KR101651635B1 - Magnetic resonance image distortion relaxation method of biomatters - Google Patents

Magnetic resonance image distortion relaxation method of biomatters Download PDF

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KR101651635B1
KR101651635B1 KR1020140193414A KR20140193414A KR101651635B1 KR 101651635 B1 KR101651635 B1 KR 101651635B1 KR 1020140193414 A KR1020140193414 A KR 1020140193414A KR 20140193414 A KR20140193414 A KR 20140193414A KR 101651635 B1 KR101651635 B1 KR 101651635B1
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South Korea
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material
magnetic
implant
stent
catheter
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KR1020140193414A
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Korean (ko)
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KR20160080691A (en
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한준현
박상진
김유찬
석현광
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충남대학교산학협력단
한국과학기술연구원
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/303Carbon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS 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
    • A61F2/00Filters 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
    • A61F2/82Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/306Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08Materials for coatings
    • A61L29/10Inorganic materials
    • A61L29/103Carbon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS 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
    • A61F2240/00Manufacturing or designing of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
    • A61F2240/001Designing or manufacturing processes

Abstract

The present invention relates to a biomedical material for magnetic resonance image distortion relaxation and a method of manufacturing the same for a stent, an implant or a catheter, A method for manufacturing a biomaterial for image distortion mitigation comprises the steps of (1) forming a biomaterial coating layer containing carbon or Bi element on a surface of a material for a stent, an implant or catheter, and a biocompatible surface modification layer (2). ≪ / RTI >

Description

[0001] MAGNETIC RESONANCE IMAGE DISTORTION RELAXATION METHOD OF BIOMATORS [0002]

TECHNICAL FIELD The present invention relates to a biological material, and more particularly, to a biological material for mitigating a magnetic resonance image distortion and a method for manufacturing the same.

Magnetic resonance imaging (MRI) plays a pivotal role in the diagnosis and treatment of cardiovascular disease, spinal and brain lesion disorders. Magnetic resonance imaging converts the spin of hydrogen atoms in the human body into one direction by injecting a specific high frequency to the human body in the magnetic field. When the high frequency is cut off, the position of the electromagnetic wave emitted while the hydrogen atom returns to the original spin state is estimated and imaged.

Magnetic resonance image distortion is caused by a stent, an implant or a catheter inserted into the human body during magnetic resonance imaging. The stent, the implant and the catheter are made of a biomaterial such as a Ti-based, Co-based, NiTi-based, Ni-based, Nb-based, Zr-based or Fe-based alloy. Therefore, the stent, the implant and the catheter are paramagnetic, and the magnetic susceptibility of the stent, the implant and the catheter is significantly different from that of the living tissue. The magnetic resonance image distortion is caused by a difference in magnetic susceptibility with respect to the living tissue.

Korean Patent Laid-Open Publication No. 2011-0108030 provides a method of mixing and sintering a paramagnetic biomaterial powder and a diamagnetic material to reduce the magnetic susceptibility of the stent, the implant and the catheter having paramagnetism (susceptibility χ> 0). However, in the above-mentioned prior art, a large amount of diamagnetism is used to reduce the magnetic susceptibility, and the manufacturing process is not simple including a manufacturing method and a manufacturing method.

In addition, as the diagnosis and analysis using magnetic resonance imaging are diversified, the magnetic resonance image distortion due to the biological material becomes more severe as the intensity of the applied magnetic field increases. It is necessary to develop materials and methods capable of mitigating the above-mentioned magnetic resonance image distortion for precise surgery and procedures. Accordingly, the present invention proposes a method for achieving excellent magnetic susceptibility reduction by coating a simple substance with a small amount of a material having excellent properties such as graphene in a semi-magnetic property (having a magnetic susceptibility x < 0) in a conventional biological material.

Korea Public Patent 2011-0108030

An object of the present invention is to provide a biomaterial for magnetic resonance image distortion relaxation wherein a surface of a material for a stent, an implant or a catheter is coated with a diamagnetic material and a method for manufacturing the same.

 The method for manufacturing a biological material for mitigating a magnetic resonance imaging distortion according to the present invention is a method for forming a biomaterial for mitigating a magnetic resonance image distortion in which a diamagnetic coating layer containing a carbonaceous material or a Bi element is formed on a surface of a material for a stent, an implant, or a catheter Step (1) and forming a biocompatible surface modification layer (2) on the semi-magnetic coating layer.

More particularly, the present invention provides a method for manufacturing a biomaterial for mitigating MRI distortion, comprising the steps of (1) forming a semi-magnetic coating layer on a surface of a material for the stent, implant or catheter, The implant, implant or catheter may further include a catalytic metal element by coating the catalytic metal on the surface of the material and forming the semi-magnetic coating layer. The catalyst metal may be Ni, Pt, Cu, Pd or PdCo.

 The method for manufacturing a biological material for magnetic resonance image distortion alleviation is characterized in that the material for the stent, the implant or the catheter is a Ti-based alloy, a Co-based alloy, a NiTi-based alloy, a Ni-based alloy, a Zr- And an Fe-based alloy.

A method for producing a biological material for magnetic resonance image distortion mitigation is characterized in that the carbonaceous material of the hemispherical body is formed from a group consisting of graphene, highly oriented pyrolytic graphite (HOPG), and carbon nanotube (CNT) And the amount of carbonaceous material of the semi-magnetic body is 3 x 10 &lt; -5 &gt; mass% to 3 x 10 &lt; -1 &gt; mass%, and the amount of Bi of the semi-magnetic body is 1.5 x 10-3 mass% %.

 The method for manufacturing a biological material for mitigating MR image distortion is characterized in that the magnetic susceptibility of the material is reduced after the formation of the semi-magnetic coating layer on the surface of the material for stent, implant or catheter.

 In the method for producing a biological material for alleviating magnetic resonance image distortion, the biocompatible surface modification layer in step (2) includes DLC (Diamond Like Carbon) and PDMS (Polydimethylsiloxane).

Further, the present invention includes a biomaterial for mitigating magnetic resonance image distortion produced by the method for manufacturing a biomaterial for mitigating a magnetic resonance image distortion described above.

A biomaterial for mitigating a magnetic resonance image distortion according to the present invention is a biomaterial for mitigating a magnetic resonance image distortion by forming a biomaterial on a surface of a stent, , The superelasticity and shape memory ability of the implant and catheter material are not impaired, and the biocompatible surface modification layer is formed on the above-mentioned antimagnetic coating layer and is harmless to the human body.

In addition, a simple coating process is added to the stent, implant and catheter manufacturing process, and the magnetic resonance image distortion of the biomaterial can be alleviated by a low-cost manufacturing method using a very small amount of a diamagnetic substance.

1 shows a biological material for mitigating a magnetic resonance image distortion according to the manufacturing method of the present invention.
FIG. 2 shows a magnetization-applied magnetic field (MH) curve measured by applying a magnetic field to a NiTi base material produced according to Examples and Comparative Examples in a horizontal direction.
FIG. 3 is a magnetization-applied magnetic field (MH) curve measured by applying a magnetic field in a direction perpendicular to the NiTi base material produced according to the examples and the comparative examples.
Fig. 4 shows the magnetic susceptibility in the horizontal direction of the NiTi base material obtained from the MH curve in Fig.
5 shows the magnetic susceptibility in a direction perpendicular to the NiTi base material obtained from the MH curve in Fig.

Hereinafter, a biomaterial for mitigating MRI distortion of the present invention and a method for producing the same will be described in detail. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a biological material for magnetic resonance image distortion mitigation according to one preferred embodiment of the present invention. FIG. As shown in FIG. 1, a method for manufacturing a biological material for magnetic resonance image distortion mitigation according to the present invention includes the steps of: forming a surface of a material 110 for a stent, an implant, or a catheter, (2) forming a biocompatible surface modification layer (130) on the semi-magnetic coating layer (120).

Specifically, the step (1) is a step of depositing a thin film of nanofibers on the surface of the material 110 for stents, implants or catheters, the nanofibers containing carbonaceous or Bi elements. As a specific example, the graphene deposition among the carbonaceous thin films can be performed in a vacuum chamber of a medium vacuum of 1 × 10 -3 at 25 torr. After the graphene deposition, a hydrogen gas may be supplied to the surface of the material 110 for the stent, the implant, or the catheter to improve the quality of the graphene in the vacuum chamber.

The step (1) includes a step of forming the semi-magnetic coating layer 120 on the substrate on which the thin film deposition of the semi-magnetic material is easy and transferring the surface to the surface of the material 110 for the stent, implant or catheter . And graphene is peeled off from the directional graphite using a tape to form a semi-magnetic coating layer 120 on the surface of the material 110 for stent, implant or catheter. After the carbon nanotubes are dispersed in a solvent And spraying the surface of the material 110 for the stent, the implant, or the catheter to form the semi-magnetic coating layer 120. As described above, the method of forming the semi-magnetic coating layer 120 is not limited as long as it can form a nanometer-scale thin film.

The material 110 for the stent, the implant or the catheter may further include a catalytic metal element by coating the catalytic metal on the surface of the material 110 and forming the semi-magnetic coating layer 120. Specifically, the material 110 for a stent, an implant or a catheter contains no catalytic metal element or an amount of 0 at% to 10 at% relative to the material 110 so that deposition of the graphene thin film is easy If not, the catalyst metal may be coated to deposit the graphene. Thus, the catalytic metal may include Ni, Pt, Cu, Pd or PdCo used in the deposition of the graphene thin film.

The material 110 for a stent, an implant or a catheter may be any one selected from the group consisting of a Ti-based alloy, a Co-based alloy, a Ni-Ti-based alloy, a Ni-based alloy, a Zr- . The magnetic material is not limited as long as it is resistant to corrosion and can be inserted into a human body and can be used as a biomaterial.

The carbonaceous material of the semi-magnetic body may include any one selected from the group consisting of graphene, aromatic graphite, and carbon nanotubes. The carbonaceous material of the diamagnetic material has a magnetic susceptibility of -1.0 x 10 -6 to -1.0 x 10 -3 . Particularly, the magnetic susceptibility of graphene, which is a carbonaceous material of the above-mentioned semi-magnetic material, has a value of -400.0 x 10 -6 to -300.0 x 10 -6 . The carbonaceous material of the semi-magnetic body is coated on the magnetic body to reduce the susceptibility.

The carbonaceous material of the semi-magnetic body may have a thickness of 0.1 nm to 100 nm. More specifically, when the carbonaceous material of the diamagnetic material is graphene, the surface of the magnetic material may be coated to a thickness of 0.1 nm to 0.5 nm, which is an atomic unit level, and CNTs or directional graphite may be coated to a thickness of 10 nm to 100 nm . Therefore, the physical and chemical properties of the material 110 for the stent, the implant, or the catheter coated with the carbonaceous material of the diamagnetic material can be maintained as it is except for the susceptibility. Particularly, the material 110 for a stent, an implant or a catheter coated with the graphene has surface roughness similar to that before coating, and elasticity and strength can be maintained.

When the amount of the carbonaceous material of the diamagnetic material increases, the magnetic susceptibility of the material 110 for the stent, the implant, or the catheter can be further reduced. On the other hand, the strength of the material 110 for the stent, the implant, or the catheter is rapidly lowered or the coating layer is likely to be peeled off. Therefore, it is preferable that the carbonaceous material of the diamagnetic substance coated on the material 110 for stent, implant or catheter is 3 × 10 -4 mass% to 3 × 10 -1 mass%, more preferably 3 × 10 -4 mass % To 3 x 10 &lt; -3 &gt; mass% may be more preferable.

The Bi element of the above-mentioned semi-magnetic body is biocompatible and has a magnetic susceptibility of -100 x 10 -6 to -200 x 10 -6 . Therefore, the Bi element may be coated on the material 110 for the stent, the implant, or the catheter to alleviate the magnetic resonance image distortion. The coated material to 110 for the stent, implant or catheter element Bi is 1.5 × 10 -2 can be a mass% to 1.5 mass%, preferably, 1.5 × 10 -2 wt% to about 1.5 × 10 - 1 % by mass may be more preferable.

The material 110 for the stent, the implant or the catheter may be coated with the diamagnetic material to reduce the susceptibility by 15% to 60%. Specifically, the degree of magnetic susceptibility of the material 110 for stents, implants, or catheters may vary depending on magnetic anisotropy.

The stent, implant or catheter material 110 may be coated with the semi-magnetic material to improve the biocompatibility and then the biocompatible surface modification layer 130 of step (2) may be formed. The biocompatible surface modification layer 130 includes a diamond like carbon (DLC) and polydimethylsiloxane (PDMS). The biocompatible surface modification layer 130 is harmless to the human body when inserted into the human body and has abrasion resistance, lubricity and biochemical stability, But it is not limited thereto as long as it modifies the surface of the welding material 110.

Furthermore, the present invention can provide a biomaterial for mitigating magnetic resonance image distortion produced by the above-described method for producing a biomaterial for mitigating MRI distortion.

Hereinafter, the present invention will be described in more detail by way of examples. It is to be understood that the present invention is not limited by the examples shown.

[Example 1]

Graphene was grown on a NiTi substrate as shown in Fig. The NiTi base material used had a composition of Ni: Ti = 50: 50 and contained no Ni catalyst metal because it contained 50% Ni. The NiTi base material was charged into a chemical vapor deposition furnace and subjected to annealing while flowing nitrogen gas at a flow rate of 100 sccm and hydrogen gas at a flow rate of 30 sccm at a pressure of 6.9 × 10 -1 Torr at 900 ° C. for 300 seconds. After the heat treatment, graphene was grown for 5 seconds while flowing 1 sccm of CH 4 and 10 sccm of hydrogen gas at a pressure of 1.2 × 10 -1 Torr. After growth, 10 sccm of hydrogen was flown for 60 seconds at a pressure of 9.7 x 10 &lt; -2 &gt; Torr to improve the quality of the graphene. Graphene was coated by cooling to 250 DEG C for 600 seconds while flowing nitrogen gas at 200 sccm under a pressure of 6.9 x 10 &lt; -1 &gt; Torr. DLC (Diamond Like Carbon) coating was applied to the biocompatible surface modification layer.

[Example 2]

In Example 2, Ni of a catalyst metal was coated to a thickness of 260 nm on a SiO 2 / Si substrate by DC sputtering, and then graphene was coated in the same manner as in Example 1. The graphene-coated SiO 2 / Si substrate was immersed in a 10% FeCl 3 solution to etch Ni to separate the graphene from the SiO 2 / Si substrate. The graphene was washed twice with distilled water, transferred to a NiTi plate, and dried to coat graphene on the NiTi substrate. DLC (Diamond Like Carbon) coating was applied to the biocompatible surface modification layer.

[Comparative Example 1]

A NiTi base material having no carbonaceous or Bi-element-containing semi-magnetic coating layer was prepared.

[Experimental Example 1]

The magnetic susceptibility of the biomaterials for magnetic resonance image distortion mitigation of the above Examples and Comparative Examples was measured by an alternating gradient force magnetometer (AGM). FIGS. 2 and 3 show magnetization-applied magnetic field (M-H) curves measured by applying a magnetic field in the horizontal and vertical directions to a living body for magnetic resonance image distortion relaxation of the above-described embodiment and comparative example. Figs. 4 and 5 show the magnetic susceptibilities obtained from the M-H curves of Figs. 2 and 3.

FIGS. 2 and 3 show that the vertical and horizontal magnetizations of the graft-coated NiTi substrates of Examples 1 and 2 have lower values compared to the vertical and horizontal magnetizations of the NiTi substrate of Comparative Example 1. FIG. 4 and 5, it can be seen that the magnetic susceptibility is reduced by coating the biomaterial of the magnetic material with graphene, which is a semi-magnetic material.

More specifically, as shown in FIG. 4, the horizontal magnetic susceptibility of the NiTi base material of Comparative Example 1 is 278.8 10 -6 . However, the horizontal magnetic susceptibility of the NiTi substrate of Example 1 was 115.6 x 10 &lt; -6 &gt; The horizontal magnetic susceptibility of the NiTi base material of Example 2 is 197.2 x 10 &lt; -6 & gt ;. Further, as shown in Fig. 5, the perpendicular magnetic susceptibility of the NiTi base material of Comparative Example 1 is 81.6 x 10 &lt; -6 & gt ;. However, the perpendicular magnetic susceptibility of the NiTi base material of Example 1 is 69.6 x 10 &lt; -6 &gt; The perpendicular magnetic susceptibility of the NiTi base material of Example 2 is 48.9 × 10 -6 .

Therefore, it can be seen that the method of coating the graphene on the NiTi substrate greatly reduces the magnetic susceptibility of the NiTi, thereby reducing the magnetic susceptibility difference with the living body, thereby greatly alleviating the MR image distortion.

110: material for stent, implant or catheter, 120: diamagnetic coating layer, 130: biocompatible surface modifying layer

Claims (11)

  1. (1) forming a semi-magnetic coating layer containing a carbonaceous or Bi element on a surface of a material for a stent, an implant or a catheter; And
    (2) forming a biocompatible surface modification layer on the semi-magnetic coating layer,
    Wherein the magnetic susceptibility of the material is reduced by 15% to 60% after the formation of the semi-magnetic coating layer on the surface of the material.
  2. The method according to claim 1,
    The method of claim 1, wherein the step (1) comprises forming the antiferromagnetic coating layer and transferring the antiferromagnetic coating layer to the surface of the material for the stent, the implant, or the catheter.
  3. The method according to claim 1,
    Wherein the material for the stent, the implant or the catheter further comprises a catalytic metal element after coating the catalytic metal on the surface of the material and forming the semi-magnetic coating layer.
  4. The method of claim 3,
    Wherein the catalyst metal comprises Ni, Pt, Cu, Pd or PdCo.
  5. The method according to claim 1,
    Wherein the material for the stent, the implant or the catheter is a magnetic material containing any one selected from the group consisting of a Ti-based alloy, a Co-based alloy, a Ni-based alloy, a Ni-based alloy, a Zr- Wherein the method comprises the steps of:
  6. The method according to claim 1,
    Wherein the carbonaceous material of the semi-magnetic body comprises any one selected from the group consisting of graphene, highly oriented pyrolytic graphite (HOPG), and carbon nanotubes.
  7. The method according to claim 1,
    Wherein the amount of the carbonaceous substance of the diamagnetic substance is 3 x 10 &lt; -4 &gt; mass% to 3 x 10 &lt; -1 &gt; mass%.
  8. The method according to claim 1,
    Wherein the amount of Bi of the diamagnetic material is 1.5 x 10 -2 to 1.5 mass%.
  9. delete
  10. The method according to claim 1,
    Wherein the biocompatible surface modification layer in step (2) comprises DLC (Diamond Like Carbon) and PDMS (Polydimethylsiloxane).
  11. A biomaterial for mitigating magnetic resonance image distortion produced by the method for producing a biological material for magnetic resonance image distortion relaxation according to any one of claims 1 to 8 and 10.

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100309485B1 (en) 1997-11-13 2002-02-19 코시 리치터 Multi-layered Metal Stent
US8029554B2 (en) 2007-11-02 2011-10-04 Boston Scientific Scimed, Inc. Stent with embedded material
KR101072825B1 (en) 2009-02-23 2011-10-14 한국과학기술연구원 Stent structure having diamond-like carbon film, surface coating method of the same, and surface coating device of the same

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KR101117712B1 (en) 2010-03-26 2012-02-24 삼성전자주식회사 Communication terminal for multiple standby and method for operating thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100309485B1 (en) 1997-11-13 2002-02-19 코시 리치터 Multi-layered Metal Stent
US8029554B2 (en) 2007-11-02 2011-10-04 Boston Scientific Scimed, Inc. Stent with embedded material
KR101072825B1 (en) 2009-02-23 2011-10-14 한국과학기술연구원 Stent structure having diamond-like carbon film, surface coating method of the same, and surface coating device of the same

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