KR101829371B1 - Zr-Si binary alloy compositions having low magnetic susceptibility and method of fabricating the same - Google Patents
Zr-Si binary alloy compositions having low magnetic susceptibility and method of fabricating the same Download PDFInfo
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- KR101829371B1 KR101829371B1 KR1020160020957A KR20160020957A KR101829371B1 KR 101829371 B1 KR101829371 B1 KR 101829371B1 KR 1020160020957 A KR1020160020957 A KR 1020160020957A KR 20160020957 A KR20160020957 A KR 20160020957A KR 101829371 B1 KR101829371 B1 KR 101829371B1
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- zirconium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
- A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
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- 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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/08—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces heated electrically, with or without any other source of heat
- F27B3/085—Arc furnaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/10—Details, accessories, or equipment peculiar to hearth-type furnaces
- F27B3/22—Arrangements of air or gas supply devices
Abstract
TECHNICAL FIELD The present invention relates to a zirconium-silicon binary alloy composition and a manufacturing method thereof, and more particularly, to a zirconium-silicon binary alloy composition capable of being used as an implant material because of its autonomous rate and a method for manufacturing the same.
According to the zirconium-silicon binary alloy composition and the manufacturing method thereof of the present invention, the magnetic susceptibility is very low, so that artificial defects on the image hardly occur during magnetic resonance imaging (MRI). Further, according to the zirconium-silicon binary alloy composition of the present invention, since it has an autocorrelation rate, it can be used as an implant material.
Description
TECHNICAL FIELD The present invention relates to a zirconium-silicon binary alloy composition and a manufacturing method thereof, and more particularly, to a zirconium-silicon binary alloy composition capable of being used as an implant material because of its autonomous rate and a method for manufacturing the same.
Metallic materials play an important role in the biomaterial industry because they exhibit excellent biochemical properties and stability in the disinfection and disinfection process. These metal materials are used in various industrial fields, and they are widely used for dental use, especially for oral implants. Materials such as gold, stainless steel, cobalt-chrome alloys, titanium alloys, etc., are currently well known metal materials for oral implants. Pure Titanium and Ti 6 Al 4 V alloys are the most widely used metals in the industry and these alloys have excellent corrosion resistance and high biocompatibility with bone and are currently used in dental implants, It is used as an amendment.
Recently, magnetic resonance imaging (MRI) has been widely used as medical image diagnostic technology and has become a very important diagnostic technique in orthopedic surgery and brain surgery. Medical image diagnostic technology uses radiographs to examine the function or anatomy of the body. MRI technology is used in hospitals to detect and track medical diagnoses and pathogens without exposing ionized radiation to the patient.
Dental implants are a modern procedure for oral cavities and trauma, and are used to reconstruct prosthetic defects. In these dental implants, attention is focused on the safety of patients, and there is a growing interest in the quality of the images in the use of MRI.
However, metal implant implants such as stainless steel, chromium-cobalt alloy, and titanium alloy used in dental implants are magnetized in strong magnetic field on MRI equipment, resulting in artificial defects on the image. The artificial defects in these images are closely related to the magnetic susceptibility, and artificial defects due to magnetic susceptibility are caused by metals in the body, namely, titanium, cobalt, and stainless steel.
Therefore, it is required to develop an implant alloy that does not cause artificial defects due to magnetic susceptibility in MRI diagnosis.
The inventors of the present invention completed the present invention by developing a zirconium (Zr) -silicon (Si) binary alloy composition and a manufacturing method thereof.
Accordingly, an object of the present invention is to provide a zirconium-silicon binary alloy composition having an autocorrelation rate and being used as an implant material.
Another object of the present invention is to provide a process for producing a zirconium-silicon binary alloy having a rate of autolysis.
The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.
To achieve the above object, an embodiment of the present invention provides a zirconium-silicon binary alloy composition having a sacrificial rate including 0.5-10% by weight of silicon (Si) and the balance of zirconium (Zr).
In a preferred embodiment, the zirconium-silicon binary alloy composition having a rate of autolysis is composed of a Zr phase and a two-phase structure of SiZr 2 phase.
In a preferred embodiment, the zirconium-silicon binary alloy composition having a rate of autolysis has a certain degree of magnetization in the range of 1 x 10 -8 to 1 x 10 -6 cm 3 g -1 .
In a preferred embodiment, the zirconium-silicon binary alloy composition comprising 5% by weight of silicon (Si) and the balance zirconium (Zr) has a susceptibility of 1 x 10 -7 cm 3 g -1 .
According to another aspect of the present invention, there is provided an implant material for use in an implant having the zirconium-silicon binary alloy composition.
In order to accomplish the above object, another embodiment of the present invention is a method for manufacturing a biaxially oriented silicon steel sheet, comprising: a dissolving step of dissolving a raw material in an arc melting furnace so as to obtain a zirconium-silicon binary alloy containing silicon in a range of 0.5-10 wt%; And a casting step of casting the molten metal to obtain an ingot. The present invention also provides a method for manufacturing a zirconium-silicon binary alloy having an autogenous rate.
In a preferred embodiment, the dissolving process is carried out in an arc furnace with a water-cooled copper crucible in an argon atmosphere.
In a preferred embodiment, the zirconium-silicon binary alloy comprises a Zr phase and a SiZr 2 phase two-phase structure.
In a preferred embodiment, the zirconium-silicon binary alloy has a certain degree of magnetization in the range of 1 × 10 -8 to 1 × 10 -6 cm 3 g -1 .
The present invention has the following excellent effects.
First, according to the zirconium-silicon binary alloy composition of the present invention and the manufacturing method thereof, the magnetic susceptibility is very low, so that artificial defects on the image hardly occur during magnetic resonance imaging (MRI) photographing.
Further, according to the zirconium-silicon binary alloy composition of the present invention, since it has an autocorrelation rate, it can be used as an implant material.
1 is a phase diagram of a zirconium-silicon binary alloy composition according to an embodiment of the present invention,
2 is a photograph showing a microstructure of a zirconium-silicon binary alloy according to an embodiment of the present invention,
3 is an XRD analysis image of a zirconium-silicon binary alloy according to an embodiment of the present invention.
4 is a graph showing the change in the susceptibility of a zirconium-silicon binary alloy according to the amount of silicon added.
Although the terms used in the present invention have been selected as general terms that are widely used at present, there are some terms selected arbitrarily by the applicant in a specific case. In this case, the meaning described or used in the detailed description part of the invention The meaning must be grasped.
Hereinafter, the technical structure of the present invention will be described in detail with reference to preferred embodiments shown in the accompanying drawings.
However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals designate like elements throughout the specification.
The zirconium-silicon binary alloy composition according to the present invention is a zirconium-silicon binary alloy containing silicon (Si) in a range of 0.5 to 10% by weight and the remainder being composed of zirconium (Zr) .
The zirconium-silicon binary alloy composition according to the present invention is composed of a Zr phase and a SiZr 2 phase two-phase structure and has a very low magnetic susceptibility. The composition is in the range of 1 × 10 -8 to 1 × 10 -6 cm 3 g -1 . Since the zirconium-silicon binary alloy composition according to the present invention has a very low rate of artificialization, artificial defects occurring on the image during MRI photography are negligibly small and can be used as a dental implant material.
FIG. 1 is a phase diagram of a zirconium-silicon binary alloy composition according to an embodiment of the present invention. In the present invention, a binary alloy of zirconium and SiZr 2 was noted.
The Zr-based alloy has characteristics of being biocompatible and non-toxic. Since Si is well known as an antiviral material and particularly has a low magnetic susceptibility, in the present invention, the Zr-Si binary alloy is subjected to arc casting The possibility of Studies have shown that amorphous Zr-Si binary alloys are present when 12 to 25 at.% Silicon (Si) is included, and these amorphous phases have been reported to have superconducting properties.
Therefore, in the present invention, binary alloys of Zr-xSi (x = 0, 1, 3, 5, 7, 9 wt.%) Were produced to avoid the formation of an amorphous alloy having superconductivity.
At this time, various methods can be used as a method of producing a Zr-Si binary alloy, but an arc melting method is used in the present invention. First, a molten metal is obtained through a dissolving process in which a raw material is dissolved in an arc melting furnace so as to become a zirconium-silicon binary alloy containing silicon (Si) in a range of 0.5-10 wt%, and then the molten metal is cast to obtain an ingot Zirconium-silicon binary alloys with autonomous rates can be produced through appropriate processing steps such as cutting, polishing, and etching.
[Example]
Zr-Si binary alloys were prepared by arc melting method using Zr (99.9 wt.%) And Si (99.99 wt.%). At this time, the Zr-Si binary alloy was prepared by adjusting the weight percent of Si to 0, 1, 3, 5, 7, and 9 weight%, respectively. The ingot of the alloy was prepared to about 60 g, and an ingot was produced by using a water-cooled copper crucible in an argon (Ar) atmosphere arc melting furnace. Each ingot was inverted seven times so that alloying elements were homogeneously dissolved.
For the analysis of the microstructure of the Zr-Si binary alloy, the part to be used as the alloy specimen in the ingot was cut (length 7 mm, width 5 mm,
FIG. 2 is a photograph showing the microstructure of a zirconium-silicon binary system alloy according to an embodiment of the present invention, FIG. 3 is an XRD analysis image of a zirconium-silicon binary system alloy according to an embodiment of the present invention, Of the zirconium-silicon binary system alloy according to the addition amount of the zirconium-silicon binary system alloy.
At this time, the surface microstructure of the alloy specimen was observed using an optical microscope (OM, Zeiss: Axio Vert. A1), and the elemental analysis for each phase was performed using an electron probe microanalyzer (EPMA, Shimadzu: 1600) Respectively. The crystal structure of the alloy specimen was analyzed by phase analysis using an X-ray diffractometer (XRD, Rigaku: X'pert PRO MPD). Diffraction peaks were obtained at 40 kV and 30 mA of single crystal Cu-Ka . The bulk density of the alloy specimen was measured according to ASTM C20-78 using a density meter (Matsuhaku: MH-124S). Finally, the magnetic hysteresis curve was measured using a magnitude sample flux meter (VSM, Lake shore: 74046). The induction voltage was obtained by a pick - up coil attached to the electromagnet in proportion to the magnetic moment of the alloy specimen. The hysteresis curve was obtained by measuring the induced magnetic field at the external electromagnetic field, and the magnetic susceptibility of each alloy specimen was measured.
FIG. 2 (a) shows a typical single-phase α-Zr phase of pure Zr, which shows a basket shape and layered lamellar microstructure.
Fig. 2 (b) shows the microstructure of the Zr-1 wt% Si alloy specimen. When 1 wt% of silicon is added to pure Zr, no basket structure is observed, and a typical cast structure, dendrite structure .
FIG. 2 (c) shows the microstructure of the Zr-3 wt% Si alloy specimen. As 3 wt% of silicon is added to pure Zr, the SiZr 2 structure appears locally while maintaining the dendrite structure Thus, the two-phase structure became clearer. In other words, it can be seen that the SiZr 2 phase appears as a bright color and the α-Zr phase appears as a dark part.
2 (d) shows the microstructure of the Zr-5 wt% Si alloy specimen. It can be seen that the SiZr 2 phase, which is shown by adding 5 wt% of silicon to pure Zr, is remarkably increased in size and exists as a large plate. Therefore, it can be confirmed that two-phase organization is evident.
2 (e) and 2 (f) show the microstructure of Zr-7 wt% Si alloy specimen and Zr-9 wt% Si alloy specimen, respectively. It can be seen that the large SiZr 2 phase, which has appeared with the addition of silicon, is significantly smaller in size and finely distributed throughout the matrix as a whole.
On the other hand, the chemical composition of the SiZr 2 phase analyzed by the wavelength dispersive spectroscope was analyzed to be 86.2 Zr 13.8 Si mol%, which indicates that the above results are also very consistent in composition.
Referring to FIG. 3, it can be seen that only the diffraction peaks corresponding to the α-Zr phase are observed in the pure Zr to which no silicon is added, and the Sir 2 diffraction peaks become more apparent as the silicon is added. Also, the intensity of the SiZr 2 diffraction peak was also greatly increased.
Referring to FIG. 4, it can be seen that the susceptibility to pure zirconium is very similar to the previously reported magnetic susceptibility (10 -6 cm 3 g -1 ).
On the other hand, the susceptibility of Zr-1wt% Si alloy specimen decreased by about 35% compared with that of pure zirconium, and the susceptibility of Zr-1wt% Si alloy specimen decreased with increasing of silicon. , Respectively. As can be observed from the microstructure, it was judged that the susceptibility was greatly reduced as the SiZr 2 process phase was elongated with the addition of silicon.
In Zr-7wt% Si alloy specimen and Zr-9wt% Si alloy specimen, the SiZr 2 phase was finely distributed in the matrix and the magnetic susceptibility was slightly increased, but the magnetic susceptibility was also very low at 10 -7 cm 3 g -1 .
That is, it can be seen that the susceptibility of a Zr-Si binary alloy containing 1 to 10 wt% of silicon has an extremely low rate of about 10 -7 cm 3 g -1 . By using such an alloy having an extremely low rate, When used, artificial defects appearing on images of MRI images are negligible enough to be negligible.
On the other hand, when compared with the magnetic susceptibility of CoCrMo and Ti 6 Al 4 V, which is mainly used as an implant material, the susceptibility of a Zr-Si binary alloy containing 1 to 10 wt% of silicon is remarkably low (about 1 / 10) can be known.
Both diamagnetic and paramagnetic materials can be called nonmagnetic, and they are magnetized only in the presence of an external magnetic field. Silicon, an alloying element, is a typical semi-magnetic material exhibiting very weak magnetic properties. It exhibits non-permanent magnetic characteristics that persist only when an external magnetic field is applied. The magnitude of the induced magnetic moment is very small and its direction is opposite to the magnetic field direction.
On the other hand, zirconium (Zr) is a typical paramagnetic material. These are irregular if the direction of the magnetic moment of the atoms does not exist in the external magnetic field, and the magnitude of the induced magnetic moment is also quite low.
The magnetic properties of biotissue show the intermediate characteristics of the half body and the paramagnetic body. The magnetic susceptibility of living tissues is about -9.05 ppm, and Zr, Mo, Ti, Cr and Nb (typical paramagnetic materials), which are most commonly used metal alloying elements, have a magnetic susceptibility of about 10 -4 cm 3 g -1 to be. However, these metal-based biomaterials are very high compared to the susceptibility of living tissue, so that the difference is still large.
Silicon is a typical semi-magnetic material with a very low magnetic susceptibility of about -4.2 ppm, which is almost similar to that of human tissue. Therefore, in the embodiment of the present invention, a Zr-Si binary alloy made of a paramagnetic material and a semi-magnetic material was designed and manufactured. In conclusion, the embodiment of the present invention successfully fabricated a Zr-Si alloy having a very low magnetic susceptibility close to that of a living body, and thus it is possible to substitute a metal-made implant material for artificial bonding at the present time in most MRI examinations And
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, Various changes and modifications will be possible.
Claims (9)
Zr phase and a two-phase structure of SiZr 2 phase. 2. The zirconium-silicon binary alloy composition according to claim 1 ,
And a casting step of casting the molten metal to obtain an ingot,
Wherein the zirconium-silicon binary alloy has a susceptibility of 1 x 10 < -7 > cm < 3 > g < -1 & gt ;.
Wherein the dissolving step is carried out in an arc melting furnace having a water-cooled copper crucible in an argon atmosphere.
Wherein the zirconium-silicon binary system alloy is composed of a Zr phase and a SiZr 2 phase two-phase structure.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002512542A (en) | 1997-06-10 | 2002-04-23 | インスティトゥート・シュトラウマン・アーゲー | Titanium-zirconium binary alloy for surgical implant and method for producing the same |
| US20080071347A1 (en) * | 2006-09-15 | 2008-03-20 | Boston Scientific Scimed, Inc. | Medical devices having alloy compositions |
| JP2010075413A (en) | 2008-09-25 | 2010-04-08 | Seiko Epson Corp | Metallic biomaterial and medical device |
| JP2014077152A (en) * | 2012-10-09 | 2014-05-01 | Tohoku Univ | Zr ALLOY AND ITS MANUFACTURING METHOD |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002512542A (en) | 1997-06-10 | 2002-04-23 | インスティトゥート・シュトラウマン・アーゲー | Titanium-zirconium binary alloy for surgical implant and method for producing the same |
| US20080071347A1 (en) * | 2006-09-15 | 2008-03-20 | Boston Scientific Scimed, Inc. | Medical devices having alloy compositions |
| JP2010075413A (en) | 2008-09-25 | 2010-04-08 | Seiko Epson Corp | Metallic biomaterial and medical device |
| JP2014077152A (en) * | 2012-10-09 | 2014-05-01 | Tohoku Univ | Zr ALLOY AND ITS MANUFACTURING METHOD |
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