graphene can be brought into desired form by changing the parameters.
  • Magnetite nanoparticles of nano-size are used in several areas from magnetic data storage to magnetic cooling, from microwave applications to biomedical applications due to easy and low cost synthesising and magnetic features. Magnetite nano-particles are convenient for biological applications.
  • Current design can be converted into a commercial product after production and trial stages. A system that is fully implantable and capable to provide hearing fully inside ear is not available in the market.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
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  • Animal Behavior & Ethology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

Invention relates to an artificial Tympana comprising a graphene/polymethylmethacrylate polymer nano-composite membrane reinforced by magnetite nano-particles and a production method.

Description

ARTIFICIAL TYMPANA OF GRAPHENE-MAGNETIC NANO-PARTICLE COMPOSITE
STRUCTURE
The Field of the Invention
Invention relates to artificial Tympana comprising a graphene magnetic nano-particle composite membrane embodiment.
Invention particularly relates to an artificial Tympana comprising a graphene /polymetylmetacrrylate polymer nano-composite membrane reinforced by magnetite nano particles and a production method.
Background of the Invention
Hearing aids or implants are used in various forms and various functions to provide hearing ability to persons suffering from full and partial hearing loss. Hearing aids used today are described below.
Receiver in Ear (RIE)
Such hearing aids are convenient for light-medium hearing loss and combination of “behind the ear” and “receiver in ear” aids.
Behind the ear (BTE)
In general offering the highest amplification and many additional features, these strong hearing aids are convenient for those suffering high hearing loss.
Specifically made hearing aids
These hearing aids are placed into ear. They are formed specifically to fit into ear and almost not visible and range from "Completely in the Canal" (CIC) model to strong In the Ear (ITE).
Since hearing problem which is the 3rd health problem commonly seen in the world and affecting life quality directly, averagely 2.000 people are to use Cochlear Implant in our country every year. Cost of implants already in use is considerably high, which is around 45000 TL. Studies to reduce costs are in progress. Daily use difficulty of already available implants causes psychological problems arising from use of cochlear implant from young ages. As the aid is kept outside ear it may encounter problems such as humidification, wetting, due to weather conditions and also sound receipt can be limited due to hat shawl, long hair. Particularly careless use and hitting may cause breaking of cables for children. The product disclosed under the invention suggests bringing solutions for such problems by use of bio-nano-technological approaches used herein. Bio-nano-technology helps in aiding display of combining biological studies with various fields of nano-technology. Among concepts developed by means of nano-technology are nano circuits, nano particulates and nano scaled parts available nano-technology discipline. This technical approach to biology allows design and creation of systems that can be used for biological studies by scientists. Use of nanomaterials may allow tracking, treatment and recreation of biological systems in human in molecular size in medicine.
In the literature following application is seen related to the subject.
European Patent application numbered EP3087761 B1 relates to hearing aid and hearing aid system that can be placed in hearing path. The invention discloses a hearing aid that can be placed into hearing path of patient and comprising an actuator providing activation of ear membrane mechanically. Actuator comprises an inner surface connected to ear membrane and an outer surface connected to hearing path and is formed in surface disk actuator shape. Deformation thereof warns ear membrane. A membrane disk is placed onto outer surface of actuator in intervals and limiting space with outer surface in lens form.
As a result, due to above described disadvantages and inadequacy of existing solutions it has been necessary to make development in the related art.
Brief Description of the Invention
The present invention relates to an artificial ear membrane meeting the needs mentioned above, eliminating all disadvantages and providing some additional advantages.
Primary purpose of the invention is to develop an artificial ear working as ear membrane in order to eliminate hearing loss of individuals having damages arising from all stages from ear membrane to hearing nerves.
Another purpose of the invention is to provide production of a nano-technological membrane which takes ear membrane as model to provide hearing functions and can be integrated to micro-electronic systems for artificial ear design developed for patients having hearing disability.
A further purpose of the invention is to prevent bio-compatibility problems that can occur in body due to device .by means of using PMMA and graphene which are biocompatible materials instead of chemical binding. Also the method applied hereunder provides reduction in costs commercially.
Another purpose of the invention is to realise immobilization of nano-particulates onto graphene surface without use of any chemicals.
The invention developed in order to achieve above mentioned purposes is an artificial ear membrane and comprises graphene magnetic nano-particulate composite membrane embodiment. Applications of the invention preferably comprise a graphene/polymethylmethacrylate polymer nanocomposite membrane embodiment reinforced by magnetite ( FeeC ) and/or magnetic nano-particulate and/or graphene/poly methyl methacrylate polymer nanocomposite membrane embodiment having sensitive ear membrane nature reinforced by magnetite ( FeeC ) nano-particulates.
Invention developed to achieve above mentioned purposes is a method for producing artificial ear membrane and comprises following process steps: i. production of graphene in one single layer on a copper surface by use of chemical steam collection method, ii. Forming graphene/PMMA nanocomposite membrane embodiment by coating produced graphene by polymethylmethacrylate polymer by spin coating method, iii. Application of chemical etching on copper surface in iron (III) nitrate (Fe(NC>3)3) solution, iv. Synthesising magnetite (FeeC ) nano-particles by sol-gel method, v. Adding FeeC nanoparticles of magnetic feature onto single layer graphene by dripping -distribution method, vi. Forming sandwich structure by adding a second single layer graphene structure onto graphene/magnetic nanoparticle composite membrane, vii. Production of graphene/magnetic nanoparticle/graphene composite structured device by lithography method, viii. Taking measurement from obtained graphene/magnetic nanoparticle/graphene composite structure and forming implant by convenient microprocessors.
The structural and characteristics features of the invention and all advantages will be understood better in detailed descriptions with the figures given below and with reference to the figures, and therefore, the assessment should be made taking into account the said figures and detailed explanations.
Brief Description of the Drawings
Figure 1 is a figurative view of graphene/magnetic nanocomposite membrane structured device.
Figure 2 is an optic microscope view of copper surface before production (a) and after production (b).
Figure 3 is a figurative view of production stages of graphene/magnetic nanoparticle composite structured device.
Figure 4 is a scanned electron microscope (SEM) view of Fe nanoparticles (a) and Fe nanoparticles (b) composed by CVD graphene.
The drawings are not necessarily to be scaled and the details not necessary for understanding the present invention might have been neglected. In addition, the components which are equivalent to great extent at least or have equivalent functions at least have been assigned the same number.
Detailed Description of the Invention
In this detailed description, the artificial ear membrane of the invention have been described in a manner not forming any restrictive effect and only for purpose of better understanding of the matter.
The invention is an artificial ear membrane comprising graphene-magnetic nanoparticle composite membrane. A preferred application of the invention comprises magnetite (FeeC ) providing sound transmission of nature similar to ear membrane structure as membrane structure magnetic nanoparticle.
Artificial membrane of the invention comprises a graphene/ polymethylmethacrylate polymer nanocomposite membrane having sensitive ear membrane nature with preferably magnetic particle reinforcement. Artificial membrane of the invention comprises a graphene/ polymethylmethacrylate polymer nanocomposite membrane reinforced with preferably magnetite (FeeC ) nanoparticles.
Manufacture method of artificial ear membrane of the invention comprises following process steps: i. production of graphene in one single layer on a copper surface by use of chemical steam collection method, ii. Forming graphene/PMMA nanocomposite membrane embodiment by coating produced graphene by polymethylmethacrylate polymer by spin coating method, iii. Application of chemical etching on copper surface in iron (III) nitrate (Fe(NC>3)3) solution, iv. Synthesising magnetite (FeeC ) nano-particles by sol-gel method, v. Adding FeeC nanoparticles of magnetic feature onto single layer graphene by dripping -distribution method, vi. Forming sandwich structure by adding a second single layer graphene structure onto graphene/magnetic nanoparticle composite membrane, vii. Production of graphene/magnetic nanoparticle/graphene composite structured device by lithography method, viii. Taking measurement from obtained graphene/magnetic nanoparticle/graphene composite structure and forming implant by convenient microprocessors.
Technical descriptions based on operating principle of said invention are provided in details below. For membrane design, FesC magnetite nanoparticles of magnetic feature are placed between two sandwich graphene layers placed into copper surface (coil) and produced by chemical vapour deposition (CVD) method. By help of the produced membrane, electric current is induced as a result of vibration of graphene/ magnetic nanoparticle/graphene composite structure by coming sound waves of various wave length. By help of graphene a 2-dimension material having single atom thickness, membrane size can be reduced to ear membrane sizes and thus is of nature enabling sensitive vibration to sound waves.
With the vibration movement that will be made by sound waves in the developed membrane, magnetic nanoparticles in the structure vibrate into copper surface and thus form electromagnetic induction. Electromagnetic induction forms an electrical current due to varying magnetic field. This case is released by Michael Faraday’s experimental studies and James Clerk Maxwell's mathematical 4 Maxwell Equations. The equations respectively indicate Gauss Rule indicating that electric field is formed by electric loads, Gauss rule for magnetism, varying magnetic field producing electric field (Faraday’s Induction Rule), loads and varying electric fields produce magnetic field (Ampere-Maxwell Rule). Faraday Induction Rule is taken as basis in this invention.
Faraday rule is also called Faraday’s induction law. Voltage occurring when a magnetic flux flows through a current circle is proportional to time change rate of flux (Equation 1). j E.ds= - FB/dt (Equation 1)
Faraday describes it with an experiment. In Faraday’s Induction Law experiment, Faraday takes a magnet and a coil and connects a galvanometer across the coil. When the magnet is moved towards the coil, the needle of the galvanometer deflects in one direction. Current is produced with movement of magnet in the coil if the magnet is held stationary, the galvanometer needle does not move. Faraday concluded that whenever there is relative motion between a conductor and a changing magnetic field, there is a flux linkage with a coil changes Current generated by induced voltage is called induction current.
In this invention, a device where an electrical signal can be generated specifically from different sound waves by use of nanotechnology similar to Faraday's experiment (Figure 1). For magnet to perform its function, it is planned to produce a magnetic nanoparticle above 100nm dimensionally having magnetizing function. It is because magnetic nanoparticles of ferromagnetic feature lose their ferromagnetic features but display super paramagnetic features when reduced into sizes under 100 nm in general. Thus as the intensity of magnetic nanoparticles obtained at nanometre level dimensionally will be bigger, total obtained magnetic flux change will be proportionally more.
Ferromagnetic materials are materials having non-doubled magnetic moments, too high sensitivity and reacting in the same direction as applied outer magnetic field. Even when placed inside a poor magnetic field they will move parallel to one another and having too strong magnetization and frequently used materials (Figure 2). Reason for such strong magnetization features is the magnetic moments directed in the same directions as one another in groups inside areas called domain in internal structures. Inner structures such as ferromagnetic have materials containing magnetic arrangements. They are called ferromagnetic materials and move in the same direction as area of ferromagnetic. Generally ferromagnetic definition is made for magnetite (FeeC ) nanoparticles which are magnetic materials frequently used in biomedical applications. Because in reverse spinal structures anti parallel Fe3+ ions I deactivate magnetic moment of one another in octahedral and tetrahedral areas and ferromagnetic effect is provided by Fe2+ ions in octahedral area. If some of Fe2+ ions in octahedral areas are oxidized, magnetic saturation value will also decrease. When sizes of magnetite nanoparticles are reduced under 30 - 40 nm in general, super paramagnetic feature is displayed.
Super paramagnetic materials act as material containing one single domain because of their sizes. Therefore, each nanoparticle becomes a single domain. When outer magnetic field is applied, field returns to field direction and when field is removed, it moves randomly and total magnetizations reset. Because of such features, hysteris behaviour seen in ferromagnetic are not observed in super paramagnetic particles. Despite having high saturation magnetization values, permanent magnetization and coercivity values are zero. Some magnetic features vary depending on coercivity and magnet grain size in particular. When reducing under 30 nm in coercivity change depending on grain size for magnetite, super paramagnetic feature is displayed.
As Fe3C>4 nanoparticles used in the invention act like permanent magnets at room temperature, nanoparticles displaying ferromagnetic feature instead of super paramagnetic feature at sizes above 40 nm will be produced by method of sol-gel (Figure 4). In addition, another reason for use of FeeC nanoparticles is that they show biocompatible feature. Such nanoparticles are already used in biomedical applications such as hyperthermia for cancer treatment. It is intended to use sol-gel method for production of FesC nanoparticles above 100 nm. Sol-gel method consists of stages of hydrolysis and intensifying of initial material. As initial material, alkoxide, inorganic and organic salts can be used. In sol-gel process a reactive metal such as metal alkoxide is hydrolysed with an initial material water and hydrolysed derivatives are allowed to concentrate with one another to form metal oxide nanoparticle sedimentations. Sedimentation is then washed and dried. At the next stage, crystal metal oxide is calcinated at high temperature for formation of nanoparticles.
Graphene is a carbon allotrope and is of plane structure having single atom thickness where carbon atoms tied with covalent bonding are packed tightly inside honey comb crystal cage structure (Figure 5) In terms of physical features, not having faults and impurities, graphene have superior natures such as high electronic motion (~ 250.000 cm2.V 1.s 1), high optic permeability (~ % 97,7), high electrical and thermal conductivity (above 3000 W.rrr1.K_1) Graphene is also of high mechanical hardness, resistance (-130 GPa) and flexibility (-1.0 TPa) Ultra low mass of graphene, its elasticity and high resistant features makes it considerably attractive material for sound transmission applications. In literature it is shown that it can be used as graphene based microphone and ultrasonic radio components as a result of simple production method using CVD and low cost thereof. The graphene used in this invention is also produced by CVD method.
For production of graphene there are several methods from bottom to top or from top to bottom. While obtaining micro structure small part graphene by chemical methods, graphene of single layer or multi-layer of high quality in metal wide surfaces can easily be produced by use of CVD method.
For production of single layer graphene after preliminary cleaning stage of 2 different coil foil in 2*2 cm2 sizes, they are placed into a thermal oven working under vacuum and media is taken under vacuum. It is heated up to 1000 O in argon/hydrogen reduction medium to remove natural oxide on the copper surface and form copper nucleic and a treatment process for about 30 minutes is applied. Then methane (CFU) is added in a certain amount in addition to gas flux. At this stage graphene formation starts with some nucleic area, then lateral growing continues with full coverage of copper surface with single atomic layer graphene crystals. Methane is separated on copper surface and adsorbed carbon atoms move on surface until combination with graphene crystals and addition to graphene crystals. Thus after a growing period of 5 minutes to 30 minutes subject to gas flow rate, single atomic layer graphene (SLG) is obtained on copper foil (Figure 6).
Poly-Methyl- Methacrylate (PMMA) intended to be used as graphene support material is thermoplastic polymer having amorph structure, linear chain and low manufacture cost. Combination of graphene and PMMA enhances micro structure and viscoelastic features of polymer considerably. Because of biocompatibility feature of PMMA, it is used as lens material in biomedical applications. Single layer graphene surface obtained on copper surface is coated with biocompatible PMMA polymer and membrane is formed. The formed graphene/PMMA composite structure provides hardness, resistant, size and thermal balance of graphene.
Graphene coated side of graphene coated 2 different copper foil produced by CVD method initially for device design is rotated for 40 seconds at 4000 RPM homogenously by use of spin coating with PMMA method, and thus coated. Before coating other empty part of copper (without graphene) with PMMA, a circular label of 1 cm diameter to center exact middle point is posted and then coated with PMMA by use of previous method. After drying of PMMA, label is removed and middle part will remain without PMMA. Thus we have 2 pieces of one side PMMA/Graphene/Cu and one other side with 1 cm diameter hollow copper foil. Purpose of creating this to expose 2 pieces of 1 cm diameter hollow copper surface to chemical etching in Ferro (III) Nitrate (Fe(NOs)3) solution. Thus upon elimination of copper foils put into Ferro (III) Nitrate solution only in hollow part of copper after a while, 1 cm diameter graphene/PMMA layer will remain.
Graphene part of copper where 1 hollow is formed is added by dropping Fe304 nanoparticles of magnetic feature produced by sol-gel method by means of drop-casting method. After fixing Fe304 nanoparticles onto graphene, non-graphene parts of second copper foil having hollow thereon are combined to have non-graphene parts are on one another and thus a sandwich structure is formed. After this stage remaining part is cut and removed by laser controlled cutting in order to obtain a circle away from 1 .25 cm diameter from centre. 2 pieces of copper wire contacts are made to read current occurring as a result of voltage generated on terminals. Thus sandwich type ear membrane design for artificial ear is produced (Figure 7). SEM views of nanoparticles reinforced onto graphene in preliminary studies are shown in Figure 4.
It is planned to encapsulate Fe304 nanoparticles with double folded (sandwich type) single layer graphene instead of covalent tie for graphene immobilization of nanoparticles to be produced (Figure 9). Electron microscope view of graphene and nanoparticles produced as a result of preliminary studies made for this purpose are shown in Figure 5.
In line with the information, FeaC nanoparticles having magnetic features are added between two graphene layers called sandwich type graphene and composite structure is formed. Hearing function is provided by sending signal to hearing nerves by help of sending electric current signal produced by means of induction to be provided by help of graphene acoustic features and magnetic nanoparticle vibrations by help of micro electronic system.
Theory: m magnetization of magnetic nanoparticle in V volume formed from m magnetic moments,
M=Nm/V=n.m (Equation 2)
Here m: Magnetic moment, V: Volume, N: Number of magnetic moment in V volume, n: Number of magnetic moments in unit volume.
B magnetic field to be produced by a nanoparticle,
B=m.(H+M) (Equation 3)
If there is no outer magnetic field, H = 0, then equation will be
B=m.M (Equation 4)
Here m is magnetic permeability of medium. B magnetization will be found out from hysterisis curve of magnetic nanoparticles obtained as a result of experiment to be obtained at around room temperature. When sound wave hits membrane functioning as diaphragm, membrane will be vibrated subject to change in pressure and frequency of sound and thus a mechanic vibration will be generated. The vibration also means vibration of magnetic nanoparticles within current circle. Here magnetic flux equation created in a surface of nanoparticles having M magnetization and acting as a magnet ,
0=\B.ds= \m.M .ds (Equation 5) ile verilir. Faraday law explains that magnetic flux change per unit time generates a voltage.
- d0 / dt=£=A V (Equation 6) e=Dn= -d/dt( ίm.M .ds) (Equation 7)
This formula indicates that current flux change generated in current circle by nanoparticles having M magnetization as a result of sound wave generates a voltage between current circle ends. The voltage to be generated is subject to speed and frequency of vibration of nanoparticles.
Similarly, voltage (£) frequency bond for current circle acting inside a fixed outer magnetic field in coils is as follows.
F= Fr Cos Q (Equation 8) e = - F / dt= - d/ dt (Fr Cos Q ) = + Fr. sin Q dQ /dt e= Fr.w .sin wΐ (Equation 9)
Here angular frequency is bonded to frequency with w=oίq / dt (Equation 10) and w=2p f (Equation 11). Similarly, in addition to frequency dependency of artificial ear membrane developed hereunder, elasticity features of graphene membrane structure are taken into account to calculate induced current value.
In the membrane product in ear membrane nature disclosed under the invention in copper surface, FeaC nanoparticles of magnetic feature synthesized by sol-gel method are reinforced between sandwich graphene layers produced by CVD method. No inter-linker bond molecule is used for grasp of the nanoparticles to graphene surface, instead particles are covered by a second graphene layer to immobilize nanoparticles. Thus in addition to keeping nanoparticles stable, strength is also increase as graphene supported by PMMA is double folded.
Product design of the invention is an original design. In literature and market there is no similar method and similar product that can be implanted into system having graphene magnetic nanoparticle composite structure developed by use of method of the invention for use in ear. Sol-gel method suggested for production of particles is seen as a multi directional and economic method. It is possible to produce nano-materials having various shapes, dimensions and structures by use of the method.
Single layer or multi-layer high quality graphene can be easily produced by CVD method. Graphene having very broad surface area can be easily synthesised. Produced graphene can easily be transferred to other surfaces for next processes for chemical etching of metal catalyst. Catalyser type of method have several various experimental parameters such as pressure, raw material, carrying gas types, temperature etc. Features of graphene can be brought into desired form by changing the parameters. Magnetite nanoparticles of nano-size are used in several areas from magnetic data storage to magnetic cooling, from microwave applications to biomedical applications due to easy and low cost synthesising and magnetic features. Magnetite nano-particles are convenient for biological applications. Current design can be converted into a commercial product after production and trial stages. A system that is fully implantable and capable to provide hearing fully inside ear is not available in the market.

Claims

1. An artificial ear membrane characterized by comprising; graphene magnetic nanoparticle composite membrane structure.
2. The artificial ear membrane according to claim 1 characterized by comprising; magnetite (FeeC ) as magnetic nanoparticle providing sound transmission in the nature similar to ear membrane structure.
3. The artificial ear membrane according to claim 1 characterized by comprising; a graphene/polymethylmethacrylate polymer nanocomposite membrane reinforced by magnetic nanoparticle.
4. The artificial ear membrane according to claim 2 characterized by comprising; a graphene/polymethylmethacrylate polymer nanocomposite membrane reinforced by magnetite (FeeC ) nanoparticle having ear membrane nature.
5. A manufacture method of artificial ear membrane characterized by comprises following process steps: i. production of graphene in one single layer on a copper surface by use of chemical steam collection method, ii. Forming graphene/PMMA nanocomposite membrane embodiment by coating produced graphene by polymethylmethacrylate polymer by spin coating method, iii. Application of chemical etching on copper surface in iron (III) nitrate (Fe(NC>3)3) solution, iv. Synthesising magnetite (FeeC ) nano-particles by sol-gel method, v. Adding FeeC nanoparticles of magnetic feature onto single layer graphene by dripping -distribution method, vi. Forming sandwich structure by adding a second single layer graphene structure onto graphene/magnetic nanoparticle composite membrane, vii. Production of graphene/magnetic nanoparticle/graphene composite structured device by lithography method, viii. Taking measurement from obtained graphene/magnetic nanoparticle/graphene composite structure and forming implant by convenient microprocessors.
PCT/TR2022/050182 2021-03-03 2022-03-01 Artificial tympana of graphene-magnetic nano-particle composite structure WO2022186804A1 (en)

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TR2021/004168 TR2021004168A2 (en) 2021-03-03 ARTIFICIAL EAR DAMMS WITH GRAPHEN-MAGNETIC NANOparticle COMPOSITE
TR2021/004168A TR202104168A2 (en) 2021-03-03 2021-03-03 ARTIFICIAL EAR DAMMS WITH GRAPHEN-MAGNETIC NANOparticle COMPOSITE

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2569670A (en) * 2017-07-05 2019-06-26 Nanoregmed Ltd Composite material and its method of production
CN110657904A (en) * 2019-09-23 2020-01-07 华南理工大学 Vertical graphene-based stretchable stress sensor and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2569670A (en) * 2017-07-05 2019-06-26 Nanoregmed Ltd Composite material and its method of production
CN110657904A (en) * 2019-09-23 2020-01-07 华南理工大学 Vertical graphene-based stretchable stress sensor and application thereof

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