KR101666672B1 - A method for preparation of metal alloy with nanostructured surface comprising heavy metal using selective plasma etching and use thereof - Google Patents
A method for preparation of metal alloy with nanostructured surface comprising heavy metal using selective plasma etching and use thereof Download PDFInfo
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- KR101666672B1 KR101666672B1 KR1020150053413A KR20150053413A KR101666672B1 KR 101666672 B1 KR101666672 B1 KR 101666672B1 KR 1020150053413 A KR1020150053413 A KR 1020150053413A KR 20150053413 A KR20150053413 A KR 20150053413A KR 101666672 B1 KR101666672 B1 KR 101666672B1
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- H—ELECTRICITY
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B1/001—Devices without movable or flexible elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
- B82B3/0014—Array or network of similar nanostructural elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
- B82B3/0019—Forming specific nanostructures without movable or flexible elements
Abstract
The present invention relates to (i) an alloy substrate capable of forming a surface of a desired shape of a heavy metal-containing nanostructure; And (ii) a first step of selecting reaction conditions for plasma etching using a heavy metal target; Applying a negative voltage to a heavy metal target in the presence of an inert gas and applying a negative voltage for bias to the alloy substrate using the alloy substrate and the plasma etching reaction conditions selected in the first step to form a heavy metal ion and an inert gas ion Containing nano-structured surface on the alloy substrate, wherein the nano-structured surface of the desired shape on the alloy substrate comprises a second step of forming a plasma that competitively generates etching and neutral metal atoms deposition The present invention relates to a method for producing an alloy substrate having a surface of a formed heavy metal-containing nanostructure and a use thereof.
Description
The present invention relates to (i) an alloy substrate capable of forming a surface of a desired shape of a heavy metal-containing nanostructure; And (ii) a first step of selecting reaction conditions for plasma etching using a heavy metal target; Applying a negative voltage to a heavy metal target in the presence of an inert gas and applying a negative voltage for bias to the alloy substrate using the alloy substrate and the plasma etching reaction conditions selected in the first step to form a heavy metal ion and an inert gas ion Containing nano-structured surface on the alloy substrate, wherein the nano-structured surface of the desired shape on the alloy substrate comprises a second step of forming a plasma that competitively generates etching and neutral metal atoms deposition The present invention relates to a method for producing a formed alloy substrate and its use.
In recent years, various new techniques have been developed for designing the surface roughness of a metal material to a nanometer level and finely adjusting the surface shape and characteristics to form a surface having a certain pattern of nanostructures such as nano pores, holes, or channels. This is because materials having nanostructures on the surface can not only provide a high specific surface area, but also have properties of being able to penetrate into pores of gases and / or liquids, Materials, and materials. Particularly, a material including a nanostructure on the surface has a possibility to maximize a biological reaction such as surface adsorption of a protein, surface attachment and proliferation of a cell while forming a direct correlation with a cell or tissues in the body. Due to the desirable properties and various potentialities exhibited by the nanostructures formed on the surface of such materials, studies are being conducted on processes that can introduce such structures into the surface of various metals.
Conventionally, lithography has been widely used as a method for manufacturing nanostructures on metal surfaces. This is a technique of copying a pattern by transferring a shadow generated when a light source of a specific wavelength passes through a mask called a mask of a desired pattern onto a metal surface. By processing only the portion exposed to the light source by a further chemical etching process, A nanostructure having a pattern can be produced. In addition, the nano imprint method is a method of replacing the role of a patterned mask in the lithography process with a stamp, contacting the metal surface with the stamp, and applying a condition such as pressure and / or heat to form a nano pattern .
However, since these methods are performed in a complicated manner including a multi-step process, it takes a long time to form a desired pattern, and it is not only economical to use expensive equipment and / or chemicals, There is a problem that flexibility of the process is deteriorated because only a nano pattern of the same type can be formed using a mask or a stamp.
On the other hand, as an electrochemical method for drastically increasing the surface area of a metal, a method of forming an nano-pore structure on a metal surface by applying an anodizing method is used. In the case of the anodic oxidation method, a nano unit pore structure is formed through the formation of an oxide film and the erosion action on a metal surface by applying a low voltage to a metal in an electrolytic solution containing a fluorine compound and phosphoric acid or sulfuric acid.
However, when the nano pores are formed by the anodic oxidation method, since the pores are formed by the erosion after forming the oxide layer on the metal surface, there is a problem that the nanopores are broken or the pore layer is easily removed due to the weak adhesion between the metal surface and the oxide layer , There is a disadvantage in that the formation of pores to be formed is fixed in a cylindrical shape.
In addition, it is known that ion-beam direct etching is the most effective method for forming various types of nanostructures on a metal surface by directly entering an ion beam on a metal surface. This is a principle in which an ion having a high energy is incident on a metal surface and the surface is etched by sputtering atoms on the metal surface. In this case, a pattern of a desired shape can be formed on the metal surface by controlling the incident ion beam in two dimensions. Such a method has excellent flexibility with respect to the pattern to be formed, but has disadvantages in that it is impossible to scale-up or make a large area because each pattern is formed one by one.
The present inventors have made intensive research to find a controllable method for introducing a desired patterned nanostructure onto various metal substrates including alloys. As a result, they have found that a selective plasma etching technique using heavy metals is used, By selectively etching the metal substrate and selecting a combination of conditions capable of forming a desired pattern of nanostructures, a selective etching process can be carried out by a competitive reaction of deposition and etching with a heavy metal, And thus the present invention has been completed.
It is an object of the present invention to provide a method for producing an alloy substrate on which an nano-structured surface of a desired shape is formed on an alloy substrate without an interface.
Another object of the present invention is to provide a composite metal structure in which a surface of a desired shape of a tantalum-containing nanostructure is formed on an alloy substrate without an interface.
According to one aspect of the present invention, there is provided a method of manufacturing an alloy substrate on which an nano-structured surface having a desired shape of a desired shape is formed on an alloy substrate without an interface.
(I) an alloy substrate capable of forming a surface of a heavy metal-containing nanostructure having a desired shape; And (ii) a first step of selecting reaction conditions for plasma etching using a heavy metal target; Applying a negative voltage to a heavy metal target in the presence of an inert gas and applying a negative voltage for bias to the alloy substrate using the alloy substrate and the plasma etching reaction conditions selected in the first step to form a heavy metal ion and an inert gas ion And a second step of forming a plasma that competitively generates etching of neutral heavy metal atoms by using the heavy metal having an atomic weight higher than that of at least one metal constituting the alloy substrate .
The present invention is based on the first finding that a desired pattern of nanostructures can be formed on the surface of the alloy substrate by selective plasma etching, by selecting suitable alloy substrates and heavy metals and suitable plasma etching reaction conditions. For example, when a nano structure containing a heavy metal is to be formed on a cobalt-chromium alloy, a heavy metal having an atomic weight higher than that of a metal constituting the chromium-cobalt alloy (Cr: 52.0, Co: 58.9) ) Is applied to the tantalum target so that a negative voltage in the range of 170 to 250 V, which is a voltage capable of generating tantalum atoms and / or ions, is applied to the tantalum target, and the thus formed tantalum atoms and / A nanostructure having a somewhat higher curvature close to a semicircular shape can be obtained by appropriately adjusting the reaction time by selecting a negative voltage higher than that applied to the heavy metal target, for example, in the range of 400 to 2000 V, Nano structures with a gentle curvature close to a straight line are superimposed from structures superimposed at intervals of several tens to several hundreds of nanometers The shape and / or size of the pattern to be formed was not selective confirmed that can be formed into.
The term "plasma" refers to a fourth state of a substance other than solid, liquid, and gas. When energy is applied to a gas, the molecule or atom loses or obtains electrons and becomes a plasma containing charged particles. That is, the plasma may include charged particles such as cations, and anions or electrons. Such a plasma may be generated by a strong electromagnetic field formed by a laser or a microwave generator or the like. Or by applying an electric field to the gas. "Plasma etching" is performed by a rapid flow of a suitable gas plasma, wherein the plasma source may be an ion or a neutral atom or radical.
In a specific embodiment of the present invention, in order to perform the selective plasma etching method, the chamber is first made to have a high degree of vacuum, and then a sputtering gas such as argon gas is supplied into the chamber to maintain a vacuum degree (about 10 -2 torr) necessary for sputtering Respectively. Next, a voltage of several hundred volts was applied to the alloy substrate to clean the surface, and then a voltage was applied to the tantalum target as a heavy metal to form tantalum atoms and ions in the plasma. At the same time, a negative voltage larger than a negative voltage applied to the heavy metal target was applied to the alloy substrate so that selective plasma etching could occur on the surface of the alloy substrate while heavy metal atoms or ions formed from the heavy metal target were accelerated toward the alloy substrate. Preferably, the voltage applied to the alloy substrate may be a negative voltage of 400 V or more. When the voltage applied to the metal substrate is a negative voltage of less than 400 V, it is not accelerated to the desired speed until it reaches the surface of the alloy substrate, since it is accelerated toward the alloy substrate surface and does not have sufficient energy to etch the ions The nanostructure may not be uniformly formed. On the other hand, when a voltage of 400 V or more is applied to the alloy substrate, ions in the surrounding plasma are accelerated strongly toward the surface of the alloy substrate and collide strongly to form a depression by etching to form a nanostructure.
The principle of forming the nanostructure on the surface of the alloy substrate by the selective plasma etching method of the present invention will be described in more detail as follows. The selective plasma etching method is an etching method that utilizes a phenomenon in which atoms of a material are strongly protruded when a material having a high atomic weight or a plasma is strongly collided against a material. In the selective plasma etching method, a heavy metal (e.g., Ta) The high-voltage ion beam is applied to the alloy substrate so as to induce a strong ion collision on the surface of the alloy substrate. When an appropriate negative voltage is applied to the heavy metal target under the above conditions, the inert gas (for example, Ar) filled to maintain a predetermined pressure in the chamber is ionized to become a positive ion (for example, Ar + ), The heavy metal atoms and the cations (for example, Ta 3 + , Ta 4 + ) are released by the impact.
At the same time, when a negative voltage higher than the voltage applied to the heavy metal target is applied to the alloy substrate, for example, a high negative voltage of 400 V or more is applied, the released heavy metal ions and the ions of the inert gas accelerate strongly to the surface of the metal substrate. On the other hand, the neutral heavy metal atoms are naturally deposited on the surface of the alloy substrate as they are released from the target, resulting in the rearrangement of heavy metal atoms on the surface due to the competitive deposition of heavy metal atoms and etching by ions. As a result of this rearrangement, the surface irregularities of the local heavy metal elements are generated, and the heavy metal ions selectively etch the surface having a relatively low content of the heavy metal element.
A target material of a heavy metal may be formed by etching a surface of an alloy substrate having a relatively low specific gravity by ion generated at the time of plasma generation and changing a shape at the surface while atoms formed together with the target are deposited on the surface to thereby change the chemical composition of the surface Lt; / RTI > Non-limiting examples of such heavy metals include tantalum (Ta), tungsten, rhenium, osmium, iridium, platinum and gold. Preferably, the heavy metal may be tantalum, but is not limited thereto. Since tantalum is highly corrosion-resistant and highly abrasion-resistant, it is a substance which is used variously in corrosion resistant materials such as batteries and electronic devices in itself or in the form of alloys, and in implants for implantation into the body or coatings thereof.
Preferably, the material of the alloy substrate is selected from the group consisting of aluminum, tantalum, niobium, vanadium, zirconium, tin, molybdenum, silicon, gold , Palladium, copper, platinum, and silver. However, the present invention is not limited thereto.
For example, the surface of the heavy metal-containing nanostructure may have a protruding portion and a depressed portion, and each of the protruding portion and the depressed portion may be independently continuous or discontinuous curved, straight, or a combination thereof. The shape of the nanostructure formed by the protrusions and depressions may be selected from the group consisting of 1) the type of the selected alloy substrate and / or the voltage applied thereto, 2) the size of the selected heavy metal target and / Can be determined according to the etching reaction time, and a desired pattern can be derived by controlling and appropriately combining these factors.
According to a specific embodiment of the present invention, the selective plasma etching method according to the present invention is applied to an alloy substrate of various materials. As a result, the protrusion and depression portions, which are different in shape depending on the material, It was confirmed that the nanostructure was formed on the surface (FIG. 2).
For example, the protrusions and depressions are formed by a competitive reaction between the deposition of heavy metal atoms and the etching by ions due to non-uniform deposition of heavy metals on the alloy substrate. In the manufacturing method of the present invention, The exposed portions are resistive to plasma etching, and thus are not etched and constitute protrusions. Accordingly, portions where relatively less heavy metals are deposited can be etched by heavy metal ions to form depressions. This can be confirmed by the vertical element composition of the nanostructure (FIG. 6). As shown in Fig. 6, the upper portion of the nanostructure on which the heavy metal was deposited contained tantalum at a high ratio, while almost no tantalum was detected at the base of the depression. At this time, since the deposited tantalum can form a composite metal nanostructure in which the content of tantalum is increased as the tantalum is continuously directed upward without an interface with the alloy substrate without forming a separate layer, It is possible to exclude that the structure is collapsed due to the layer falling off.
Preferably, but not exclusively, polishing the alloy substrate surface prior to the step of plasma etching.
Also, preferably, the method of the present invention may be applied to a machined method, an atmospheric pressure plasma treatment, a vacuum plasma treatment, a high temperature plasma treatment, Metal beads sintering method, particle blasting method, acid treatment, alkali treatment, anodic oxidation method, ion implantation method, or the like. But not limited thereto. Using methods well known in the art, various nanostructures can be further formed using the optional plasma etch of the present invention before or after forming large micrometer-level patterns (e.g., irregularities) Respectively.
Preferably, the plasma etch comprises: a vacuum chamber comprising a heavy metal target and an alloy substrate spaced apart from each other; And a direct current power supply device connected to the heavy metal target and the alloy substrate, respectively, using a sputter-based device. One embodiment of such a device is schematically shown in Fig. Preferably, a negative voltage is applied to the heavy metal target and the alloy substrate, which are spaced apart from each other, while applying a negative voltage (-400 V or more vs -200 V) larger than that of the heavy metal target to the metal substrate, Ions and atoms to accelerate toward the metal substrate.
Preferably, an inert gas such as argon gas is injected into the vacuum chamber to maintain a predetermined pressure required for the sputtering process. The pressure required for the sputtering process may be 0.5 to 5 x 10 < -2 > torr, but is not limited thereto, and may be suitably selected by those skilled in the art.
Preferably, the method for producing an alloy substrate, in which a surface of a heavy metal-containing nanostructure having a desired shape is formed without an interface on an alloy substrate, comprising plasma etching using a heavy metal according to the present invention, A voltage of -150 to -300 V was applied to ionize the argon gas filled in the vacuum chamber to form a plasma to collide with the heavy metal target to generate heavy metal atoms and ions. At this time, the voltage applied to the heavy metal target may be a negative voltage higher than a voltage capable of emitting heavy metal atoms or ions from the heavy metal target. For example, when tantalum is used as a heavy metal target, a negative voltage in the range of 150 to 300 may be applied, but the present invention is not limited thereto, and the applied voltage can be controlled according to the type of heavy metal used. Also, by applying a negative voltage to the heavy metal target and simultaneously applying a negative voltage of 400 V or more to the alloy substrate, the heavy metal atoms and ions are accelerated toward the alloy substrate.
As described above, depending on the kind of the heavy metal target, deposition of heavy metal atoms and etching with heavy metal ions may occur competitively on the alloy substrate during the plasma etching using the heavy metal.
Preferably, the nanostructures formed on the surface may have a depth of 200 to 1500 nm. In addition, the nanostructure may have a width of 50 to 300 nm. The depth may be an average of the height difference between the lowermost portion of the depression and the uppermost portion of the adjacent protrusion, and the width may be an average distance between the adjacent depression portion including the one protrusion portion and the depression portion, And may be an average distance between adjacent protrusions and projections spaced apart including one depression.
In another aspect, the present invention provides a composite metal structure in which a surface of a desired shape of a tantalum-containing nanostructure is formed on an alloy substrate without an interface.
The composite metal structure of the present invention is characterized in that the surface of the tantalum-containing nanostructure partially or completely shields the chemical reaction of the alloy by in vivo or atmospheric exposure.
Preferably, the composite metal structure can be manufactured according to the manufacturing method of the present invention described above.
The composite metal structure can provide a significantly increased specific surface area and is a structure having improved biocompatibility such as cell adhesion, and still has a feature of metal, for example, conductivity, so that it can be used for implant or cell culture. In addition, since the composite metal structure not only provides a significantly increased specific surface area but also exhibits improved electrochemical, mechanical, physical and / or chemical properties therefrom, it can be widely applied to batteries, catalysts, sensors, and actuators, Are not limited thereto.
For example, when the composite metal structure of the present invention is applied to an implant, it is not limited to the shape of the implant itself, and can be applied to all types of implants. Preferably, the implant can be in the form of a screw, a block, a plate, a film, a filament, a membrane, a mesh, a woven fabric, a nonwoven, a knit, a grain, a particle, a bolt, a nut, The implantable implant is not limited to its shape.
The implant of the present invention is characterized in that the implant is plasma-etched with a heavy metal having a low toxicity to have a structure on the surface of the nanometer and the surface is modified so that the biocompatible heavy metal content is increased. Accordingly, the implant is harmless when inserted into the body, and the contact and / or bonding area with the surrounding tissue cells is greatly enlarged, so that it can exhibit a remarkably increased new bone formation promoting effect and an osseointegration effect by the improvement of the bone tissue reaction. Therefore, the implant may be inserted into a living body to replace damaged tissue, or may be used to promote regeneration of the tissue. Or to support or treat damaged or missing skeletal tissue. A support, joint, and bone fixation device for regenerating and supporting hard tissue such as dental and orthopedic implants, abutments, artificial bones, artificial joints, small bones of the jawbone and facial area, fillers, porcelain, , Spinal processing devices, and the like. Preferably, the implant of the present invention can be used as an artificial tooth root, an artificial root, an artificial joint, or an artificial bone, but is not limited thereto.
The selective plasma etching method using the heavy metal of the present invention can form an ordered nanostructure of several hundreds of nanometers on the surface of an alloy substrate in a much simpler process than a method of forming a nanostructure on the surface of a conventional alloy substrate. In particular, this method can control the shape, width, and depth of nanostructures formed by controlling the selection of the underlying alloy substrate and appropriate reaction conditions, and it is possible to fabricate nanostructures deep enough to 1 μm or more. This is because the nanostructure is formed by selectively etching the surface of the alloy substrate rather than forming the pore structure by using the deposition or the ceramic layer, and thus the nanostructure can be easily removed due to its excellent mechanical stability. Accordingly, the selective plasma etching method using the heavy metal of the present invention can be effectively used as a method for forming nanostructures of various sizes and / or shapes having excellent mechanical properties on metal surfaces.
1 is a schematic view illustrating a selective plasma etching method according to the present invention.
FIG. 2 is a scanning electron microscope image showing nanopores formed on various alloys (Ni-Ti, SUS and Co-Cr) substrates by selective plasma etching according to the present invention.
FIG. 3 is a scanning electron microscope (SEM) image showing the change of nanopore shape formed on various alloy substrates by the selective plasma etching method according to the present invention with time.
FIG. 4 is a scanning electron microscope image of a Co-Cr specimen showing the change in depth of the nano-pores formed on various alloy substrates by the selective plasma etching method according to the present invention, .
FIG. 5 is a scanning electron microscope (SEM) image showing changes in the width and depth of pores according to the magnitude of the negative voltage applied to the nanostructure formed on the cobalt-chromium alloy by the selective plasma etching method according to the present invention.
FIG. 6 is a view showing the structure and compositional analysis results of the surface of a cobalt-chromium alloy having nanostructures formed by selective plasma etching according to the present invention. (a) shows a transmission electron microscope image showing a cross section showing a specific shape of the nanostructure, and (b) shows a chemical composition ratio at the upper and lower ends of the pore.
FIG. 7 is an optical microscope image and a scanning electron microscope image showing changes in surface structure according to the strain applied to the surface of cobalt-chromium including the nanostructure according to the present invention. FIG.
8 is a graph showing the degree of adhesion of vascular endothelial cells to the surface of cobalt-chromium including the nanostructure according to the present invention. (a) and (b) are scanning electron microscope images of vascular endothelial cells adhered on a cobalt-chromium surface and a cobalt-chromium surface having a nanostructure formed by a selective plasma etching method according to the present invention, respectively (c ) Is a graph showing the degree of adhesion of cells to the surfaces in terms of surface coverage percentage.
FIG. 9 is a graph showing the extent of vascular endothelial cell proliferation on a cobalt-chromium surface including a nanostructure according to the present invention measured by the MTS method. As a control group, cobalt - chromium which was not subjected to plasma etching was used.
Hereinafter, the constitution and effects of the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and the scope of the present invention is not limited by these examples.
Example
1: An alloy substrate containing nanostructures on its surface
plasma
Manufacturing method using etching method
In the present invention, a base material made of a nickel-titanium alloy, a stainless steel, or a cobalt-chromium alloy is used as an alloy specimen. First, the surface was polished sequentially from # 220 to # 1200 using SiC paper, ultrasonically treated with acetone and ethanol for 15 minutes, and then dried at room temperature for 24 hours. The sufficiently dried specimen was attached to the substrate holder inside the vacuum chamber and evacuated using a vacuum pump. When the degree of vacuum is less than 1.0 × 10 -5 torr, 30 SCCM of argon gas is injected to clean the substrate, the degree of vacuum is adjusted to 3.0 × 10 -2 torr, and a voltage of 600 V is applied to the DC power supply for substrate bias The substrate was cleaned for 10 minutes. Then, a negative voltage was applied to the tantalum type DC power supply under the conditions of 215 V and 250 mA, and the voltage applied to the substrate was raised to 800 V to perform selective plasma etching for 1 hour. According to the above process, a nano-pore structure having a desired shape was formed on the surface of each alloy substrate, and then the process was completed. A plasma etching mechanism for forming a nanostructure on the surface of the alloy substrate according to the present invention is illustrated in FIG. Through this mechanism, etching by tantalum ions and argon ions formed by plasma on the surface of the alloy substrate and deposition of neutral tantalum atoms competitively occur.
Example
2:
plasma
A method for controlling the shape of a nanostructure formed on a surface of a metal substrate by controlling an etching time
A metal substrate having nanostructures formed on its surface was prepared in the same manner as in Example 1 except that the time for performing the selective plasma etching was adjusted to 5 minutes, 30 minutes, 60 minutes, and 90 minutes.
Example
3:
plasma
A method for controlling the shape of a nanostructure formed on a surface of a metal substrate by voltage regulation applied during etching
A metal substrate having a nanostructure on its surface was prepared in the same manner as in Example 1 except that a cobalt-chromium alloy was used as a substrate and the negative voltage applied to the substrate was adjusted to 400 V, 800 V, 1200 V, and 1600 V, respectively .
Experimental Example
One:
plasma
By etching,
On the surface
Identification of formed nanostructures
In order to confirm whether or not the nanostructure was successfully formed on the surface of the metal substrate according to Example 1, the surface was directly observed with a field emission-scanning electron microscope (FE-SEM). An electric field scanning electron microscope for the above three materials of an alloy substrate (nickel-titanium alloy; Ni-Ti, stainless steel, SUS, cobalt-chromium alloy, Co-Cr) is shown in Fig. As shown in FIG. 2, nanometer-scale structures were formed on the surfaces of the three metal substrates, and the size and shape of these nanostructures were found to be different depending on the material of the metal specimen.
Experimental Example
2:
plasma
Analysis of morphological change of nanostructures formed on the surface of alloy substrate by controlling etching time
In order to confirm the change of the nanostructure formed on the surface of the alloy base material of the three materials manufactured according to Example 2 according to the plasma etching time, the surface was observed with an electric field scanning electron microscope and the results are shown in FIG. As shown in Table 3, the nanostructures formed on the surface of the alloy substrate showed a large change according to the selective plasma etching time. Specifically, when the processing time is short, a small-sized nanostructure having a certain curvature is formed at the beginning of the process. However, as the processing time becomes longer, the curvature gradually increases without changing the width of the nanopore, Finally, aligned nanostructures were formed with long-range order.
In addition, the depth change of the nanopores according to the etching time was measured, and the results are shown in FIG. As shown in FIG. 4, the nano pores of the alloy specimens of all materials were gradually deepened with the etching time, but they did not exceed the maximum of 400 nm under the corresponding etching conditions. And converged to a depth of 400 nm. However, if the applied voltage or other etching conditions are kept constant, the width and / or depth of the pores are not increased beyond a certain level even if the etching time is increased Lt; / RTI >
Experimental Example
3:
plasma
Analysis of morphological change of nanostructures formed on the surface of cobalt-chromium alloy substrate by controlling voltage applied during etching
In order to confirm the shape change of the nanostructure according to the voltage applied to the alloy substrate during the plasma etching, the surface and the cross section of the cobalt-chromium alloy substrate formed with the nanostructure according to Example 3 were observed with an electric field scanning electron microscope, The image is shown in Fig. As shown in FIG. 5, nanopores start to form on the surface of the cobalt-chromium alloy when a negative voltage of 400 V is applied. The width and depth of the formed nano pores increase as the magnitude of the applied negative voltage increases When a negative voltage of 1600 V was applied, nanopores of 240 nm width and 1200 nm depth were formed. This indicates that the size of the nanostructure formed on the surface of the alloy substrate can be effectively controlled by controlling the magnitude of the negative voltage applied to the alloy substrate to be patterned.
Experimental Example
4:
On the surface
plasma
Analysis of surface structure of alloy substrate including nanostructure formed by etching
In order to specifically analyze the pore structure formed on the surface of the cobalt-chromium alloy base material including the nanostructures on the surface prepared according to Example 1, a cut surface was formed, and the distribution of the component according to the depth of the pores formed therefrom was measured. The sample was observed with a transmission electron microscope (TEM) image, and energy dispersive X-ray spectrometry (EDS) was performed. The results are shown in FIG. As shown in FIG. 6, a large amount (about 50% by weight) of tantalum (Ta) was locally detected at the upper part of the nano pores as a result of checking the composition of the surface on which the pore structure was formed. (Fig. 6B). This indicates that the compositional distribution of tantalum in the direction of depth contributes greatly to the formation of nanostructures. Plasma etching occurs due to the high voltage applied to the alloy substrate. At this time, the portion having a relatively high tantalum composition has a higher resistance to the plasma etching than the portion having a low tantalum composition, A portion having a relatively low tantalum composition may be etched faster to form protrusions and depressions, thereby forming a nanostructure. That is, the surface is locally etched by the plasma ions (Ar + , Ta 3 + , Ta 4 + ) selectively on the surface having a low tantalum composition to form a nanoporous structure having a depth of several hundred nanometers.
Experimental Example
5: on the surface
plasma
An alloy substrate comprising a nanostructure formed by etching
Strain rate
Physical Stability for
In order to confirm the mechanical and / or physical stability of the cobalt-chromium alloy substrate including the nanostructures on the surface prepared according to Example 1, tensile strain was applied to the substrate, and the change in the surface structure at this time was observed using an optical microscope It was observed with a scanning electron microscope and is shown in Fig. As shown in FIG. 7, when a strain of up to 20% was applied to a cobalt-chromium alloy substrate including a nanostructure, it was confirmed that many deformed portions appearing in black on the surface of the alloy parent material were observed, There was no surface defects or surface layer detachment. As a result of the observation by the electric field scanning electron microscope, although the tensile strain applied greatly deformed the shape of the substrate itself, only the deformation due to the deformation of the substrate was observed in the nanostructure formed on the surface, It was confirmed that it was not dropped or not.
Experimental Example
6: on the surface
plasma
Biocompatibility evaluation of alloy substrates containing nanostructures formed by etching
In order to evaluate the biocompatibility of the cobalt-chromium alloy substrate including the nanostructure on the surface prepared according to Example 1, the adhesion form of the cell, attachment (adhesion) And degree of proliferation were evaluated by an electric field scanning electron microscope and an MTS assay, respectively, and the results are shown in FIGS. 8 and 9, respectively. Specifically, vascular endothelial cells were placed on a cobalt-chromium alloy having a nanostructure prepared according to Example 1 as a control and a cobalt-chromium alloy not subjected to a plasma etching treatment. After culturing for 24 hours, Respectively. Furthermore, in order to confirm cell proliferation on each of the above surfaces, cells were divided on each surface and incubated for 3 days before performing MTS assay. Chromium alloys having the nanostructures by the plasma etching treatment according to Example 1 because the nanostructures of the nanostructures contain nanostructures on the surface of the nanostructures and also provide protrusions containing a large amount of tantalum components having excellent biocompatibility. It was confirmed that the endothelial cells not only adhere more widely but also improved intercellular junction (FIG. 8). In addition, it was confirmed that the proliferation of vascular endothelial cells was also improved on the surface having the nanostructure (FIG. 9).
In general, an alloy substrate including a nanostructure formed by plasma etching according to the present invention can provide an increased surface area through the pore structure of the nano-scale level of unevenness, and can provide a stable surface Nanostructures can be provided. Also, the size of the nanostructure may be controlled by controlling the material of the substrate, the magnitude of the negative voltage applied to the substrate, and / or the etching time, thereby finely controlling the shape, width, and depth. In addition, since the nanostructure has improved adhesion and proliferation rate of cells, it can provide an implant having improved biocompatibility by being applied to an implant or the like.
Claims (20)
(I) an alloy substrate capable of forming a surface of a desired shape of a heavy metal-containing nanostructure; And (ii) a first step of selecting reaction conditions for plasma etching using a heavy metal target; And
A negative voltage is applied to the heavy metal target in the presence of an inert gas and a negative voltage for bias is applied to the alloy substrate using the alloy substrate and the plasma etching reaction conditions selected in the first step to remove the heavy metal ions and the inert gas ions And a second step of forming a plasma that competitively induces etching and deposition of neutral heavy metal atoms,
Wherein the heavy metal has a higher atomic weight than the atomic weight of at least one kind of metal constituting the alloy base material.
Wherein the material of the alloy substrate is a cobalt-chromium alloy, a nickel-titanium alloy, or a stainless steel.
Wherein the material of the alloy substrate further comprises at least one metal selected from the group consisting of aluminum, tantalum, niobium, vanadium, zirconium, tin, molybdenum, silicon, gold, palladium, copper, platinum and silver.
Wherein the heavy metal is tantalum (Ta), tungsten, rhenium, osmium, iridium, platinum or gold.
Wherein the surface of the heavy metal-containing nanostructure has a protruding portion and a depressed portion, wherein the protruding portion and the depressed portion are independently continuous or discontinuous curved, linear, or a combination thereof.
And polishing or cleaning the surface of the alloy substrate prior to the second step.
Forming a micro-level pattern on the surface of the alloy substrate before or after the second step so as to have a hierarchical surface structure on the alloy substrate surface.
Wherein the portion where the heavy metal is deposited in the second step is resistant to plasma etching.
Wherein the plasma etching comprises: a vacuum chamber including a heavy metal target spaced apart from each other and an alloy substrate for forming a nanostructure on the surface; And a direct current power supply connected to the heavy metal target and the alloy substrate, respectively, the device being based on a sputter.
And an inert gas is injected into the vacuum chamber to maintain a predetermined pressure.
Wherein the inert gas is an argon gas.
Wherein the voltage applied to the heavy metal target is a negative voltage greater than or equal to a voltage capable of emitting heavy metal atoms or ions from the heavy metal target.
Wherein a voltage applied to the alloy substrate is a negative voltage greater than a negative voltage applied to a heavy metal target.
Wherein the nanostructure has a depth of 200 to 1500 nm.
Wherein the nanostructure has a width of 50 to 300 nm.
A composite metal structure in which a surface of a tantalum-containing nanostructure having a desired shape is formed on an alloy substrate without an interface is characterized in that the surface of the tantalum-containing nanostructure is a composite metal which is characterized in that it partially or wholly blocks the chemical reaction of the alloy by in- structure.
Wherein the implant is a screw, a block, a plate, a film, a filament, a membrane, a mesh, a woven fabric, a nonwoven fabric, a knit, a grain, a particle, a bolt, a nut or a combination thereof.
Wherein the implant is an artificial tooth root, artificial root, artificial joint or artificial bone.
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