CN110607545A - Electrochemical additive manufacturing method of antibacterial fluorinated hydroxyapatite bionic cicada wing patterned surface - Google Patents
Electrochemical additive manufacturing method of antibacterial fluorinated hydroxyapatite bionic cicada wing patterned surface Download PDFInfo
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- CN110607545A CN110607545A CN201910894737.5A CN201910894737A CN110607545A CN 110607545 A CN110607545 A CN 110607545A CN 201910894737 A CN201910894737 A CN 201910894737A CN 110607545 A CN110607545 A CN 110607545A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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Abstract
The invention discloses an electrochemical additive manufacturing method of a fluorinated hydroxyapatite bionic cicada wing patterned surface with antibacterial property. The prepared fluorinated hydroxyapatite bionic cicada wing patterned surface provides a non-medication strategy which does not depend on pharmaceutical ingredients such as antibiotics and the like, but depends on chemical ingredients and physical morphology to generate a synergistic antibacterial effect; the antibacterial effect is obtained without depending on antibiotics and other medicines, so that the anaphylactic reaction of the patient can be effectively avoided, and the physical burden of the patient is greatly reduced; the surface has antibacterial property, and has good biocompatibility and bioactivity.
Description
Technical Field
The invention belongs to the technical field of bionic engineering and biomedical engineering material preparation, and particularly relates to an electrochemical additive manufacturing method of a fluorinated hydroxyapatite bionic cicada wing patterned surface with antibacterial property.
Background
In recent years, the aging problem of the population is increasingly remarkable, and orthopedic disorders such as hip joint diseases, knee joint diseases, intervertebral diseases and the like increasingly trouble the daily life of middle-aged and elderly people. In view of the ever-increasing medical health care requirements of the people, orthopedic implant surgery medical treatment such as artificial joint replacement surgery is receiving more and more extensive attention of families and society. However, there is still a proportion of postoperative infections in such surgery, and the infections can cause complete failure of the surgery, even death of the patient with serious consequences. Therefore, there is a need to develop a new highly effective anti-infective orthopedic implant. However, it is very challenging that how to effectively prevent the formation of the biofilm on the surface of the orthopedic implant is one of the problems yet to be solved in the biomedical field, because the infection of the orthopedic implant is mainly attributed to the formation of the biofilm on the surface, and the biofilm is extremely difficult to eradicate once formed. The formation of the biofilm is caused by adhesion, propagation and inhabitation of bacteria on the surface of the orthopedic implant material. The adhesion of bacteria on the surface of the material is the first step of the formation of a biofilm on the surface of the orthopedic implant and the subsequent infection. Therefore, imparting antibacterial adhesion properties and bactericidal properties to the surface of the orthopedic implant is an effective strategy to prevent biofilm formation.
Orthopedic implant infections are difficult to treat by antibiotics alone given that biofilms can protect bacteria from antibiotics; moreover, as more and more kinds of bacteria generate drug resistance to common antibiotics, the drug effect of the bacteria is greatly weakened; the development period of the new antibiotics is very long; therefore, scientific researchers pay attention to the strategy of obtaining good antibacterial adhesion and sterilization performance on the surface of the orthopedic implant by a non-medication strategy.
Disclosure of Invention
The invention aims to overcome the defect of poor drug-resistant antibacterial effect in the prior art, comprehensively exert the chemical antibacterial effect of the fluorinated hydroxyapatite and the physical antibacterial effect of the patterned surface of the bionic cicada wing, and further improve the antibacterial capability of the surface of a biological material, thereby providing the electrochemical additive manufacturing method of the patterned surface of the fluorinated hydroxyapatite bionic cicada wing with antibacterial property.
The technical scheme of the invention is an electrochemical additive manufacturing method of a fluorinated hydroxyapatite bionic cicada wing patterned surface with antibacterial property, which comprises the following steps:
step (1): taking a metal substrate as a cathode material for electrochemical additive manufacturing;
step (2): the electrochemical additive manufacturing reaction unit comprises an anode, a cathode, a reference electrode and three electrodes;
and (3): the electrolyte consists of three solutions, 0.042M Ca (NO) respectively3)2，0.025M NH4H2PO40.001M NaF, wherein the volume ratio of the three solutions is 1:1: 1;
and (4): adjusting the pH value of the electrolyte to 3;
and (5): the electrochemical additive manufacturing reaction uses a constant voltage mode, and the voltage is controlled to be-1.6V; introducing nitrogen into the electrolyte during reaction; the reaction temperature is 65 ℃; the reaction time is 2 minutes;
and (6): and after the sample is dried in the air, obtaining the fluorinated hydroxyapatite bionic cicada wing patterned surface on the metal substrate.
Advantageous effects
1. The prepared fluorinated hydroxyapatite bionic cicada wing patterned surface provides a non-medication strategy which does not depend on pharmaceutical ingredients such as antibiotics and the like, but depends on chemical ingredients and physical morphology to generate a synergistic antibacterial effect;
2. the invention can effectively avoid the drug anaphylactic reaction of the patient and greatly reduce the physical burden of the patient because the invention does not rely on drugs such as antibiotics to obtain the antibacterial effect;
3. the fluorinated hydroxyapatite bionic cicada wing patterned surface prepared by the method has antibacterial performance and good biocompatibility and bioactivity.
Drawings
Fig. 1 is a scanning electron microscope photograph of a patterned surface of a fluorinated hydroxyapatite bionic cicada wing prepared by an electrochemical additive manufacturing method, and shows a surface topological structure similar to a nanometer cone array on the surface of the cicada wing.
Detailed Description
The invention is further illustrated by the following specific examples and the accompanying drawings. The examples of the present invention are for better understanding of the present invention by those skilled in the art, and do not limit the present invention in any way.
Examples
An electrochemical additive manufacturing method of a fluorinated hydroxyapatite bionic cicada wing patterned surface with antibacterial performance comprises the following steps:
step (1): taking a pure titanium substrate as a cathode material for electrochemical additive manufacturing;
step (2): the electrochemical additive manufacturing reaction unit comprises an anode (platinum), a cathode (pure titanium), a reference electrode (saturated calomel electrode) and three electrodes;
and (3): the electrolyte consists of three solutions, 0.042M Ca (NO) respectively3)2，0.025M NH4H2PO40.001M NaF, wherein the volume ratio of the three solutions is 100mL to 100 mL;
and (4): adjusting the pH value of the electrolyte to 3;
and (5): the electrochemical additive manufacturing reaction uses a constant voltage mode, and the voltage is controlled to be-1.6V; introducing nitrogen into the electrolyte during reaction; the reaction temperature is 65 ℃; the reaction time is 2 minutes;
and (6): and drying the sample in the air to obtain the fluoridated hydroxyapatite bionic cicada wing patterned surface on the pure titanium substrate.
Fig. 1 shows a scanning electron microscope photograph of a patterned surface of a fluorinated hydroxyapatite biomimetic cicada wing prepared by an electrochemical additive manufacturing method, which shows a surface topological structure similar to a nano-cone array on the surface of the cicada wing. The research is subsidized by the natural science fund (No.18JCYBJC19500) in Tianjin.
It should be understood that the embodiments and examples discussed herein are illustrative only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims.
Claims (4)
1. The electrochemical additive manufacturing method of the bionic cicada wing patterned surface of the fluorinated hydroxyapatite with antibacterial property is characterized by comprising the following steps of:
step (1): taking a metal substrate as a cathode material for electrochemical additive manufacturing;
step (2): the electrochemical additive manufacturing reaction unit comprises an anode, a cathode, a reference electrode and three electrodes;
and (3): the electrolyte consists of three solutions, Ca (NO) respectively3)2Solution, NH4H2PO4The volume ratio of the three solutions is 1:1: 1;
and (4): adjusting the pH value of the electrolyte to 3;
and (5): the electrochemical additive manufacturing reaction uses a constant voltage mode, and the voltage is controlled to be-1.6V; introducing nitrogen into the electrolyte during reaction; the reaction temperature is 65 ℃; the reaction time is 2 minutes;
and (6): and after the sample is dried in the air, obtaining the fluorinated hydroxyapatite bionic cicada wing patterned surface on the metal substrate.
2. The electrochemical additive manufacturing method for the bionic cicada wing patterned surface of fluorinated hydroxyapatite with antibacterial property as claimed in claim 1, wherein the Ca (NO) is3)2The solution concentration was 0.042M.
3. The electrochemical additive manufacturing method for the bionic cicada wing patterned surface of fluorinated hydroxyapatite with antibacterial property as claimed in claim 1, wherein the NH is4H2PO4The concentration of the solution was 0.025M.
4. The electrochemical additive manufacturing method for the bionic cicada wing patterned surface of fluorinated hydroxyapatite with antibacterial property as claimed in claim 1, wherein the concentration of the NaF solution is 0.001M.
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| CN201910894737.5A CN110607545A (en) | 2019-09-20 | 2019-09-20 | Electrochemical additive manufacturing method of antibacterial fluorinated hydroxyapatite bionic cicada wing patterned surface |
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Citations (10)
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| CN1587442A (en) * | 2004-07-06 | 2005-03-02 | 厦门大学 | Electrochemical preparing method for nano ordered hydroxy apatite coating |
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| CN101703797A (en) * | 2009-12-07 | 2010-05-12 | 上海交通大学 | Fluorine-substituted apatite coating on surface of biologic medical magnesium or alloy thereof and preparation method |
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