TWI571535B - Electrolyte for surface treatment of metal implant and method for surface treatment of metal implant using said electrolyte - Google Patents

Description

Electrolyte for surface treatment of metal implants and method for surface treatment using the same

The present invention relates to an electrolyte, and more particularly to an electrolyte for surface treatment of a metal implant, and a method of surface treatment of a metal implant using the electrolyte.

Metal implants are implantable materials that are widely used in human hard tissues such as teeth, bones or joints for reinforcement or fixation. Generally, a porous oxide film layer must be formed on the surface of the metal implant by surface treatment, so that the metal implant can be bonded to the human body after being implanted into the human body to avoid the metal. The implant is detached.

The electrolytic solution for surface treatment of metal implants comprises a sulfur-containing compound, a phosphorus-containing compound, an oxidizing agent and water, and a surface treatment method of a conventional metal implant is to impregnate a metal implant into the metal implant. The porous oxide film layer is formed on the surface of the metal implant by means of micro-arc discharge in the electrolyte. An embodiment of the above-described electrolyte and metal implant surface treatment method for metal implant surface treatment is disclosed in the Republic of China Publication No. I435955.

However, since a reactive gas such as hydrogen gas is generated during the micro-arc discharge process, if the metal implant originally has a microscopic shape such as a minute hole or a channel, the reaction gas easily adheres to the surface of the metal implant, affecting the porous body. Formation of an oxide film layer. Therefore, not only the porous oxide film layer cannot be formed, but also the surface of the metal implant is pitting, and even hydrogen embrittlement occurs. Accordingly, conventionally used for the surface treatment of metal implants and the surface of metal implants The method is less suitable for metal implants having a three-dimensional appearance.

The invention provides an electrolyte for surface treatment of a metal implant, which can prevent the reaction gas generated by the micro-arc discharge from adhering to the surface of a metal implant.

The invention further provides a surface treatment method for a metal implant, which can prevent the reaction gas generated by the micro-arc discharge from adhering to the surface of a metal implant.

The invention provides an electrolyte for surface treatment of a metal implant, comprising 10 to 30% by weight of an aqueous solution of a sulfur compound, 3 to 10% of an aqueous solution of a phosphorus compound, and 0.5 to 2% of an oxidant. An aqueous solution, 0.5 to 5% of an aqueous solution of a surfactant, and the remainder is supplemented with water; wherein the concentration of the aqueous solution of the sulfur-containing compound is 0.1 to 3 M, and the concentration of the aqueous solution of the phosphorus-containing compound is 0.05 to 2 M, and the concentration of the aqueous solution of the oxidizing agent is 0.05~1M, and the concentration of the surfactant aqueous solution is 0.05~5M. Thereby, it is possible to prevent the reaction gas generated by the micro-arc discharge reaction from adhering to the surface of the metal implant and hinder the formation of the porous oxide film layer, thereby achieving "forming the porous oxide film layer on the surface of the metal implant". efficacy.

The electrolyte for surface treatment of a metal implant according to the present invention, wherein the aqueous solution of the sulfur-containing compound is an aqueous solution of sulfuric acid or an aqueous solution of potassium persulfate; and the aqueous solution of the phosphorus-containing compound is an aqueous solution of phosphoric acid or an aqueous solution of sodium hypophosphite; An aqueous solution of hydrogen peroxide or an aqueous solution of ozone; and the aqueous solution of the surfactant is a monoalkyl phosphate, a glutamine, a potassium N-acyl glutamine, an alkane An aqueous solution of an alkyl polyglucoside or a polyethylene glycol. Thereby, the effect of "making the metal implant highly biocompatible" can be achieved.

The invention further provides a surface treatment method for a metal implant, comprising: shaking a metal implant with a solvent until the surface of the metal implant is removed; and removing the metal implant of the dirt In an anode, and immersed in the electrolyte, with a cathode, and a reaction voltage of 150 ~ 500V, and adjust the reaction temperature of 0 ~ -10 ° C, so that the metal plant The input material generates a micro-arc discharge reaction in the electrolyte until a porous oxide film layer is formed on the surface of the metal implant. Thereby, the effect of "increasing the bonding strength of the metal implant to the hard tissue of the human body" can be achieved.

The surface treatment method of the metal implant of the present invention, wherein the porous oxide film layer has a thickness of 0.5 to 30 μm, the porous oxide film layer has a pore diameter of 0.5 to 15 μm, and the porous oxide film layer has a pore depth of 0.5 to 0.5 3 μm. Thereby, the effect of "increasing the bonding strength between the metal implant and the hard tissue of the human body" can be achieved.

In the surface treatment method of the metal implant of the present invention, the metal implant can generate a micro-arc discharge reaction in the electrolyte for 10 to 60 minutes to form the porous oxide film layer on the surface of the metal implant. Thereby, the effect of "increasing the bonding strength between the metal implant and the hard tissue of the human body" can be achieved.

In the surface treatment method of the metal implant of the present invention, after the porous oxide film layer is formed on the surface of the metal implant, the metal implant having the porous film layer is further immersed at a temperature of 15 to 30 ° C and a pH. 5.0~7.0 weak acid solution for 10~30 minutes. Thereby, the effect of "removing residual electrolyte and impurities on the surface of the metal implant" can be achieved.

The surface treatment method of the metal implant of the present invention, wherein the weak acid solution may be an oxalic acid solution, a citric acid solution, a lactic acid solution, a formic acid solution or a carbonic acid solution. Thereby, the weak acid solution remaining on the surface of the metal implant can be avoided to cause harm to the human body.

The electrolyte for surface treatment of a metal implant can prevent micro-arc discharge reaction from being generated by containing an appropriate concentration of the sulfur-containing compound, the phosphorus-containing compound, the oxidizing agent and the surfactant in the electrolyte. The reaction gas adheres to the surface of the metal implant to hinder the formation of the porous oxide film layer, and the effect of "forming the porous oxide film layer on the surface of the metal implant" is achieved.

The method for surface treatment of the metal implant of the present invention can be used for the metal implant by using the electrolyte and a reaction voltage of 150 to 500 V and a reaction temperature of 0 to -10 ° C. The porous oxide film layer having a crater shape is formed on the surface to increase the surface roughness of the metal implant, thereby achieving the effect of "increasing the bonding strength of the metal implant to the hard tissue of the human body".

The method for surface treatment of the metal implant of the invention has the advantages of simple operation, saving time and cost for surface treatment, and achieving the effect of "improving the efficiency of metal implant surface treatment".

Figure 1: SEM image of a metal implant without surface treatment.

Figure 2a: SEM image of the metal implant of group A1 (1).

Figure 2b: SEM image of the metal implant of Group A1 (2).

Figure 3a: SEM image of the metal implant of group A2 (1).

Figure 3b: SEM image of the metal implant of Group A2 (2).

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The metal implant to which the present invention pertains is made of metal or alloy and can be used for reconstruction and repair of teeth, bones or joints of the human body. Similarly, the metal implant can also be used in other animal bodies. The metal implant can be made of titanium metal, titanium alloy or a metal material containing titanium element, and has good biocompatibility and is suitable for use in human body. In addition, the metal implant can be made by 3D printing or the like, and has a three-dimensional appearance such as micro holes and channels to facilitate bonding with hard tissues of the human body.

The invention provides an electrolyte comprising an aqueous solution of a sulfur-containing compound, an aqueous solution of a phosphorus-containing compound, an aqueous solution of an oxidizing agent, an aqueous solution of a surfactant, and the electrolyte is used for surface treatment of a metal implant.

In detail, the electrolyte contains 10 to 30% by weight of the vulcanization. An aqueous solution of the compound, 3 to 10% of the aqueous solution of the phosphorus-containing compound, and 0.5 to 2% of the aqueous solution of the oxidizing agent. Wherein, the aqueous solution of the sulfur compound comprises a sulfur-containing compound having a concentration of 0.1 to 3 M, and the sulfur-containing compound may be sulfuric acid, potassium persulfate or the like; and the aqueous solution of the phosphorus-containing compound comprises a phosphorus-containing compound at a concentration of 0.05 to 2 M. The phosphorus-containing compound may be phosphoric acid, sodium hypophosphite or the like; the oxidizing agent aqueous solution contains an oxidizing agent at a concentration of 0.05 to 1 M, and the oxidizing agent may be hydrogen peroxide, ozone or the like, but the invention is not limited thereto.

In addition, the electrolyte further comprises 0.5 to 5% by weight of the surfactant aqueous solution, and the concentration of the surfactant aqueous solution is 0.05-5 M, and any surfactant active solution may be selected, preferably selected for the human body. Non-toxic. For example, the surfactant aqueous solution may be monoalkyl phosphate, glutamine, potassium N-acyl glutamine, alkyl polydextrose (alkyl Polyglucoside) or polyethylene glycol (PEG), and may be selected from PEG-200, PEG-400 or PEG-3350.

In the present embodiment, the aqueous solution of the sulfur-containing compound is selected to be an aqueous solution of sulfuric acid, and the concentration is 2M; the aqueous solution of the phosphorus-containing compound is selected as an aqueous solution of phosphoric acid, and the concentration is 1M; the aqueous solution of the oxidizing agent is selected as an aqueous solution of hydrogen peroxide, and the concentration is selected. It is 0.1 M; the aqueous surfactant solution is an aqueous solution of PEG-200 selected at a concentration of 2.5 M. According to the above concentration, after the aqueous solution of the sulfur-containing compound, the aqueous solution of the phosphorus-containing compound, the aqueous solution of the oxidizing agent and the aqueous solution of the surfactant are prepared, 10 to 30% by weight of the aqueous solution of the sulfur-containing compound, 3 to 10% by weight is continuously obtained. The aqueous solution of the phosphorus-containing compound, 0.5 to 2% of the aqueous solution of the oxidizing agent, and 0.5 to 5% of the aqueous solution of the surfactant are mixed with water to prepare the electrolytic solution.

By immersing the metal implant in the electrolyte and applying an appropriate voltage through the composition and ratio of the electrolyte, the crucible can immediately form an oxide film on the surface of the metal implant and pass through The dissociated charged ions repeatedly penetrate through, and micro-arc discharge phenomenon occurs, so that the arc or spark swims on the surface of the metal implant until the surface of the metal implant is discharged by micro-arc The high temperature melts to form a porous oxide film layer. Further, since the electrolyte contains an appropriate concentration of the surfactant, the sulfur-containing compound, the phosphorus-containing compound and the oxidizing agent are appropriately mixed, and even if a reaction gas is generated during the micro-arc discharge reaction, the metal can be quickly obtained from the metal. The surface of the implant is dissipated and does not adhere to the surface of the metal implant, thereby preventing the reaction gas from affecting the formation of the porous oxide film layer.

Therefore, the sulfur component contained in the sulfur-containing compound, the phosphorus component contained in the phosphorus-containing compound, and the aqueous solution of the oxidant can electrochemically and plasmaly react with the metal particles on the surface of the metal implant, and subsequently the metal plant The porous oxide film layer having a ceramic property is formed on the surface of the input. Therefore, when the metal implant is implanted into the hard tissue of the human body, the cells of the hard tissue of the human body can be closely attached to the porous oxide film to further enhance the biological activity of the metal implant, and can be easily hardened with the human body. The tissue is firmly bonded.

The invention further provides a surface treatment method for a metal implant, wherein the metal implant is surface-treated with the electrolyte solution, comprising: shaking the metal implant with a solvent, and continuously immersing the metal implant in the metal implant; In the electrolyte, a voltage is applied to form the porous oxide film layer.

More specifically, the solvent may be ultrapure water, acetone or alcohol, etc., and the invention is not limited. By shaking the metal implant with the solvent, dirt on the surface of the metal implant, such as processing oil or metal impurities remaining during processing, can be removed. In the present embodiment, the metal implant is sequentially shaken in the order of ultrapure water, acetone, ultrapure water, and alcohol to thoroughly wash away the dirt on the surface of the metal implant to avoid contamination. The substance affects the progress of the subsequent reaction.

Then, the metal implant is placed on an anode, and immersed in the electrolyte, and a cathode is used to pass a reaction voltage of 150 to 500 V, and the reaction temperature is adjusted to 0 to -10 ° C to make the metal implant. The substance generates a micro-arc discharge reaction in the electrolyte until the porous oxide film layer is formed on the surface of the metal implant. Wherein, the cathode may be a platinum, graphite or titanium electrode.

In detail, when the metal implant is immersed in the electrolyte and an appropriate current is applied at a reaction voltage of 150 to 500 V, the surface of the metal implant can immediately form the oxidation. Membrane; and the charged ion that is free from the electrolyte will penetrate the weaker region of the oxide film after the voltage exceeds a certain critical value, thereby generating a micro-arc discharge phenomenon, so that the metal implant The surface gathers arcs or sparks that swim.

At the same time, the surface of the metal implant generates a reaction gas such as hydrogen due to the above reaction. If the reaction gas cannot be removed, the subsequent charged ions are prevented from approaching the surface of the metal implant, thereby affecting the surface treatment effect. In the present case, since the surface tension of the electrolyte used is low, the reaction gas can quickly leave the surface of the metal implant without affecting the formation of the porous oxide film layer. Further, the speed at which the reaction gas leaves the surface of the metal implant can be further accelerated by performing the reaction at a low temperature.

In this way, the micro-arc discharge phenomenon can occur repeatedly, and the high temperature of the arc spot discharge forces the metal implant to interact with the electrolyte and melt on the surface of the metal implant, thereby forming a volcano. The pores of the mouth shape, and after 10 to 60 minutes of electrochemical and plasma reaction, the porous oxide film layer such as a nano network is formed on the surface of the metal implant.

In the surface treatment method of the metal implant of the present invention, after the porous oxide film layer is formed, the metal implant having the porous oxide film layer can be cleaned, for example, the metal implant is immersed at a temperature of 15 to 30 ° C. And the weak acid solution of pH 5.0~7.0 for 10~30 minutes to remove the electrolyte and impurities remaining on the surface. The weak acid solution is preferably selected to be non-toxic to the human body, such as oxalic acid solution, citric acid solution, lactic acid solution, formic acid solution or carbonic acid solution, etc., so that even a small amount of the weak acid solution remains in the metal implant. The surface is not harmful to the human body.

In addition, in the present invention, the thickness of the porous oxide film layer is preferably 0.5 to 30 μm, the pore diameter of the porous oxide film layer is 0.5 to 15 μm, and the pore depth of the porous oxide film layer is 0.5 to 3 μm, so that the metal implant The porous oxide film layer forms a more stable bond with the hard tissue of the human body, and further enhances the effect of human cells adsorbing on the metal implant.

The method of performing surface treatment of the metal implant by using the above electrolyte solution can prevent the reaction gas from affecting the formation of the porous oxide film layer under the reaction voltage, temperature, and interaction of the electrolyte and the metal implant. Therefore, the surface treatment method of the present invention can form the porous oxide film layer on the surface of the metal implant to further stabilize the bonding effect between the metal implant and the human hard tissue, so that the adhesive protein in the cell matrix is closer to the surface. The porous oxide film layer guides the cells to adhere to the effect of accelerating hard tissue integration. Moreover, the method for surface treatment of the metal implant further eliminates the time and cost required for surface treatment by simple manipulation, so as to achieve the effect of improving the surface treatment efficiency of the metal implant, and further capable of mass production in the industry. widely used.

In order to confirm that the metal implant treated by the present invention can form the porous oxide film layer of the crater type, the following experiment is carried out:

In this experiment, the metal implant was selected as a 3D printed titanium material with tiny holes. The internal morphology of the pores of the metal implant was examined by SEM before the reaction was carried out, as shown in Fig. 1. The metal implant is shaken according to the above steps, and the surface treatment is performed to form the porous oxide by an electrolyte solution in which the surfactant solution (Group A1) is not added and the surfactant solution (Group A2) is added. Membrane layer. After washing with the weak acid solution, the inside of the pore of the metal implant was examined by SEM.

In the present experiment, an aqueous solution of sulfuric acid, an aqueous solution of hydrogen peroxide, and an aqueous solution of PEG-200 are used as the aqueous solution of the sulfur-containing compound, the aqueous solution of the phosphorus-containing compound, the aqueous solution of the peroxidizing agent, and the aqueous solution of the surfactant, and the oxalic acid solution is used as the solution. Weak acid solution. Here, the concentrations of the components of the groups A1 and A2 are as shown in the first table, and are mixed at a weight percentage as described above to obtain an electrolyte solution of the groups A1 and A2. The SEM images of Group A1 are Figures 2a and 2b; the SEM images of Group A2 are Figures 3a and 3b.

Referring to Figures 2a and 2b, when the surfactant solution is not added, the reaction gas easily adheres to the surface of the metal implant, thereby preventing the electrolyte from entering the pores of the metal implant, and is not in the hole. The porous oxide film layer is formed such that the surface of the metal implant maintains the morphology before the reaction. On the contrary, referring to the figures 3a and 3b, when the aqueous solution of the surfactant is added to the electrolyte, the surfactant can help the reaction gas to detach from the surface of the metal implant without affecting the formation of the porous oxide film layer. . Therefore, the porous oxide film layer having a crater pattern can be formed.

In summary, the electrolyte for surface treatment of a metal implant of the present invention can avoid the formation of a micro-arc discharge reaction by including an appropriate concentration of the sulfur-containing compound, the phosphorus-containing compound, the oxidizing agent and the surfactant. The reaction gas adheres to the surface of the metal implant to hinder the formation of the porous oxide film layer, and the effect of "forming the porous oxide film layer on the surface of the metal implant" is achieved.

In addition, the electrolyte for surface treatment of a metal implant of the present invention uses sulfuric acid or potassium persulfate as the sulfur-containing compound, and phosphoric acid or sodium hypophosphite is selected as the phosphorus-containing compound, and hydrogen peroxide or ozone is selected as the As the oxidizing agent, monoalkyl phosphate, glutamic acid, potassium N-decyl glutamate, alkyl polydextrose or polyethylene glycol is used as the surfactant, and since each component is harmful to living organisms, It can achieve the effect of "making the metal implant highly biocompatible".

Furthermore, the method for surface treatment of the metal implant of the present invention can form a volcano on the surface of the metal implant by using the electrolyte and a reaction voltage of 150 to 500 V and a reaction temperature of 0 to -10 ° C. The porous oxide film layer in the form of a mouth is used to increase the surface roughness of the metal implant, thereby achieving the effect of "increasing the bonding strength of the metal implant to the hard tissue of the human body".

In addition, the method for surface treatment of the metal implant of the present invention is simple in operation, and can save time and cost for surface treatment, and achieve the effect of "improving the efficiency of metal implant surface treatment".

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Claims (6)

An electrolyte for surface treatment of a metal implant, comprising 10 to 30% by weight of an aqueous solution of a sulfur compound, 3 to 10% of an aqueous solution of a phosphorus compound, 0.5 to 2% of an aqueous solution of an oxidizing agent, 0.5 ~5% of an aqueous solution of surfactant, and the rest is supplemented with water; wherein the concentration of the aqueous solution of the sulfur compound is 0.1 to 3 M, the concentration of the aqueous solution of the phosphorus compound is 0.05 to 2 M, and the concentration of the aqueous solution of the oxidizing agent is 0.05 to 1 M. And the concentration of the surfactant aqueous solution is 0.05~5M. The electrolyte for surface treatment of a metal implant according to claim 1, wherein the aqueous solution of the sulfur compound is an aqueous solution of sulfuric acid or an aqueous solution of potassium persulfate. The electrolyte for surface treatment of a metal implant according to claim 1, wherein the aqueous solution of the phosphorus-containing compound is an aqueous solution of phosphoric acid or an aqueous solution of sodium hypophosphite. The electrolyte for surface treatment of a metal implant according to claim 1, wherein the oxidizing agent aqueous solution is an aqueous hydrogen peroxide solution or an aqueous ozone solution. The electrolyte for surface treatment of a metal implant according to claim 1, wherein the aqueous solution of the surfactant is monoalkyl phosphate, glutamine, polyethylene. An aqueous solution of polyethylene glycol, potassium N-acyl glutamine or alkyl polyglucoside. A method for surface treatment of a metal implant using an electrolyte according to any one of claims 1 to 5, comprising: shaking a metal implant with a solvent until the surface of the metal implant The dirt is removed; the metal implant for removing the dirt is placed on an anode, and immersed in the electrolyte, with a cathode, and a reaction voltage of 150 to 500 V is passed, and the reaction temperature is adjusted to 0~- At 10 ° C, the metal implant generates a micro-arc discharge reaction in the electrolyte until a porous oxide film layer is formed on the surface of the metal implant.