Calcium-phosphorus implant and preparation method thereof

Abstract

The invention discloses a calcium-phosphorus implant and a preparation method thereof, and the preparation method comprises the following steps: carrying out sand blasting and double acid etching on metal processed into an implant shape to obtain metal with rough surface and micropores; the metal with the micropores is cleaned, subjected to ultrasonic treatment and dried, and a base body is obtained; under the vacuum condition, calcium ions and phosphate ions are injected into the surface layer of the preheated matrix; and annealing the matrix into which the calcium ions and the phosphate ions are injected to obtain the calcium-phosphorus implant, and sealing the calcium-phosphorus implant. According to the calcium-phosphorus implant and the preparation method thereof, the structure is more stable, and the problem that the calcium-phosphorus coating falls off is solved.

Description

Technical Field

[0001] This invention belongs to the field of dental implant technology, and specifically relates to a calcium-phosphorus implant and its preparation method. Background Technology

[0002] Traditional sandblasting and acid etching (SLA) techniques for preparing implants only provide a rough surface, failing to induce osteoblast differentiation, resulting in poor interfacial adhesion and prolonged bone healing time. Calcium and phosphate ions are core ions for bone mineralization, serving as "raw materials" for bone formation. When calcium and phosphate ions encounter blood or body fluids, they form bone-like apatite, promoting rapid osteoblast adhesion. Calcium-phosphate implants can enhance surface chemical reactions, promoting osteoblast adhesion, differentiation, and spread, thus shortening the healing cycle. However, existing calcium-phosphate implants are prepared using methods such as electrodeposition, sputtering, and thermal spraying. Essentially, these methods involve covering the implant surface with a coating. The coating adheres to the titanium metal surface only mechanically, rather than chemically, leading to risks such as detachment, uncontrollable particle size and thickness, morphological masking, and unstable crystal phases. Long-term bone remodeling can thin the coating.

[0003] For example, particle shedding can lead to macrophage phagocytosis and trigger chronic inflammation; surface morphology being covered can fill in the rough surface prepared by SLA, destroying the microporous advantage; thickness is difficult to control, resulting in poor consistency and easy crack formation; uneven calcium / phosphorus ratio can lead to local calcium enrichment and phosphorus depletion; structural discontinuity between titanium and coating can generate high interfacial stress; increased coating thickness can affect the fit between the implant and precision fitting components; the coating is sensitive to processing residues, and if particles are not completely removed after SLA preparation of the implant microporous surface, local "void" areas can form; subsequent ultrasonic cleaning and packaging become more difficult and can easily damage the coating. Summary of the Invention

[0004] Objective: In order to overcome the shortcomings of the existing technology, the present invention provides a calcium-phosphorus implant and its preparation method.

[0005] Technical solution: To solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0006] In a first aspect, a method for preparing a calcium-phosphorus implant is provided, comprising:

[0007] S1. Sandblasting and double acid etching are performed on the metal processed into the shape of an implant to obtain a metal with a rough surface and micropores.

[0008] S2. The metal with micropores is cleaned and ultrasonically treated, and then dried to obtain the matrix;

[0009] S3. Under vacuum conditions, calcium ions and phosphate ions are injected into the preheated substrate surface.

[0010] S4. Anneal the matrix after calcium and phosphate ion injection to obtain calcium-phosphate implants and seal them.

[0011] This method provides a way to directly inject calcium and phosphate ions into implants, completely avoiding problems such as easy coating peeling and uncontrollable morphology in coated implants. The preparation method is simple and easy to implement, and the prepared implants are more stable, which is conducive to rapid postoperative recovery.

[0012] In some embodiments, in S1, the sandblasting is performed using corundum sandblasting to form a surface with a roughness Ra of 1.2-1.8 μm.

[0013] In some embodiments, in S1, the dual acid etching uses a combination of hydrochloric acid and sulfuric acid or a combination of hydrofluoric acid and nitric acid to form micropores of 1-3 μm.

[0014] In some embodiments, the metal is selected from at least one of titanium, Ti-6Al-4V alloy, and Ti-15Zr alloy.

[0015] In some embodiments, S2, the cleaning includes degreasing agent cleaning, ethanol cleaning, and pure water cleaning.

[0016] In some embodiments, in S3, the vacuum condition is: The temperature of the preheated substrate is 80-120℃.

[0017] In some embodiments, in S3, the implantation of calcium ions satisfies at least one of the following:

[0018] The injected energy is 10-30 keV;

[0019] Injection dose is ;

[0020] The injection time is 2-15 minutes;

[0021] The injection depth is 0.3-1.65 μm;

[0022] And / or, in S3, the implantation of phosphate ions satisfies at least one of the following:

[0023] The injected energy is 5-25 keV;

[0024] Injection dose is ;

[0025] The injection time is 3-10 minutes;

[0026] The injection depth is 0.2-1.35 μm.

[0027] In some embodiments, the implantation of calcium ions and phosphate ions into the matrix includes:

[0028] Simultaneous injection of calcium ions and phosphate ions;

[0029] Alternatively, inject calcium ions for 10-30 seconds, then inject phosphate ions for 10-30 seconds, alternating the cycle 6-30 times.

[0030] Alternatively, inject phosphate ions for 10-30 seconds, then inject calcium ions for 10-30 seconds, alternating the cycle 6-30 times.

[0031] In this embodiment, calcium ions and phosphate ions can be injected simultaneously or alternately to form a more stable gradient structure without covering the micropores.

[0032] In some embodiments, the annealing process satisfies at least one of the following:

[0033] Use nitrogen or argon gas;

[0034] The annealing temperature is 200-400℃;

[0035] Annealing time is 30-60 minutes.

[0036] Further annealing at the phase transition point temperature promotes the formation of Ti-O-Ca and Ti-OP bonds.

[0037] In some embodiments, the seal is sealed in an inert brine solution, or encapsulated under a nitrogen or argon atmosphere;

[0038] The inert brine is a 0.9 wt% sodium chloride solution.

[0039] In a second aspect, a calcium-phosphorus implant is provided, prepared by the method for preparing calcium-phosphorus implants according to any one of the first aspects; the calcium-phosphorus implant retains intact micropores, has no adhering layer on its surface, and no continuous membrane; the calcium-phosphorus implant satisfies at least one of the following:

[0040] The 2p peak of calcium is 347-351 eV;

[0041] The 2p peak of phosphorus is 133-134.2 eV;

[0042] The calcium / phosphorus ratio is 1.2-1.7;

[0043] The total calcium and phosphorus injection depth was 0.5-3 μm.

[0044] Beneficial effects: The calcium-phosphorus implant and its preparation method provided by this invention have the following advantages:

[0045] 1. Calcium phosphate implants formed by direct injection of calcium and phosphate ions are functional modifications of the matrix, resulting in a more stable structure and eliminating the risk of coating peeling.

[0046] 2. Sandblasting and dual acid etching provide roughness and microstructure, while calcium and phosphate ions increase surface chemical activity. The combined effect accelerates the transition from mechanical to biological stability, reducing the risk of postoperative instability. Injection forms Ti-O-Ca and Ti-OP bonds, inducing preferential protein adsorption (especially osteopontin and fibronectin). The calcium-phosphate composite surface can improve cell function through bioactivation, partially compensating for poor bone quality, particularly beneficial for osteoporosis, elderly patients, and those with poor bone quality due to long-term tooth loss. Treatment with calcium and phosphate ions can enhance osteoblast adhesion and proliferation rates, reducing the risk of postoperative complications. Attached Figure Description

[0047] Figure 1 These are images of the implant surface morphology before and after calcium-phosphorus injection in Example 1 of the present invention.

[0048] Figure 2 The images show the clinical results 8 weeks after implantation of the titanium implant (left) of Comparative Example 1 and the calcium phosphate implant (right) of Example 3 of this invention.

[0049] Figure 3 The images show the clinical results 8 weeks after implantation of the titanium implant (left) of Comparative Example 2 and the calcium-phosphorus implant (right) of Example 4 of this invention.

[0050] Figure 4 This is an XPS test result image of the calcium-phosphorus implant in Example 6 of the present invention;

[0051] Figure 5 This is an XPS detection result of calcium element in Example 6 of the present invention;

[0052] Figure 6 This is an XPS detection result of phosphorus element in Example 6 of the present invention;

[0053] Figure 7 This is an XPS test result image of the Ti-6Al-4V alloy matrix calcium phosphate implant of Example 7 of the present invention;

[0054] Figure 8 This is an XPS test result image of the Ti-15Zr alloy matrix calcium phosphate implant in Example 8 of the present invention. Detailed Implementation

[0055] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0056] The present invention will be further described below with reference to specific embodiments.

[0057] Example 1: Titanium metal processed into the shape of an implant was sandblasted with corundum to form a surface with a roughness Ra of 1.2 μm; a combination of hydrochloric acid and sulfuric acid was used for double acid etching to form micropores of 1 μm, resulting in titanium metal with a rough surface and micropores.

[0058] The titanium metal with micropores was cleaned once with a degreasing agent and once with ethanol, and then cleaned three times with pure water. Ultrasonic cleaning was used during the cleaning process, and the substrate was dried to obtain the matrix.

[0059] Place the substrate into the vacuum chamber and evacuate it until... The substrate was preheated to 80°C to remove the water film. Calcium and phosphate ions were simultaneously injected into the preheated substrate surface using a 20 kV high-voltage pulse power supply; the calcium ion injection energy was 10 keV; and the injection dose was... The injection time was 2 min; the injection depth was 0.3 μm; the injection energy of the phosphate ions was 5 keV; and the injection dose was... The injection time was 3 minutes; the injection depth was 0.2 μm.

[0060] Nitrogen gas was introduced into a vacuum chamber, and the substrate after calcium and phosphate ion implantation was annealed at 200℃ for 60 min to obtain a calcium-phosphate implant, which was then sealed in a 0.9% sodium chloride solution. The resulting calcium-phosphate implant retained intact micropores, did not form an adhesion layer on the surface, lacked a continuous film, and exhibited uniform calcium and phosphate distribution. The peak value is 347 eV. The peak is 350.6 eV, which is the phosphorus element. The peak value is 133 eV. The peak value was 133.3 eV, and the calcium / phosphorus ratio was 1.2. Figure 1 The images on the left and right are the surface morphology of the implants before and after the injection of calcium and phosphate ions, respectively. There is no significant difference in the surface morphology before and after injection, indicating that this method only modifies the matrix itself and does not add an attachment layer.

[0061] Example 2: Titanium metal processed into the shape of an implant was sandblasted with corundum to form a surface with a roughness Ra of 1.5 μm; a combination of hydrofluoric acid and nitric acid was used for double acid etching to form micropores of 2 μm, resulting in titanium metal with a rough surface and micropores.

[0062] The titanium metal with micropores was cleaned once with a degreasing agent and once with ethanol, and then cleaned three times with pure water. Ultrasonic cleaning was used during the cleaning process, and the substrate was dried to obtain the matrix.

[0063] Place the substrate into the vacuum chamber and evacuate it until... The substrate was preheated to 100°C to remove the water film; calcium and phosphate ions were simultaneously injected into the preheated substrate surface using a 30 kV high-voltage pulse power supply; the calcium ion injection energy was 20 keV; and the injection dose was... The injection time was 9 min; the injection depth was 0.98 μm; the injection energy of the phosphate ions was 15 keV; and the injection dose was... The injection time was 6 min; the injection depth was 0.78 μm.

[0064] Argon gas was introduced into a vacuum chamber to anneal the substrate after calcium and phosphate ion implantation at 300℃ for 45 min, resulting in a calcium-phosphate implant which was then sealed in a nitrogen atmosphere. The resulting calcium-phosphate implant exhibited intact micropores, no surface adhesion layer, no continuous film, and uniform calcium-phosphate distribution. The peak value is 349 eV. The peak is 351 eV, which is the phosphorus element. The peak value is 133 eV. The peak value was 134.2 eV, and the calcium / phosphorus ratio was 1.45.

[0065] Example 3: Titanium metal processed into the shape of an implant was sandblasted with corundum to form a surface with a roughness Ra of 1.8 μm; a combination of hydrochloric acid and sulfuric acid was used for double acid etching to form micropores of 3 μm, resulting in titanium metal with a rough surface and micropores.

[0066] The titanium metal with micropores was cleaned once with a degreasing agent and once with ethanol, and then cleaned three times with pure water. Ultrasonic cleaning was used during the cleaning process, and the substrate was dried to obtain the matrix.

[0067] Place the substrate into the vacuum chamber and evacuate it until... The substrate was preheated to 120°C to remove the water film; calcium and phosphate ions were simultaneously injected into the preheated substrate surface using a 40 kV high-voltage pulse power supply; the calcium ion injection energy was 30 keV; and the injection dose was... The injection time was 15 min; the injection depth was 1.65 μm; the injection energy of the phosphate ions was 25 keV; and the injection dose was... The injection time was 10 minutes; the injection depth was 1.35 μm.

[0068] Nitrogen gas was introduced into a vacuum chamber, and the substrate after calcium and phosphate ion implantation was annealed at 400℃ for 30 min to obtain a calcium-phosphate implant, which was then sealed in an argon atmosphere. The resulting calcium-phosphate implant retained intact micropores, did not form an adhesion layer on the surface, lacked a continuous film, and exhibited uniform calcium-phosphate distribution. The peak value is 347.2 eV. The peak is 351 eV, which is the phosphorus element. The peak value is 133.2 eV. The peak value is 133.8 eV, and the calcium / phosphorus ratio is 1.7. (For example...) Figure 2 (Right) shows the condition of the calcium-phosphorus implant prepared in this embodiment 8 weeks after the procedure.

[0069] Comparative Example 1: Following the preparation method described in Example 3, a titanium implant was prepared without the injection of calcium and phosphate ions. The condition of the titanium implant without calcium and phosphate ion injection 8 weeks post-implantation is shown below. Figure 2 (Left).

[0070] Example 4: Titanium metal processed into the shape of an implant was sandblasted with corundum to form a surface with a roughness Ra of 1.35 μm; a combination of hydrochloric acid and sulfuric acid was used for double acid etching to form micropores of 1.5 μm, resulting in titanium metal with a rough surface and micropores.

[0071] The titanium metal with micropores was cleaned once with a degreasing agent and once with ethanol, and then cleaned three times with pure water. Ultrasonic cleaning was used during the cleaning process, and the substrate was dried to obtain the matrix.

[0072] Place the substrate into the vacuum chamber and evacuate it until... The substrate was preheated to 110°C to remove the water film. Calcium ions were injected into the preheated substrate surface using a 40 kV high-voltage pulse power supply for 10 seconds, followed by phosphate ions for 10 seconds, alternating 6 times. The calcium ion injection energy was 30 keV, and the injection dose was... The implantation depth was 1 μm; the implantation energy of the phosphate ions was 25 keV; and the implantation dose was... The injection depth was 0.8 μm.

[0073] Argon gas was introduced into a vacuum chamber to anneal the substrate after calcium and phosphate ion implantation at 350℃ for 35 minutes, resulting in a calcium-phosphate implant which was then sealed in an argon atmosphere. The resulting calcium-phosphate implant exhibited intact micropores, no surface adhesion layer, no continuous film, and uniform calcium-phosphate distribution. The peak value is 347.5 eV. The peak is 350.4 eV, which is related to phosphorus. The peak value is 133.6 eV. The peak value is 134 eV, and the calcium / phosphorus ratio is 1.25. (For example...) Figure 3 (Right) shows the condition of the calcium-phosphorus implant prepared in this embodiment 8 weeks after the procedure.

[0074] Comparative Example 2: Following the preparation method described in Example 4, a titanium implant was prepared without the injection of calcium and phosphate ions. The condition of the titanium implant without calcium and phosphate ion injection 8 weeks post-implantation is shown below. Figure 3 (Left).

[0075] Based on Examples 3 and 1, and Examples 4 and 2, it is evident that 8 weeks after calcium-phosphorus implantation, osteoblast protrusions surround and attach to the threaded surface of the implant, osteoblasts mature, and there is no connective tissue at the interface; the bone tissue exhibits a lamellar bone morphology and is arranged parallel to the implant. 8 weeks after titanium implantation, fibrous bone fills the space around the implant, the matrix gradually mineralizes, and immature woven bone forms within the membrane. The woven bone is sparsely arranged. This indicates that the calcium-phosphorus implant provided by this invention promotes faster osteoblast secretion and is more conducive to bone growth.

[0076] Example 5: Titanium metal processed into the shape of an implant was sandblasted with corundum to form a surface with a roughness Ra of 1.65 μm; a combination of hydrochloric acid and sulfuric acid was used for double acid etching to form micropores of 2.5 μm, resulting in titanium metal with a rough surface and micropores.

[0077] The titanium metal with micropores was cleaned once with a degreasing agent and once with ethanol, and then cleaned three times with pure water. Ultrasonic cleaning was used during the cleaning process, and the substrate was dried to obtain the matrix.

[0078] Place the substrate into the vacuum chamber and evacuate it until... The substrate was preheated to 90°C to remove the water film. Phosphate ions were injected into the preheated substrate surface using a 30 kV high-voltage pulse power supply for 20 seconds, followed by calcium ions for 20 seconds, alternating 18 times. The calcium ion injection energy was 30 keV. The injection dose was... The implantation depth was 0.3 μm; the implantation energy of the phosphate ions was 25 keV; and the implantation dose was... The injection depth was 0.9 μm.

[0079] Argon gas was introduced into a vacuum chamber to anneal the substrate after calcium and phosphate ion implantation at 250℃ for 50 min, resulting in a calcium-phosphate implant which was then sealed in a 0.9% sodium chloride solution. The resulting calcium-phosphate implant exhibited intact micropores, no surface adhesion layer, no continuous film, and uniform calcium-phosphate distribution. The peak value is 349 eV. The peak is 350.8 eV, which is related to phosphorus. The peak value is 133.2 eV. The peak value was 133.8 eV, and the calcium / phosphorus ratio was 1.67.

[0080] Example 6: Titanium metal processed into the shape of an implant was sandblasted with corundum to form a surface with a roughness Ra of 1.4 μm; a combination of hydrochloric acid and sulfuric acid was used for double acid etching to form micropores of 2 μm, resulting in titanium metal with a rough surface and micropores.

[0081] The titanium metal with micropores was cleaned once with a degreasing agent and once with ethanol, and then cleaned three times with pure water. Ultrasonic cleaning was used during the cleaning process, and the substrate was dried to obtain the matrix.

[0082] Place the substrate into the vacuum chamber and evacuate it until... The substrate was preheated to 110°C to remove the water film. Phosphate ions were injected into the preheated substrate surface using a 20 kV high-voltage pulse power supply for 30 seconds, followed by calcium ions for 30 seconds, alternating cycles 30 times. The calcium ion injection energy was 30 keV. The injection dose was... The implantation depth was 1 μm; the implantation energy of the phosphate ions was 25 keV; and the implantation dose was... The injection depth was 0.4 μm.

[0083] Argon gas was introduced into the vacuum chamber to anneal the matrix after calcium and phosphate ion injection. The annealing temperature was 360℃ and the annealing time was 30 min, resulting in a calcium-phosphate implant, which was then sealed in a 0.9% sodium chloride solution. Figure 4 , Figure 5 and Figure 6 The image shown is the XPS detection result of the calcium-phosphorus implant prepared in this embodiment. It shows the presence of a 1s peak for oxygen, a 2p peak for titanium, a 1s peak for carbon, a 2p peak for calcium, and a 2p peak for phosphorus. (The text also mentions calcium, but the connection to the image is unclear.) The peak value is 347.2 eV. The peak is 350.8 eV, which is related to phosphorus. The peak value is 133.3 eV. The peak value was 134.2 eV, the calcium / phosphorus ratio was 1.3, the micropores of the obtained calcium-phosphorus implant were intact, no adhesion layer was formed on the surface, there was no continuous film, and the calcium and phosphorus were evenly distributed.

[0084] Example 7: Referring to the preparation method of Example 6, the matrix material was changed from titanium metal to Ti-6Al-4V alloy, and the calcium ion implantation dosage was... The phosphate ion injection dose was: XPS analysis was performed on the prepared calcium-phosphorus implants, and the results are referenced. Figure 7 .

[0085] Example 8: Referring to the preparation method of Example 6, the matrix material was changed from titanium metal to Ti-15Zr alloy, and the calcium ion implantation dosage was... The phosphate ion injection dose was: XPS analysis was performed on the prepared calcium-phosphorus implants, and the results are referenced. Figure 8 .

[0086] Combination Figure 1 , Figure 7 and Figure 8 It can be seen that there was no significant statistical difference in the detection results of Examples 1, 7 and 8 (p>0.05), indicating that this method is effective for different matrix materials.

[0087] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a calcium-phosphorus implant, characterized in that, include: S1. Sandblasting and double acid etching are performed on the metal processed into the shape of an implant to obtain a metal with a rough surface and micropores. S2. The metal with micropores is cleaned and ultrasonically treated, and then dried to obtain the matrix; S3. Under vacuum conditions, calcium ions and phosphate ions are injected into the preheated substrate surface. S4. Anneal the matrix after calcium and phosphate ion injection to obtain calcium-phosphate implants and seal them.

2. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, In S1, the sandblasting is performed using corundum sandblasting to form a surface with a roughness Ra of 1.2-1.8 μm; And / or, the dual acid etching uses a combination of hydrochloric acid and sulfuric acid or a combination of hydrofluoric acid and nitric acid to form micropores of 1-3 μm.

3. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, The metal is selected from at least one of titanium, Ti-6Al-4V alloy, and Ti-15Zr alloy.

4. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, In S2, the cleaning includes degreasing agent cleaning, ethanol cleaning, and pure water cleaning.

5. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, In S3, the vacuum condition is: The temperature of the preheated substrate is 80-120℃.

6. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, In S3, the implantation of calcium ions shall satisfy at least one of the following: The injected energy is 10-30 keV; Injection dose is ; The injection time is 2-15 minutes; The injection depth is 0.3-1.65 μm; And / or, in S3, the implantation of phosphate ions satisfies at least one of the following: The injected energy is 5-25 keV; Injection dose is ; The injection time is 3-10 minutes; The injection depth is 0.2-1.35 μm.

7. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, The injection of calcium ions and phosphate ions into the matrix includes: Simultaneous injection of calcium ions and phosphate ions; Alternatively, inject calcium ions for 10-30 seconds, then inject phosphate ions for 10-30 seconds, alternating the cycle 6-30 times. Alternatively, inject phosphate ions for 10-30 seconds, then inject calcium ions for 10-30 seconds, alternating the cycle 6-30 times.

8. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, The annealing process must satisfy at least one of the following: Use nitrogen or argon gas; The annealing temperature is 200-400℃; Annealing time is 30-60 minutes.

9. The method for preparing calcium-phosphorus implants according to claim 1, characterized in that, The seal is made in an inert brine solution or encapsulated in a nitrogen or argon atmosphere. The inert brine is a 0.9 wt% sodium chloride solution.

10. A calcium-phosphorus implant, characterized in that, The calcium phosphorus implant is prepared by the method for preparing the calcium phosphorus implant according to any one of claims 1-9; the calcium phosphorus implant satisfies at least one of the following: The 2p peak of calcium is 347-351 eV; The 2p peak of phosphorus is 133-134.2 eV; The calcium / phosphorus ratio is 1.2-1.7; The total calcium and phosphorus injection depth was 0.5-3 μm.

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