CN115006601A - Antibacterial nano composite coating and preparation method thereof - Google Patents
Antibacterial nano composite coating and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of biomedical materials, and particularly relates to an antibacterial nano composite coating and a preparation method thereof. The invention provides an antibacterial nano composite coating, which comprises the following components in percentage by volume: ti 95-99%, and antibacterial particles 1-5%; the antibacterial particles are ZnO or TiO 2 . The invention adopts ZnO or TiO 2 The particles are used as antibacterial particles in the antibacterial nano composite coating, and the content of the antibacterial particles is limited, so that the antibacterial nano composite coating not only has good antibacterial property, but also has no cytotoxicity, meets the safety standard of biological materials, and can be used as teethAn antibacterial coating of an implant. The data of the embodiment shows that the antibacterial rate of the antibacterial nano composite coating provided by the invention to the fusobacterium nucleatum is more than 70%, and the antibacterial nano composite coating has no cytotoxicity and meets the standard of biosafety materials.
Description
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to an antibacterial nano composite coating and a preparation method thereof.
Background
Pure titanium has become one of the most commonly used dental implant materials in clinic because of ideal mechanical strength, processability and good biocompatibility, but because the dental implant is implanted in the oral environment for a long time, bacteria in the oral cavity can adhere to the surface of the dental implant and form a bacterial biofilm, and peri-implantitis caused by the bacterial biofilm is an important reason for implant failure. In order to prevent peri-implantitis, an antibacterial coating can be loaded on the surface of the implant, and the method has the characteristics of small side effect, easiness in control, excellent antibacterial performance and the like.
At present, the active coating containing zinc is prepared on the surface of a pure titanium substrate by a plasma electrolytic oxidation method in the prior art, and with the increase of the zinc content, although the quantity of streptococcus mutans adhered to the surface of the substrate is reduced, the cytotoxicity of the coating is overlarge.
Disclosure of Invention
In view of the above, the present invention provides an antibacterial nanocomposite coating, which can make a titanium implant have excellent antibacterial properties and the coating has low cytotoxicity.
In order to achieve the aim, the invention provides an antibacterial nano composite coating, which comprises the following components in percentage by volume: 95-99% of Ti and 1-5% of antibacterial particles; the antibacterial particles are ZnO or TiO 2 。
Preferably, the thickness of the antibacterial nano composite coating is 150-300 nm.
The invention also provides a preparation method of the antibacterial nano composite coating, which comprises the following steps:
carrying out ultrasonic cleaning on the base material to obtain a cleaned base material;
depositing a Ti-based composite target material on the surface of the cleaned substrate through magnetron sputtering to obtain the antibacterial nano composite coating;
the volume ratio of Ti to antibacterial particles in the Ti-based composite target material is 95-99: 1 to 5.
Preferably, the antibacterial particles are TiO 2 And then, after magnetron sputtering deposition, ultraviolet irradiation is also included.
Preferably, the wavelength of the ultraviolet radiation is 365nm, and the time is 30 min.
Preferably, the ultrasonic cleaning is acetone ultrasonic cleaning and absolute ethyl alcohol ultrasonic cleaning sequentially.
Preferably, the ultrasonic power of the ultrasonic cleaning is 80-100W.
Preferably, the magnetron sputtering conditions include: vacuum degree lower than 1.5X 10 -3 Pa, sputtering power of 140-160W, working pressure of 0.8-0.9 Pa, argon flow of 35-45 sccm, and sputtering time of 10 min.
Preferably, the substrate is a Ti implant.
The invention provides an antibacterial nano composite coating, which comprises the following components in percentage by volume: 95-99% of Ti and 1-5% of antibacterial particles; the antibacterial particles are ZnO or TiO 2 . The invention adopts ZnO or TiO 2 The particles are used as antibacterial particles in the antibacterial nano composite coating, and the content of the antibacterial particles is limited, so that the antibacterial nano composite coating not only has good antibacterial property, but also has no cytotoxicity, meets the safety standard of biological materials, and can be used as the antibacterial coating of the dental implant. The data of the embodiment shows that the antibacterial rate of the antibacterial nano composite coating provided by the invention to the fusobacterium nucleatum is more than 70%, and the antibacterial nano composite coating has no cytotoxicity and meets the standard of biosafety materials.
In addition, the results of the examples of the present invention show that the antibacterial nanocomposite coating provided by the present invention has good roughness and hydrophobicity.
The invention also provides a preparation method of the antibacterial nano composite coating, which comprises the following steps: sequentially carrying out ultrasonic cleaning on the base material to obtain a cleaned base material; depositing a Ti-based composite target material on the surface of the cleaned substrate through magnetron sputtering to obtain the antibacterial nano composite coating; the volume ratio of Ti to antibacterial particles in the Ti-based composite target material is 95-99: 1 to 5. The invention adopts a magnetron sputtering deposition mode to obtain the antibacterial nano composite coating, and has the advantages of compact structure, uniform grain size and tight combination between the coating and the matrix.
Description of the drawings:
FIG. 1 is an XRD spectrum of the coating prepared in example 1;
FIG. 2 is a SEM image of the surface topography of the coating prepared in example 1;
FIG. 3 is an atomic force profile of the coating prepared in example 1;
FIG. 4 is a graph of the water contact angle of the coating prepared in example 1 and pure Ti;
FIG. 5 is a graph for testing cytotoxicity of the coating layer prepared in example 1 and the pure Ti group;
FIG. 6 is a photograph of a colony of F.nucleatum in the coating and pure Ti groups prepared in example 1;
FIG. 7 is a bar graph of the percent bacteriostatic efficiency of F.nucleatum for the coatings and pure Ti groups prepared in example 1;
FIG. 8 is an XRD spectrum of the coating prepared in example 2;
FIG. 9 is a SEM image of the surface topography of a coating prepared by the method of example 2;
FIG. 10 is an atomic force profile of the coating prepared in example 2;
FIG. 11 is a graph of the water contact angle of the coating prepared in example 2 and pure Ti;
FIG. 12 is a graph for testing cytotoxicity of the coating layer prepared in example 2 and the pure Ti group;
FIG. 13 is a photograph of a colony of F.nucleatum in the coating and pure Ti groups prepared in example 2;
FIG. 14 is a bar graph of the percent bacteriostatic efficiency of F.nucleatum for the coatings and pure Ti groups prepared in example 2.
Detailed Description
The invention provides an antibacterial nano composite coating, which comprises the following components in percentage by volume: 95-99% of Ti and 1-5% of antibacterial particles;
the antibacterial particles are ZnO or TiO 2 。
In the invention, the antibacterial nano composite coating comprises 95-99% of Ti by volume percentage, and preferably 95%.
In the invention, the antibacterial nano composite coating comprises 1-5% by volume of antibacterial particles, preferably 5%. In the present invention, the antibacterial agentThe particles are ZnO or TiO 2 。
In the invention, the thickness of the antibacterial nano composite coating is preferably 150-300 nm, and more preferably 200 nm.
The invention also provides a preparation method of the antibacterial nano composite coating, which comprises the following steps:
carrying out ultrasonic cleaning on the base material to obtain a cleaned base material;
depositing a Ti-based composite target material on the surface of the cleaned substrate through magnetron sputtering to obtain the antibacterial nano composite coating;
the volume ratio of Ti to antibacterial particles in the Ti-based composite target material is 95-99: 1 to 5.
The method comprises the step of ultrasonically cleaning a base material to obtain the cleaned base material.
In the present invention, the Ti base material is preferably a Ti implant. In the embodiment of the invention, the diameter of the Ti implant is 10mm, and the thickness of the Ti implant is 1 mm.
In the present invention, the ultrasonic cleaning is preferably performed by sequentially performing acetone ultrasonic cleaning and absolute ethyl alcohol ultrasonic cleaning. In the invention, the ultrasonic power of the ultrasonic cleaning is preferably 80-100W, and more preferably 90W. In the invention, the time for the acetone ultrasonic cleaning and the absolute ethyl alcohol ultrasonic cleaning is preferably 25-35 min independently, and more preferably 30 min.
After the cleaned substrate is obtained, the Ti-based composite target material is deposited on the surface of the cleaned substrate through magnetron sputtering, and the antibacterial nano composite coating is obtained.
In the invention, the volume ratio of Ti to antibacterial particles in the Ti-based composite target material is 95-99: 1-5, preferably 95: 5.
In the present invention, the magnetron sputtering conditions include: the degree of vacuum is preferably less than 1.5X 10 -3 Pa; the sputtering power is preferably 140-160W, and more preferably 150W; the working air pressure is preferably 0.8-0.9 Pa, and more preferably 0.8 Pa; the argon flow is preferably 35-45 sccm, and more preferably 40 sccm; the sputtering time is preferably 10 min.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The apparatus used in the examples is as follows:
JGP-450 magnetron sputtering system, Shenyang scientific instruments research center, Inc., of Chinese academy of sciences;
x-ray diffractometer model D8Advance, Bruker, germany;
a ZF-7 type dark box three-purpose ultraviolet analyzer is used for ultraviolet irradiation activation;
QuantaFEG450 type scanning electron microscope, FEI usa;
a Dimension Icon type atomic force microscope, Bruker, germany;
JC2000C1 type interfacial tension measuring instrument, shanghai midmorning digital technology equipment ltd;
inductively coupled plasma mass spectrometer model agilent 7800, agilent technologies, inc.
Example 1
(1) Group ZnO-1
Putting a Ti matrix (the diameter is 10mm, the thickness is 1mm) into a beaker containing 100mL of acetone, and ultrasonically cleaning for 30min with the power set to 90W; and then putting the matrix into a beaker containing 100mL of absolute ethyl alcohol, and adopting ultrasonic cleaning for 30min, wherein the power is set to be 90W.
Performing magnetron sputtering on the surface of the cleaned substrate by adopting a Ti-ZnO composite target (the splicing ratio of the Ti target to the ZnO target is 99:1) to obtain a Ti-ZnO nano composite coating, wherein the magnetron sputtering conditions are as follows: vacuum degree lower than 1.5X 10 -3 Pa, sputtering power of 150W, working pressure of 0.8Pa, argon flow of 40sccm, sputtering time of 10min, and control of the rotation speed of the substrate fixed disk to be 1r/s, wherein the coating is marked as ZnO-1 group.
(2) Group ZnO-2
The preparation differs from (1) only in that: the splicing ratio of the Ti target material to the ZnO target material in the Ti-ZnO composite target is 98: 2. The coatings prepared in this example were designated as ZnO-2 group.
(3) ZnO-3 group
The preparation of (1) and (1) differs only in that: the splicing ratio of the Ti target material to the ZnO target material in the Ti-ZnO composite target is 97: 3. the coatings prepared in this example were designated as ZnO-3 group.
(4) ZnO-4 group
The only differences between (1) and (1) are: the splicing ratio of the Ti target material to the ZnO target material in the Ti-ZnO composite target is 96: 4. the coatings prepared in this example were identified as ZnO-4 group.
(5) ZnO-5 group
The only differences between (1) and (1) are: the splicing ratio of the Ti target material to the ZnO target material in the Ti-ZnO composite target is 95: 5. the coatings prepared in this example were designated as ZnO-5 group.
XRD tests are carried out on ZnO-1 group to ZnO-5 group prepared in example 1, the test results are shown in figure 1, and the results are shown in figure 1: the pattern shapes of the ZnO-1 group to the ZnO-1 group coatings are similar, and a diffraction peak of a ZnO (101) crystal face and a diffraction peak of a Ti (101) crystal face are generated. The diffraction peak of the sample is sharp and has no impurity peak, which indicates that the prepared nano zinc oxide and nano titanium have good crystallinity and high purity, the sample has a ZnO (101) crystal face diffraction peak at about 36 degrees, the crystal structure of the prepared nano ZnO is a hexagonal wurtzite structure, the nano ZnO grows along a single (101) orientation in the growth process, and the intensity of the ZnO (101) diffraction peak gradually increases along with the gradual increase of the ZnO content.
The surface morphology of the ZnO-1 group to ZnO-5 group coatings prepared in example 1 is SEM tested, the test results are shown in figure 2, and the results are shown in figure 2: the nano particles on the surface of the sample are arranged smoothly and compactly, Ti particles and ZnO particles with different sizes can be obviously seen in the graph 2(d) and the graph 2(e), the particle sizes of the Ti particles and the ZnO particles are both nano-scale, the particle size of the nano ZnO particles is obviously larger than that of the nano Ti particles, and the nano ZnO particles are gradually increased along with the increase of the content of ZnO.
The surface roughness of the coatings of groups ZnO-1 to ZnO-5 prepared in example 1 was also measured. The test results are shown in FIG. 3 and Table 1, FIG. 3 is an atomic force appearance graph of the surface coating of each group of samples prepared on a pure Ti substrate observed by an atomic force microscope, and FIGS. 3(a) to (e) respectively correspond to the test results of the coatings of ZnO-1 group to ZnO-5 group. As can be seen from FIG. 3, the surface coating morphology of each group of samples has more nanoparticles uniformly distributed, and the nano Ti particles and the nano ZnO particles completely cover the surface of the substrate Ti and are in a film shape. The nanometer Ti particles on the surface of each group of samples are uniform in size, and the nanometer ZnO particles with larger particle sizes on the surface of the sample are gradually increased along with the gradual increase of the ZnO content. As can be seen from Table 1, the Ti-ZnO coatings on the surfaces of the prepared groups of samples are flat and smooth, the surface roughness of the Ti-ZnO coatings is gradually increased along with the gradual increase of the ZnO content, the surface roughness of the sample ZnO-5 group is the largest, and the contour arithmetic mean deviation value of the group is 0.547 +/-0.008 nm.
TABLE 1 ZnO-1 group-ZnO-5 group coating surface roughness
The invention also measures the water contact angles of the ZnO-1 group to ZnO-5 group coatings prepared in the example 1 and the pure Ti group, and the test result is shown in figure 4. As can be seen from figure 4, the contact angle of the pure Ti substrate surface without the coating is less than 90 degrees, which indicates that the surface of the pure Ti substrate is hydrophilic, and the contact angles of all the coating group surfaces are more than 90 degrees, which indicates that the coatings have better hydrophobicity. When the surface contact angle is greater than 90 °, the contact angle gradually increases and the surface of the material becomes more hydrophobic as the roughness of the surface increases. The surface of the coating has better hydrophobicity, so that bacteria can be reduced from being adhered to the surface of the implant, and a biological film formed by the bacteria can be inhibited.
The invention adopts a CCK-8 method to test cytotoxicity of the ZnO-1 group to ZnO-5 group coatings and the pure Ti group obtained in the example 1, the test results are shown in a figure 5 and tables 2-3, the figure 5 is the absorbance values of each group of L929 cells at different times of culture, and as can be seen from the figure 5, the absorbance values of a negative control group, a blank control group and the pure Ti group are basically consistent at the same time point; table 2 shows the statistical analysis of the absorbance values of each group of L929 cells cultured at different times (SPSS 22.0 software was used to perform single factor analysis on the absorbance values of the experimental groups, and P <0.05 indicates that the difference is statistically significant). As can be seen from the results in Table 2, the difference in absorbance values among the coating groups was not statistically significant (P >0.05) and the difference in absorbance values among the coating groups was not statistically significant (P >0.05) as compared with the negative control group, the blank control group and the pure Ti group. Compared with the positive control group, the negative control group, the blank control group, the pure Ti group and the coating group have obvious statistical significance (P is less than 0.01). Table 3 shows the relative viability of the cells in each group of L929 cells at different times. As can be seen from the results in Table 3, the negative control group, the pure Ti group and each coating group showed relatively good cell viability and no toxicity. At different time points, the relative activities of the L929 cells of the negative control group, the pure Ti group, the ZnO-1 group, the ZnO-2 group, the ZnO-3 group, the ZnO-4 group and the ZnO-5 group are all more than 90 percent, and the method belongs to a safety material. From this, it can be seen that, from the ZnO-1 group to the ZnO-5 group, although the content of nano ZnO is increased, the relative activity of the L929 cell is still more than 90%, and the pure Ti group and each coating group have no cytotoxicity, and meet the standard of biosafety materials.
TABLE 2 statistical analysis of absorbance values at different times for various groups of L929 cell cultures
A, comparing a pure Ti group, each coating group and a positive control group; b, comparing the pure Ti group, each coating group and the negative control group
TABLE 3 relative cell viability for various groups of L929 cells cultured at different times
The ZnO-1 group to ZnO-5 group coatings and the pure Ti group obtained in the example 1 are subjected to antibacterial performance test by adopting a flat coating counting method, the detection results are shown in figures 6-7, and figure 6 is a photograph of flat bacterial colonies of different sample groups of fusobacterium nucleatum. As can be seen from FIG. 6, the colony count of Fusobacterium nucleatum was gradually decreased with the increasing amount of nano ZnO in the sample in the coating group, and the colony count of ZnO-5 group was significantly decreased compared to the pure Ti group, as compared to the uncoated pure Ti group. FIG. 7 is a bar graph of the percent of inhibition efficiency of F.nucleatum for coatings from ZnO-1 group to ZnO-5 group and pure Ti group. As can be seen from FIG. 7, the bacteriostasis rate of the sample gradually increases with the gradual increase of the content of nano ZnO in the sample, the bacteriostasis rate of the ZnO-1 group is 52.95% because of the minimum content of nano ZnO, the bacteriostasis rates of the ZnO-2 group to the ZnO-5 group are all greater than 70%, and the bacteriostasis rate of the ZnO-5 group reaches 91.05%.
Example 2
(1)TiO 2 -1 group
Putting a Ti matrix (the diameter is 10mm, the thickness is 1mm) into a beaker containing 100mL of acetone, and ultrasonically cleaning for 30min with the power set to 90W; and then putting the matrix into a beaker containing 100mL of absolute ethyl alcohol, and cleaning for 30min by adopting ultrasonic waves, wherein the power is set to be 90W.
By using Ti-TiO 2 Composite target (Ti target material and TiO) 2 The splicing ratio of the target material is 99:1) carrying out magnetron sputtering on the surface of the cleaned substrate to obtain Ti-TiO 2 The nano composite coating has the following magnetron sputtering conditions: vacuum degree lower than 1.5X 10 -3 Pa, sputtering power of 150W, working pressure of 0.8Pa, argon flow of 40sccm, sputtering time of 10min, and rotation speed of the substrate fixing disk controlled to be 1r/s, wherein the coating is marked as TiO 2 -1 group.
(2)TiO 2 -2 groups
TiO 2 Preparation of group-2 with TiO 2 The preparation of group-1 differs only in that Ti-TiO 2 Ti target material and TiO in composite target 2 The splicing ratio of the target materials is 98: 2. The coating is denoted as TiO 2 -2 groups.
(3)TiO 2 -3 groups
TiO 2 Preparation of group-3Prepared with TiO 2 The preparation of group-1 differs only in that Ti-TiO is used 2 Ti target material and TiO in composite target 2 The splicing ratio of the target material is 97: 3. The coating is denoted as TiO 2 -3 groups.
(4)TiO 2 -4 groups
TiO 2 Preparation of group-4 with TiO 2 The preparation of group-1 differs only in that Ti-TiO is used 2 Ti target material and TiO in composite target 2 The splicing ratio of the target material is 96: 4. The coating prepared in this example is denoted TiO 2 -4 groups.
(5)TiO 2 -5 groups
TiO 2 Preparation of group-5 with TiO 2 The preparation of group-1 differs only in that Ti-TiO is used 2 Ti target material and TiO in composite target 2 The splicing ratio of the target material is 95: 5. The coating prepared in this example is denoted TiO 2 -5 groups.
Inventive TiO prepared in example 2 2 group-1-TiO 2 XRD was performed on group-5, and the results are shown in FIG. 8, from which in FIG. 8 TiO can be seen 2 group-1-TiO 2 The pattern shapes of the coatings of the-5 groups are similar, and TiO appears 2 (101) A diffraction peak of a crystal plane and a diffraction peak of a Ti (101) crystal plane. The diffraction peak of the sample is sharp and has no impurity peak, which indicates that the prepared nano TiO 2 The crystallinity of the nano Ti is good, the purity is high, and TiO appears on a sample at about 36 DEG 2 (101) The diffraction peak of the crystal face indicates the prepared nano TiO 2 Is rutile crystal form, and rutile crystal form nano TiO 2 Has better photocatalytic activity and nano TiO 2 Growing in a single (101) orientation during the growth process.
The invention also relates to the TiO prepared in example 2 2 group-1-TiO 2 The surface topography of-5 groups was SEM tested, and the results are shown in FIG. 9, from which FIG. 9 it can be seen that: the surface of the sample is flat and smooth, has no defects, and the crystal grains of the film have small spacing and compact arrangement. Ti particles and TiO 2 The grain diameter of the particles is nano-grade, nano TiO 2 The particle size of the particles is obviously larger than that of the nano Ti particles, and the particle size is changed along with TiO 2 Gradually increased in the content of (C) in nanometersTiO 2 The particles gradually increase.
The invention also relates to the TiO prepared in example 2 2 group-1-TiO 2 The surface roughness of the-5 coating groups was measured. The test results are shown in FIG. 10 and Table 4, FIG. 10 is an atomic force morphology of the surface coating of each group of samples prepared on a pure Ti substrate observed by an atomic force microscope, and FIGS. 10(a) - (e) respectively correspond to TiO 2 group-1-TiO 2 Test results for 5 groups of coatings. As can be seen from FIG. 10, the surface coating morphology of each group of samples has more nanoparticles uniformly distributed, and the nanoparticles of Ti and TiO are uniformly distributed 2 The particles completely cover the surface of the substrate Ti and are in a film shape, the fluctuation of the surface of the coating is small, and the arrangement of the nano particles on the surface of each group of samples is smooth and compact. As can be seen from Table 4, the Ti-ZnO coatings on the surfaces of the prepared groups of samples were smooth and even with TiO 2 The content is gradually increased, the surface roughness of the coating is gradually increased, and the sample TiO 2 The surface roughness was the largest for the group 5, which had an arithmetic mean deviation of the profile of 1.280. + -. 0.011 nm.
TABLE 4 TiO 2 group-1-TiO 2 -5 coating surface roughness groups
The invention also relates to the TiO prepared in example 2 2 group-1-TiO 2 The water contact angles of 5 groups of coatings and pure Ti groups are measured, and the test results are shown in FIG. 11, and can be known from FIG. 11: the contact angle of the uncoated pure Ti substrate surface was less than 90 °, indicating that the pure Ti substrate surface was hydrophilic and the contact angle of all coating group surfaces was greater than 90 °, indicating that these coatings all had better hydrophobicity. When the surface contact angle is greater than 90 °, the contact angle gradually increases and the surface of the material becomes more hydrophobic as the roughness of the surface increases. The surface of the coating has better hydrophobicity, so that the adhesion of bacteria on the surface of the implant can be reduced, and the formation of a biological film by the bacteria can be inhibited.
Inventive TiO obtained in example 2 2 group-1-TiO 2 Group 5 coatings and puritiesThe cytotoxicity of the Ti group was tested, and the test results are shown in FIG. 12 and tables 5-6, FIG. 12 is the absorbance values of each group of L929 cells cultured at different times, as can be seen from FIG. 12: at the same time point, the absorbance values of the negative control group, the blank control group and the pure Ti group are basically consistent; table 5 is a statistical analysis of the absorbance values of each set of L929 cells cultured at different times. As can be seen from the results in Table 5, the difference in absorbance values of the coated groups was not statistically significant (P) as compared with the negative control group, the blank control group and the pure Ti group>0.05), the difference in absorbance values between the coating groups was also not statistically significant (P)>0.05). The negative control group, the blank control group, the pure Ti group and the coating group have obvious statistical significance (P) compared with the positive control group<0.01). Table 6 shows the relative viability of the cells in each group of L929 cells at different times. As can be seen from the results in Table 6, the negative control group, the pure Ti group and each coating group showed relatively good cell viability and no toxicity. Negative control group, pure Ti group, TiO at different time points 2 Group-1, TiO 2 Group 2, TiO 2 Group-3, TiO 2 Group-4 and TiO 2 The relative activity of the L929 cells of the group-5 is more than 90 percent, and the L929 cells belong to safety materials. Thus, it is known that from TiO 2 1 group to TiO 2 Group 5, albeit nano TiO 2 The content of the pure Ti group is increased, but the relative activity of the L929 cell is still more than 90 percent, and the pure Ti group and each coating group have no cytotoxicity and meet the standard of biosafety materials.
TABLE 5 statistical analysis of absorbance values at different times for various groups of L929 cell cultures
A, comparing a pure Ti group, each coating group and a positive control group; b, comparing the pure Ti group, each coating group and the negative control group
TABLE 6 relative cell viability of groups of L929 cells cultured at different times
Inventive TiO obtained in example 2 2 group-1-TiO 2 The antibacterial performance of the-5 groups of coatings and the pure Ti group is tested, the detection result is shown in figures 13-14, and figure 13 is a plate colony photo of different sample groups of fusobacterium nucleatum. As can be seen in FIG. 13, the coating groups followed the nano TiO in the sample compared to the uncoated pure Ti group 2 The content of the extract gradually increases, the colony number of the Fusobacterium nucleatum gradually decreases, and the TiO content gradually decreases 2 The colony count of the-5 group was significantly reduced compared to that of the pure Ti group, which may be a greater amount of nano TiO 2 More active oxygen is generated under the excitation of ultraviolet light, and the active oxygen can destroy bacterial biofilms to enter bacterial bodies, thereby playing the antibacterial role. FIG. 14 is a graph of the percent bacteriostatic efficiency of F.nucleatum for different sample groups. As can be seen from FIG. 14, with the nano TiO in the sample 2 The content is gradually increased, the bacteriostasis rate of the sample is gradually increased, and TiO 2 Group-1 due to nano TiO 2 With a minimum content of nano TiO, i.e. with only a small amount of nano TiO 2 Activated oxygen is generated by the excitation of ultraviolet light, so the bacteriostasis rate is 62.73 percent, and TiO is 2 Group-2 to TiO 2 The bacteriostatic rate of the group-5 is more than 70 percent, wherein the TiO is 2 The bacteriostasis rate of the group 5 reaches 90.94 percent.
Note: the invention is directed to the TiO prepared in example 2 2 group-1-TiO 2 All tests on the 5 coating groups were carried out after UV irradiation (365 nm for UV wavelength and 30min for UV time) of the coating.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. An antibacterial nano composite coating is characterized by comprising the following components in percentage by volume: 95-99% of Ti and 1-5% of antibacterial particles;
the antibacterial particles are ZnO or TiO 2 。
2. The antibacterial nanocomposite coating according to claim 1, wherein the antibacterial nanocomposite coating has a thickness of 150 to 300 nm.
3. The method for preparing the antibacterial nanocomposite coating according to any one of claims 1 to 2, characterized by comprising the steps of:
carrying out ultrasonic cleaning on the base material to obtain a cleaned base material;
depositing a Ti-based composite target material on the surface of the cleaned substrate through magnetron sputtering to obtain the antibacterial nano composite coating;
the volume ratio of Ti to antibacterial particles in the Ti-based composite target material is 95-99: 1 to 5.
4. The method according to claim 3, wherein the antibacterial particles are TiO 2 And then, after magnetron sputtering deposition, ultraviolet irradiation is also included.
5. The method according to claim 4, wherein the ultraviolet radiation has a wavelength of 365nm and a duration of 30 min.
6. The production method according to claim 3, wherein the ultrasonic cleaning is acetone ultrasonic cleaning and absolute ethyl alcohol ultrasonic cleaning in this order.
7. The preparation method according to claim 3 or 6, wherein the ultrasonic power of the ultrasonic cleaning is 80-100W.
8. The method according to claim 3, wherein the magnetron sputtering conditions include: low degree of vacuumAt 1.5X 10 -3 Pa, sputtering power of 140-160W, working pressure of 0.8-0.9 Pa, argon flow of 35-45 sccm, and sputtering time of 10 min.
9. The method of claim 3, wherein the substrate is a Ti implant.
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