CN115634310A - Preparation method of gradient cobalt-loaded cellular nanofiber coating - Google Patents
Preparation method of gradient cobalt-loaded cellular nanofiber coating Download PDFInfo
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Abstract
The invention discloses a preparation method of a multifunctional gradient cobalt-loaded cellular nanofiber coating on the surface of a titanium-based implant, which constructs a gradient cobalt-loaded nanofiber bionic coating with the cobalt atom percentage of 4.52 to 8.28 percent and can adapt to environments with different antibacterial requirements. Firstly adopting hydrothermal process to prepare Na on the surface of the titanium substrate 2 Ti 4 O 9 A complex-phase bionic layer is arranged on the surface of the substrate,then carrying out secondary hydrothermal treatment on the complex phase layer under the specific cobalt-containing hydrothermal environment condition. The obtained two-layer structure coating has the following structural and performance characteristics: the inner layer (adjacent to the substrate) is a dense structure; the surface layer is cobalt-loaded nano fibrous Na 2 Ti 4 O 9 The bionic layer is characterized in that the fibers are in a porous cellular shape. The double-layer structure coating has no discontinuous interface with a matrix, has high bonding strength, good hydrophilicity and strong biological corrosion resistance, promotes the adhesion and proliferation of cells, continuously and stably releases cobalt ions in body fluid, has strong killing capacity on gram positive bacteria and gram negative bacteria, and has the sterilization rate of more than 99 percent.
Description
Technical Field
The invention belongs to the technical field of medical metal surface biological activation modification, relates to a preparation technology of a titanium-based medical implant surface bioactive coating, and particularly relates to a preparation method of a titanium-based implant surface gradient cobalt-loaded cellular nanofiber coating.
Background
There is an urgent clinical need for multifunctional titanium-based bone implants with antibacterial, angiogenic and osteogenic activity that can be achieved by the addition of appropriate inorganic bioactive elements. The present study developed a cobalt-doped titanium surface nanofiber coating with layered micro/nano structures. The coating has obvious inhibiting effect on the colonization and growth of gram-positive bacteria and gram-negative bacteria, and has no cytotoxicity. In addition, the coating can stimulate the expression of key angiogenesis factors of the bone marrow stem cells of mice and obviously enhance the osteogenic differentiation of MSC. The multifunctional cobalt-loaded nanofiber coating with antibacterial, angiogenesis and osteogenesis activities is a promising titanium implant coating for orthopedics and dentistry, and can improve clinical performance. Titanium (Ti) is widely used in the production of bone implant devices such as joint prostheses, fracture fixation devices, dental implants, etc. due to its excellent biocompatibility and high corrosion resistance. However, titanium itself has no antibacterial activity and bacteria can attach and colonize thereon to form biofilms that are tough and highly resistant to antibacterial therapy, often leading to persistent infections and implant failure. It is considered as an effective measure against implant-related infection that an implant is rendered antibacterial by killing initially attached bacteria, thereby being able to prevent biofilm formation thereon.
Another aspect of titanium implants that needs to be augmented is osseointegration. The basis for long-term normal function of bone implants is rigid osteointegration with intimate contact with the bone/implant surface. Although titanium-based bones have been implanted with up to 95% success in healthy patients, they still exhibit a lack of bioactivity, which can lead to impaired longevity and implant failure, particularly when complex conditions are encountered, which are detrimental to the establishment of osteointegration, such as osteoporosis. Mesenchymal Stem Cells (MSCs) are generally thought to play a key role in implant/bone integration. Most osteoblasts that colonize the surface of the implant to form bone originate from MSCs. In order to achieve good osseointegration, it is critical that the implant be able to preferentially promote differentiation of mesenchymal stem cells into osteoblasts. Furthermore, the ideal osseointegration process also requires good neovascularization, which not only provides a nutrient supply for new bone formation, but also helps bone marrow mesenchymal stem cells home to the osteogenesis at a distance from the implant surface. In fact, good vascularization is also beneficial for preventing infections.
Common surface modification methods include sol-gel, anodic oxidation, micro-arc oxidation, vapor deposition, ion implantation, laser or plasma cladding, and the like. Each modification technology has the characteristics, but the film forming is difficult on the surface of the titanium implant with complex appearance, such as at the edge or in a hole.
Disclosure of Invention
The technical problem to be solved by the invention is to provideA preparation method of a gradient cobalt-loaded nanofiber coating is provided, which firstly adopts a hydrothermal process to grow porous cellular Na on the titanium surface in situ 2 Ti 4 O 9 And (3) coating the nano-fiber, and then carrying out secondary hydrothermal treatment on the complex phase layer in a specific hydrothermal environment.
In order to solve the technical problem, the invention comprises the following steps:
1) Hydrothermal preparation of titanium-based nanofiber coating
Soaking the pretreated pure titanium sample in an alkaline mixed solution, and carrying out hydrothermal treatment for 5-7 hours at the temperature of 240-250 ℃ to grow a porous cellular nanofiber coating on the surface of the pure titanium in situ;
2) Hydrothermal preparation of gradient cobalt-loaded nanofiber coating
CoCl with the concentration of 1mM to 1M 2 •6H 2 And injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 30-40%, placing the primary hydrothermal sample into the hydrothermal reaction kettle again, and carrying out secondary hydrothermal treatment for 2-6 hours at the temperature of 100-200 ℃ to obtain the gradient cobalt-loaded nanofiber coating with the cobalt element atomic percentage of 4.52-8.28%.
The alkaline mixed solution in the step 1) is prepared from NaOH solution and hydrogen peroxide according to the volume ratio of 1: and 4, preparing. The molar concentration of the NaOH solution is 3-5M, and the mass fraction of the hydrogen peroxide is 30%.
The step 1) is specifically as follows: the pretreated pure titanium sample is soaked in an alkaline mixed solution for primary hydrothermal treatment, the solution filling degree is 35%, uniform porous cellular nanofibers formed by gathering and surrounding clustered long fibers can grow on the surface of the titanium matrix in situ, holes are communicated with one another to form a multi-level three-dimensional structure, the micron-sized porous structure is implanted into human tissues to facilitate absorption and conveying of nutrients, and the annular porous wall provides a sufficient contact area of adhesion spots for cell adhesion, so that the cell adhesion is facilitated.
The step 2) is specifically as follows: adding CoCl 2 •2H 2 Injecting the O solution into a hydrothermal reaction kettle with the solution filling degree of 30-40%, and placing a primary hydrothermal sample in a hydrothermal reaction kettleAnd performing secondary hydrothermal treatment in a reactor to obtain the cellular cobalt-loaded nanofiber uniformly paved on the surface of the titanium matrix, wherein the fiber shape is not obviously changed compared with the fiber shape in the step 1), but the components are changed, stem cells on the surface of the coating are larger than the titanium matrix surface in size, are more pseudo-abundant and are flatly spread, the adhesion and growth of cells are obviously promoted, the atomic percentage content of the cobalt element of the coating is 4.52 to 8.28 percent, and the coating has gradient cobalt-loaded amount and can adapt to different environments with different antibacterial requirements.
The present invention has the following advantageous effects
The invention solves the difficult problem of preparing the gradient cobalt-loaded nanofiber coating, realizes the construction of the nanofiber active coating on the surface of the titanium implant by a simple and feasible two-step hydrothermal method, and the construction of the coating is uniform and consistent without dead angles and shielding parts on all surfaces immersed in the solution.
The nanofiber coating prepared by the method has no discontinuous interface between the coating and the matrix, and has high bonding strength.
The nanofiber structure with high specific surface area enhances surface wettability, referring to fig. 6-8, surface hydroxylation is promoted, uniform porous cellular nanofibers formed by gathering and surrounding clustered long fibers are communicated with each other in pores to form a multi-level three-dimensional structure, a micron-sized porous structure is implanted into human tissues to facilitate absorption and conveying of nutrients, an annular porous wall provides a sufficient contact area of adhesion spots for cell adhesion to facilitate cell adhesion, and cell experiments show that after mouse mesenchymal stem cells are cultured on a cobalt-loaded nanofiber coating for 48 hours, compared with a titanium matrix (referring to fig. 10), a large number of filamentous false feet appear at the cell edge (referring to fig. 11), and the bioactivity of the titanium matrix is obviously improved.
Cobalt-loaded Na prepared by the invention 2 Ti 4 O 9 The nanofiber coating obviously improves the corrosion resistance of the titanium-based implant in physiological saline, compared with a titanium matrix and Na 2 Ti 4 O 9 Nano-fiber coating cobalt-loaded Na 2 Ti 4 O 9 The corrosion potential of the nanofiber coating is shifted positively, the corrosion current density is reduced, and the electrochemical corrosion Tafel is referred toFig. 5, the long-term stability of the implant in vivo can be ensured.
Cobalt-loaded Na prepared by the invention 2 Ti 4 O 9 The nanofiber coating has strong contact sterilization capability, see fig. 7; can release active cobalt ion Co in normal saline for a long time and in a balanced manner 2+ Referring to fig. 9, the coating is provided with a sustained balance of antimicrobial activity; meanwhile, the prepared cobalt-loaded nanofiber coating has the gradient cobalt atom percentage content of 4.52 to 8.28 percent, and can adapt to environments with different antibacterial requirements.
The hydrothermal solution prepared by the method has simple components, is easy to control, does not contain easily decomposed components, and has stable process; preparing cobalt-loaded Na on the surface of pure titanium by adopting a simple and feasible composite two-step hydrothermal method 2 Ti 4 O 9 And (3) a nanofiber antibacterial active coating. The invention has simple process and low production cost.
Drawings
The following detailed description of embodiments of the invention is provided in conjunction with the accompanying drawings:
FIG. 1 cobalt-loaded Na of the invention 2 Ti 4 O 9 SEM photograph of surface topography and spectral EDS values of nanofiber coating (example 1);
FIG. 2 cobalt-loaded Na of the present invention 2 Ti 4 O 9 SEM photograph of the cross-sectional morphology of the nanofiber coating (example 1);
FIG. 3 Co-loaded Na of the invention 2 Ti 4 O 9 XPS full spectrum of surface photoelectron spectroscopy of nanofiber coating (example 1);
FIG. 4 Co-loaded Na according to the invention 2 Ti 4 O 9 XPS high resolution spectra of cobalt on the surface of nanofiber coating (example 1).
FIG. 5 cobalt-loaded Na according to the present invention 2 Ti 4 O 9 Electrochemical corrosion Tafel plot of nanofiber coating (example 1);
FIG. 6 is a graph of the contact angle of a titanium substrate;
FIG. 7 invention Na 2 Ti 4 O 9 Contact angle plot of nanofiber coating (example 1);
FIG. 8 cobalt-loaded Na of the present invention 2 Ti 4 O 9 Contact angle plot of nanofiber coating (example 1);
FIG. 9 Co-loaded Na according to the invention 2 Ti 4 O 9 Ion elution ICP profile of nanofiber coating (example 1) in 10ml of physiological saline;
FIG. 10 is an SEM image of the surface cell growth of titanium substrate after co-culturing with mouse mesenchymal stem cells for 48 hours;
FIG. 11 shows that after the co-culture of mouse mesenchymal stem cells for 48 hours, the cobalt-loaded Na is adopted in the invention 2 Ti 4 O 9 SEM morphology picture of cell growth on the surface of the nanofiber coating (example 1);
FIG. 12 is a graph of a Staphylococcus aureus-coated bacterial growth plate adhered to the surface of a titanium substrate after 24 hours of co-culture with Staphylococcus aureus.
FIG. 13 Co-culture with Staphylococcus aureus for 24 hours, inventive Na 2 Ti 4 O 9 The surface of the nanofiber coating is adhered with a staphylococcus aureus coating bacterial culture plate.
FIG. 14 Co-loaded Na according to the present invention after 24 hours of coculture with Staphylococcus aureus 2 Ti 4 O 9 Picture of staphylococcus aureus coated bacterial growth plate adhered to the surface of nanofiber coating (example 1).
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
Placing the pretreated titanium sheet with the right side facing upwards at the bottom of a high-pressure reaction kettle, and mixing a 5M NaOH solution and hydrogen peroxide according to the weight ratio of 1:4, the solution filling degree is 35 percent, and the first step of hydrothermal treatment is carried out for 7 hours at 240 ℃ to obtain a uniform porous cellular three-dimensional structure formed by gathering and surrounding clustered long fibers; coCl was added at a concentration of 100mM 2 •6H 2 Injecting an O solution into the hydrothermal reaction kettle, wherein the solution filling degree is 40%, placing a primary hydrothermal sample into the hydrothermal reaction kettle again, carrying out secondary hydrothermal treatment for 4 hours at 200 ℃, wherein the appearance of the nanofiber is not obviously changed compared with the first step of hydrothermal treatment, but the components are changed, the surface micro-appearance SEM and EDS refer to the figure 1, the cross-section micro-appearance SEM refers to the figure 2, the atomic percent of cobalt is 7.957%, the element valence state of the coating is tested by using photoelectron spectroscopy, cobalt exists in a divalent ion state, the XPS full spectrum refers to the figure 3, and the cobalt high-resolution spectrum refers to the figure 4; the bond strength of the coating to the titanium substrate was measured using an automatic scratch coating tester, which showed a critical load of 42.05N at the point where the coating was peeled off. The corrosion resistance of the coating is tested by using an electrochemical workstation, and the corrosion voltage in normal saline is 0.074V, which is lower than that of a titanium substrate (-0.465V) and Na 2 Ti 4 O 9 The nano-fiber bionic coating (-0.269V) is obviously forward-shifted, and the corrosion current density is 1.408 multiplied by 10 -9 mA cm -2 Titanium matrix (3.477X 10) -6 mA cm -2 ) And Na 2 Ti 4 O 9 Nano-fiber bionic coating (7.072 is multiplied by 10) -8 mA cm -2 ) The corrosion resistance is high, and the electrochemical corrosion Tafel graph of the coating is shown in figure 5; the hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 9.4 degrees, the hydrophilicity of the coating is good compared with that of a titanium matrix (57.3 degrees),see fig. 6, 7 and 8. After the sample is soaked in 10ml of normal saline for 2d, 4d, 7d, 14d and 21d, the ion precipitation of the coating is tested by using an inductively coupled plasma-atomic emission spectrum, and the result shows that Co in the coating is precipitated 2+ Sustained release was equalized, the amount eluted in 21 days was 1.85925ppm, and the ion elution condition in 10ml of physiological saline is shown in FIG. 9. After the cells are co-cultured for 48 hours, the surface of the coating (figure 11) can significantly promote the adhesion and growth of mouse mesenchymal stem cells relative to the surface of the titanium substrate (figure 10), and SEM morphology photographs of the growth of the cells on the surface of the coating and the titanium substrate are shown in figures 10 and 11; staphylococcus aureus (S. Aureus) is used as a gram-positive bacteria model, the number of the staphylococcus aureus adhered to the surface of the coating is remarkably reduced after the cobalt-loaded coating is co-cultured for 24 hours, the contact sterilization rate is more than 99%, and the plate-shaped culture plate of the staphylococcus aureus coated bacteria is shown in figure 12, figure 13 and figure 14.
Example 2
Placing the pretreated titanium sheet with the right side facing upwards at the bottom of a high-pressure reaction kettle, and mixing a 4M NaOH solution and hydrogen peroxide according to the weight ratio of 1:4, the solution filling degree is 35 percent, and the first step of hydrothermal treatment is carried out for 6 hours at 245 ℃ to obtain the porous cellular nanofiber coating; coCl with the concentration of 1M 2 •6H 2 And injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 35%, soaking the porous cellular nanofiber coating obtained by one-step hydrothermal treatment into the solution, and performing a second-step hydrothermal treatment on the solution at 150 ℃ for 4 hours, wherein the shape of the nanofiber is not obviously changed, the components are changed, and the atomic percent of the cobalt element is 8.28%. The hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 9.47 degrees, the contact angle is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 3
Placing the pretreated titanium sheet with the right side facing upwards at the bottom of a high-pressure reaction kettle, and mixing 3M NaOH solution and hydrogen peroxide according to the weight ratio of 1:4, mixing and injecting into a kettle at the duty ratio of 35%, and carrying out first-step hydrothermal treatment at 250 ℃ for 5 hours to obtain a porous cellular nanofiber coating; coCl was added at a concentration of 100mM 2 •6H 2 Injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 37 percent, and mixingSoaking the porous cellular nanofiber coating obtained in the step of hydrothermal treatment into the solution, and carrying out the second step of hydrothermal treatment on the porous cellular nanofiber coating for 2 hours at the temperature of 200 ℃, wherein the shape of the nanofiber is not obviously changed, the components are changed, and the atomic percent of cobalt element is 7.78%. The hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 8.82 degrees, the hydrophilicity of the coating is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 4
CoCl with the concentration of 1M 2 •6H 2 And injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 40%, soaking the hydrothermal sample obtained in the step 1 in the solution, and performing a second-step hydrothermal treatment on the solution at 150 ℃ for 6 hours, wherein the shape of the nanofiber is not obviously changed, the components are changed, and the atomic percent of cobalt is 7.46%. The hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 8.3 degrees, the contact angle is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 5
CoCl was added at a concentration of 10mM 2 •6H 2 And injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 40%, soaking the hydrothermal sample obtained in the step 1 in the solution, and performing a second-step hydrothermal treatment on the solution at 150 ℃ for 2 hours, wherein the shape of the nanofiber is not obviously changed, the components are changed, and the atomic percent of cobalt is 7.293%. The hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 8.27 degrees, the hydrophilicity of the coating is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 6
CoCl was added at a concentration of 100mM 2 •6H 2 And injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 40%, soaking the hydrothermal sample obtained in the step 1 in the solution, and performing a second-step hydrothermal treatment on the hydrothermal sample for 6 hours at the temperature of 150 ℃, wherein the shape of the nanofiber is not obviously changed, the components are changed, and the atomic percent of the cobalt element is 7.243%. The hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 8.19 degrees, the contact angle is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 7
CoCl with the concentration of 1M 2 •6H 2 Injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 40%, soaking the hydrothermal sample obtained in the step 1 in the solution, and performing a second-step hydrothermal treatment on the sample for 2 hours at the temperature of 150 ℃, wherein the shape of the nanofiber is not obviously changed, the components are changed, and the atomic percent of cobalt is 7.193%. The hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 7.78 degrees, the contact angle is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 8
CoCl was added at a concentration of 100mM 2 •6H 2 And injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 40%, soaking the hydrothermal sample obtained in the step 1 in the solution, and performing a second-step hydrothermal treatment on the hydrothermal sample for 6 hours at the temperature of 100 ℃, wherein the shape of the nanofiber is not obviously changed, the components are changed, and the atomic percent of the cobalt element is 7.06%. The hydrophilicity of the coating is tested by using a contact angle measuring instrument, the contact angle is 7.22 degrees, the hydrophilicity of the coating is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 9
CoCl was added at a concentration of 100mM 2 •6H 2 The O solution is injected into a hydrothermal reaction kettle, the solution filling degree is 40 percent, the hydrothermal sample obtained in the step 1 is soaked into the solution, the second-step hydrothermal treatment is carried out on the solution for 2 hours at the temperature of 150 ℃, the shape of the nanofiber is not obviously changed, the components are also changed, the atomic percent of cobalt is 7.053 percent, a contact angle measuring instrument is used for testing the hydrophilicity of the coating, the contact angle is 7.11 degrees, the contact angle is obviously reduced compared with that of a titanium matrix (57.3 degrees), and the hydrophilicity of the coating is good.
Example 10
CoCl with the concentration of 1M 2 •6H 2 Injecting an O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 40%, soaking the hydrothermal sample obtained in the step 1 in the solution, carrying out a second-step hydrothermal treatment on the hydrothermal sample for 6 hours at 100 ℃, wherein the shape of the nanofiber is not obviously changed, the components are changed, the atomic percent of cobalt is 6.97%, a contact angle measuring instrument is used for testing the hydrophilicity of the coating, the contact angle is 7.0 degrees, and the surface is bright compared with a titanium matrix (57.3 degrees)Obviously reduces the content of the active carbon and has good hydrophilicity of the coating.
Example 11
CoCl was added at a concentration of 1mM 2 •6H 2 The O solution is injected into a hydrothermal reaction kettle, the solution filling degree is 40 percent, the hydrothermal sample obtained in the step 1 is soaked into the solution, the second-step hydrothermal treatment is carried out on the solution for 4 hours at the temperature of 100 ℃, the shape of the nanofiber is not obviously changed, the components are changed, the atomic percent of cobalt is 5.9 percent, a contact angle measuring instrument is used for testing the hydrophilicity of the coating, the contact angle is 6.75 degrees, the contact angle is obviously reduced compared with that of a titanium substrate (57.3 degrees), and the hydrophilicity of the coating is good.
Example 12
CoCl was added at a concentration of 0.1mM 2 •6H 2 The O solution is injected into a hydrothermal reaction kettle, the solution filling degree is 40%, the hydrothermal sample obtained in the step 1 is soaked into the solution, the second-step hydrothermal treatment is carried out on the solution for 4 hours at the temperature of 100 ℃, the shape of the nanofiber is not obviously changed, the components are changed, the atomic percent of cobalt is 4.523%, a contact angle measuring instrument is used for testing the hydrophilicity of the coating, the contact angle is 6.41 degrees, the contact angle is obviously reduced compared with that of a titanium substrate (57.3 degrees), and the hydrophilicity of the coating is good.
The embodiments are illustrative of many, not to scale, and are not to be construed as being limited thereto.
The double-layer structure coating obtained by the method is characterized in that: the inner layer (adjacent to the substrate) is a dense structure; the surface layer is loaded with cobalt Na 2 Ti 4 O 9 The nano-fiber bioactive antibacterial coating is in a porous cellular shape, and the diameter of the fiber is about 60-70 nanometers. The double-layer structure coating has no discontinuous interface with the substrate, has high bonding strength, good hydrophilicity and strong biological corrosion resistance, promotes the adhesion and growth of cells, and has strong contact sterilization capability. Meanwhile, the invention also constructs a gradient cobalt-loaded nanofiber bionic coating with the cobalt atom percentage content of 4.52-8.28%, and the bionic coating can adapt to environments with different antibacterial requirements.
Claims (5)
1. A preparation method of a gradient cobalt-loaded nanofiber coating is characterized by comprising the following steps:
1) Hydrothermal preparation of titanium-based nanofiber coating
Soaking a pretreated pure titanium sample in an alkaline mixed solution, wherein the solution filling degree is 35%, and carrying out hydrothermal treatment for 5-7 hours at the temperature of 240-250 ℃ to obtain a nanofiber coating, wherein the surface appearance of the coating is a uniform porous cellular shape formed by gathering and surrounding clustered long fibers, and the pores are communicated with one another to form a multi-level three-dimensional structure;
2) Hydrothermal preparation of gradient cobalt-loaded nanofiber coating
CoCl with the concentration of 1mM to 1M 2 •6H 2 Injecting the O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 30-40%, placing the primary hydrothermal sample into the hydrothermal reaction kettle again, carrying out secondary hydrothermal treatment for 2-6 hours at the temperature of 100-200 ℃, wherein the fiber appearance is not obviously changed compared with the step 1), and only the fiber components are changed, so that the porous cellular cobalt-loaded nano fiber uniformly paved on the surface of the titanium matrix is obtained, the atomic percentage content of the cobalt element of the coating is 4.52-8.28%, and the coating has gradient cobalt loading capacity and can adapt to environments with different antibacterial requirements.
2. The method for preparing the gradient cobalt-loaded nanofiber coating according to claim 1, wherein the alkaline mixed solution in the step 1) is prepared from a NaOH solution and hydrogen peroxide according to a volume ratio of 1: and 4, preparing.
3. The method for preparing the gradient cobalt-loaded nanofiber coating according to claim 2, wherein the molar concentration of the NaOH solution is 3-5M, and the mass fraction of hydrogen peroxide is 30%.
4. The preparation method of the gradient cobalt-loaded nanofiber coating according to claim 1, wherein the step 1) is specifically: and (3) injecting the alkaline mixed solution into a hydrothermal reaction kettle, wherein the solution filling degree is 35%, soaking the pure titanium sample into the solution for primary hydrothermal treatment, and growing a cellular nanofiber coating on the titanium surface in situ.
5. The method for preparing the multifunctional gradient cobalt-loaded cellular nanofiber coating according to claim 1, wherein the step 2) specifically comprises: adding CoCl 2 •2H 2 Injecting an O solution into a hydrothermal reaction kettle, wherein the solution filling degree is 30-40%, placing a primary hydrothermal sample into the hydrothermal reaction kettle, and carrying out secondary hydrothermal treatment to obtain the porous cellular cobalt-loaded nanofiber uniformly paved on the surface of the titanium substrate, wherein the fiber morphology is not obviously changed compared with the step 1), but the components are changed, the stem cells on the surface of the coating are larger than the body type of the surface of the titanium substrate, have more pseudo-feet and are flatly paved, the adhesion and growth of the cells can be obviously promoted, the atomic percentage content of the cobalt element of the coating is 4.52-8.28%, and the coating has gradient cobalt loading capacity and can adapt to environments with different antibacterial requirements.
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| CN112251751A (en) * | 2020-09-14 | 2021-01-22 | 西安交通大学 | Preparation method of 3D-configuration high-bonding-strength sodium titanate nanofiber coating |
| CN114686881A (en) * | 2022-03-24 | 2022-07-01 | 西安交通大学 | High-bonding-strength coating based on ion slow release and shape retention design and preparation method and application thereof |
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| JP2008161423A (en) * | 2006-12-28 | 2008-07-17 | Saga Univ | Antibacterial titanate coating titanium-based member |
| US20090117028A1 (en) * | 2007-06-13 | 2009-05-07 | Lehigh University | Rapid synthesis of titanate nanomaterials |
| CN112156233A (en) * | 2020-09-14 | 2021-01-01 | 西安交通大学 | Preparation method of hydroxyl calcium titanate fiber coating on surface of titanium-based implant with complex morphology |
| CN112251751A (en) * | 2020-09-14 | 2021-01-22 | 西安交通大学 | Preparation method of 3D-configuration high-bonding-strength sodium titanate nanofiber coating |
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