TWI532883B - Titanium or titanium alloy having antibacterial surface and method for manufacturing the same - Google Patents

Description

Titanium or titanium alloy with antibacterial surface and preparation method thereof

The invention relates to a titanium or titanium alloy with an antibacterial surface and a preparation method thereof, in particular to a titanium oxide layer and an antibacterial layer formed on the surface of a titanium or titanium alloy substrate by anodizing treatment or micro-arc oxidation treatment and cathodic deposition treatment. The manufacturing method and the prepared titanium or titanium alloy having an antibacterial surface.

Titanium or titanium alloys have been widely used as artificial hip joints, artificial knee joints, humeral bases, artificial knuckles, elbow joints and spinal fixation devices because of their low density, high specific strength and good thermal stability. However, after the titanium metal is implanted in the human body, it is corroded by body fluids in the human body and the metal ions are released outward, and a strong and long-term stable combination with the bone tissue cannot be formed. Moreover, titanium or titanium alloys have problems such as poor bioactivity, lack of osteoinductive action, poor wear resistance and corrosion resistance in physiological environments and under load conditions. Therefore, attempts have been made in the art to coat the surface of titanium or titanium alloy implants with a biocompatible material by various surface treatment methods to improve the above problems. However, to date, the ideal clinical response has not been achieved. Use the effect. The fundamental problem is mainly due to insufficient bonding strength between the surface of the titanium or titanium alloy and the coated biocompatible material or the manufacturing cost is too high. In addition, in allogeneic transplantation such as bone replacement, antibiotic treatment is often used to avoid concurrent infection, but long-term use can easily lead to microbial resistance, which is unfavorable to the overall health of patients.

Since titanium or titanium alloy is a biocompatible material, it is widely used in medical applications. In the surface treatment of titanium or titanium alloy, titanium oxide is mainly used as a main application, such as the use of high voltage pulse disclosed in Chinese Patent Application No. 201010294772.2 The discharge forms a titanium dioxide film on the surface of the titanium or titanium alloy material; and the wear resistance of the titanium or titanium alloy is increased to apply to the artificial joint. Chinese Patent Application No. 200410041155.6 discloses that nitrogen ions are first introduced at a high temperature. Oxygen ions are introduced at high temperature to form a titanium oxide-titanium nitride film with high hardness and high lubricity. However, this method is a high-temperature process, in addition to high-temperature and easy-to-shape artificial bone deformation, and high temperature The process is slow and costly, and it is difficult to apply it.

Since some antibacterial metal particles, such as copper particles, zinc particles, and silver particles, are close to viruses, fungi, bacteria, or phage, they can directly enter the cells and rapidly metabolize with oxygen (-SH). Combining, blocking the metabolism of the bacteria, causing the cells to lose their activity and then naturally die. This long-acting antibacterial method can kill more than 600 kinds of bacteria. Therefore, many studies have focused on the surface of medical devices that can be implanted into the human body, and metal particles having antibacterial ability such as copper particles, zinc particles, and silver particles are attached to the surface of these medical devices to achieve the antibacterial ability of medical devices. However, in order to have good antibacterial ability, these metal particles have a good life by miniaturization (or reaching the nanometer level). Sex, so how to have nanometer size and maintain good activity on the surface of medical equipment has been a bottleneck for medical equipment research.

In the prior art, in order to increase the antibacterial ability of titanium or titanium alloy, Chinese Patent Application No. CN201110295804.5 discloses that a porous nanostructure is formed by pretreatment corrosion of a titanium metal surface with hydrogen peroxide, and then immersed in a plasma ion. The method (Plasma immersion ion implantation technique) injects silver particles into the nanostructure, and implants silver ions in the plasma as dopants into the nanostructure under high voltage pulsed direct current and vacuum to perform surface modification. Sexuality produces antibacterial properties by nano-sized silver particles; however, in this technique, silver particles can only be distributed on the surface of a porous nanostructure, and relatively speaking, silver particles are liable to fall off and are not easily covered.

In addition, in the above-mentioned Japanese Patent Application No. 101149724, the method of positive and negative pulse circulating power supply control can further improve the content of silver adhered to the titanium oxide film layer, but also adopts such a method. The silver content of the titanium oxide film that can be increased is still limited. Therefore, the antibacterial effect which can be provided by a method for preparing a titanium oxide film having an antibacterial function as currently known in the art is very limited.

Accordingly, if a titanium metal implant capable of effectively binding to a living tissue, having high antibacterial activity, low manufacturing cost, and high surface bonding strength can be developed, the patient does not need to use a large amount of antibiotics for medical related industries and countries. The improvement in overall medical quality will help.

The main object of the present invention is to provide a method for preparing titanium or a titanium alloy having an antibacterial surface, which can form an antibacterial surface on the surface of the titanium or titanium alloy by surface treatment to facilitate cell attachment on the surface thereof. When growing, reduce the likelihood of infection and the degree of infection.

In order to achieve the above object, an aspect of the present invention provides a method for producing titanium or a titanium alloy having an antibacterial surface, the steps comprising: (A) providing a substrate which is titanium or a titanium alloy; (B) The substrate is immersed in a first electrolyte solution, and a surface of the substrate is formed into a titanium oxide layer by an oxidation treatment, wherein the first electrolyte solution may include an active modifier, and the titanium oxide layer It may be titanium dioxide (TiO ₂ ), titanium oxide (Ti ₂ O ₃ ), or other titanium oxide composition, preferably the titanium oxide layer may be titanium dioxide (TiO ₂ ); and (C) the substrate and The titanium oxide layer is immersed in a second electrolyte, and the pores and the surface of the titanium oxide layer form an antibacterial layer by a cathode deposition process, wherein the second electrolyte comprises an antibacterial additive.

In the above method for producing titanium or titanium alloy having an antibacterial surface of the present invention, the active modifier may be at least one selected from the group consisting of calcium acetate, hydroxyapatite (or hydroxyapatite, HA) powder. a group of phosphates, combinations thereof. Therefore, in one aspect of the present invention, in addition to forming a titanium oxide layer on the surface of the substrate (titanium or titanium alloy), the first electrolyte may be used in the oxidation treatment of the electrolyte. The active modifier, in the process of oxidation treatment, forms a structure with biocompatibility (such as hydroxyapatite or the like) on the pores and surface of the titanium oxide layer, thereby facilitating cell attachment and growth.

Titanium or titanium alloy having an antibacterial surface of the present invention described above In the manufacturing method, in addition to the second electrolyte solution, the first electrolyte solution may further comprise the antibacterial additive, thereby preparing a titanium oxide layer containing the antibacterial additive, and forming the antibacterial layer thereon. . Further, in order to promote the formation of the titanium oxide layer or the surface of the titanium oxide layer containing the antibacterial additive to form an antibacterial layer having more remarkable antibacterial effect, after the step (C), the titanium or titanium alloy having the antibacterial surface of the present invention is produced. The method can repeat step (B) and step (C) at least once. However, it should be understood that the present invention does not particularly limit the number of repetitions thereof, and those skilled in the art can set according to process conditions such as operating parameters and composition components. Preferably, in an embodiment of the present invention, after step (C), the step (B) and the step (C) may be repeated at least three times, that is, in this embodiment, the step (B) And the step (C) can be carried out four times in total to achieve an antibacterial effect of improving the prepared titanium or titanium alloy having an antibacterial surface.

In the above-described method for producing titanium or a titanium alloy having an antibacterial surface of the present invention, the titanium oxide layer formed by the oxidation treatment may have a porous structure.

In the above method for producing titanium or titanium alloy having an antibacterial surface of the present invention, the oxidation treatment may be an anodization method or a micro-arc oxidation method. The electrolytes selected may be different depending on the oxidation treatment selected. In other words, the present invention does not particularly limit the composition of the electrolyte as long as it can meet the electrolytes required for various oxidation treatments. For example, the first electrolyte may be a solution selected from at least one of the group consisting of sulfuric acid, phosphoric acid, hydrogen peroxide, nitrate, acetate, citrate, and hypophosphite. However, it should be understood that as long as the electrolyte is configured In the above anodizing method or micro-arc oxidation method, the electrolyte may further include other constituents, and the present invention is not limited thereto.

In the above method for producing titanium or titanium alloy having an antibacterial surface of the present invention, the cathode deposition treatment may be an electrochemical electrolysis method or an electroless plating (electroless plating) method. Further, the present invention does not particularly limit the composition of the second electrolyte as long as it can conform to the second electrolyte required for various cathode deposition processes. For example, when the cathode deposition treatment is electrochemical electrolysis, the second electrolyte may be selected from the group consisting of sulfuric acid, phosphoric acid, hydrogen peroxide, nitrate, acetate, citrate, and hypophosphite. a solution of at least one of the groups. However, it should be understood that the second electrolyte used in the electrochemical electrolysis method may further contain other additives to improve the effect of the electrolytic deposition treatment as long as it does not affect the properties of the titanium oxide layer formed by the oxidation treatment. The invention is not limited to this.

In the above method for producing titanium or titanium alloy having an antibacterial surface of the present invention, any kind of antibacterial additive may be contained in the second electrolyte as long as it can be formed on the titanium oxide layer by the above-described cathodic deposition treatment. . For example, the antibacterial additive may be a metal ion having an antibacterial function or a salt thereof. In more detail, in one aspect of the invention, the antimicrobial additive may be a salt formed from copper, zinc, silver, or a combination thereof. Preferably, in one embodiment of the present invention, the antibacterial additive may be silver halide, silver nitrate, silver sulfate, or a combination thereof to produce better antibacterial efficacy. Furthermore, as long as the purpose of forming the antibacterial layer can be achieved, those skilled in the art can arbitrarily adjust the content of the antibacterial additive according to the requirements of the operating parameter conditions, and the present invention is not particularly limited. For example, one of the inventions In an embodiment, the antibacterial additive may be included in an amount of 0.1 to 10 g/L.

In the above-described method for producing titanium or a titanium alloy having an antibacterial surface of the present invention, the temperature of the first electrolyte of the present invention can be appropriately adjusted to facilitate formation of a titanium oxide layer. For example, in one aspect of the invention, the temperature of the first electrolyte may be 0 to 30 ° C, preferably 0 to 10 ° C. Furthermore, in order to form the titanium oxide layer on the surface of the titanium and titanium alloy, the oxidation treatment may have a constant current density of 1 to 10 A/dm ² , or a constant voltage of 100 V to 600 V, and the oxidation treatment may be oxidized. The time can be from 1 to 30 minutes for subsequent cathodic deposition processing. Similarly, the temperature of the second electrolyte of the present invention can also be appropriately adjusted to facilitate formation of the antibacterial layer. For example, in one aspect of the invention, the temperature of the second electrolyte may be 0 to 30 ° C, preferably 0 to 10 ° C. Furthermore, in order to form the antibacterial layer on the surface of the titanium oxide layer, the cathode deposition treatment may have a constant current density of 1 to 5 A/dm ² , or a constant voltage may be 10 V to 50 V, and the cathode deposition treatment time may be 1 to 10 minutes. In the present invention, ions formed by copper, zinc, silver, or a combination thereof are obtained by a cathode deposition process to obtain electrons via a cathode to form metal particles; further, the formed metal particles are nano-sized, by nanometer. The high specific area of the metal particles of the grade size gives the metal particles a high activity and a good antibacterial activity.

In the above method for producing titanium or titanium alloy having an antibacterial surface of the present invention, in order to facilitate formation of the titanium oxide layer on the substrate, after step (A) and before step (B), it may further comprise: A1) removing the oxide film on the surface of the substrate by a pretreatment step and roughening the surface of the substrate. Similarly, in order to make the antibacterial layer easy to form on the titanium oxide layer, in step (B) After the step (C), the method further includes: (B1) cleaning the substrate and the titanium oxide layer to remove the first electrolyte and the oxide which is easily detached from the substrate and the surface of the titanium oxide layer. Debris such as titanium. Furthermore, after the step (C), the method further comprises: (C1) cleaning the substrate, the titanium oxide layer, and the antibacterial layer, thereby removing the second electrolyte solution and the titanium oxide and the antibacterial layer which are easy to fall off. And other debris. Furthermore, as described above, when the method for producing titanium or titanium alloy having an antibacterial surface of the present invention comprises repeating steps (B) and (C) at least once, step (B1) and step (C1) may follow Step (B) and step (C) are repeated at least once, or step (B1) and step (C1) may not be repeated with step (B) and step (C), and the invention is not particularly limited thereto. Preferably, in an embodiment of the present invention, the step (B), the step (B1), the step (C), and the step (C1) can be performed four times in order to improve the prepared antibacterial surface. The antibacterial effect of titanium or titanium alloy.

Another object of the present invention is to provide a titanium or titanium alloy having an antibacterial surface, which can form a surface having an antibacterial function on the surface of the substrate through the above-mentioned method for producing titanium or a titanium alloy having an antibacterial surface, and Titanium or titanium alloy with antibacterial surface has good antibacterial activity, so that when the cell attaches and grows on its surface, it reduces the possibility of infection and the degree of infection.

In order to achieve the above object, another aspect of the present invention provides a titanium or titanium alloy having an antibacterial surface, which is produced according to the above-described method for producing titanium or a titanium alloy having an antibacterial surface, comprising: a substrate, The substrate is titanium or a titanium alloy; a titanium oxide layer formed on the surface of the substrate by an oxidation treatment; and an antibacterial layer formed on the substrate The pores and surface of the titanium oxide layer.

In the above titanium or titanium alloy having an antibacterial surface of the present invention, the titanium oxide layer may have a thickness of 1 μm to 50 μm, preferably 5 μm to 25 μm, and the hardness of the titanium oxide layer may be 200 Hv or more. It is preferably 200 to 800 Hv.

In the above titanium or titanium alloy having an antibacterial surface of the present invention, any shape and structure of the antibacterial layer can be used as long as the antibacterial effect can be exerted, and the present invention is not limited thereto. For example, in one aspect of the present invention, the antibacterial layer may be a continuous or discontinuous silver-containing titanium oxide film layer, and the silver content may be 1% to 20% based on the surface of the titanium oxide film layer. It is preferably from 1% to 5%. Furthermore, for cell attachment growth, the antimicrobial layer (or the antimicrobial layer and the titanium oxide layer) can form a rough and suitably hydrophilic surface for cell attachment and growth, such as the antimicrobial layer (or The surface roughness (Ra) of the antibacterial layer and the titanium oxide layer may be 0.1 micrometer to 3 micrometers, and the surface of the antibacterial layer (or the antibacterial layer and the titanium oxide layer) has a pure water contact angle at 25 ° C It can be 10 to 90 degrees. Accordingly, the titanium or titanium alloy having an antibacterial surface obtained by the above-described method for producing titanium or a titanium alloy having an antibacterial surface is quite suitable for use in dental implants, human bones, or artificial joints.

1‧‧‧Oxidation treatment unit

11‧‧‧ Electrolyzer

111‧‧‧Circular cooling water

112‧‧‧ electrolyte

113‧‧‧ cathode

12‧‧‧Stirring unit

13‧‧‧Control unit

14‧‧‧Power supply

15‧‧‧Anode

20‧‧‧Substrate

21‧‧‧Titanium oxide layer

211‧‧‧ pores

212‧‧‧ surface

22‧‧‧Antibacterial layer

200‧‧‧Titanium or titanium alloy with antibacterial surface

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of the apparatus of the oxidation treatment apparatus of the present invention.

2A and 2B are flow charts showing a method of fabricating titanium or a titanium alloy having an antibacterial surface according to Embodiments 1 and 19 of the present invention.

3A to 3C are schematic views showing a manufacturing process of titanium or a titanium alloy having an antibacterial surface according to Embodiment 1 of the present invention.

4A to 4D are diagrams showing the results of scanning electron microscopy of Examples 1 to 3 and Comparative Example 1.

5A to 5D are diagrams showing the results of scanning electron microscopy of Examples 7 to 9 and Comparative Example 2.

6A to 6D are diagrams showing the results of scanning electron microscopy of Examples 13 to 15 and Comparative Example 3.

Figure 7 is a graph showing the results of X-ray diffractors of Examples 1 to 3, 7 to 9 and 13 to 15 of the present invention.

Figure 8 is a graph showing the results of energy dispersive analyzers of Examples 1 to 3, 7 to 9 and 13 to 15 of the present invention.

Fig. 9 is a graph showing the results of surface average roughness analysis of Comparative Examples 1 to 3 and Examples 1 to 3, 7 to 9 and 13 to 15 of the present invention.

Fig. 10 is a graph showing the results of analysis of the contact angle of pure water of Comparative Examples 1 to 3 and Examples 1 to 3, 7 to 9 and 13 to 15 of the present invention.

11A to 11C are graphs showing the results of cell viability analysis of Comparative Examples 1 to 4 and Examples 1 to 3, 7 to 9 and 13 to 15 of the present invention.

12A to 12D are diagrams showing the results of antibacterial analysis of Comparative Example 1 and Examples 1 to 3 of the present invention.

13A to 13D are diagrams showing the results of antibacterial analysis of Comparative Example 2 and Examples 7 to 9 of the present invention.

14A to 14D are diagrams showing the results of antibacterial analysis of Comparative Example 3 and Examples 13 to 15 of the present invention.

1 is a schematic diagram of an apparatus for forming an oxidation treatment device 1 for forming a titanium oxide layer on a substrate, wherein the oxidation treatment apparatus 1 comprises: an electrolytic cell 11 for accommodating an electrolyte 112; A stirring unit 12 is used for stirring the electrolyte 112; a control unit 13 is used for controlling the current density, voltage and the like outputted by a power source 14. Further, the electrolytic cell 11 is designed as a hollow casing to maintain the temperature of the electrolyte 112 by a circulating cooling water 111. Further, the cathode 113 required for the oxidation treatment is the inner wall of the electrolytic cell; and the anode 15 required for the oxidation treatment is the substrate.

Preparation Example

In the present invention, the substrate used is a titanium test piece. Before the oxidation treatment, the substrate first removes the surface oxide film by a pretreatment step and roughens the surface to facilitate subsequent surface treatment. The pretreatment steps in this embodiment are as follows: First, the substrate is first polished with 400 to 1000 water sandpaper to remove the surface oxide film; then, the substrate is immersed in the Klos reagent for 3 to 10 minutes to homogenize. The surface roughness of the substrate; in the foregoing, the main purpose of the pretreatment step is to remove the surface oxide film and the surface roughness of the uniformized substrate, and is not limited to the use of water sandpaper or immersion in the Klos reagent.

"Embodiment 1"

Please refer to FIG. 2A and refer to FIG. 3A to FIG. 3C, wherein FIG. 2A is a flow chart of a method for manufacturing titanium or titanium alloy having an antibacterial surface of FIG. 2A, and FIGS. 3A to 3C are corresponding titanium having an antibacterial surface or Schematic diagram of the manufacturing process of titanium alloy 200. As shown in FIG. 2A and FIG. 3A, a substrate 20 is provided which is the above-described treated titanium test piece (S101). Next, referring to FIG. 1 together, the substrate 20 is connected to the power source 14 of FIG. 1 and immersed in a first electrolyte for a micro-arc oxidation process (S102), wherein the first electrolysis The liquid system was disposed in a ratio of sulfuric acid and phosphoric acid (H ₂ SO ₄ : 154.6 ml/L; H ₃ PO ₄ : 17.4 ml/L). In addition, a person skilled in the art can also add a chelating agent, a dispersing agent or an inorganic nanoparticle to the first electrolyte to adjust the surface properties of the formed titanium oxide layer. During the micro-arc oxidation treatment, the temperature of the first electrolyte is maintained at 15 to 20 ° C through the circulating cooling water 111 in FIG. 1 , and the pH is maintained at about 2. Referring to Table 1, the voltage of the micro-arc oxidation treatment process of Example 1 is 150V, and the oxidation time is 5 minutes. Therefore, referring to FIG. 3B, after the micro-arc oxidation treatment process is completed, the surface of the substrate 20 forms a porous structure and is a crystalline phase of the titanium oxide layer 21. Next, the titanium oxide layer 21 and the substrate 20 (S103) are washed and dried with double distilled water, and then immersed as a cathode in a second electrolyte, and a cathode deposition treatment is performed using the titanium sheet as an anode. (S104), wherein, as shown in Table 1, the voltage of the cathode deposition treatment is 20 V, and the time is 5 minutes, and the second electrolyte is disposed in a certain ratio with sulfuric acid and phosphoric acid (H ₂ SO ₄ : 154.6 Ml/L; H ₃ PO ₄ : 17.4 ml/L) and contains a silver nitrate (8 g/L) as an antibacterial additive. Therefore, as shown in FIG. 3C, the pores 211 and the surface 212 of the titanium oxide layer 21 form an antibacterial layer 22. Finally, the titanium oxide layer 21, the substrate 20, and the antibacterial layer 22 (S105) are washed and dried with double distilled water to obtain a desired titanium or titanium alloy 200 having an antibacterial surface (S106).

Accordingly, a flow chart of the manufacturing method of the titanium or titanium alloy having the antibacterial surface shown in FIG. 2A and FIGS. 3A to 3C and a corresponding process diagram of the titanium or titanium alloy 200 having the antibacterial surface can be prepared to have an antibacterial effect. a surface titanium or titanium alloy 200 comprising: a substrate 20 as the above-described treated titanium test piece; a titanium oxide layer 21 which is a porous structure; and a titanium oxide layer 21 formed thereon The antibacterial layer 22 of the aperture 211 and the surface 212.

<<Examples 2~18>>

Referring to FIG. 2A and FIGS. 3A to 3C and referring to Table 1, the embodiments 2 to 18 are substantially similar to the embodiment 1, except that the operational parameters of the oxidation treatment and the cathode deposition treatment are different. Therefore, the flow of the manufacturing method thereof will not be described here.

Example 19

Referring to FIG. 2B, the embodiment 19 is substantially similar to the embodiment 1, except that the embodiment 19 repeats steps S202 to S205 four times. Therefore, the operational parameters of the oxidation treatment and the cathode deposition treatment will not be described herein.

<<Example 20》

Example 20 is substantially similar to Example 1, except that the oxidation treatment is employed as an anodizing treatment process. Therefore, the titanium oxide layer formed in the step (B) is a titanium oxide layer having a porous structure and an amorphous phase formed by anodization. Further, any conventional electrolyte which can be used for anodizing titanium metal to form a titanium oxide layer required for the present invention can be used, and the present invention is not particularly limited in its composition. Therefore, the operating parameters of the anodizing treatment and the cathode deposition processing will not be described herein.

"Example 21"

Example 21 is substantially similar to Example 1, except that the first electrolyte which is oxidized is slightly different and includes an active modifier. The first electrolyte solution of Example 21 is sodium hypophosphite (NaH ₂ PO ₂ .H ₂ O, 5 g/L), sodium citrate (Na ₂ SiO ₃ , 2 g/L), and as a chelating agent An aqueous solution of disodium edetate (EDTA-2Na, 4 g/L) and calcium acetate (Ca(CH ₃ COO) ₂ .H ₂ O, 10 g/L) as an activity modifier. Therefore, in the step (B), in addition to forming a titanium oxide layer on the surface of the substrate (titanium or titanium alloy), it can be directly formed on the surface of the substrate by the active modifier of the first electrolyte. The structure of hydroxyapatite or the like, or in the process of surface treatment, the structure of hydroxyapatite or the like may be directly formed on the pores and surface of the titanium oxide layer, thereby improving the prepared Biocompatibility of titanium or titanium alloys on antimicrobial surfaces. The operation parameters of the micro-arc oxidation treatment and the cathode deposition treatment are shown in Table 2, and the production process thereof is similar to that of Embodiment 1, and will not be described herein. The obtained product was analyzed by EDS, and the analysis results are shown in Table 3.

Comparative Example 1~3

Comparative Examples 1 to 3 were substantially the same as Examples 1, 7, and 13, respectively, except that the titanium test pieces of Comparative Examples 1 to 3 were not subjected to the cathodic deposition treatment, and the titanium oxides of Comparative Examples 1 to 3 were used. The pores and surfaces of the layer do not have an antibacterial layer.

Comparative Example 4

Comparative Example 4 is a titanium test piece which was treated only by the pretreatment step of the above preparation example without subsequent oxidation treatment and cathodic deposition treatment.

The samples prepared in the above Examples 1 to 19 and Comparative Examples 1 to 4 were respectively subjected to scanning electron microscopy (Scanning Electron). Microscope, SEM) observed the surface morphology, X-ray diffraction (XRD), Energy Dispersive Spectrometer (EDS) analysis of its surface composition, and roughness analysis and pure water contact angle The surface characteristics were analyzed, and the effects of the samples on cell viability were analyzed by cell viability assay (MTT assay), and the antibacterial efficacy of the samples was analyzed by plate medium method.

The results of Examples 1 to 3, 7 to 9, 13 to 15, and Comparative Examples 1 to 4 are shown in the following series.

Physical Property Analysis

Please refer to FIGS. 4A to 4D, FIGS. 5A to 5D, and FIGS. 6A to 6D, which are Comparative Examples 1 to 3 (FIGS. 4A, 5A, 6A) and Embodiments 1 to 3 (FIGS. 4B to 4D), 7 to 9 (FIG. SEM results of 5B to 5D), 13 to 15 (Figs. 6B to 6D). As shown in FIGS. 4A to 4D, the reduced silver particles are increased as the cathode deposition voltage is increased from 20 V to 40 V and agglomerated and attached to the pores. Similarly, in Figures 5A through 5D, the reduced silver particles are also agglomerated in the pores, and when the cathode deposition voltage is higher, most of the silver particles are combined into a block. Furthermore, as shown in FIGS. 6A to 6D, since the formed titanium oxide layer is in the form of a molten block, at a cathode deposition voltage of 20 V, the reduced silver particles are mostly distributed on the surface thereof, and as the cathode deposition voltage is increased to 40 V, A small number of silver particles begin to bind into a block, but most of the silver particles remain attached to the surface of the molten titanium oxide layer. Therefore, as shown by the SEM results shown in FIGS. 4B to 4D, FIGS. 5B to 5D, and FIGS. 6B to 6D, the surfaces of the titanium oxide layers of Examples 1 to 3, 7 to 9, and 13 to 15 all formed discontinuous contents. Silver antibacterial layer.

Please refer to FIG. 7 for Embodiments 1 to 3, 7 to 9 and 13 to A graph of XRD analysis results of a titanium or titanium alloy having an antibacterial surface. As shown in Fig. 7, the XRD spectrum results of Examples 1 to 3, 7 to 9 and 13 to 15 showed that the surface thereof had silver crystals. Please refer to FIG. 8 , which is a graph of EDS analysis results of titanium or titanium alloys having antibacterial surfaces of Examples 1 to 3, 7 to 9 and 13 to 15, wherein the horizontal axis is the oxidation treatment voltage (V) and the vertical axis is The weight percentage (wt%) of the silver content, and the pattern represents the cathode deposition processing voltage (V). Therefore, please refer to Table 1 together, and each of the histograms respectively indicates the corresponding embodiment. As shown in Fig. 8, as the voltage of the cathode deposition reaction increases, the silver content of the surface of the titanium oxide layer also increases, and the higher the voltage of the micro-arc oxidation treatment, the higher the silver content of the subsequently formed antibacterial layer.

Please refer to FIG. 9 and FIG. 10 , which are graphs of surface average roughness analysis results and pure water contact angle analysis results of Comparative Examples 1 to 3 and Examples 1 to 3, 7 to 9 and 13 to 15, respectively. 9 and the horizontal axis of FIG. 10 are all cathode deposition processing voltages (V), and each of the broken lines represents the same oxidation processing voltage. Therefore, please refer to Table 1, Figure 9 and Figure 10 for each of the line graphs. Each point indicates a corresponding embodiment. As shown in FIG. 9 and FIG. 10, after the cathodic deposition treatment, the surfaces of the titanium oxide layers of the titanium or titanium alloy having the antibacterial surface of Examples 1 to 3, 7 to 9 and 13 to 15 become rough and hydrophilic. This is due to the formation of an antibacterial layer containing silver on the surface.

Accordingly, it can be confirmed from the results of FIGS. 7 to 10 that the antibacterial layer formed by the pores and the surface of the titanium oxide layers of Examples 1 to 3, 7 to 9 and 13 to 15 after the cathodic deposition treatment does contain silver, and The minimum silver content was 2% (Example 1) and the highest was 31% (Example 15).

Cellular Activity Analysis

Referring to Figures 11A to 11C, the results of cell activity analysis of titanium or titanium alloys having antimicrobial surfaces of Comparative Examples 1 to 4 and Examples 1 to 3, 7 to 9 and 13 to 15 are shown. From the results of FIGS. 11A to 11C, it is known that the silver-containing antibacterial layer causes a decrease in cell biological activity, and as the silver content increases, the optical density (OD) reflecting the cell activity is smaller, and compared with oxidation. As a result of the titanium or titanium alloy having an antibacterial surface prepared at a voltage of 270 V, titanium or a titanium alloy having an antibacterial surface prepared at an oxidation voltage of 150 V and 210 V has better cell activity. This is because the pores on the surface are conducive to cell attachment growth. On the contrary, the molten bulk titanium oxide layer prepared by the oxidation voltage of 270 V is not conducive to cell attachment growth, so that its cell activity is low.

Antibacterial Efficacy Analysis

Please refer to FIGS. 12A to 12D, FIGS. 13A to 13D, and FIGS. 14A to 14D for Comparative Examples 1 to 3 (FIGS. 12A, 13A, and 14A) and Embodiments 1 to 3 (FIGS. 12B to 12D) and 7 to 9 (FIG. Antimicrobial analysis results of 13B to 13D), 13 to 15 (Figs. 14B to 14D). As shown in FIGS. 12A to 12D, as compared with the result of Comparative Example 1, as the cathode deposition voltage was increased from 20 V to 40 V (i.e., the silver content of the antibacterial layer was increased), the titanium having an antibacterial surface prepared in Examples 1 to 3 or The amount of bacteria around the titanium alloy began to decrease, and even an antibacterial ring appeared on the periphery of the titanium or titanium alloy having the antibacterial surface prepared in Example 3, indicating that the antibacterial effect increased as the silver content of the antibacterial layer increased. Similarly, as shown in the results of FIGS. 13A to 13D and FIGS. 14A to 14D, the antibacterial effects of the titanium or titanium alloy having an antibacterial surface prepared in Examples 7 to 9 and 13 to 15 also increase with the silver content of the antibacterial layer. And increase.

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

The figure is a flow chart, so there is no component representative symbol.

Claims (9)

A method for producing titanium or a titanium alloy having an antibacterial surface, comprising: (A) providing a substrate, the substrate being titanium or a titanium alloy; (B) immersing the substrate in a first electrolyte, Forming a titanium oxide layer on the surface of the substrate by an oxidation treatment, wherein the first electrolyte solution comprises an active modifier, and the active modifier is at least one selected from the group consisting of calcium acetate, HA powder, and phosphate. And (C) immersing the substrate and the titanium oxide layer in a second electrolyte, and forming a pore and a surface of the titanium oxide layer by a cathode deposition treatment An antibacterial layer, wherein the second electrolyte system comprises an antibacterial additive, wherein the antibacterial additive is silver halide, silver nitrate, silver sulfate, or a combination thereof, and the content of the antibacterial additive is 0.1 to 10 g/L; wherein The first electrolyte may be a solution selected from at least one of the group consisting of sulfuric acid, phosphoric acid, hydrogen peroxide, nitrate, acetate, citrate, and hypophosphite; the second electrolyte system Is selected from the group consisting of sulfuric acid, phosphoric acid, hydrogen peroxide, nitrate, vinegar a solution of at least one of the group consisting of an acid salt, a citrate, and a hypophosphite; the temperature of the first electrolyte is 0 to 30 ° C; and the temperature of the second electrolyte is 0 30 ° C; the oxidation treatment has a constant current density of 1 to 10 A/dm ² or a constant voltage of 100 V to 600 V, and the treatment time is 1 to 30 minutes; and the constant current density of the cathode deposition treatment The system is 1 to 5 A/dm ² or the constant voltage system is 10 V to 50 V, and the processing time is 1 to 10 minutes. The method for producing titanium or a titanium alloy having an antibacterial surface according to claim 1, wherein after the step (C), the step (B) and the step (C) are repeated at least once. The method for producing titanium or a titanium alloy having an antibacterial surface according to claim 1, wherein the oxidation treatment is an anodization method or a micro-arc oxidation method. The method for producing titanium or a titanium alloy having an antibacterial surface according to claim 1, wherein the cathodic deposition treatment is an electrochemical electrolysis method. The method for preparing titanium or titanium alloy having an antibacterial surface according to claim 1, after step (A) and before step (B), further comprising: (A1) removing the base by a pretreatment step An oxide film on the surface of the material and roughening the surface of the substrate. A titanium or titanium alloy having an antibacterial surface, which is produced according to the method for producing titanium or titanium alloy having an antibacterial surface according to claims 1 to 5, which comprises: a substrate, the substrate is a titanium or titanium alloy; a titanium oxide layer formed on the surface of the substrate by an oxidation treatment; and an antibacterial layer formed on the pore of the titanium oxide layer by a cathode deposition treatment And a surface; wherein the titanium oxide layer has a thickness of 1 micrometer to 50 micrometers, the titanium oxide layer has a hardness of 200 to 800 Hv, and the antibacterial layer is a continuous or discontinuous silver-containing titanium oxide film layer. The titanium or titanium alloy having an antibacterial surface as described in claim 6, wherein the antibacterial layer based on the titanium oxide film layer has a silver content of 1% to 50%. The titanium or titanium alloy having an antibacterial surface according to claim 6, wherein the antibacterial layer has a surface average roughness of 0.1 μm to 3 μm, and the surface of the antibacterial layer is in contact with pure water at 25 ° C. The horn is 10 to 90 degrees. The titanium or titanium alloy having an antibacterial surface as described in claim 6, wherein the titanium or titanium alloy having an antibacterial surface is applied to a dental implant, a human bone, or an artificial joint.