CN108785740B - Preparation method of titanium denture material plated with nano carbon crystal film on surface - Google Patents

Preparation method of titanium denture material plated with nano carbon crystal film on surface Download PDF

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CN108785740B
CN108785740B CN201810745797.6A CN201810745797A CN108785740B CN 108785740 B CN108785740 B CN 108785740B CN 201810745797 A CN201810745797 A CN 201810745797A CN 108785740 B CN108785740 B CN 108785740B
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nano carbon
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carbon crystal
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张建华
文炯
刘永奇
郭留希
杨晋中
刘创勋
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Zhengzhou Synthetic Diamond and Products Engineering Technology Research Center Co Ltd
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Abstract

The invention discloses a preparation method of a titanium denture material plated with a nano carbon crystal film on the surface, which comprises the following steps: 1) pretreating a titanium sheet; 2) primary coating: placing the pretreated titanium sheet obtained in the step 1) in acetone, ultrasonically cleaning for 30-40min, drying, and immersing in TiO2Dip-coating the solution, drying for 1-2h, heat-treating for 2-3h, and cooling; 3) secondary coating: immersing the pretreated titanium sheet coated once in the step 2) into TiO2In the modified nano carbon crystal dip-coating solution, standing for 50-60s, taking out, drying for 1-2h, performing heat treatment for 2-3h, and cooling; 4) coating for three times: and (3) immersing the pretreated titanium sheet coated twice in the step 3) into the modified nano carbon crystal dip-coating solution, standing for 50-60s, taking out, drying for 1-2h, performing heat treatment for 2-3h, and cooling to obtain the denture material coated with the nano carbon crystal film on the surface. The invention adopts a step coating method, effectively improves the stress stability of the nano carbon crystal coating, and the prepared denture material has better biocompatibility and can effectively improve the bacterial adhesion performance of the denture metal material.

Description

Preparation method of titanium denture material plated with nano carbon crystal film on surface
Technical Field
The invention relates to the technical field of medical materials, in particular to a preparation method of a titanium denture material plated with a nano carbon crystal film on the surface.
Background
Metal is an essential material in dental prosthesis. Due to the complex acid-base environment and microbial environment in the oral cavity, after the metal material type denture is used in the oral cavity for a period of time, the phenomena of corrosion, discoloration, bacterial adhesion and the like of the surface of the denture can occur in different degrees, the adhesion of bacteria on the surface of the denture can easily cause the problems of denture stomatitis, gingivitis, caries, oral odor and the like, the beauty and the service life of the prosthesis are seriously influenced, and more serious adverse reactions and complications harmful to the health of a human body can be caused, so that the improvement of the surface performance of the denture metal material has very important clinical significance.
Meanwhile, as a denture material which is in close contact with oral mucosa for a long time, some harmful substances on the surface of the material can permeate and transfer to mucosal tissues and trigger tissue inflammatory reactions of different degrees, including pigmentation, ulcer, erosion, anaphylactic reaction and the like. Therefore, the degree of local irritation of the denture material to the oral mucosa depends mainly on the chemical stability of the material surface or itself, the better the chemical stability, the less the irritation.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium denture material plated with a nano carbon crystal film on the surface.
Based on the purpose, the invention adopts the following technical scheme:
a method for preparing a titanium denture material plated with a nano carbon crystal film on the surface comprises the following steps:
1) titanium sheet pretreatment: polishing, ultrasonically cleaning and drying to obtain a pretreated titanium sheet;
2) primary coating: placing the pretreated titanium sheet obtained in the step 1) in acetone, ultrasonically cleaning for 30-40min, drying, and immersing in TiO2Dip-coating the solution, standing for 50-60s, taking out, drying at 70-80 deg.C for 1-2h, heat treating at 500-600 deg.C for 2-3h, and cooling;
3) secondary coating: immersing the pretreated titanium sheet coated once in the step 2) into TiO2Standing the solution for 50-60s, taking out, drying at 70-80 ℃ for 1-2h, performing heat treatment at 400-500 ℃ for 2-3h, and cooling;
4) coating for three times: immersing the pretreated titanium sheet coated twice in the step 3) into the modified nano carbon crystal dip-coating solution, standing for 50-60s, taking out, drying for 1-2h at 70-80 ℃, then carrying out heat treatment for 2-3h at 600-700 ℃, and cooling to obtain the denture material with the nano carbon crystal film plated on the surface;
a)TiO2preparation of dip coating solution: dissolving 20-30mL of deionized water in 200-230mL of isopropanol, and stirring for 30-40min to obtain a solution A; dissolving 14-15g of tetraisopropyl titanate in 90-100mL of isopropanol, and stirring for 30-40min to obtain a solutionAnd (2) adding the solution B into the solution A at a rate of 0.5-0.6mL/min, continuing to react for 30-40min to obtain a white suspension, performing suction filtration, washing with deionized water for 2-5 times to obtain a white precipitate, adding 150-200mL deionized water into the white precipitate, stirring at 60-70 ℃ for 30-40min, adding 15-16g of 10% nitric acid, and aging for 20-24h to obtain TiO2Dip-coating the solution;
b)TiO2preparation of modified nano carbon crystal dip-coating solution: adding 2-10g of modified nano carbon crystal into the TiO prepared in the step a)2Dipping in solution, ultrasonic dispersing for 1-2h to obtain TiO2Modified nano carbon crystal dip-coating solution;
c) preparing a modified nano carbon crystal dip-coating solution: adding 2-10g of modified nano carbon crystal into 20-25mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 1-2h to obtain a modified nano carbon crystal dip-coating solution;
the preparation method of the modified nano carbon crystal in the steps b) and c) comprises the following steps: weighing 2-10g of nano carbon crystal, placing in a reflux device, adding 30-50mL of concentrated nitric acid, refluxing for 15-16h at 90 ℃, separating, adding sodium hydroxide solution, mixing, and centrifuging to obtain precipitate which is modified nano carbon crystal.
Step 1) a titanium sheet pretreatment method: and (3) polishing the titanium sheet by using sand paper, polishing for 2 times by using alumina with the granularity of 0.5um, removing the alumina on the surface of the titanium sheet, sequentially placing the titanium sheet in acetone, absolute ethyl alcohol and distilled water for ultrasonic cleaning, and drying by blowing to obtain the pretreated titanium sheet.
In the steps 2), 3) and 4), when the glass is taken out, the vertical pulling speed is 1.5-2.0 mm/s; the ultrasonic dispersion conditions of the steps b) and c): the ultrasonic power is 90W, and the ultrasonic frequency is 59 KHz.
The total thickness of the coatings of step 2) primary coating, 3) secondary coating and 4) tertiary coating is 100-150 μm.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts a step coating method, effectively improves the stress stability of the nano carbon crystal coating, and the prepared denture material has no stimulation, better biocompatibility and can effectively improve the bacterial adhesion performance of the denture metal material;
2. the invention introduces the nano carbon crystal film into the field of oral restoration science, effectively improves the surface performance of the oral restoration material, improves the quality and the service life of the false tooth, reduces or avoids clinical complications and adverse reactions related to the false tooth, and has good application prospect.
Detailed Description
Example 1
A method for preparing a titanium denture material plated with a nano carbon crystal film on the surface comprises the following steps:
1) titanium sheet pretreatment: processing a pure titanium bar (Ti 99.9 wt%) with the diameter of 30mm and the length of 300mm into a round bar with the diameter of 12mm, then cutting out titanium sheets with the diameter of 12mm and the thickness of 2mm by adopting a linear cutting method, polishing the titanium sheets by using water-resistant sand paper with 400 meshes, 600 meshes, 800 meshes, 1000 meshes, 1200 meshes and 1500 meshes in sequence, polishing the titanium sheets by using aluminum oxide with the granularity of 0.5um for 2 times, polishing each titanium sheet for 5min each time, removing the aluminum oxide on the surface of the titanium sheet, then placing the titanium sheets in acetone, absolute ethyl alcohol and distilled water in sequence, ultrasonically cleaning the titanium sheets for 10min, and drying the titanium sheets by using an air gun to obtain pretreated titanium sheets (sealing and storing for later use);
2) primary coating: vertically immersing the pre-treated titanium sheets (30 randomly selected pre-treated titanium sheets) obtained in the step 1) in acetone, ultrasonically cleaning for 30min, drying, and immersing in TiO2Dip-coating the solution, standing for 55s, taking out at a vertical pulling speed of 1.5mm/s, drying at 70 deg.C for 2h, placing in a muffle furnace, heating to 500 deg.C at 1.5 deg.C/min, heat treating for 3h, and cooling to room temperature;
3) secondary coating: vertically immersing the pretreated titanium sheet coated in the step 2) into TiO2Standing for 55s in the modified nano carbon crystal dip-coating solution, taking out at the vertical pulling speed of 1.5mm/s, drying for 2h at 70 ℃, then placing in a muffle furnace, heating to 400 ℃ at 1.5 ℃/min, carrying out heat treatment for 3h, and cooling to room temperature;
4) coating for three times: vertically immersing the pretreated titanium sheet coated twice in the step 3) into the modified nano carbon crystal dip-coating solution, standing for 55s, taking out at vertical pulling speeds of 1.5mm/s, drying at 70 ℃ for 2h, then placing in a muffle furnace, heating to 600 ℃ at 1.5 ℃/min, carrying out heat treatment for 3h, and cooling to room temperature to obtain the denture material with the surface plated with the nano carbon crystal film;
a)TiO2preparation of dip coating solution: dissolving 20mL of deionized water in 200mL of isopropanol, and stirring for 30min to obtain a solution A; dissolving 14g of tetraisopropyl titanate in 90mL of isopropanol, stirring for 30min to obtain a solution B, dripping the solution B into the solution A at a rate of 0.5mL/min, continuing to react for 30min to obtain a white suspension, performing suction filtration, washing with deionized water for 2 times to obtain a white precipitate, adding 150mL of deionized water into the white precipitate, magnetically stirring at 60 ℃ for 30min, adding 15g of 10% nitric acid, and aging for 20h to obtain TiO2Dip-coating the solution;
b)TiO2preparation of modified nano carbon crystal dip-coating solution: adding 2g of modified nano carbon crystal into the TiO prepared in the step a)2In the dip-coating solution, ultrasonic dispersion is carried out for 1h under the ultrasonic power of 90W and the ultrasonic frequency of 59KHz to obtain TiO2Modified nano carbon crystal dip-coating solution;
c) preparing a modified nano carbon crystal dip-coating solution: adding 2g of modified nano carbon crystal into 20mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 1h under the ultrasonic power of 90W and the ultrasonic frequency of 59KHz to obtain a modified nano carbon crystal dip-coating solution;
the preparation method of the modified nano carbon crystal in the steps b) and c) comprises the following steps: weighing 2g of nano carbon crystal, placing the nano carbon crystal into a conical return pipe, adding 30mL of concentrated nitric acid, refluxing for 15h at 90 ℃, separating, adding a sodium hydroxide solution, mixing (neutralizing residual concentrated nitric acid), and centrifuging to obtain a precipitate which is a modified nano carbon crystal.
The total thickness of the coatings of step 2) primary coating, 3) secondary coating and 4) tertiary coating was 150 μm.
Example 2
A method for preparing a titanium denture material plated with a nano carbon crystal film on the surface comprises the following steps:
1) titanium sheet pretreatment: processing a pure titanium bar (Ti 99.9 wt%) with the diameter of 30mm and the length of 300mm into a round bar with the diameter of 12mm, then cutting out titanium sheets with the diameter of 12mm and the thickness of 2mm by adopting a linear cutting method, polishing the titanium sheets by using water-resistant sand paper with 400 meshes, 600 meshes, 800 meshes, 1000 meshes, 1200 meshes and 1500 meshes in sequence, polishing the titanium sheets by using aluminum oxide with the granularity of 0.5um for 2 times, polishing each titanium sheet for 8min each time, removing the aluminum oxide on the surface of the titanium sheet, then placing the titanium sheets in acetone, absolute ethyl alcohol and distilled water in sequence, ultrasonically cleaning the titanium sheets for 10min, and drying the titanium sheets by using an air gun to obtain pretreated titanium sheets (sealing and storing for later use);
2) primary coating: vertically immersing the pre-treated titanium sheets (30 randomly selected pre-treated titanium sheets) obtained in the step 1) in acetone, ultrasonically cleaning for 40min, drying, and immersing in TiO2Dip-coating the solution, standing for 60s, taking out at a vertical pulling speed of 2.0mm/s, drying at 80 ℃ for 1h, then placing in a muffle furnace, heating to 600 ℃ at a speed of 1.5 ℃/min, carrying out heat treatment for 2h, and cooling to room temperature;
3) secondary coating: vertically immersing the pretreated titanium sheet coated in the step 2) into TiO2Standing for 55s in the modified nano carbon crystal dip-coating solution, taking out at the vertical pulling speed of 2.0mm/s, drying at 80 ℃ for 1h, then placing in a muffle furnace, heating to 500 ℃ at 1.5 ℃/min, carrying out heat treatment for 2h, and cooling to room temperature;
4) coating for three times: vertically immersing the pretreated titanium sheet coated twice in the step 3) into the modified nano carbon crystal dip-coating solution, standing for 55s, taking out at vertical pulling speeds of 2.0mm/s, drying at 80 ℃ for 1h, then placing in a muffle furnace, heating to 700 ℃ at 1.5 ℃/min, carrying out heat treatment for 2h, and cooling to room temperature to obtain the denture material with the surface plated with the nano carbon crystal film;
a)TiO2preparation of dip coating solution: dissolving 30mL of deionized water in 230mL of isopropanol, and stirring for 40min to obtain a solution A; dissolving 15g of tetraisopropyl titanate in 100mL of isopropanol, stirring for 40min to obtain a solution B, dripping the solution B into the solution A at a rate of 0.6mL/min, continuing to react for 40min to obtain a white suspension, performing suction filtration, washing with deionized water for 5 times to obtain a white precipitate, adding 200mL of deionized water into the white precipitate, magnetically stirring at 70 ℃ for 40min, adding 16g of 10% nitric acid, and aging for 24h to obtain TiO2Dip-coating the solution;
b)TiO2modified nano carbon crystal dip coating solutionPreparation of the solution: adding 10g of modified nano carbon crystal into the TiO prepared in the step a)2In the dip-coating solution, ultrasonic dispersion is carried out for 2 hours under the ultrasonic power of 90W and the ultrasonic frequency of 59KHz, and TiO is obtained2Modified nano carbon crystal dip-coating solution;
c) preparing a modified nano carbon crystal dip-coating solution: adding 10g of modified nano carbon crystal into 25mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 2h under the ultrasonic power of 90W and the ultrasonic frequency of 59KHz to obtain a modified nano carbon crystal dip-coating solution;
the preparation method of the modified nano carbon crystal in the steps b) and c) comprises the following steps: weighing 10g of nano carbon crystal, placing the nano carbon crystal into a reflux device (a conical reflux pipe), adding 50mL of concentrated nitric acid, refluxing for 16h at 90 ℃, separating, adding a sodium hydroxide solution, mixing (neutralizing residual concentrated nitric acid), and centrifuging to obtain a precipitate which is modified nano carbon crystal.
The total thickness of the coatings of step 2) primary coating, 3) secondary coating and 4) tertiary coating was 100 μm.
Example 3
A method for preparing a titanium denture material plated with a nano carbon crystal film on the surface comprises the following steps:
1) titanium sheet pretreatment: processing a pure titanium bar (Ti 99.9 wt%) with the diameter of 30mm and the length of 300mm into a round bar with the diameter of 12mm, then cutting out titanium sheets with the diameter of 12mm and the thickness of 2mm by adopting a linear cutting method, polishing the titanium sheets by using water-resistant sand paper with 400 meshes, 600 meshes, 800 meshes, 1000 meshes, 1200 meshes and 1500 meshes in sequence, polishing the titanium sheets by using aluminum oxide with the granularity of 0.5um for 2 times, polishing each titanium sheet for 6min each time, removing the aluminum oxide on the surface of the titanium sheet, then placing the titanium sheets in acetone, absolute ethyl alcohol and distilled water in sequence, ultrasonically cleaning the titanium sheets for 10min, and drying the titanium sheets by using an air gun to obtain pretreated titanium sheets (sealing and storing for later use);
2) primary coating: vertically immersing the pre-treated titanium sheets (30 randomly selected pre-treated titanium sheets) obtained in the step 1) in acetone, ultrasonically cleaning for 35min, drying, and immersing in TiO2Dip-coating the solution, standing for 50s, taking out at a vertical pulling speed of 1.8mm/s, drying at 75 ℃ for 2h, then placing in a muffle furnace, heating to 550 ℃ at a rate of 1.5 ℃/min, carrying out heat treatment for 3h, and cooling to room temperature;
3) secondary coating: vertically immersing the pretreated titanium sheet coated in the step 2) into TiO2Standing for 55s in the modified nano carbon crystal dip-coating solution, taking out at the vertical pulling speed of 1.8mm/s, drying for 2h at 75 ℃, then placing in a muffle furnace, heating to 450 ℃ at 1.5 ℃/min, carrying out heat treatment for 3h, and cooling to room temperature;
4) coating for three times: vertically immersing the pretreated titanium sheet coated twice in the step 3) into a modified nano carbon crystal dip-coating solution, standing for 55s, taking out at vertical pulling speeds of 1.8mm/s, drying at 75 ℃ for 2h, then placing in a muffle furnace, heating to 650 ℃ at 1.5 ℃/min, carrying out heat treatment for 3h, and cooling to room temperature to obtain the denture material with the surface plated with the nano carbon crystal film;
a)TiO2preparation of dip coating solution: dissolving 25mL of deionized water in 220mL of isopropanol, and stirring for 40min to obtain a solution A; dissolving 15g of tetraisopropyl titanate in 90mL of isopropanol, stirring for 40min to obtain a solution B, dripping the solution B into the solution A at a rate of 0.6mL/min, continuing to react for 30min to obtain a white suspension, performing suction filtration, washing with deionized water for 4 times to obtain a white precipitate, adding 180mL of deionized water into the white precipitate, magnetically stirring at 65 ℃ for 40min, adding 16g of 10% nitric acid, and aging for 22h to obtain TiO2Dip-coating the solution;
b)TiO2preparation of modified nano carbon crystal dip-coating solution: adding 6g of modified nano carbon crystal into the TiO prepared in the step a)2In the dip-coating solution, ultrasonic dispersion is carried out for 2 hours under the ultrasonic power of 90W and the ultrasonic frequency of 59KHz, and TiO is obtained2Modified nano carbon crystal dip-coating solution;
c) preparing a modified nano carbon crystal dip-coating solution: adding 6g of modified nano carbon crystal into 23mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 2h under the ultrasonic power of 90W and the ultrasonic frequency of 59KHz to obtain a modified nano carbon crystal dip-coating solution;
the preparation method of the modified nano carbon crystal in the steps b) and c) comprises the following steps: weighing 6g of nano carbon crystal, placing the nano carbon crystal in a reflux device (a conical reflux pipe), adding 40mL of concentrated nitric acid, refluxing for 15h at 90 ℃, separating, adding a sodium hydroxide solution, mixing (neutralizing residual concentrated nitric acid), and centrifuging to obtain a precipitate which is modified nano carbon crystal.
The total thickness of the coatings of step 2) primary coating, 3) secondary coating and 4) tertiary coating was 120 μm.
Example 4 Performance testing
4.1 in vitro cytotoxicity assay
3 experimental groups were randomly selected from the denture materials prepared in example 1, and 3 negative control groups were randomly selected from the pre-treated titanium plate not coated in step 1) of example 1. And (3) sequentially putting the titanium sheets of the test group and the control group into acetone, absolute ethyl alcohol and distilled water, carrying out ultrasonic cleaning for 10min respectively, blow-drying by using an air gun, and sealing for later use.
According to ISO 10993-5 and ISO 10993-12, preparing cell culture solution containing calf serum, adding test pieces of experimental group and negative control group into the cell culture solution, respectively, and culturing at 37 deg.C for 24 hr to obtain leaching solution. Preparing the L-929 fibroblast strain subjected to subculture for 48h into 1X 10 by using a cell culture solution5Cell suspension per mL. Will be 1 × 105And inoculating the cell suspension per mL into a 36-well cell culture plate, wherein 36 wells are averagely divided into 3 groups, the first 2 groups are respectively added with the leaching solution of the experimental group and the leaching solution of the negative control group, and the 3 rd group is a blank control. Then, the cell culture plate is placed in a carbon dioxide incubator at 37 ℃ for culturing for 24h, and after the cells grow adherently, the supernatant is removed. After culturing for 1, 3 and 5 days, the cells were taken out and the OD value of their absorbance was measured at 490nm using an enzyme-linked immunosorbent assay.
To calculate the relative proliferation rate (RGR) of each group of cells and to evaluate the cytotoxicity of the material according to the toxicity rating scale. The toxicity rating is less than or equal to 1 grade, which indicates that the material has no cytotoxicity. RGR = OD mean of each experimental group/OD mean of negative control group × 100%. The results of the experiment are shown in table 1.
Figure 555065DEST_PATH_IMAGE001
As can be seen from Table 1, the OD values of each group increased with time; at each time point, the relative cell proliferation rate of the experimental group is greater than 100%, and the toxicity rating is 0 grade. Therefore, the denture material prepared by the invention has good biocompatibility, and the reason is that the nano carbon crystal film is composed of carbon elements which are nontoxic to human bodies; secondly, the film has good chemical stability and corrosion resistance, and can effectively avoid adverse chemical reactions.
4.2 mucosal contact test
The nano carbon crystal film plated on the surface of the denture material prepared by the invention is bound to be in direct contact with oral mucosa tissues, so whether the film can generate adverse stimulation on the oral mucosa or not is a key factor for evaluating the biocompatibility of the denture material. The experiment strictly performs a mucosa contact experiment on the nano carbon crystal film plated on the surface of the pure titanium in the dentistry according to the GB/T16886 medical instrument biological evaluation standard.
10 hamsters with the age of 60-70 days are selected for the experiment, the same strain is not limited by male and female, the constitution is healthy, and bilateral cheek sacs are free of any lesion. Hamsters were weighed, anesthetized, sterilized with 75% alcohol for medical use inside and outside the oral cavity of hamsters, and then the titanium sheets of the test group and the negative control group (specifically, the group was the same as the 4.1 in vitro cytotoxicity test) were sequentially fixed to the mucous membrane of the hamster buccal pouch by suturing. One side of each hamster was sutured with a piece of titanium, and the other side of the buccal pouch was used as a blank control. The film-coated surface of the invention is closely contacted with the buccal pouch mucosa, and the sewing mode is full-layer sewing penetrating through the inside and outside of the oral cavity. The fixation was checked daily after surgery and the mucosal tissue response around the titanium plate was recorded. All hamsters were sacrificed after 14 days, and buccal pouch mucosal tissue was excised from the area in contact with the titanium sheet for visual scoring and histologic scoring under a microscope. The scoring results are shown in table 2.
Through visual observation, no obvious pathological reactions such as congestion, erythema, rottenness and the like are found in the contact area of the buccal pouch mucosa and the titanium sheet of each experimental animal, and the visual evaluation score of the experimental group is 0. Histological sections of the buccal pouch mucosal area in contact with the experimental titanium sheets showed: the mucosa epithelium is intact, and no pathological phenomena such as leukocyte infiltration, blood vessel congestion, edema and the like are found at the mucosa basal layer and the submucosa; the histological evaluation of the experimental groups was 0 point. Finally, the stimulation indexes of the experimental groups are all 0, which indicates no stimulation to the mucosa.
Figure 472206DEST_PATH_IMAGE002
In the whole experimental stage, hamsters have normal diet, strong mobility and sensitive response to external stimulation, and mucosa tissues around the titanium sheets of the experimental group have no obvious adverse reactions such as congestion, swelling, decay and the like. The nano carbon crystal film has no stimulation to oral tissues, has good biocompatibility and can be applied to surface treatment of dental titanium sheets. This is because the nanocarbon crystal has sp2And sp3The carbon atoms form, the two carbon elements in the chemical bond state are stably combined, are not easy to precipitate, are not easy to generate chemical reaction with surrounding substances, and have good corrosion resistance and chemical stability, so that the bad stimulation to contacted tissues can be effectively avoided.
4.3 bacterial adhesion experiments
9 experimental groups were randomly selected from the denture materials prepared in example 1, and 9 test pieces were randomly selected from the pre-treated titanium plate which had not been coated in step 1) of example 1 to constitute a control group. And then, sequentially putting each group of titanium sheets into acetone, absolute ethyl alcohol and distilled water for ultrasonic cleaning for 10min respectively, blow-drying by using an air gun, and sealing for later use.
The test strains were Streptococcus mutans, Candida albicans and Actinomyces viscosus. Culturing the above three strains in culture medium to obtain the final product with concentration of 1.5 × 107Bacterial suspension per mL, then inoculating the three bacterial liquids on the test surfaces of the test pieces of the experimental group and the control group respectively, and then inoculating the three bacterial liquids on agar culture medium for culturing for 24 h. Finally, colony counts were performed at the end of the incubation. The course of the experiment was repeated 3 times and the mean of 3 colony counts per sample was taken for analysis. The colony counting results are shown in table 3.
Figure 251943DEST_PATH_IMAGE003
As can be seen from Table 3, the adhesion of the three bacteria showed that the number of bacteria adhered was significantly higher in the control group than in the experimental group. The nano carbon crystal is applied to the surface treatment of the denture material, and the main purposes are to improve the surface performance of the denture material, improve the quality and the service life of the denture and reduce or avoid clinical complications and adverse reactions related to the denture. The adhesion of bacteria on the surface of the denture can easily cause adverse effects such as denture stomatitis, gingivitis, caries, oral odor and the like, and seriously threatens the physical and psychological health of a patient, so that the improvement of the bacterial adhesion performance of the denture material has important clinical significance. The experimental result shows that after the surface treatment of the nano carbon crystal film, the adhesion levels of the denatured streptococcus, the candida albicans and the viscous actinomycetes on the surface of the denture material are obviously reduced, so that the nano carbon crystal film can obviously reduce the adhesion number of the denatured streptococcus, the candida albicans and the viscous actinomycetes on the surface of the dental pure titanium, and further improve the bacterial adhesion performance of the metal surface.

Claims (4)

1. A preparation method of a titanium denture material plated with a nano carbon crystal film on the surface is characterized by comprising the following steps:
1) titanium sheet pretreatment: polishing, ultrasonically cleaning and drying to obtain a pretreated titanium sheet;
2) primary coating: placing the pretreated titanium sheet obtained in the step 1) in acetone, ultrasonically cleaning for 30-40min, drying, and immersing in TiO2Dip-coating the solution, standing for 50-60s, taking out, drying at 70-80 deg.C for 1-2h, heat treating at 500-600 deg.C for 2-3h, and cooling;
3) secondary coating: immersing the pretreated titanium sheet coated once in the step 2) into TiO2Standing the solution for 50-60s, taking out, drying at 70-80 ℃ for 1-2h, performing heat treatment at 400-500 ℃ for 2-3h, and cooling;
4) coating for three times: immersing the pretreated titanium sheet coated twice in the step 3) into the modified nano carbon crystal dip-coating solution, standing for 50-60s, taking out, drying for 1-2h at 70-80 ℃, then carrying out heat treatment for 2-3h at 600-700 ℃, and cooling to obtain the denture material with the nano carbon crystal film plated on the surface;
the preparation method of the dip coating solution used in the steps 2), 3) and 4) comprises the following steps:
a)TiO2preparation of dip coating solution: dissolving 20-30mL of deionized water in 200-230mL of isopropanol, and stirring for 30-40min to obtain a solution A; dissolving 14-15g of tetraisopropyl titanate in 90-100mL of isopropanol, stirring for 30-40min to obtain a solution B, dripping the solution B into the solution A at 0.5-0.6mL/min, continuing to react for 30-40min to obtain a white suspension, performing suction filtration, washing with deionized water for 2-5 times to obtain a white precipitate, adding 150-200mL of deionized water into the white precipitate, stirring for 30-40min at 60-70 ℃, adding 15-16g of 10% nitric acid, and aging for 20-24h to obtain TiO2Dip-coating the solution;
b)TiO2preparation of modified nano carbon crystal dip-coating solution: adding 2-10g of modified nano carbon crystal into the TiO prepared in the step a)2Dipping in solution, ultrasonic dispersing for 1-2h to obtain TiO2Modified nano carbon crystal dip-coating solution;
c) preparing a modified nano carbon crystal dip-coating solution: adding 2-10g of modified nano carbon crystal into 20-25mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 1-2h to obtain a modified nano carbon crystal dip-coating solution;
the preparation method of the modified nano carbon crystal in the steps b) and c) comprises the following steps: weighing 2-10g of nano carbon crystal, placing in a reflux device, adding 30-50mL of concentrated nitric acid, refluxing for 15-16h at 90 ℃, separating, adding sodium hydroxide solution, mixing, and centrifuging to obtain precipitate which is modified nano carbon crystal.
2. The method for preparing a titanium denture material plated with a nanocarbon crystal film on the surface according to claim 1, wherein the step 1) titanium sheet pretreatment method comprises the following steps: and (3) polishing the titanium sheet by using sand paper, polishing for 2 times by using alumina with the granularity of 0.5um, removing the alumina on the surface of the titanium sheet, sequentially placing the titanium sheet in acetone, absolute ethyl alcohol and distilled water for ultrasonic cleaning, and drying by blowing to obtain the pretreated titanium sheet.
3. The method for preparing a titanium denture material plated with a nanocarbon crystal film on the surface according to claim 1, wherein in the steps 2), 3) and 4), the vertical pulling speed is 1.5-2.0mm/s when the titanium denture material is taken out; the ultrasonic dispersion conditions of the steps b) and c): the ultrasonic power is 90W, and the ultrasonic frequency is 59 KHz.
4. The method for preparing a titanium denture material coated with a nanocarbon crystal film according to claim 1, wherein the total thickness of the coating layers of the step 2) primary coating, the step 3) secondary coating and the step 4) tertiary coating is 100-150 μm.
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