Single / multi-element coating dental implant and preparation method thereof

Abstract

The invention discloses a single / multi-element coating dental implant and a preparation method thereof.The preparation method of the single / multi-element coating dental implant comprises the following steps that S1, a dental implant is pretreated, and the pretreated dental implant is obtained; s2, performing sand blasting and drying treatment on the pretreated dental implant to obtain a sand-blasted dental implant; s3, performing acid etching treatment on the dental implant subjected to sand blasting to obtain a dental implant subjected to acid etching; s4, isopropanol and purified water are mixed to obtain a mixed solvent, at least one of zirconium chloride, niobium chloride, molybdenum chloride and copper chloride is dissolved in the mixed solvent, and suspension liquid with the concentration being 0.5 M is obtained; and S5, coating and calcining to obtain the single / multi-element coating dental implant. By introducing the multi-element functional coating and regulating and controlling the calcination temperature, the roughness and surface holes of the dental implant are increased under the condition of ensuring the safety of the matrix, and meanwhile, the implant is endowed with better mechanical properties, antibacterial properties and the like.

Description

Technical Field

[0001] This invention relates to the field of dental implant surface modification technology, specifically to a single / multi-element coated dental implant and its preparation method. Background Technology

[0002] With the continuous development of oral prosthetics technology, dental implants have become one of the mainstream solutions for tooth loss restoration. Traditional titanium and titanium alloy implants are widely used due to their excellent biocompatibility and mechanical properties. To further enhance the osseointegration capacity of titanium implants, the industry has developed various surface treatment technologies, such as Nobel Biocare's TiUnite porous titanium oxide surface, Straumann's SLA (large particle blasting and etching) and its upgraded SLActive hydrophilic surface technology, and Dentium's RBM (absorbable blasting media) treatment. These technologies effectively increase the bone contact area and promote osseointegration by creating a micron-level rough structure on the implant surface.

[0003] Patent CN105854080A addresses the potential titanium allergy in some patients by inventing a "method for surface treatment of zirconia dental implants." This method involves cleaning, sandblasting, acid etching, soaking in a zirconia suspension, and high-temperature sintering to treat the zirconia implant surface. The core of this method lies in: initially increasing roughness through sandblasting and acid etching; controlling the pore size of the zirconia ceramic implant surface by utilizing the different particle sizes of the ball-milled zirconia powder; and further increasing the surface roughness of the prosthesis through sandblasting and acid etching before soaking. Subsequent sintering significantly increases the surface roughness, thereby enhancing the bonding ability between the implant and bone.

[0004] However, this existing technical solution has the following obvious defects and shortcomings: 1. Single surface functional element: This method only uses zirconia powder to construct the surface coating, and its composition is exactly the same as that of the implant matrix. Although this ensures the chemical compatibility of the coating, it fails to introduce any new bioactive elements or functional elements (such as zirconium, niobium, molybdenum, etc.), and does not introduce new elements to improve other properties of the implant, such as mechanical properties and antibacterial properties. 2. Excessive sintering temperature may damage the matrix: This technology requires sintering at an extremely high temperature of 1500-1600℃. Although the high sintering temperature can densify the zirconia coating, there is a risk of abnormal grain growth, phase transformation, and even a decrease in mechanical strength of the zirconia implant matrix, which is not conducive to the long-term stability of the implant.

[0005] Therefore, a single / multi-element coated dental implant and its preparation method are provided to solve the above-mentioned technical problems. Summary of the Invention

[0006] The purpose of this invention is to provide a single / multi-element coated dental implant and its preparation method. By introducing a multi-element functional coating and controlling the calcination temperature, the roughness and surface porosity of the dental implant are increased while ensuring the safety of the substrate, thereby giving the implant better mechanical properties, antibacterial properties and other properties.

[0007] The objective of this invention is achieved as follows:

[0008] A method for preparing a single / multi-element coated dental implant includes the following steps:

[0009] S1. Pre-treat the dental implant to obtain a pre-treated dental implant for later use;

[0010] S2. The pretreated dental implant obtained in S1 is subjected to sandblasting and drying to obtain sandblasted dental implants for later use.

[0011] S3. The sandblasted dental implant obtained in S2 is subjected to acid etching treatment to obtain an acid-etched dental implant.

[0012] S4. Mix isopropanol and purified water to obtain a mixed solvent, and dissolve at least one of zirconium chloride, niobium chloride, molybdenum chloride and copper chloride in the mixed solvent to obtain a suspension with a concentration of 0.5M.

[0013] S5. Using a brush, apply 50 μL of the suspension obtained from S4 evenly to the surface of the dental implant (including the threaded grooves), dry it at 80°C for 10 min, then transfer it to a muffle furnace and calcine it at 300°C-1000°C for 20 min under static air atmosphere; repeat the above application, drying and calcination steps 4 times (cumulative application of 200 μL); after the last calcination, maintain the same temperature in the muffle furnace and continue calcining for 1-3 h, then cool it naturally to room temperature to obtain the calcined dental implant; after cleaning and drying the calcined dental implant, obtain a single / multi-element coated dental implant.

[0014] The specific operation of S1 is as follows: polish the dental implant with 1200# sandpaper to remove surface oxides and impurities, then ultrasonically clean it with acetone, anhydrous ethanol and purified water for 15 minutes in sequence, take it out and rinse it with purified water, and place it in an oven at 30-70℃ to dry for 10 minutes.

[0015] The specific operation of S2 is as follows: use a sandblasting machine to vertically sandblast the dental implant obtained by machine S1 with Al2O3 particles with a diameter of less than 1000μm. After sandblasting is uniform, immerse it in purified water for ultrasonic cleaning for 10 minutes, take it out and dry it in an oven at 30-70℃ for 10-30 minutes.

[0016] The specific operation of S3 is as follows: the acid etching solution is a mixture of hydrochloric acid with a volume fraction of 2-10% and sulfuric acid with a volume fraction of 50-80% in a volume ratio of (1-4):(1-4), and acid etching is performed at 50-80℃ for 5-30 minutes.

[0017] The specific steps for cleaning and drying the calcined dental implant in step S5 are as follows: ultrasonically clean with purified water for 10 minutes to remove unbound particles, and air dry naturally for 30-60 minutes.

[0018] In step S4, isopropanol and purified water are mixed in a volume ratio of 1:1.

[0019] A single / multi-element coated dental implant, obtained by a method for preparing single / multi-element coated dental implants.

[0020] The beneficial effects of this invention are as follows: 1. This invention uses a chloride suspension containing one or more elements such as zirconium (Zr), niobium (Nb), molybdenum (Mo), and copper (Cu) for coating, followed by calcination at 300-1000°C. This results in dental implants with increased mechanical properties and bioactivity. Niobium (Nb) and molybdenum (Mo) have been proven to have good biocompatibility and are active elements that promote osteoblast differentiation. Through the process of this invention, these elements are successfully loaded and firmly bonded to the implant surface, increasing both surface roughness and biocompatibility, thereby improving the mechanical properties, bioactivity, and osseointegration capacity of the dental implant surface. This overcomes the technical shortcomings of existing technologies that only use zirconium oxide suspensions, whose composition is the same as the matrix, which can only increase roughness without introducing new functions.

[0021] 2. This invention limits the final calcination temperature to the range of 300~1000℃, which is much lower than the sintering temperature of zirconium oxide. This temperature range is sufficient to complete the thermal decomposition, oxidation, and solid-state reaction of the precursor, thereby forming a robust coating and avoiding microstructural degradation caused by high temperatures. It overcomes the technical defects of existing technologies that sinter at 1500~1600℃, which easily leads to abnormal growth of zirconium oxide grains, phase transformations (such as the transformation from tetragonal to monoclinic phase), and the generation of microcracks, seriously threatening the mechanical strength and long-term service life of the implant. Attached Figure Description

[0022] Figure 1 This is a scanning electron microscope image of Embodiment 1 of the present invention;

[0023] Figure 2 This is a scanning electron microscope image of Comparative Example 3 of the present invention. Detailed Implementation

[0024] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0025] Example 1:

[0026] Surface modification of single-element molybdenum (Mo) titanium-based implants

[0027] A method for preparing a single / multi-element coated dental implant includes the following steps:

[0028] S1. Pretreatment: Polish the titanium-based dental implant with 1200# sandpaper to remove surface oxides and impurities. Then, ultrasonically clean it with acetone, anhydrous ethanol and purified water for 15 minutes in sequence. Take it out, rinse it with purified water, and dry it in a 60℃ oven for 10 minutes.

[0029] S2. Sandblasting and drying treatment: Use a sandblasting machine to vertically sandblast the machined titanium implant with Al2O3 particles with a diameter of less than 1000μm. After the sandblasting is uniform (i.e., a uniform gray surface is formed), immerse it in purified water for ultrasonic cleaning for 10 minutes, and then take it out and dry it in a 60℃ oven for 10 minutes.

[0030] S3. Acid etching treatment: The acid etching solution is a mixture of 10% hydrochloric acid and 50% sulfuric acid in a volume ratio of 1:1. The acid etching is carried out at 75℃ for 20 minutes.

[0031] S4. Preparation of suspension: Dissolve MoCl5 in a mixed solvent of isopropanol and purified water in a ratio of 1:1 (v / v) to prepare a 0.5M MoCl5 suspension.

[0032] S5. Coating and Calcination: Apply 50 μL of the suspension evenly to the implant surface (including the threaded groove) with a brush, dry at 80°C for 10 min, transfer to a muffle furnace, and calcine at 500°C for 20 min under static air atmosphere; repeat the above coating → drying → calcination steps 4 times (cumulative coating of 200 μL); after the last calcination, maintain the muffle furnace temperature at 500°C and continue calcining for 1 h, then cool naturally to room temperature; ultrasonically clean with purified water for 10 min to remove unbound particles, and air dry naturally for 30 min to obtain a single-element coated dental implant.

[0033] Example 2:

[0034] Surface modification of dual-element molybdenum, copper (Mo, Cu) titanium-based implants

[0035] A method for preparing a single / multi-element coated dental implant includes the following steps:

[0036] S1. Pretreatment is the same as in Example 1.

[0037] S2. Sandblasting and drying treatment is the same as in Example 1.

[0038] S3. Acid etching treatment is the same as in Example 1.

[0039] S4. Suspension preparation: The difference is that a mixed suspension of 0.5M MoCl5 and 0.5M CuCl2 is prepared.

[0040] S5. Coating and calcination are the same as in Example 1.

[0041] Example 3:

[0042] Surface modification of titanium-based implants using zirconium, niobium, and copper (Zr, Nb, Cu)

[0043] A method for preparing a single / multi-element coated dental implant includes the following steps:

[0044] S1. Pretreatment is the same as in Example 1.

[0045] S2. Sandblasting and drying treatment is the same as in Example 1.

[0046] S3. Acid etching treatment is the same as in Example 1.

[0047] S4. Suspension preparation: The difference from Example 1 is that a mixed suspension of 0.5M ZrCl4, 0.5M NbCl5, and 0.5M CuCl2 is prepared.

[0048] S5. Coating and calcination are the same as in Example 1.

[0049] Example 4:

[0050] Surface modification of titanium-based implants using quaternary elements: zirconium, niobium, molybdenum, and copper (Zr, Nb, Mo, Cu).

[0051] A method for preparing a single / multi-element coated dental implant includes the following steps:

[0052] S1. Pretreatment is the same as in Example 1.

[0053] S2. Sandblasting and drying treatment is the same as in Example 1.

[0054] S3. Acid etching treatment is the same as in Example 1.

[0055] S4. Suspension preparation: The difference from Example 1 is that a mixed suspension of 0.5M ZrCl4, 0.5M NbCl5, 0.5M MoCl5, and 0.5M CuCl2 is prepared.

[0056] S5. Coating and calcination are the same as in Example 1.

[0057] Comparative Example 1:

[0058] Zirconia implants.

[0059] The specific steps are as follows:

[0060] 1. The zirconia dental implant is ultrasonically cleaned with anhydrous ethanol and deionized water for 15 minutes, then rinsed with purified water and dried in a 60℃ oven for 10 minutes.

[0061] 2. The sandblasting and drying process is the same as in Example 1.

[0062] 3. The acid etching treatment is the same as in Example 1.

[0063] 4. Preparation of suspension: Prepare a suspension by using water to prepare the ball-milled zirconia powder. The mass concentration of the suspension is 0.005%. Immerse the dental implant after acid etching in step 3 in the suspension for 4 seconds.

[0064] 5. Sintering: The soaked dental implant is sintered at 1500℃ for 1 hour.

[0065] Comparative Example 2:

[0066] SLA implants

[0067] The specific steps are as follows:

[0068] 1. Pretreatment is the same as in Example 1.

[0069] 2. The sandblasting and drying process is the same as in Example 1.

[0070] 3. The acid etching treatment is the same as in Example 1.

[0071] Comparative Example 3:

[0072] 1500℃ High-Temperature Calcined Single-Element Molybdenum-Titanium Based Dental Implants

[0073] The specific steps are as follows:

[0074] 1. Pretreatment is the same as in Example 1.

[0075] 2. The sandblasting and drying process is the same as in Example 1.

[0076] 3. The acid etching treatment is the same as in Example 1.

[0077] 4. The preparation of the suspension is the same as in Example 1.

[0078] 5. Coating and calcination: The difference is that the calcination temperature is 1500℃, otherwise it is the same as in Example 1.

[0079] Test 1:

[0080] Scanning electron microscope (SEM)

[0081] Figure 1 and Figure 2The scanning electron microscope images of Example 1 and Comparative Example 3 show that when the sintering temperature is too high, the crystals will grow abnormally, which proves that excessively high temperature calcination can easily lead to the deterioration of the microstructure of the material.

[0082] Test 2:

[0083] 1. After sterilizing the cut samples from Examples 1-4 and Comparative Examples 1-2, place them in sterile petri dishes, ensuring that the sample surface is in close contact with the petri dish. Take 0.1 mL of Staphylococcus aureus (bacterial concentration 1×10⁻⁶). 6 A bacterial suspension (CFU / mL) was evenly added dropwise to the sample surface; a blank control group (no sample, only 0.1 mL of bacterial suspension was evenly added to a petri dish) was set up; both the sample group and the blank control group were placed in a 37℃ incubator and incubated for 24 h. After incubation, the number of colonies on each plate was counted using a colony counter to obtain the average colony count for each sample and the blank control group. Finally, the inhibition rate of each sample was calculated according to the inhibition rate formula. The calculated inhibition rates are listed in Table 1.

[0084] 2. After sterilizing the cut samples from Examples 1-4 and Comparative Examples 1-2, place them in sterile petri dishes, ensuring that the sample surface is in close contact with the petri dish. Take 0.1 mL of *E. coli* (bacterial concentration 1×10⁻⁶) and aspirate. 6 A bacterial suspension (CFU / mL) was evenly added dropwise to the sample surface; a blank control group (no sample, only 0.1 mL of bacterial suspension was evenly added to a petri dish) was set up; both the sample group and the blank control group were placed in a 37℃ incubator and incubated for 24 h. After incubation, the number of colonies on each plate was counted using a colony counter to obtain the average colony count for each sample and the blank control group. Finally, the inhibition rate of each sample was calculated according to the inhibition rate formula. The calculated inhibition rates are listed in Table 1.

[0085] Antibacterial rate (%) = [(Average colony count in blank control group - Average colony count in test sample group) ÷ Average colony count in blank control group] × 100%

[0086] 3. As shown in Table 1, the samples with added Cu (Examples 2-4) showed excellent antibacterial rate, while those without Cu had no antibacterial effect, proving that Cu is the core of antibacterial performance.

[0087] Table 1. Antibacterial rate of each sample

[0088] project Staphylococcus aureus inhibition rate (%) Escherichia coli inhibition rate (%) Example 1 4.9±1.5 6.1±1.1 Example 2 97.5±1.6 98.7±1.2 Example 3 98.2±1.3 97.7±1.5 Example 4 95.4±1.8 96.2±2.1 Comparative Example 1 5.4±0.9 7.6±1.4 Comparative Example 2 6.8±1.0 8.3±1.2

[0089] Test 3:

[0090] 1. After sterilization, the samples from Examples 1 and 4, and Comparative Examples 1-2, were placed in 24-well plates. Osteoblasts in the logarithmic growth phase were digested, centrifuged, and counted at 1 × 10⁻⁶ cells per well. 5 / mL. After incubation at 37℃ for 7 days, the cells adhering to the implant surface were quantitatively detected by crystal violet staining.

[0091] 2. As shown in Table 2, the number of cells adhering in the examples after 7 days of culture was significantly higher than that in the comparative example, indicating that the introduced elements have good biological activity and can promote osteoblast adhesion. Furthermore, Cu can work synergistically with other elements, increasing antibacterial activity while maintaining the original biocompatibility.

[0092] Table 2 Cell adhesion experiment

[0093] project Osteoblast proliferation (OD) Example 1 2.798±0.187 Example 4 3.023±0.195 Comparative Example 1 2.369±0.229 Comparative Example 2 2.343±0.196

Claims

1. A method for preparing a single / multi-element coated dental implant, characterized in that, Includes the following steps: S1. Pre-treat the dental implant to obtain a pre-treated dental implant for later use; S2. The pretreated dental implant obtained in S1 is subjected to sandblasting and drying to obtain sandblasted dental implants for later use. S3. The sandblasted dental implant obtained in S2 is subjected to acid etching treatment to obtain an acid-etched dental implant. S4. Mix isopropanol and purified water to obtain a mixed solvent, and dissolve at least one of zirconium chloride, niobium chloride, molybdenum chloride and copper chloride in the mixed solvent to obtain a suspension with a concentration of 0.5M. S5. Apply 50 μL of the suspension obtained by S4 evenly to the surface of the dental implant using a brush, dry it at 80°C for 10 min, transfer it to a muffle furnace, and calcine it at 300°C-1000°C for 20 min in a static air atmosphere; repeat the above application, drying and calcination steps 4 times; after the last calcination, maintain the same temperature of the muffle furnace and continue calcining for 1-3 h, and cool it naturally to room temperature to obtain the calcined dental implant; after cleaning and drying the calcined dental implant, obtain a single / multi-element coated dental implant.

2. The method for preparing a single / multi-element coated dental implant according to claim 1, characterized in that, The specific operation of S1 is as follows: polish the dental implant with 1200# sandpaper to remove surface oxides and impurities, then ultrasonically clean it with acetone, anhydrous ethanol and purified water for 15 minutes in sequence, take it out and rinse it with purified water, and place it in an oven at 30-70℃ to dry for 10 minutes.

3. The method for preparing single / multi-element coated dental implants according to claim 1, characterized in that, The specific operation of S2 is as follows: use a sandblasting machine to vertically sandblast the dental implant obtained by machine S1 with Al2O3 particles with a diameter of less than 1000μm. After sandblasting is uniform, immerse it in purified water for ultrasonic cleaning for 10 minutes, take it out and dry it in an oven at 30-70℃ for 10-30 minutes.

4. The method for preparing a single / multi-element coated dental implant according to claim 1, characterized in that, The specific operation of S3 is as follows: the acid etching solution is a mixture of hydrochloric acid with a mass fraction of 2-10% and sulfuric acid with a mass fraction of 50-80% in a volume ratio of (1-4):(1-4), and acid etching is performed at 50-80℃ for 5-30 minutes.

5. The method for preparing a single / multi-element coated dental implant according to claim 1, characterized in that, The specific steps for cleaning and drying the calcined dental implant in step S5 are as follows: ultrasonically clean with purified water for 10 minutes to remove unbound particles, and air dry naturally for 30-60 minutes.

6. The method for preparing a single / multi-element coated dental implant according to claim 1, characterized in that, In step S4, isopropanol and purified water are mixed in a volume ratio of 1:

1.

7. A single / multi-element coated dental implant, obtained by the preparation method of any one of claims 1-6 for a single / multi-element coated dental implant.

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