CN112974843B - Surface treatment process for 3D printed implant - Google Patents
Surface treatment process for 3D printed implant Download PDFInfo
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- CN112974843B CN112974843B CN202110167876.5A CN202110167876A CN112974843B CN 112974843 B CN112974843 B CN 112974843B CN 202110167876 A CN202110167876 A CN 202110167876A CN 112974843 B CN112974843 B CN 112974843B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
- A61C8/0087—Means for sterile storage or manipulation of dental implants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/06—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for producing matt surfaces, e.g. on plastic materials, on glass
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- 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
- B33Y10/00—Processes of additive manufacturing
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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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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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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- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- B33Y80/00—Products made by additive manufacturing
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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
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- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
- C25F3/22—Polishing of heavy metals
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Abstract
The invention discloses a surface treatment process for a 3D printed implant. Firstly, melting TA1 powder layer by layer through laser selective area to obtain an implant; and then sequentially carrying out sand blasting treatment, acid etching treatment and electropolishing oxidation treatment on the implant to obtain the 3D printed implant with high biological safety, excellent osseointegration and good mechanical property. Has the advantages that: the first-level and second-level nested pits are generated on the surface of the implant by utilizing sand blasting and acid etching, so that the attachment, proliferation and differentiation of osteoblasts are enhanced in a synergistic manner, and osseointegration is promoted; an ultrasonic device added in the acid etching treatment is utilized to promote the ion exchange in the pore channel and the pit and reduce the acid etching treatment time; the oxygen concentration in the acid liquid is increased by utilizing the oxygen dissolving step added in the perchloric acid-glacial acetic acid electropolishing oxidation process, and the surface roughness of the implant is accurately controlled by combining the optimized setting of various parameters, so that a thicker oxidation film is formed on the surface, and the hydrophilicity is increased.
Description
Technical Field
The invention relates to the technical field of implants, in particular to a surface treatment process for a 3D printed implant.
Background
The oral implant is used as an artificial tooth root to replace a natural tooth root, has the characteristics of high comfort level, high chewing recovery efficiency, no damage to adjacent teeth and the like, and becomes a preferred treatment scheme for clinically repairing dentition deficiency and dentition defect in the oral cavity. The vast majority of commercial oral implants on the market today are solid bodies, which despite their good biocompatibility, still present their own problems: the bone combination performance of the solid oral implant is not high, the elastic modulus is obviously higher than that of surrounding bone tissues, a stress shielding effect is formed, the surrounding bone tissues are absorbed, and the clinical wide popularization of the solid oral implant is restricted.
In order to solve the above problems, the scholars design the oral implant as a porous structure to microscopically promote the growth of tissue cells, especially bone tissue cells, and macroscopically reduce the elastic modulus of the material. In the prior art, the method is used for manufacturing the oral implant with a porous structure by a foaming method, namely, a foaming agent is added into a manufacturing material, and bubbles generated by the reaction of the foaming agent are utilized to form a porous structure in the oral implant, but the method has the technical problem that the pore structure and the pore size cannot be controlled, so that the bone combination performance and the mechanical performance of the oral implant are reduced due to unreasonable pore size and pore structure, and the clinical requirement of an oral cavity is difficult to meet.
In addition, the hydrophilicity of the implant is important for the biocompatibility of the dental implant; however, due to the porous structure, the surface treatment process has the problem that the deep hole cannot completely remove impurities, and therefore, a series of treatment modes are required to cooperatively treat the surface of the 3D printed implant.
In summary, it is an urgent need in the art to provide an oral implant with good mechanical properties, biological safety and biocompatibility for clinical application.
Disclosure of Invention
The invention aims to provide a surface treatment process for a 3D printing implant, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a surface treatment process for 3D printing of an implant comprises the following steps:
s1: the 3D printing process of the implant comprises the following steps: (1) designing an implant 3D model; (2) slicing the 3D model and planning a scanning path; (3)3D printing to obtain an implant A;
s2: the surface treatment process of the 3D printed implant comprises the following steps: (1) performing sand blasting treatment to obtain an implant B; (2) carrying out acid etching treatment to obtain an implant C; (3) cleaning to obtain a 3D printing implant;
s3: 3D prints the planting body and stores: the 3D printing implant is stored in 0.1mol/L NaOH solution at normal temperature.
Preferably, step S1 includes the following steps: (1) designing a 3D model of the implant with the porous structure; (2) slicing the 3D model, wherein the thickness of the slices is 22-28 micrometers, and planning a scanning path; (3) and setting laser selection area process parameters, taking TA1 powder as a raw material, and performing 3D printing to obtain the implant A.
Preferably, in the step (3) of the step S1, the specific step is: pumping the forming chamber to a vacuum state, filling high-purity argon to finally obtain an argon environment with oxygen content lower than 100ppm and pressure of 18-32 mbar; dispersing TA1 powder on a printing bed, and setting the laser selective area printing parameters: the laser power of the physical scanning is 335-365W, and the laser power of the profile scanning is 160-200W; the laser power for supporting scanning is 335-365W; the diameter of the light spot is 70 μm; the entity scanning speed is 2300-2600 mm/s, the outline scanning speed is 420-480 mm/s, and the support scanning speed is 2300-2600 mm/s; the scanning interval is 0.06-0.08; and melting and superposing layer by layer according to a preset 3D model to obtain the implant A.
Preferably, step S2 includes the following steps: (1) sand blasting treatment: under the conditions that the pressure of compressed air is 3-5 bar and the jet distance is 60-120 mm, performing sand blasting treatment on the implant A for 10-50 s by adopting one or a mixture of 35-100 meshes of white corundum and titanium oxide to obtain an implant B; (2) acid etching treatment: placing the implant B in an acid etching solution, adding an ultrasonic device, setting the acid etching temperature to be 40-80 ℃, and performing acid etching treatment for 10-80 min to obtain an implant C; (3) cleaning: and spraying purified water for 1-5 min, ultrasonically cleaning with a Micro90 cleaning solution for 25-45 min, and washing with the purified water for 1-5 min to obtain the 3D printed implant.
Preferably, in step (2) of S2, the acid etching solution is prepared from 60-95 wt% sulfuric acid, 20-32 wt% hydrochloric acid, and deionized water in a volume ratio of (2.5-3.5) to (2-4) to (3-5).
More preferably, an electropolishing oxidation process is added between (2) and (3) of step S2.
Preferably, the electropolishing oxidation treatment comprises the following steps: perchloric acid-glacial acetic acid aqueous solution is used as electrolyte, the implant C is used as an anode, and the net-shaped stainless steel is used as a cathode; setting the current density to 0.28-0.32A/cm2And treating for 5-15 min to obtain the implant D.
Preferably, the perchloric acid-glacial acetic acid aqueous solution is prepared by the following steps: perchloric acid, glacial acetic acid and deionized water are prepared into a solution according to the volume ratio of 1 (8-12) to (1.2-1.6), and oxygen is dissolved in a water bath at the temperature of 28-32 ℃ for 30-60 min to obtain a perchloric acid-glacial acetic acid aqueous solution.
Preferably, the 3D printing implant is prepared by a 3D printing method; the raw material of the 3D printing implant is TA1 powder; the particle size range of the TA1 powder is 20-50 mu m.
Preferably, the composition of TA1 powder includes the following elements: according to the mass percent, the Fe is less than or equal to 0.25 percent; c is less than or equal to 0.10 percent; n is less than or equal to 0.03 percent; h is less than or equal to 0.015 percent; o is less than or equal to 0.20 percent; the balance being Ti.
In the technical scheme, the implant with a porous structure is directly printed by selective laser melting, and then the surface is subjected to sand blasting and acid etchingForming a first-level nested pit and a second-level nested pit in a physical mode, and increasing the bone combination area; then, carrying out electropolishing oxidation treatment to stabilize the Ra value of the surface of the implant to be 1-5 mu m, enhancing bone guiding property and promoting mechanical embedding of the implant and surrounding bone tissues; meanwhile, the oxygen is utilized for electropolishing oxidation treatment to form TiO on the surface of the implant2The membrane enhances the corrosivity, the hydrophilicity and the biological compatibility. And finally, soaking the implant in a sodium hydroxide solution at normal temperature to improve the stability and the hydrophilicity of the 3D printed implant. The Vickers hardness of the prepared implant is 420-500 kg/mm2The yield strength is 300-400 MPa, the elastic modulus is 15-50 Gpa, the problem of 'stress shielding' of the implant is effectively inhibited, and the mechanical property is good.
Firstly, in the scheme, a 3D printing method of the implant is provided, TA1 powder is used as a raw material, and the implant with a porous structure is prepared by adopting laser selective layering melting and superposition. Microscopically promoting bone tissue cells to grow into the implant, macroscopically reducing the elastic modulus of the material, and effectively avoiding the problem of stress shielding generated in the implant. The TA1 powder is safe and nontoxic, and the prepared implant has high bending strength and compression strength and excellent mechanical property; has better surface roughness and hydrophilicity, is beneficial to the adhesion and proliferation of osteocytes, has good osseointegration performance, and is very suitable for clinical requirements. In addition, the corrosion resistance of the implant is increased by controlling the laser power and the scanning speed.
Secondly, in order to improve the hydrophilicity of the implant and the adhesion of the bone cells, the surface thereof needs to be treated. However, because the surface treatment is carried out in a porous structure, the problem that deep holes cannot be treated or pores are blocked occurs in the surface treatment, and therefore, a series of treatment methods are needed to cooperatively treat the surface of the 3D printing implant.
(1) And carrying out sand blasting treatment on the surface of the implant by using titanium oxide particles of 35-100 meshes of white corundum. By utilizing the characteristics of high hardness and high strength, a primary pit with the diameter of 20-55 mu m is formed on the surface of the implant; meanwhile, due to the characteristic that the sand blasting agent is not easy to break, the residue and the pollution after sand blasting are reduced.
(2) The surface of the implant is further modified by using the hydrochloric acid-sulfuric acid mixed acid formed by the optimized proportion. The first is that: by utilizing the corrosion effect of the mixed acid on titanium, uniform honeycomb-shaped secondary pits with the average size of about 3-6 mu m are formed on the surface of the implant, the appearance of the secondary pits is superior to that of a market mainstream implant, and a nested structure is formed by the secondary pits and the primary pits, so that osteoblast attachment and subsequent proliferation and differentiation are enhanced in cooperation, and osseointegration is promoted. Secondly, the following steps: the residual powder generated in the 3D printing process and the sand blasting process is dissolved, the cytotoxicity is reduced, the harm to human health through blood circulation is avoided, the arrangement of the ultrasonic device increases the ion exchange speed in the pore channel and the pits, the acid etching time is reduced, and the uniformity of the secondary pits is increased.
(3) Modifying the surface of the implant by using perchloric acid-glacial acetic acid aqueous solution dissolved with oxygen. The first is that: controlling current density to polish the surface by using the conductivity of perchloric acid, stabilizing the Ra value (surface roughness) of the surface of the implant to 1-5 mu m, and increasing the mechanical property of osseointegration; secondly, the following steps: perchloric acid is chlorine-containing oxidizing acid and has a tendency to spontaneously form an oxide film; further, the titanium alloy is sensitive to oxygen, and forms an oxide film on the surface of the implant.
In the electropolishing oxidation process, the mixed acid liquid is subjected to dissolved oxygen treatment, the oxygen density in the solution is increased while the air in the original solution is removed, the internal reaction process is increased, and therefore the thickness of an oxide film is increased, and the corrosion resistance of the implant is increased in cooperation with the optimized 3D printing process; and the increase of oxygen is beneficial to the process of cathode oxidation reduction, and more hydroxyl groups are formed at the cathode and are attached to the generated oxide film, so that the hydrophilicity of the implant is increased. The cathode uses the mesh type stainless steel, which can reduce the polishing rate, inhibit excessive corrosion caused by electropolishing, and accurately control the Ra value within the range of 1-5 μm, and the specific reaction is as follows: anodic (oxidation process): ti4++O2+＝TiO2；2H2O＝O2+4e-+4H+；Ti+O2＝TiO2(ii) a Cathode (reduction process): o is2+2H2O+4e-＝4OH-. At the same time, the proportion of the electrolyte is requiredThe reason for this is: perchloric acid is an oxidizing acid and plays a decisive role in the surface roughness of the implant, but H is ionized by both acid solutions+Whereas the weak electrolyte glacial acetic acid hinders the ionization of the strong electrolyte perchloric acid. The temperature of the electropolishing oxidation also needs to be controlled because the temperature affects the activity of perchloric acid, which is too high and over-corrosion occurs, and too low activity, which fails to achieve the polishing effect.
Finally, storing the prepared 3D printing implant in 0.1mol/L NaOH solution at normal temperature, isolating the implant polluted by organic matters in the air, and adding TiO2The stability of the film layer keeps the hydrophilicity of the implant. The implant with biological activity has blood compatibility after being implanted into a human body, can increase cell adhesion, proliferation and differentiation and promote osseointegration.
In summary, compared with the prior art, the invention has the following beneficial effects: (1) the implant with the porous structure is obtained by using a 3D printing technology, so that the problem of stress shielding of the implant is effectively inhibited; (2) by utilizing the optimized setting of laser power and scanning rate in the 3D printing technology, combining the following steps of electropolishing and oxidizing the implant by using perchloric acid-glacial acetic acid mixed acid, the corrosion resistance of the implant is synergistically increased; (3) the sand blasting surface treatment and the acid etching treatment are utilized to generate primary and secondary nested pits, so that the adhesion and subsequent proliferation and differentiation of osteoblasts are synergistically enhanced, and the osseointegration is promoted; (4) an ultrasonic device is added in the acid etching treatment to promote the ion exchange between substances in the pore structure and the pits and the acid liquor, so that the acid etching treatment time and the acid etching temperature are reduced while impurities are removed; (5) the perchloric acid-glacial acetic acid electropolishing oxidation process is utilized, the step of dissolving oxygen is added, so that the oxygen density in the acid liquid is increased, the optimal setting of various parameters in the combined process is combined, the surface roughness of the implant is accurately controlled, and a better oxidation film is formed on the surface, so that the hydrophilicity is increased; (6) the process is simple and suitable for commercial production, and the 3D printing implant has good biological safety, osseointegration performance and mechanical performance due to the combination of multiple steps.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an SEM image (x 10000 times) of the 3D-printed implant obtained in example 5 after acid etching treatment;
FIG. 2 is an SEM image (6000 times) of the 3D-printed implant obtained in example 5 after acid etching treatment;
FIG. 3 is an SEM image (magnification ×. 3000) of the 3D-printed implant obtained in example 5 after acid etching treatment;
FIG. 4 is a graph of surface roughness data for a 3D-printed implant obtained in example 5;
FIG. 5 is a cell culture SEM image of a 3D printed implant obtained from comparative example 7;
fig. 6 is a cell culture SEM image of the 3D printed implant obtained in example 5.
Detailed Description
In order that the present invention may be more readily and clearly understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings. It should be understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the present invention.
Example 1:
a surface treatment process for 3D printing of an implant comprises the following steps:
s1: the 3D printing process of the implant comprises the following steps: (1) designing a 3D model of the implant with the porous structure; (2) slicing the 3D model, wherein the slice thickness is 28 micrometers, and planning a scanning path; the Sudoku mode is adopted for scanning in a partition mode, the size of an area is 2 multiplied by 2mm, the scanning direction deflects for a certain angle when different layers are scanned, and the deflection angle is set to be 37 degrees. (3) The selective laser melting equipment adopts a mode of combining vacuumizing and replacement, firstly vacuumizing to 80KPa, and then filling high-purity Ar gas into a forming chamber, and repeatedly replacing for many times to finally obtain an argon environment with oxygen content lower than 100ppm and pressure of 30 mbar; during printing, the substrate is preheated through the preheating function, the preheating temperature is 100 ℃, a layer of novel TA1 powder with the thickness of 28 microns is paved on the substrate through the powder paving mechanism after the substrate is preheated, and the powder supply amount is set to be 2 times of the powder paving thickness. Setting laser selective printing parameters: the laser power of the entity scanning is 350W, and the laser power of the outline scanning is 200W; the laser power for supporting scanning is 350W; the diameter of the light spot is 70 μm; the entity scanning speed is 2500mm/s, the outline scanning speed is 450mm/s, and the support scanning speed is 2500 mm/s; the scanning pitch is 0.07; and melting and superposing layer by layer according to a preset 3D model to obtain the implant A.
S2: the surface treatment process of the 3D printed implant comprises the following steps: (1) sand blasting treatment: under the conditions that the pressure of compressed air is 4bar and the jet distance is 60mm, 35-mesh white corundum is adopted to perform sand blasting treatment on the implant A for 10s until the surface forms uniform gray, so that a three-dimensional porous structure is formed on the surface of the dental implant, and the diameter of a primary pit is 20-55 mu m. Obtaining an implant B; (2) acid etching treatment: preparing an acid etching solution according to the volume ratio of 60 wt% sulfuric acid, 20 wt% hydrochloric acid and deionized water of 3:3: 4; placing the implant B in an acid etching solution, adding an ultrasonic device, setting the acid etching temperature to be 60 ℃ and the acid etching time to be 45min, and performing acid etching treatment to form a secondary pit with the diameter of 3-6 microns, wherein the secondary pit is gradually reduced on the surface of the dental implant, so as to obtain an implant C; (3) cleaning: and (3) spraying purified water for 2min, ultrasonically cleaning by using a Micro90 cleaning solution for 30min, and washing by using the purified water for 2min to obtain the 3D printed implant.
S3: 3D prints the planting body and stores: the 3D printing implant is stored in 0.1mol/L NaOH solution at normal temperature.
Example 2:
a surface treatment process for 3D printing of an implant comprises the following steps:
s1: the 3D printing process of the implant comprises the following steps: (1) designing a 3D model of the implant with the porous structure; (2) slicing the 3D model, wherein the slice thickness is 22 mu m, and planning a scanning path; the Sudoku mode is adopted for scanning in a partition mode, the size of an area is 2 multiplied by 2mm, the scanning direction deflects for a certain angle when different layers are scanned, and the deflection angle is set to be 37 degrees. (3) The selective laser melting equipment adopts a mode of combining vacuumizing and replacement, firstly vacuumizing to 80KPa, and then filling high-purity Ar gas into a forming chamber, and repeatedly replacing for many times to finally obtain an argon environment with oxygen content lower than 100ppm and pressure of 18 mbar; during printing, the substrate is preheated through the preheating function, the preheating temperature is 100 ℃, a layer of novel TA1 powder with the thickness of 22 mu m is paved on the substrate through the powder paving mechanism after the substrate is preheated, and the powder supply amount is set to be 2 times of the powder paving thickness. Setting laser selective printing parameters: the laser power of the entity scanning is 335W, and the laser power of the outline scanning is 160W; the laser power for supporting scanning is 335W; the diameter of the light spot is 70 μm; the entity scanning speed is 2300mm/s, the outline scanning speed is 420mm/s, and the support scanning speed is 2300 mm/s; the scanning pitch is 0.06; and melting and superposing layer by layer according to a preset 3D model to obtain the implant A.
S2: the surface treatment process of the 3D printed implant comprises the following steps: (1) sand blasting treatment: under the conditions that the pressure of compressed air is 3bar and the spraying distance is 120mm, the implant A is subjected to sand blasting for 50s by adopting one or a mixture of 100-mesh titanium oxide until the surface forms uniform gray, so that a three-dimensional porous structure is formed on the surface of the dental implant, and the diameter of a primary pit is 20-55 mu m. Obtaining an implant B; (2) acid etching treatment: preparing an acid etching solution according to the volume ratio of 95 wt% sulfuric acid, 32 wt% hydrochloric acid and deionized water of 2.5:2: 3; placing the implant B in an acid etching solution, adding an ultrasonic device, setting the acid etching temperature to be 40 ℃, and performing acid etching treatment for 10min to form a secondary pit with the diameter of 3-6 microns, wherein the secondary pit is gradually reduced on the surface of the dental implant, so as to obtain an implant C; (3) cleaning: and spraying purified water for 1min, ultrasonically cleaning the Micro90 cleaning solution for 45min, and washing the purified water for 1min to obtain the 3D printed implant.
S3: 3D prints the planting body and stores: the 3D printing implant is stored in 0.1mol/L NaOH solution at normal temperature.
Example 3:
a surface treatment process for 3D printing of an implant comprises the following steps:
s1: the 3D printing process of the implant comprises the following steps: (1) designing a 3D model of the implant with the porous structure; (2) slicing the 3D model, wherein the slice thickness is 24 mu m, and planning a scanning path; the Sudoku mode is adopted for scanning in a partition mode, the size of an area is 2 multiplied by 2mm, the scanning direction deflects for a certain angle when different layers are scanned, and the deflection angle is set to be 37 degrees. (3) The selective laser melting equipment adopts a mode of combining vacuumizing and replacement, firstly vacuumizing to 80KPa, and then filling high-purity Ar gas into a forming chamber, and repeatedly replacing for many times to finally obtain an argon environment with oxygen content lower than 100ppm and pressure of 32 mbar; during printing, the substrate is preheated through the preheating function, the preheating temperature is 100 ℃, a layer of novel TA1 powder with the thickness of 24 mu m is paved on the substrate through the powder paving mechanism after the substrate is preheated, and the powder supply amount is set to be 2 times of the powder paving thickness. Setting laser selective printing parameters: the laser power of the entity scanning is 365W, and the laser power of the outline scanning is 180W; the laser power for supporting scanning is 365W; the diameter of the light spot is 70 μm; the entity scanning speed is 2600mm/s, the outline scanning speed is 480mm/s, and the supporting scanning speed is 2600 mm/s; the scanning interval is 0.08; and melting and superposing layer by layer according to a preset 3D model to obtain the implant A.
S2: the surface treatment process of the 3D printed implant comprises the following steps: (1) sand blasting treatment: under the conditions that the pressure of compressed air is 3-5 bar and the spraying distance is 90mm, the implant A is subjected to sand blasting for 30s by adopting a mixture of 60-mesh white corundum and titanium oxide until the surface of the implant A forms uniform gray, so that a three-dimensional porous structure is formed on the surface of the dental implant, and the diameter of a primary pit is 20-55 mu m. Obtaining an implant B; (2) acid etching treatment: preparing an acid etching solution according to the volume ratio of 80 wt% sulfuric acid, 25 wt% hydrochloric acid and deionized water of 3.5:4: 5; placing the implant B in an acid etching solution, adding an ultrasonic device, setting the acid etching temperature to be 80 ℃, and performing acid etching treatment for 80min to form a secondary pit with the diameter of 3-6 microns, wherein the secondary pit is gradually reduced on the surface of the dental implant, so as to obtain an implant C; (3) cleaning: and spraying purified water for 5min, ultrasonically cleaning by using a Micro90 cleaning solution for 25min, and washing by using the purified water for 5min to obtain the 3D printed implant.
S3: 3D prints the planting body and stores: the 3D printing implant is stored in 0.1mol/L NaOH solution at normal temperature.
Example 4: an electropolishing oxidation process is added between (2) and (3) of step S2, the rest being the same as in example 1; the specific steps are as follows:
electropolishing oxidation treatment: preparing perchloric acid, glacial acetic acid and deionized water into a solution according to a volume ratio of 1:8:1.2, and dissolving oxygen in a water bath at 28 ℃ for 30min to obtain a perchloric acid-glacial acetic acid aqueous solution; perchloric acid-glacial acetic acid aqueous solution is used as electrolyte, the implant C is used as an anode, and the net-shaped stainless steel is used as a cathode; setting the current density at 0.28A/cm2Treating for 15min to obtain an implant D;
example 5: an electropolishing oxidation process is added between (2) and (3) of step S2, the rest being the same as in example 1; the specific steps are as follows:
electropolishing and oxidizing treatment: preparing perchloric acid, glacial acetic acid and deionized water into a solution according to a volume ratio of 1:10:1.4, and dissolving oxygen in water bath at 30 ℃ for 45min to obtain a perchloric acid-glacial acetic acid aqueous solution; perchloric acid-glacial acetic acid aqueous solution is used as electrolyte, the implant C is used as an anode, and the net-shaped stainless steel is used as a cathode; setting the current density at 0.30A/cm2Treating for 10min to obtain an implant D;
example 6: example 4: an electropolishing oxidation process is added between (2) and (3) of step S2, the rest being the same as in example 1; the specific steps are as follows:
electropolishing and oxidizing treatment: preparing perchloric acid, glacial acetic acid and deionized water into a solution according to a volume ratio of 1:12:1.6, and dissolving oxygen in a water bath at 32 ℃ for 60min to obtain a perchloric acid-glacial acetic acid aqueous solution; perchloric acid-glacial acetic acid aqueous solution is used as electrolyte, the implant C is used as an anode, and the net-shaped stainless steel is used as a cathode; setting the current density at 0.32A/cm2Treating for 5min to obtain an implant D;
comparative example 7: the implant prepared by direct printing was used as a comparative example, surface treatment was not performed, and the printing process was the same as in example 1.
Experiment 1: the implant prepared in example 5 is subjected to morphology characterization, and SEM images are measured and shown in figures 1-3;
and (4) conclusion: from fig. 1 to 3, it can be seen that: the surface of the implant is a uniform honeycomb-shaped secondary pit, the uniformity and compactness of the appearance of the secondary pit of the implant are superior to those of the mainstream implants in the market, the average size is 2-6 mu m, and the adjacent pits form a nested structure, so that osteoblast attachment and subsequent proliferation and differentiation are facilitated, and osseointegration is promoted.
Experiment 2: the implants prepared in examples 1-6 and comparative example 7 were subjected to a contact test to characterize hydrophilicity. Specific data are shown in table 1;
experiment 3: the implants prepared in examples 1-6 and comparative example 7 were subjected to a salt spray test to characterize corrosion resistance, and the specific conditions were as follows: the experimental solution was a 5 wt% aqueous sodium chloride solution; the experimental temperature is 35 ℃, and the continuous atomization is carried out for 600 hours; after cleaning and drying, taking the time of pitting corrosion as a basis for judging the corrosion resistance; specific data are shown in table 1;
TABLE 1
And (4) conclusion: in examples 1 to 3, the best laser process parameters are the process parameters of example 1: the laser power of the scanning entity is 350W, the laser power of the scanning contour is 200W, the laser power of the scanning support is 350W, the spot diameter is 70 μm, the entity scanning speed is 2500mm/s, the contour scanning speed is 450mm/s, the support scanning speed is 2500mm/s, and the scanning interval is 0.07.
Examples 4 to 6 are examples 1 in which an electropolishing oxidation step is added, and it can be found that: the method has the advantages that the surface roughness is reduced and the hydrophilicity is increased due to the fact that perchloric acid is used as conducting acid to polish the surface of the implant; secondly, the corrosion resistance is increased because the increased oxygen dissolving step increases the oxygen density in the acid solution, so that a thicker oxide film is formed; the hydrophilicity is increased because more hydroxyl groups are obtained by reduction due to the increase of oxygen density in the electro-oxidation process. And from the data point of view, the optimal technical parameters are as follows: the volume ratio of perchloric acid to glacial acetic acid to deionized water is 1:10:1.4, and the current density is 0.30A/cm2The treatment time was 10 min.
Experiment 4: according to the above experimental results, the dental implant prepared in example 5, which has superior overall performance, was subjected to a cell adhesion experiment using comparative example 7 as a control group. The method comprises the following specific steps:
pbs washed cells 2 times;
b.4% paraformaldehyde fixed for 10 minutes at room temperature, PBS washing cells for 2 times;
c.0.1% TritonX-100 at room temperature for 7min, washing cells with PBS for 2 times;
D. adding FITC-phalloidin 5 μ g/ml, staining for 30min at room temperature, and washing cells with PBS 3 times;
e, staining cell nuclei with DAPI for 10 minutes, washing the cells with PBS for 3 times at 37 ℃; absorbing excessive water, adding fluorescent mounting solution, covering with a cover glass, and observing under a fluorescent or confocal microscope; or directly blocking with Dapi-containing fluorescent blocking solution.
And (4) conclusion: the SEM observations obtained are shown schematically in FIGS. 5-6, from which it can be seen that the difference in the amount of adhesion between the two implants is significant, and the 3D-printed implant samples prepared in example 5 have significantly more cell adhesion than in example 1. Meanwhile, cytoskeleton in the graph is very clear, each adhered cell has excellent spreading state, is mostly irregular polygon, and is abundant in false. Thus, the hydrophilicity data in experiment 3 was laterally verified, indicating that a series of surface treatments resulted in the preparation of implants with excellent cell adhesion.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The surface treatment process for the 3D printed implant is characterized by comprising the following steps of: the method comprises the following steps:
s1: the 3D printing process of the implant comprises the following steps: (1) designing an implant 3D model; (2) slicing the 3D model and planning a scanning path; (3)3D printing to obtain an implant A;
s2: the surface treatment process of the 3D printed implant comprises the following steps: (1) performing sand blasting treatment to obtain an implant B; (2) carrying out acid etching treatment to obtain an implant C; (2-2) electropolishing oxidation treatment: preparing perchloric acid, glacial acetic acid and deionized water into a solution according to the volume ratio of 1 (8-12) to (1.2-1.6), and dissolving oxygen in a water bath at the temperature of 28-32 ℃ for 30-60 min to obtain a perchloric acid-glacial acetic acid aqueous solution; perchloric acid-glacial acetic acid aqueous solution is used as electrolyte, the implant C is used as an anode, and the net-shaped stainless steel is used as a cathode; setting the current density to 0.28-0.32A/cm2Treating for 5-15 min to obtain an implant D; (3) cleaning to obtain a 3D printing implant;
s3: 3D prints the planting body and stores: the 3D printing implant is stored in 0.1mol/L NaOH solution at normal temperature.
2. The surface treatment process of the 3D printed implant according to claim 1, wherein: in step S1, the method includes the steps of: (1) designing a 3D model of the implant with the porous structure; (2) slicing the 3D model, wherein the thickness of the slices is 22-28 micrometers, and planning a scanning path; (3) and setting laser selection area process parameters, taking TA1 powder as a raw material, and performing 3D printing to obtain the implant A.
3. The surface treatment process of the 3D printed implant according to claim 2, wherein: in step (3) of step S1, the specific steps are: pumping the forming chamber to a vacuum state, filling high-purity argon to finally obtain an argon environment with oxygen content lower than 100ppm and pressure of 18-32 mbar; dispersing TA1 powder on a printing bed, and setting the laser selective area printing parameters: the laser power of the physical scanning is 335-365W, and the laser power of the profile scanning is 160-200W; the laser power for supporting scanning is 335-365W; the diameter of the light spot is 70 μm; the entity scanning speed is 2300-2600 mm/s, the outline scanning speed is 420-480 mm/s, and the support scanning speed is 2300-2600 mm/s; the scanning interval is 0.06-0.08; and melting and superposing layer by layer according to a preset 3D model to obtain the implant A.
4. The surface treatment process of the 3D printed implant according to claim 1, wherein: in step S2, the method includes the steps of: (1) sand blasting treatment: under the conditions that the pressure of compressed air is 3-5 bar and the jet distance is 60-120 mm, performing sand blasting treatment on the implant A for 10-50 s by adopting one or a mixture of 35-100 meshes of white corundum and titanium oxide to obtain an implant B; (2) acid etching treatment: placing the implant B in an acid etching solution, adding an ultrasonic device, setting the acid etching temperature to be 40-80 ℃, and performing acid etching treatment for 10-80 min to obtain an implant C; (3) cleaning: and spraying purified water for 1-5 min, ultrasonically cleaning with a Micro90 cleaning solution for 25-45 min, and washing with the purified water for 1-5 min to obtain the 3D printed implant.
5. The surface treatment process of the 3D printed implant according to claim 4, wherein: in step (2) of step S2, the acid etching solution is prepared from (2.5-3.5) to (2-4) to (3-5) by volume of 60-95 wt% sulfuric acid, 20-32 wt% hydrochloric acid, and deionized water.
6. The surface treatment process of the 3D printed implant according to claim 1, wherein: the 3D printing implant is prepared by a 3D printing method; the raw material of the 3D printing implant is TA1 powder; the particle size range of the TA1 powder is 20-50 mu m.
7. The surface treatment process of the 3D printed implant according to claim 6, wherein: the TA1 powder included the following elements: according to the mass percentage, Fe is less than or equal to 0.25 percent; c is less than or equal to 0.10 percent; n is less than or equal to 0.03 percent; h is less than or equal to 0.015 percent; o is less than or equal to 0.20 percent; the balance being Ti.
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