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    • 专利摘要:
    The present invention by providing a method for improving the corrosion resistance of the dental magnetic attachment material used in the oral cavity by sputter plating by selecting any one of gold, platinum, titanium, chromium and cobalt directly on the surface of the dental magnetic material It is possible to provide a dental magnetic attachment material having a much longer life expectancy than conventional dental magnetic attachment materials.
    公开号:KR20020024639A
    申请号:KR1020000056395
    申请日:2000-09-26
    公开日:2002-04-01
    发明作者:최한철；고영무；정재헌
    申请人:최한철；정재헌；고영무；
    IPC主号:
    专利说明:

    Improvement method for corrosion resistance of dental magnetic materials {Improvement method of corrosion resistance for dental magnetic materials}
    [1] The present invention relates to a method of improving the corrosion resistance of a dental magnetic material, and more particularly, to a method of having a better corrosion resistance in the oral cavity by sputter plating metal surface of the dental magnetic material used as a magnetic attachment material in dentistry. .
    [2] Since dental magnetic materials were first introduced for the maintenance of prostheses, various clinical applications such as overdenture, removable local dentures, maxillofacial prostheses, obturators, implants, and orthodontic areas have been attempted. However, the dental magnetic material may have various problems in a special environment such as oral cavity, and corrosion is particularly reported as the most important problem. In other words, due to corrosion, the weight loss of the samarium-cobalt based magnets is not only large in 1% lactic acid and 0.05% HCl, but the rare earth magnets are easy to oxidize, and the neodymium-iron-boron series (Nd-Fe-) B based) According to the corrosion and corrosion between the magnet and the samarium-cobalt-based magnet, the permanent magnet has low corrosion resistance to saliva in the oral cavity. Once it is corroded, the magnetic force is rapidly decreased by demagnetization, and the samarium-cobalt-based magnet is 1%. Sm and Co ions are eluted in the lactic acid and 0.05% HCl solution.
    [3] Therefore, in order to solve the above-mentioned discomfort, the magnetic surface is encapsulated in stainless steel, but it is difficult to use for small teeth by increasing the volume of the magnetic material, and the distraction force is reduced by increasing the distance from the holding device. Has
    [4] The present invention by providing a method for improving the corrosion resistance of the dental magnetic attachment material used in the oral cavity by sputter plating by selecting any one of gold, platinum, titanium, chromium and cobalt directly on the surface of the dental magnetic material An object of the present invention is to provide a dental magnetic attachment material having a much longer life expectancy than conventional dental magnetic attachment materials.
    [5] In order to achieve the above object, the present invention uses a radio frequency magnetron sputter to place a dental magnetic body on an anode and the target metal is fixed by sputtering the target metal on a cathode of a vacuum chamber. Corrosion resistance can be improved by sputter plating on the magnetic material.
    [6] Sputtering is a phenomenon in which ions with kinetic energy of several tens of keV or more are irradiated to a solid target to obtain a portion of the energy of the incident ions near the target surface and released into the air separated from the surface of the target. This is caused by the collision between the high energy particles and the surface atoms emitted.
    [7] As the accelerated particles, ions, atoms, neutrons, electrons, or optoelectronics are used. Plating by sputtering is performed by the deposition of atoms or molecules emitted from a target through collisions with gases in the plasma.
    [8] In particular, the magnetron sputtering method is used to increase the formation efficiency of ions, and to increase the rate of formation of the thin film by increasing the rate at which the sputtered atoms in the target are scattered by the atoms of the discharge gas to reach the substrate.
    [9] In addition, the present invention used a samarium-cobalt-based (Sm-Co based) magnetic material and a neodymium-iron-boron-based (Nd-Fe-B based) magnetic material, which is currently used as the most dental magnetic material, gold (Au) , Platinum (Pt), titanium (Ti), chromium (Cr) and cobalt (Co) were used as target metals.
    [10] Hereinafter, the present invention will be described in detail by way of examples.
    [11] Radio wave magnetron sputter (RFMS, DVSE-43T, Daeryung Vacuum Co. Ltd., Seoul, Korea) was used for sputtering plating of magnetic magnetic materials. Gold (Au), platinum (Pt), titanium ( Ti), chromium (Cr) and cobalt (Co) targets were fixed, and the samarium-cobalt-based and neodymium-iron-boron-based magnetic substrates were fixed to the anode.
    [12] Next, the exhaust gas was exhausted for 15 to 20 minutes with a rotary pump and 45 to 60 minutes with a diffusion pump, and when the desired degree of vacuum was reached, argon gas was injected under the control using a mass flow controller. Raise the radio wave power (RF power) to form a plasma. At this time, the main valve was adjusted to easily form the plasma to adjust the base pressure to 9 × 10-6 Torr, and after the plasma was stabilized, the pressure was controlled by slowly opening the main valve. Before sputtering, preliminary sputtering was performed for 3 minutes, and then the shutter was opened for 6 minutes.
    [13] At this time, the dental magnetic material specimen was obtained by the following method.
    [14] Use a samarium-cobalt based magnetic material and a neodymium-iron-boron based magnetic ingot, and after demagnetization, cut with a diamond wheel to cut 7 mm × 7 mm. A specimen having a size of 1 mm was prepared. The cut specimens were polished in the order of # 1,000, # 1200, # 1,500, # 2,000 and # 2,400 using a silicon carbide polishing cloth, and after final polishing with 0.1 m Al2O3 powder, washed with an ultrasonic cleaner and dried. Before sputtering the magnetic material, demagnetization was performed with a magnetizer (着 磁器, magnetizier, Magnet-physik, Munchen, Germany). In the case of a magnetized magnetic material, sputtering plating of the metal prevented the interference. Because I receive. After sputtering plating was remagnetized and washed with alcohol.
    [15] Sputtering conditions of the target metals are shown in Table 1 below.
    [16]
    [17] Table 2 shows the coded types of each specimen.
    [18] CodeScSm-Co Dental Magnetic Materials without Sputtering Plating SAuSm-Co Dental Magnetic Materials with Au Sputter Plating SPtSm-Co Dental Magnetic Materials with Pt Sputtering Plating STiSm-Co Dental Magnetic Materials with Ti Sputtering Plating SCrSm-Co Dental Magnetic Materials with Cr Sputter Plating SCoSm-Co Dental Magnetic Materials with Co Sputtering Plating NdNd-Fe-B Dental Magnetic Materials without Sputtering Plating NAuNd-Fe-B Dental Magnetic Materials with Au Sputter Plating NPtNd-Fe-B Dental Magnetic Materials with Pt Sputtering Plating NTiNd-Fe-B Dental Magnetic Materials with Ti Sputtering Plating NCrNd-Fe-B Dental Magnetic Materials with Cr Sputter Plating NCoNd-Fe-B Dental Magnetic Materials with Co Sputtering Plating
    [19] The specimens were analyzed by the following method.
    [20] 1. Surface observation and composition analysis of magnetic materials
    [21] Surfaces were observed by scanning electron microscopy (SEM) and metal microscopy, and the composition was X-ray diffractometer (XRD) and energy dispersive X-ray spectroscopy (EDX). Analyze using.
    [22] As a result, the surface of the Sm-Co-based magnetic material observed by scanning electron microscopy (SEM) showed almost no grain boundary phase, whereas the Nd-Fe-B-based magnetic material had a Nd2Fe14B phase of about 10 µm in diameter. It consisted of Nd rich phase.
    [23] X-ray diffractometer and energy dispersive X-ray spectroscopy showed that the composition of the specimens was Sm-Co magnetic material, Sm 29.9%, Co 52.2%, Fe 14.1% and Cu 3.8%, Nd-Fe-B magnetic Ash was composed of 37.5% Nd and 62.5% Fe.
    [24] 2. Electrochemical Corrosion Test
    [25] After the magnetization, 700 ml of four electrolytes (0.9% NaCl, 1% lactic acid, 0.05% HCl, Modified Fusayamas artificial saliva) were placed in a polarization test container with a capacity of 1,000 ml. After connecting to the device, the saturated calomel electrode (SCE) was used as the standard electrode, and the distance between the specimen and the reference electrode was adjusted to about 1 mm, and the counter electrode was made of a high density carbon electrode. It was.
    [26] In order to obtain an anodic polarization curve, the potential is applied from -1,500 ㎷ (SCE) to +1,000 ㎷ (SCE) at a scanning rate of 1.25 ㎷ / sec using the coincidence method in an electrolyte solution of 37 ± 1 ° C. The secondary electrochemical corrosion test was performed and the specimen and electrolyte were exchanged every time. The X axis represents the logarithm of the current density and the Y axis represents the potential. Subsequently, the same specimen was subjected to secondary electrochemical corrosion by applying an electric potential of 1,000 mA artificially for 10 minutes.
    [27] As a result, the Sm-Co-based magnetic material in the 0.9% NaCl solution showed the current density increased to the right in the case of the control Sc specimen, but the polarization curves of the SAu, SPt, SCr, and SCo specimens shifted to the left. Showed a tendency to decrease.
    [28] From the polarization curve, Nd-Fe-B-based magnetic material tends to have lower corrosion potential than Sm-Co-based magnetic material and is severely eroded by Cl- because it does not form a passivation film on its surface.
    [29] In addition, in the 1% lactic acid solution, the Sm-Co-based magnetic material showed that all the curves were shifted to the left than in the 0.9% NaCl solution. In the polarization curve, in 1% lactic acid (C3H6OH3) solution, the passivation film was formed, and the film was destroyed by COOH- again, and the corrosion product was formed on the surface.
    [30] In the Nd-Fe-B-based magnetic material, the corrosion potential of NPt2 was high as -528㎷ and low as -647㎷ for Nd2. In all specimens, the plated film suddenly collapsed and the current density increased to nearly 1.0 × 10-2 A / cm2, showing corrosion on the front surface. At 500 mA, the current density of NTi2 and NPt2 was the lowest at 7.0 × 10-3 and 9.0 × 10-3A / cm2, respectively, and Nd2 was increased to 2.0 × 10-2.
    [31] In the 0.05% HCl solution, the Sm-Co-based magnetic material was on the left side rather than the 0.9% NaCl solution, but showed the same polarization form as the 0.9% NaCl solution.
    [32] The Nd-Fe-B-based magnetic material showed a much more polarized polarization curve than the 0.9% NaCl or 1% lactic acid solution, which greatly reduced the corrosion resistance of all specimens. Corrosion potentials of NAu3 and NPt3 were -679㎷ and -648 높게, and Nd3 showed -682㎷, and, like 0.9% NaCl solution, did not form passivation film in solution containing Cl-. The corrosion rate obtained from the Tafel analysis was also higher than that of other solutions. At 500 ㎷, the current density value was the smallest at 1.5 × 10-2A / ㎠ and NPd3 was 2.0 × 10-1A / ㎠ at Nd3. .
    [33] In the modified Fusayama, s artificial saliva solution, the Sm-Co-based magnetic material showed better corrosion resistance as the polarization curve shifted to the left than the 0.05% HCl solution. However, although slightly to the left of the 1% lactic acid solution, the corrosion resistance was decreased due to the lowering of the official potential and the corrosion potential.
    [34] Nd-Fe-B-based magnetic material exhibited better corrosion resistance due to a lower current density than the polarization curve of 0.05% HCl, and a passivation zone. The corrosion potential of NAu4 was high at -550㎷ and Nd4 was lowest at -752㎷. The official potential of Nd4 was the lowest at -600㎷, and the current density at 500㎷ was the lowest for NAu4, NPt4, NCo4, and Nd4 showed the highest value of 3.5 × 10-2A / ㎠.
    [35] 3. Quantitative analysis of eluted elements
    [36] Samarium-Cobalt-based spectroscopy using inductively coupled plasma emission spectroscopy (ICP, Model: 38 plus, Jobin Yvon Co., Paris, France) to measure the amount of eluted element due to electrochemical corrosion Au, Pt, Ti, Cr, and Co were quantitatively analyzed for Sm and Co, the main components of the material, and Nd, Fe, and B, the main components of the neodymium-iron-boron-based magnetic material.
    [37] As a result, Sm-Co-based magnetic materials were eluted with Sm and Co as the main components. Especially, the dissolution amount of Sm was 57.321 and 60.692 ppm / ㎠ in Sc1 and Sc3, and the amount of Co was 282.349 and 167.692 ppm / ㎠ in Sc1 and Sc3. The more, the less sputter plated magnetic material eluted the amount of eluted element than the unsputtered magnetic material.
    [38] In the Nd-Fe-B-based magnetic material, Nd and Fe were eluted, especially the amount of Nd eluted was 148.3 and 146.5 ppm / cm2 in Nd1 and Nd3, and the amount of Fe was 1312.4 and 3569.4 ppm / cm2 in Nd1 and Nd3. Many also showed similar results with Sm-Co-based magnetic materials. Among the four electrolytes, the amount of elements eluted in 0.9% NaCl and 0.05% HCl solution was high.
    [39] 4. Measurement of magnetic flux density
    [40] Before the corrosion test of 12 specimens, the magnetic strength was measured using a magnetic field meter (Gaussmeter, FW Bell, series 9900, New York, USA), and the specimens were subjected to electrochemical primary corrosion in four electrolytes under given conditions. The magnetic flux density was measured, and after the secondary corrosion, the magnetic strength was measured and divided by the area of the specimen to determine the change of magnetic flux density due to corrosion. The magnetic flux density represents the strength of the magnetic force and means the number of magnetic force lines per unit area.
    [41] As a result, the value of the changed magnetic flux density decreased more than that of the sputter-plated test group (p <0.05). As a result of observing the change of magnetic flux density in the sputter-plated test group, the magnetic flux density was statistically significant than that of the sputter-plated test group. There was a decrease.
    [42] 5. Surface roughness measurement
    [43] In order to compare the surface roughness caused by corrosion in 12 specimens, the surface roughness and primary corrosion of the specimens before the corrosion test were tested using a surface roughness measuring instrument (Surfcorder SE 1700, Kosaka lab. Ltd., Tokyo, Japan). The surface roughness after making it was measured. The stylus of the surface roughness tester moved in a straight line across the center of the specimen surface, and averaged surface roughness (Ra), average peak-to valley height (Rz) (DIN Standard 4768). , 1974) and the maximum peak-to valley height (Rmax) at the top of the curve were measured at 10 locations on a given curve.
    [44] As a result, when comparing the average value of surface roughness (Ra) of the specimens due to the corrosion effect, the surface roughness increased after corrosion in all cases, especially in Sc, STi, SCo, Nd, Nd3 and NCr. (P <0.05).
    [45] 6. Measurement of surface microhardness
    [46] Twelve specimens were subjected to surface corrosion before and after primary corrosion and secondary corrosion in four electrolytes, using a surface microhardness tester (Vicker, s hardness tester, Wilson, New York, USA). The Vickers hardness value (VHN) was calculated using a load of 100 g, a load time of 30 seconds, and a load speed of 50 µm / sec, and the surface microhardness difference was compared.
    [47] As a result, the change in hardness after primary corrosion was small in SAu and relatively large in Sc and Nd. The change of hardness after the secondary corrosion was the largest in Nd, and SAu and SPt showed the smallest decrease in surface microhardness.
    [48] 7. Observation of corrosion surface
    [49] Twelve specimens were observed with a metallurgical microscope (Olympus, Tokyo, Japan) to investigate changes in metal structure due to corrosion after primary corrosion in four electrolytes.
    [50] As a result, Sc showed that a lot of formulas were formed in the site where pores existed, and the grain boundary had a lot of corrosion.
    [51] Nd was much more corroded than the Sm-Co-based magnetic material, indicating that the corrosion resistance was low. In particular, the presence of Nd rich phases at the grain boundaries showed that the grain boundaries were severely destroyed by chemical concentration gradients. In particular, unlike Sm-Co-based magnetic materials, the color of the specimen surface is red because the eluted Fe forms iron oxides such as Fe2O3, Fe3O4, and Fe (OH) 3, and not only Cl-containing solutions. Severe corrosion was also seen in the 1% lactic acid solution.
    [52] SAu was found to be found a lot of large formula in Cl- containing solution. However, a gold plated film formed a formula, which was thought to be due to the presence of pores, which were easily eroded by Cl-.
    [53] NAu is less corroded than Nd, and when NAu is corroded in 0.05% HCl solution (NAu3), the photograph shows gold-plated and non-plated site corrosion behavior. there was. Even in the gold-plated area, the pore area has been shown to act as a formula.
    [54] SPt showed the same corrosion pattern as SCr. When SPt was corroded in 0.9% NaCl solution, corrosion occurred on the front surface and many formulas were shown.However, when SPt was corroded in 1% lactic acid solution, pores and grain boundaries in the material were preferentially corroded, but SPt was 0.9 Unlike the corrosion test in the% NaCl solution, it was well coincided with the presence of the non-corrosive surface on the SPt polarization to form the passivation film.
    [55] Also, when SPt was corroded in 0.05% HCl solution, it was corroded with a large formula, and even when SPt was corroded in modified artificial saliva, the coating was covered and some parts were severely corroded.
    [56] NPt was found in a large amount of the formula between the films in the 0.9% NaCl solution in the state that the plated film has not yet peeled off. The amount of iron oxide formed in the Cl-containing electrolyte was higher than that in 1% lactic acid, and the corrosion was severe.
    [57] It was found that STi was highly corrosive in Cl- containing solution, but corrosion resistance was so high that only grain boundary was corroded in 1% lactic acid solution, and the surface of the specimen appeared when Ti was corroded. Could. As shown in the white part covered with Ti, STi corroded to the modified saliva shows that the formula is formed in the film and many corrosion products are formed.
    [58] NTi showed a surface color that appeared when Ti was added even at 1% lactic acid, indicating that a stable film was formed.
    [59] SCr showed a severe corrosion pattern in Cl- containing solution, but SCr corroded in 1% lactic acid solution tended to be resistant to corrosion.
    [60] NCr also showed a reddish surface by Fe oxidation in Cl- containing solutions but different corrosion patterns in 1% lactic acid solution. In the 0.05% HCl solution, many large formulas showed that the corrosion was severe.
    [61] SCo was correlated well with the results of low current density or formula potential of the 0.05% HCl solution mentioned above. In the case of corrosion test in modified artificial saliva, many corrosion products were formed on the surface, which showed that the corrosion resistance was greatly reduced, but it was not. In fact, it was found that the grain boundary and the mouth were significantly eroded in 1% lactic acid solution and 0.05% HCl solution.
    [62] As such, the present invention is a group in which sputter-plated gold, platinum, titanium, chromium and cobalt are coated on the surface of the Sm-Co-based magnetic material and Nd-Fe-B-based magnetic material mainly used in dentistry. Electrochemical corrosion in four electrolytes (0.9% NaCl, 1% lactic acid, 0.05% HCl, modified Fusayama, s artificial saliva) using as a control group, their corrosion patterns, the amount of eluted elements, magnetic flux density, surface roughness As a result of observing the surface microhardness and metal surface, the control group had lower formal potential than the plating group, which caused more corrosion. In the plating group, the amount of elemental leaching was significantly decreased (p <0.05) in all corrosion solutions.
    [63] The decrease in magnetic flux density was significantly lower in the same plating solution than the control group after the first corrosion (p <0.05), and the decrease in the magnetic flux density was increased in all the test groups after the second corrosion.
    [64] In addition, the surface roughness of the plating group was not different from that of the control group. After corrosion, the Sm-Co-based magnetic material increased the most in the modified saliva solution and the Nd-Fe-B-based magnetic material increased the most in the 0.05% HCl solution. It was.
    [65] The surface microhardness of the pre-corrosion plating group was not different from that of the control group, and the surface microhardness after corrosion was decreased in all the test groups, the control group was more reduced than the plating group and the secondary corrosion was more than the primary corrosion. Erosion occurred and corrosion occurred all over the surface. In the plating group, only the locality of the pores existed, and the surface of the dental magnetic material was sputtered with gold, platinum, titanium, chromium, and cobalt. It was concluded that corrosion can be significantly reduced.
    [66] As described above, by sputtering plating gold, platinum, titanium, chromium and cobalt on the surface of the dental magnetic material by the method of the present invention, the corrosion resistance in the oral cavity can be remarkably improved and the life can be prolonged significantly. The magnetic magnetic attachment material is to have an effect that can be provided to users.
    权利要求:
    Claims (2)
    [1" claim-type="Currently amended] Method for improving the corrosion resistance of dental magnetic materials characterized by improving the corrosion resistance by sputter plating by selecting any one of gold, platinum, titanium, chromium and cobalt on the surface of the magnetic material used as dental magnetic attachment material .
    [2" claim-type="Currently amended] The method of claim 1, wherein the dental magnetic material is selected from one of a samarium-cobalt-based magnetic material and a neodymium-iron-boron-based magnetic material.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-09-26|Application filed by 최한철, 정재헌, 고영무
    2000-09-26|Priority to KR1020000056395A
    2002-04-01|Publication of KR20020024639A
    优先权:
    申请号 | 申请日 | 专利标题
    KR1020000056395A|KR20020024639A|2000-09-26|2000-09-26|Improvement method of corrosion resistance for dental magnetic materials|
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