CN111631833A - Manufacturing method of 3D printed multi-coating antibacterial teeth - Google Patents

Manufacturing method of 3D printed multi-coating antibacterial teeth Download PDF

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CN111631833A
CN111631833A CN202010579107.1A CN202010579107A CN111631833A CN 111631833 A CN111631833 A CN 111631833A CN 202010579107 A CN202010579107 A CN 202010579107A CN 111631833 A CN111631833 A CN 111631833A
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film
antibacterial
coating
manufacturing
teeth
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景财年
雷启腾
叶道珉
吴聪
张志浩
赵顺治
刘磊
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Shandong Jianzhu University
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Shandong Jianzhu University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0006—Production methods
    • A61C13/0019—Production methods using three dimensional printing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
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    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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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
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2420/08—Coatings comprising two or more layers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Metallurgy (AREA)
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Abstract

The invention provides a manufacturing method of a 3D printing multi-coating antibacterial tooth. Mainly comprises the following steps of firstly adopting titanium reinforced by nano particlesNickel alloy is used as the substrate of false tooth, then the magnetron sputtering technique is adopted to sequentially use Ta2O5The multi-coating antibacterial tooth produced by the invention has high strength and corrosion resistance, and can greatly reduce the occurrence of inflammation due to the dual antibacterial performance of the modified β -TCP material and the modified nano silver-loaded zirconium phosphate material.

Description

Manufacturing method of 3D printed multi-coating antibacterial teeth
Technical Field
The invention relates to the field of 3D printing of teeth, in particular to a manufacturing method of 3D printing multi-coating antibacterial teeth.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
With the development of modern life, more and more patients with tooth loss caused by various accident reasons are provided, and the gradual application of the 3D printing technology can manufacture a plurality of materials with high biocompatibility and physical and mechanical properties into an implant required by a patient, then implant the implant into the alveolar bone of the lost part of the tooth of the patient, enable the implanted implant and the alveolar bone of the patient to be tightly and firmly combined together through an integration period of about 6 months, and then connect an artificial tooth on the implant. The application of the 3D printing technology can ensure that the implant of the patient is more fit with the implantation site, relieve the pain of the patient and enable doctors to more intuitively predict the postoperative condition of the patient through a computer.
At present, the materials applied to 3D printing of teeth mainly comprise nickel-chromium alloy, cobalt-chromium alloy, titanium alloy and the like, but the nickel-chromium alloy and the cobalt-chromium alloy can generate chemical reaction in a complex oral environment to seriously affect the use performance of the teeth, and the nickel and chromium elements are heavy metal elements and are harmful to human bodies, so that various anaphylactic reactions are easily caused, and the body health of patients is affected. Titanium alloy is used as an excellent biocompatible material, but the strength and the wear resistance are poor, and the requirement of long-term use of teeth in a complex oral cavity environment cannot be met. The calcium pyrophosphate (CPP) bioactive ceramic has good bioactivity, and a titanium-based bioactive composite material obtained by functionally compounding the calcium pyrophosphate with a titanium alloy material not only has high specific strength, low elastic modulus and good corrosion resistance of the titanium alloy, but also has good bioactivity, and is one of common medical materials at present.
Vapor deposition refers to the process of depositing gaseous (including plasma) plating material on a substrate to form a thin film. The sputtering coating is one kind of PVD (physical vapor deposition), and is to bombard cathode target material at high speed under the action of electric field by means of positive ions generated by gas discharge, so that atoms (or molecules) in the target material escape and are deposited on the surface of a coated substrate, thereby preparing a required film. The magnetron sputtering coating overcomes the defect of low deposition rate of the conventional sputtering process, greatly reduces the possibility of film pollution, increases the energy of atoms incident to the surface of a substrate, improves the quality of the film to a great extent, and is the most widely applied method for sputtering and depositing the film at present.
Patent CN105458257A discloses a method for manufacturing a 3D printed titanium-based composite denture, which improves the disadvantages of pure titanium alloy such as insufficient hardness and abrasion resistance to some extent, but is not suitable for the biological environment of oral cavity complicated for a long time.
Patent CN106725944A discloses a process for 3D printing graphene teeth with laser assistance, which uses graphene materials, and although the process has good use performance, the process has poor biocompatibility, cannot adapt to the oral environment, and affects the use comfort of patients.
In summary, the current 3D printing technology has achieved good results in the medical field of dental implantation, but due to the limitation of conventional materials, the requirements of the market in terms of strength, wear resistance, biocompatibility and the like cannot be met. Although the application of some new materials or composite materials improves the situation to a certain extent at present, the situation is far from sufficient for adapting to complex oral environment, and comfortable use experience cannot be brought to patients.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a method for manufacturing a 3D printed multi-coating antibacterial tooth, which is characterized in that a titanium-nickel alloy reinforced by nano particles is used as a base material of a false tooth, and a Ti film and Ta are magnetically sputtered on the surface of the base material2O5Thin film and Sr2+、Ag+The multi-coating antibacterial tooth produced by the process has high strength and corrosion resistance, and can greatly reduce the occurrence of inflammation due to the dual antibacterial performance of the modified β -TCP material and the modified nano silver-loaded zirconium phosphate material, has better biocompatibility, can also shorten the swelling time of a postoperative gum, reduce rejection and relieve the postoperative pain of a patient.
In order to achieve the above purpose, the present invention discloses the following technical solutions.
(1) Preparing a matrix, namely mixing Ti35Nb7Zr-CPP mixed powder with nano-SiO2And mixing the CNTS according to the mass fraction, and printing the matrix by using a selective laser cladding 3D printing technology.
(2) The multilayer composite coating adopts magnetron sputtering technology to sequentially form a Ti film and Ta2O5-Ti film, Ta2O5Film, Ta2O5-modified β -TCP film, Sr2+、Ag+The modified β -TCP film was plated on top of the substrate.
(3) And printing the modified nano silver-loaded zirconium phosphate coating, and printing the modified nano silver-loaded zirconium phosphate coating on the surface of the multilayer composite coating by using a photocuring 3D printing technology to obtain the modified nano silver-loaded zirconium phosphate coating.
As a further technical scheme, in the step (1), the preparation method of the Ti35Nb7Zr-CPP mixed powder comprises the steps of putting Ti powder, Nb powder and Zr powder into a planetary ball mill vacuum ball milling tank according to the mass fraction ratio of (40.6-58) to (24.5-35) to (4.9-7), adding stainless steel balls according to the ball-to-material ratio of 3:1, simultaneously adding absolute ethyl alcohol, vacuumizing to 10Pa, and mechanically alloying for 10 hours at the speed of 300 r/min; then CPP (chlorinated polypropylene) powder accounting for 10-30% of the total mass of the powder is respectively added as a bioactive additive, and the powder is mixed for 2 hours at the speed of 300r/min, so as to obtain Ti35Nb7Zr-CPP mixed powder.
As a further technical scheme, the mixing ratio of the mixed powder in the step (1) is Ti35Nb7Zr-CPP mixed powder and nano-silicon dioxide (nano-SiO)2) And the Carbon Nano Tubes (CNTS) are fully mixed according to the mass fraction ratio of 92:5: 3.
As a further technical scheme, an SLM3D printer is adopted in the step (1), the laser spot diameter is (40-100 μm), and the scanning speed is 250 mm/min.
As a further technical proposal, Ag in the step (2)+、Sr2 +The preparation method of the modified β -TCP powder adopts a sol-gel self-combustion method, and concretely comprises the steps of using Ca (NO)3)2、AgNO3、Sr(NO3)2And 2-phosphonobutane-1, 2, 4-tricarboxylic acid (C)7H11O9P) is taken as a raw material, the corresponding raw material is weighed according to the molar ratio of (Ca + Sr + Ag)/P being 1.50, the raw material is placed into deionized water to be uniformly mixed, hydrolysis reaction is carried out under the condition of magnetic stirring, the reaction temperature is 80-90 ℃, and the rotor speed is 100 r/min. And after full reaction, drying the precursor in a constant-temperature drying oven at 180 ℃ for 6 h. Taking out the cauterized body, placing in a crucible, sintering with a muffle furnace, setting the temperature rise rate of the muffle furnace at 5 ℃/min, heating to 1000 ℃, keeping the temperature for 2h, and cooling with the furnace to obtain Sr2+、Ag+Modified β -TCP powder.
As a further technical scheme, the operation method of the magnetron sputtering coating machine in the step (2) comprises the steps of firstly respectively and finely polishing the denture substrate by adopting W5 diamond grinding paste and W1.5 aluminum oxide polishing solution, then respectively ultrasonically cleaning for 15min in acetone and absolute ethyl alcohol, and then drying in a vacuum drying oven. And (3) putting the dried substrate into a magnetron sputtering coating machine, wherein the distance between the substrate and the target material is 75 mm.
Before the coating is deposited, the substrate and the target are sequentially cleaned by adopting plasma, and the ion cleaning parameter is that the vacuum degree is 1.0 × 10-3Pa, argon flow rate of 20mL/min under a standard state, cleaning power of 200W and cleaning time of 20 min. The deposition sequence of the coating is Ti film and Ta2O5-Ti film, Ta2O5Film, Ta2O5-modified β -TCP film, Sr2 +、Ag+The modified β -TCP film had deposition parameters as shown in Table 1.
TABLE 1 deposition parameters of magnetron sputtered films
Figure BDA0002551743940000031
As a further technical scheme, the preparation method of the modified nano silver-loaded zirconium phosphate coating in the step (3) comprises the steps of placing 6S-NP3 in water for ultrasonic dispersion for 1h, dropwise adding glacial acetic acid by using a rubber head dropper in the dispersion process, and controlling the mass ratio of 6S-NP3 to the glacial acetic acid to water to be 4: 1: 200. Placing the dispersed suspension into a four-neck flask, dropwise adding a mixed solution of MPS and cyclohexane (the mass ratio is 1: 20) into the flask by using a constant-pressure funnel within 1h under the condition of mechanical stirring (200r/min), heating to 30 ℃ for reaction for 0.5h, and then heating to 65 ℃ for reaction for 1.5 h. After the reaction is finished, filtering out supernatant liquor after the suspension is settled, carrying out vacuum filtration on the residual product, then placing the product in a vacuum drying box, and drying the product for 12 hours at 80 ℃ to obtain an MPS surface modified 6S-NP3 product (M-6S-NP 3).
Weighed M-6S-NP3 and xylene (mass ratio of 1: 50) were weighed into a four-necked flask and ultrasonically dispersed for 0.5h with mechanical stirring (200 r/min). Under the protection of nitrogen, the temperature is raised to 80 ℃, metered BPO (with the mass ratio of M-6S-NP3 being 1: 10) is added, and metered MMA (with the mass ratio of MPS-6S-NP3 being 4: 1) is added dropwise in a constant pressure funnel within 0.5h after 10 min. After the dropwise addition, the reaction was carried out at 80 ℃ for 8 hours. After the reaction is finished, cooling to below 25 ℃, carrying out centrifugal separation (7000r/min) on the suspension, oscillating and washing the centrifugal product for 3 times by acetone, then placing the centrifugal product in a vacuum drying oven, and drying for 12h at 80 ℃ to obtain the organic modified nano silver-loaded zirconium phosphate (P-6S-NP 3).
As a further technical scheme, in the step (3), a certain amount of P-6S-NP3 and a modified product thereof are weighed and added into PMMA resin powder according to the proportion of 3%, the mixed resin powder is dispersed for 1h by using a high-speed dispersion machine (200r/min), and then the organic modified nano silver-loaded zirconium phosphate coating is directly printed on the surface of the denture by using a photocuring 3D printer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the matrix of the invention adopts Ti35Nb7Zr-CPP mixed powder and nano-SiO2The titanium-based bioactive composite material not only has high specific strength, low elastic modulus and good corrosion resistance of titanium alloy, but also has good bioactivity, namely nano SiO2The addition of the carbon nano tube enables the matrix to have better biocompatibility, can also adapt to more complex oral biological environment, and prolongs the service life.
(2) Sequentially coating Ti film and Ta by using a multi-layer gradient coating2O5-Ti film, Ta2O5Film, Ta2O5-modified β -TCP film, Sr2+、Ag+Coating modified β -TCP film on substrate, arranging transition coating between coatings of different materials to ensure close adhesion between coatings, and coating Ta2O5The multilayer composite coating has good corrosion resistance and antibacterial property, can promote the healing of damaged tissues, and respectively improves the hardness, the anti-friction strength, the sterilization and the biocompatibility from inside to outside; the coating adopts a magnetron sputtering coating technology, thereby greatly reducing the pollution of the film and improving the coating quality.
(3) The outermost layer adopts a modified beta-TCP material and an organic modified nano silver-loaded zirconium phosphate coating, the silver-loaded antibacterial material has no toxic or harmful effect on human bodies, is stable and safe, the organic modified nano silver-loaded zirconium phosphate (P-6S-NP3) has good heat resistance, mechanical strength and impact resistance, and the silver has strong killing effect on various pathogenic bacteria (such as escherichia coli, staphylococcus aureus and the like). The two materials are compounded, so that the denture strength is ensured, the antibacterial performance is improved, and the inflammation is reduced; the biocompatibility is good, rejection can be greatly reduced, the postoperative tooth swelling time of a patient is shortened, the use comfort of the patient is improved, and the service life of the patient is prolonged.
Description of the drawings:
FIG. 1 is a 3D printed multi-coat antibacterial dental structure view;
the specific implementation mode is as follows:
it is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms also are intended to include the plural forms as well, unless the context clearly indicates otherwise, and it should be further understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The invention will now be further illustrated by means of specific embodiments.
Putting Ti powder, Nb powder and Zr powder into a planetary ball mill vacuum ball milling tank according to the mass fraction ratio of 58:35:7, adding stainless steel balls according to the ball-to-material ratio of 3:1, simultaneously adding absolute ethyl alcohol, vacuumizing to 10Pa, and mechanically alloying for 10 hours at the speed of 300 r/min; then CPP (chlorinated polypropylene) powder accounting for 20 percent of the total mass of the powder is respectively added as a bioactive additive, and the powder is mixed for 2 hours at the speed of 300r/min, so as to obtain Ti35Nb7Zr-CPP mixed powder. Then Ti35Nb7Zr-CPP mixed powder and nano silicon dioxide (nano-SiO)2) And the Carbon Nano Tubes (CNTS) are fully mixed according to the mass fraction ratio of 92:5: 3. The substrate was then printed using an SLM3D printer with a laser spot diameter (80 μm) and a scanning speed of 250 mm/min.
With Ca (NO)3)2、AgNO3、Sr(NO3)2And 2-phosphonobutane-1, 2, 4-tricarboxylic acid (C)7H11O9P) is taken as a raw material, the corresponding raw material is weighed according to the molar ratio of (Ca + Sr + Ag)/P being 1.50, the raw material is placed into deionized water for uniform mixing, and hydrolysis reaction is carried out under the condition of magnetic stirring, the reaction temperature is 85 ℃, and the rotor speed is 100 r/min. And after full reaction, drying the precursor in a constant-temperature drying oven at 180 ℃ for 6 h. Taking out the cauterized body, placing in a crucible, sintering with a muffle furnace, setting the temperature rise rate of the muffle furnace at 5 ℃/min, heating to 1000 ℃, keeping the temperature for 2h, and cooling with the furnace to obtain Sr2+、Ag+Modifying β -TCP powder, fine polishing the false tooth substrate with W5 diamond grinding paste and W1.5 aluminum oxide polishing liquid, ultrasonic cleaning in acetone and absolute ethyl alcohol for 15min, stoving in a vacuum drying oven, and cleaning the substrate and target with plasma before depositing coating, wherein the ion cleaning parameter is vacuum degree of 1.0 × 10-3Pa, argon flow rate of 20mL/min under a standard state, cleaning power of 200W and cleaning time of 20 min. Then the substrate is loaded into a magnetron sputtering coating machine, and the distance between the substrate and the target material is 75 mm. The deposition sequence of the coating is Ti film and Ta2O5-Ti film, Ta2O5Film, Ta2O5-modified β -TCP film, Sr2 +、Ag+β -TCP film was modified.
Placing 6S-NP3 in water, ultrasonically dispersing for 1h, dropwise adding glacial acetic acid by using a rubber head dropper in the dispersing process, and controlling the mass ratio of 6S-NP3, glacial acetic acid and water to be 4: 1: 200. Placing the dispersed suspension into a four-neck flask, dropwise adding a mixed solution of MPS and cyclohexane (the mass ratio is 1: 20) into the flask by using a constant-pressure funnel within 1h under the condition of mechanical stirring (200r/min), heating to 30 ℃ for reaction for 0.5h, and then heating to 65 ℃ for reaction for 1.5 h. After the reaction is finished, filtering out supernatant liquor after the suspension is settled, carrying out vacuum filtration on the residual product, then placing the product in a vacuum drying box, and drying the product for 12 hours at 80 ℃ to obtain an MPS surface modified 6S-NP3 product (M-6S-NP 3). Weighed M-6S-NP3 and xylene (mass ratio of 1: 50) were weighed into a four-necked flask and ultrasonically dispersed for 0.5h with mechanical stirring (200 r/min). Under the protection of nitrogen, the temperature is raised to 80 ℃, metered BPO (with the mass ratio of M-6S-NP3 being 1: 10) is added, and metered MMA (with the mass ratio of MPS-6S-NP3 being 4: 1) is added dropwise in a constant pressure funnel within 0.5h after 10 min. After the dropwise addition, the reaction was carried out at 80 ℃ for 8 hours. After the reaction is finished, cooling to below 25 ℃, carrying out centrifugal separation (7000r/min) on the suspension, oscillating and washing the centrifugal product for 3 times by acetone, then placing the centrifugal product in a vacuum drying oven, and drying for 12h at 80 ℃ to obtain the organic modified nano silver-loaded zirconium phosphate (P-6S-NP 3). And then weighing a certain amount of P-6S-NP3 and a modified product thereof, respectively adding the weighed amount of P-6S-NP3 and the modified product thereof into PMMA resin powder in an adding proportion of 3%, dispersing the mixed resin powder for 1h by using a high-speed dispersion machine (200r/min), and then directly printing the organic modified nano silver-loaded zirconium phosphate coating on the surface of the denture by using a photocuring 3D printer, thus completing the process.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.

Claims (5)

1. A manufacturing method of 3D printed multi-coating antibacterial teeth is characterized in that titanium-nickel alloy reinforced by nano particles is used as a base material, and then a Ti film and Ta are sequentially subjected to magnetron sputtering on the surface of the base material2O5-Ti film, Ta2O5Film, Ta2O5-modified β -TCP film, Sr2+、Ag+Modifying β -TCP film, and finally curing a layer of antibacterial porcelain film on the surface of the denture.
2. The method for manufacturing 3D printed multi-coated antibacterial teeth according to claim 1, characterized in that the matrix material is Ti35Nb7Zr-CPP mixed powder and nano-SiO2And the CNTS is fully mixed according to the mass fraction ratio of 92:5: 3.
3. The method for manufacturing 3D printed multi-coated antibacterial teeth according to claim 1, wherein the substrate is printed by selective laser cladding technology, the printing parameters are laser spot diameter (40-100 μm), and the scanning speed is 250 mm/min.
4. The manufacturing method of 3D printing multi-coating antibacterial teeth as claimed in claim 1, characterized in that the transition layer adopts magnetron sputtering technology, the sputtering mode is DC sputtering and RF sputtering, and the sputtering power is 200W.
5. The manufacturing method of 3D printing multi-coating antibacterial teeth according to claim 1 is characterized in that the organic modified nano silver-loaded zirconium phosphate coating on the outermost layer is printed on the surface of the denture by adopting a photo-curing printing technology.
CN202010579107.1A 2020-06-23 2020-06-23 Manufacturing method of 3D printed multi-coating antibacterial teeth Pending CN111631833A (en)

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