CN109758605B - Magnesium alloy surface fine needle-shaped hydroxyapatite micro-nano structure coating and preparation method thereof - Google Patents
Magnesium alloy surface fine needle-shaped hydroxyapatite micro-nano structure coating and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of surface modification of degradable magnesium alloy implants, and particularly relates to a fine needle-shaped hydroxyapatite micro-nanostructure coating on the surface of a magnesium alloy and a preparation method thereof. The preparation method comprises the following steps: soaking the pretreated magnesium alloy matrix in an electrolyte solution for electrochemical deposition, connecting a direct current stabilized power supply with a platinum electrode as an anode and magnesium alloy as a cathode for electrochemical deposition, and then performing alkali heat treatment to obtain a hydroxyapatite coating on the surface of the magnesium alloy. The electrolyte for electrochemical deposition has a simple formula, does not need to add any promoter or oxidant, and does not need to adjust the pH value of the electrolyte; the electrochemical deposition mode with low temperature and low current density is adopted, so that the control is easy and the cost is low; the prepared hydroxyapatite coating is uniform and compact, has high purity and good corrosion resistance, has a fine needle-shaped micro-nano structure, is beneficial to the adhesion and growth of cells on the surface of the coating, and improves the implantation success rate of the magnesium alloy implant.
Description
Technical Field
The invention belongs to the technical field of surface modification of degradable magnesium alloy implants, and particularly relates to a fine needle-shaped hydroxyapatite micro-nanostructure coating on the surface of a magnesium alloy and a preparation method thereof.
Background
The magnesium alloy is used as a biomedical implant material, and has good biocompatibility, biological activity and excellent biodegradability. Compared with the common metal materials of cobalt-based alloy, stainless steel, titanium alloy and the like in clinical medicine, the elasticity modulus and the density of the magnesium alloy are the closest to those of human bones, and the magnesium alloy is an ideal bone repair material. However, because the magnesium alloy has poor corrosion resistance in a physiological environment and an excessively fast degradation rate, the pH value of the local environment of the implanted part is often too high and a large amount of hydrogen is released in a short period, so that inflammation is caused, and the implanted part is slowly healed even so that implantation failure is caused; in addition, the mechanical property of the bone tissue is reduced rapidly due to the excessively fast degradation speed, and the time requirement of bone tissue healing cannot be met. Therefore, it is one of the important directions of current research to perform surface modification treatment on medical magnesium alloy to improve the corrosion resistance and biocompatibility of the medical magnesium alloy in physiological environment.
Hydroxyapatite (Ca) 10 (PO 4 ) 6 (OH) 2 HAp) is a major inorganic component of human bones and teeth, has excellent bioactivity and biocompatibility, and is considered as one of the most potential human implant substitute materials. But the HAp has the defects of large brittleness, low strength, poor toughness and the like, so that the application of the HAp to a human body bearing part is limited to a great extent. The hydroxyapatite coating is prepared on the surface of the magnesium alloy, so that the mechanical property of the magnesium alloy and the bioactivity of the hydroxyapatite can be combined. And after being implanted into a human body, the magnesium alloy can form bonding combination with the bone tissue of the human body in a short time, can stabilize and reduce the corrosion rate of the magnesium alloy, and better plays an important role of the magnesium alloy in bone repair treatment, so that the preparation of the hydroxyapatite coating on the surface of the magnesium alloy has good development prospect.
At present, various methods for modifying the surface of magnesium alloy have been developed, and the common surface coating methods mainly include: sol-gel method, laser cladding, micro-arc oxidation, thermal spraying, electrochemical deposition and the like. Among them, the electrochemical deposition method has attracted much attention because it has a low deposition temperature and can perform deposition on a complicated workpiece. The Chinese invention patent (application number is CN 201710881395) "a method for preparing a medical magnesium alloy surface active coating", discloses a method for preparing a hydroxyapatite coating deposited on the surface of a medical magnesium alloy by a hydrothermal electrochemical deposition method, and adopts high-temperature and high-pressure reaction conditions in the preparation process, so that the prepared HAp coating is short and rod-shaped and has high purity; the Chinese invention patent (application number is CN 201510310437) "a surface modification method of medical magnesium alloy" discloses a pulse electrodeposition method for preparing a hydroxyapatite coating on the surface of a medical magnesium alloy material with a remelted layer to complete the modification of the surface of the medical magnesium alloy, firstly, a high-current pulse electron beam is adopted to irradiate the surface of a medical magnesium alloy substrate, then the hydroxyapatite coating is deposited on the surface by adopting a pulse electrodeposition method, and the rough surface generated in the irradiation process of the high-current pulse electron beam is utilized to ensure that the HAp coating forms a mechanical locking structure, thereby improving the bonding strength and biocompatibility of the coating and the substrate; chinese invention patent (application number CN 201510125339) "a method for biomedical magnesium or magnesium alloy surface electrochemical treatment with high bioactivity and low degradation rate" discloses a method for preparing an HAp composite coating by combining micro-arc oxidation and electrochemical deposition, and improves the corrosion resistance and bioactivity of the material.
However, the above method for preparing a hydroxyapatite coating on the surface of a medical magnesium alloy often has the problems of complex equipment, high requirement on conditions, complex formula and the like, for example, a high-temperature and high-pressure reaction condition is usually required in the preparation process, other additives are doped to improve the performance of the coating, and an electrochemical workstation is utilized to perform electrochemical deposition by adopting pulse current; some of them require surface modification of magnesium alloy before electrochemical deposition, which makes the process complicated.
Disclosure of Invention
The invention aims to overcome the defects of high preparation temperature, multiple defects of coatings, insufficient uniformity and compactness and complex equipment and formula in the prior art, and provides a preparation method for preparing a fine needle-shaped hydroxyapatite micro-nano structure coating on the surface of a medical magnesium alloy.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of a fine needle-shaped hydroxyapatite micro-nano structure coating on the surface of a magnesium alloy, which comprises the following steps:
(1) Pretreatment of the magnesium alloy substrate: polishing, cleaning and drying the magnesium alloy matrix;
(2) Preparing an electrolyte solution for electrochemical deposition: weighing soluble calcium salt and dihydric phosphate, respectively dissolving in deionized water to make the concentration of calcium salt be 0.01-0.05mol/L and the concentration of dihydric phosphate be 0.006-0.03mol/L; mixing the calcium salt solution with the dihydrogen phosphate solution to obtain an electrolyte for electrochemical deposition;
(3) Electrochemical deposition: immersing the magnesium alloy substrate obtained by pretreatment in the step (1) into an electrolyte for electrochemical deposition by using a platinum electrode as an anode and a magnesium alloy as a cathode, placing the cathode and the anode in parallel, and switching on a direct-current stabilized power supply to perform an electrochemical deposition process;
(4) And (3) post-treatment: and (3) placing the deposited magnesium alloy in alkali liquor for alkali heat treatment, washing with deionized water, and drying to form a compact hydroxyapatite coating on the surface of the magnesium alloy substrate obtained by pretreatment.
Further, the pretreatment process in the step (1) comprises the steps of sequentially polishing the magnesium alloy matrix by using 400#, 600#, 800#, and 1200# abrasive paper, sequentially ultrasonically cleaning the polished magnesium alloy matrix in absolute ethyl alcohol, acetone, and deionized water by using an ultrasonic cleaning instrument, and drying.
Further, in the step (2), the calcium salt solution and the dihydrogen phosphate solution are mixed according to a molar ratio of calcium ions to dihydrogen phosphate of 1.67.
Further, in the step (3), the distance between the cathode and the anode is 2-4cm, and the current density is 0.5-2.5mA/cm 2 The deposition temperature is 85 ℃, and the deposition time is 0.5-1.5h.
Further, the concentration of the alkali liquor in the step (4) is 0.01-0.1mol/L, the heat treatment temperature is 70-90 ℃, and the heat treatment time is 2-4h.
Further, the calcium salt in the step (2) is Ca (NO) 3 ) 2 ·4H 2 O、CaCl 2 One or a combination thereof; the dihydric phosphate is NH 4 H 2 PO 4 、KH 2 PO 4 Or NaH 2 PO 4 One or a combination thereof.
Furthermore, the magnesium alloy substrate is medical magnesium alloy, preferably AZ31B magnesium alloy.
The invention also provides a micro-nano structural coating of the needle-shaped hydroxyapatite on the surface of the magnesium alloy, which is prepared by the preparation method.
The invention has the following technical effects:
(1) The hydroxyapatite coating is prepared by adopting a low-temperature and low-current-density electrochemical deposition method, and because the electrochemical deposition is carried out at low current density, the adverse effect of concentration polarization on the coating can be obviously reduced, so that the coating has a uniform and compact structure; the low-temperature preparation condition can ensure that the mechanical property of the magnesium alloy matrix is not influenced; magnetic stirring is carried out in the electrochemical deposition process, so that the phenomenon of hydrogen evolution can be avoided, and the bonding strength between the hydroxyapatite coating and the magnesium alloy substrate is higher.
(2) The electrolyte for electrochemical deposition has a simple formula, only consists of calcium salt and dihydric phosphate, does not need to add any promoter or oxidant, does not need to adjust the pH value of the electrolyte, can ensure that the growth of hydroxyapatite is not influenced by additives, and can grow along the c axis of the hydroxyapatite, thereby growing into a fine needle-shaped micro-nano structure.
(3) The method has simple process and lower cost, can prepare the uniform and compact hydroxyapatite coating with high purity on the surface of the magnesium alloy, and the coating has a fine needle-shaped micro-nano structure, improves the anti-corrosion capability of the magnesium alloy, and is beneficial to the adhesion and growth of cells on the surface of the coating, thereby promoting the bonding between the implant and the surrounding bone tissues and improving the success rate of implantation.
Drawings
Fig. 1 is an SEM photograph of a hydroxyapatite coating layer prepared in example 1 of the present invention;
fig. 2 is a sectional SEM photograph of a hydroxyapatite coating layer prepared in example 1 of the present invention;
fig. 3 is an XRD pattern of the hydroxyapatite coating layer prepared in example 1 of the present invention;
fig. 4 is an SEM photograph of a hydroxyapatite coating layer prepared in example 2 of the present invention;
fig. 5 is a Nyquist plot in SBF of the hydroxyapatite coating prepared in example 2 of the present invention;
FIG. 6 shows the Nyquist spectra in SBF of the hydroxyapatite coating prepared in example 2 of the present inventionThe abscissa is 20-400 omega cm 2 Magnified view of a portion of the range.
Detailed Description
The following will clearly and completely describe the technical solutions 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 embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
(1) Pretreatment of the magnesium alloy substrate: sequentially grinding an AZ31B magnesium alloy substrate by using 400#, 600#, 800# and 1200# abrasive paper; sequentially carrying out ultrasonic cleaning on the polished magnesium alloy matrix in absolute ethyl alcohol, acetone and deionized water for 10min by using an ultrasonic cleaning instrument, and drying;
(2) Preparing an electrolyte solution for electrochemical deposition: weighing Ca (NO) 3 ) 2 ·4H 2 O and NH 4 H 2 PO 4 Respectively dissolved in deionized water to make Ca (NO) 3 ) 2 ·4H 2 O concentration of 0.01mol/L, NH 4 H 2 PO 4 The concentration of (A) is 0.006mol/L; uniformly mixing the two solutions according to the calcium-phosphorus molar ratio of 1.67:1 to obtain an electrolyte for electrochemical deposition;
(3) Electrochemical deposition: using a platinum electrode as an anode and magnesium alloy as a cathode, immersing the platinum electrode and the magnesium alloy in an electrolyte solution, placing the cathode and the anode in parallel, keeping the distance at 2cm, switching on a direct current stabilized voltage power supply, and adjusting the current density to be 1.5mA/cm 2 The deposition temperature is 85 ℃, and the deposition time is 1h;
(4) And (3) post-treatment: and (3) placing the deposited sample in a 1mol/L NaOH solution, carrying out alkali heat treatment at 80 ℃ for 2h, washing the sample with deionized water, and drying to form a compact hydroxyapatite coating on the surface of the magnesium alloy substrate.
The SEM of the hydroxyapatite coating prepared in the example is shown in figure 1, the coating is uniform and compact, and is penetrated and inserted into flower-shaped and thorn-ball-shaped structures by fine needle-shaped structures, the diameter of the needle-shaped structures is about 230-670nm, and the length of the needle-shaped structures is about 2.5-15 μm. The sectional SEM of the hydroxyapatite coating of this example is shown in FIG. 2, and the coating has a uniform thickness of about 10 μm and has good interface bonding with the substrate. Fig. 3 is an XRD pattern of the prepared coating, and it can be seen from X-ray diffraction analysis that the prepared coating is hydroxyapatite and has high purity.
Example 2:
(1) Pretreatment of the magnesium alloy substrate: sequentially polishing medical magnesium alloy samples by using 400#, 600#, 800# and 1200# sandpaper; and (3) ultrasonically cleaning the polished magnesium alloy in absolute ethyl alcohol, acetone and deionized water for 15min by using an ultrasonic cleaning instrument in sequence, and drying.
(2) Preparing an electrolyte solution for electrochemical deposition: weighing CaCl 2 And KH 2 PO 4 Respectively dissolving in deionized water to obtain CaCl 2 The concentration of (b) is 0.05mol/L, KH 2 PO 4 The concentration of (A) is 0.03mol/L; and uniformly mixing the two solutions according to the calcium-phosphorus molar ratio of 1.67:1 to obtain the electrolyte for electrochemical deposition.
(3) Electrochemical deposition: using a platinum electrode as an anode and magnesium alloy as a cathode, immersing the platinum electrode and the magnesium alloy in an electrolyte solution, placing the cathode and the anode in parallel, keeping the distance at 2cm, switching on a direct current stabilized voltage power supply, and adjusting the current density to be 2.5mA/cm 2 The deposition temperature is 85 ℃, and the deposition time is 0.5h.
(4) And (3) post-treatment: and (3) placing the deposited sample in 1mol/L NaOH solution for alkali heat treatment at 80 ℃ for 2h, washing the sample with deionized water, and drying to form a compact hydroxyapatite coating on the surface of the magnesium alloy substrate.
The SEM of the hydroxyapatite coating prepared in the example is shown in figure 4, and the coating is uniform and compact and consists of a needle structure and a flower-like structure, wherein the diameter of the needle structure is about 200-600nm, and the length of the needle structure is about 2-13 mu m. FIG. 5 is an AC impedance spectrum of a coating prepared according to the present example, and FIG. 6 is a partially enlarged AC impedance spectrum of a magnesium alloy bare chip having an AC impedance of 94ohm cm 2 The alternating current impedance of the magnesium alloy coated with hydroxyapatite is 780ohm cm 2 The corrosion resistance is remarkably improved.
Example 3:
(1) Pretreatment of the magnesium alloy substrate: sequentially polishing medical magnesium alloy samples by using 400#, 600#, 800# and 1200# sandpaper; sequentially carrying out ultrasonic cleaning on the polished magnesium alloy in absolute ethyl alcohol, acetone and deionized water for 10min by using an ultrasonic cleaning instrument, and drying;
(2) Preparing an electrolyte solution for electrochemical deposition: weighing Ca (NO) 3 ) 2 ·4H 2 O and NH 4 H 2 PO 4 Respectively dissolved in deionized water to make Ca (NO) 3 ) 2 ·4H 2 The concentration of O is 0.0417mol/L, NH 4 H 2 PO 4 The concentration of (A) is 0.025mol/L; uniformly mixing the two solutions according to the calcium-phosphorus molar ratio of 1.67:1 to obtain an electrolyte for electrochemical deposition;
(3) Electrochemical deposition: using a platinum electrode as an anode and magnesium alloy as a cathode, immersing the platinum electrode and the magnesium alloy in an electrolyte solution, placing the cathode and the anode in parallel, keeping the distance at 4cm, switching on a direct current stabilized voltage power supply, and adjusting the current density to 0.5mA/cm 2 The deposition temperature is 85 ℃, and the deposition time is 1.5h;
(4) And (3) post-treatment: and (3) placing the deposited sample in 1mol/L NaOH solution for alkali heat treatment at 70 ℃ for 2h, washing the sample with deionized water, and drying to form a compact hydroxyapatite coating on the surface of the magnesium alloy substrate.
Example 4:
(1) Pretreatment of the magnesium alloy substrate: sequentially polishing medical magnesium alloy samples by using 400#, 600#, 800# and 1200# sandpaper; sequentially carrying out ultrasonic cleaning on the polished magnesium alloy in absolute ethyl alcohol, acetone and deionized water for 10min by using an ultrasonic cleaning instrument, and drying;
(2) Preparing an electrolyte solution for electrochemical deposition: weighing Ca (NO) 3 ) 2 ·4H 2 O and NH 4 H 2 PO 4 Respectively dissolved in deionized water to make Ca (NO) 3 ) 2 ·4H 2 The concentration of O is 0.0417mol/L, NH 4 H 2 PO 4 The concentration of (A) is 0.025mol/L; mixing the above two solutions at a ratio of calcium to phosphorus of 1.67:1 to obtain electrochemical depositionUsing an electrolyte;
(3) Electrochemical deposition: using a platinum electrode as an anode and magnesium alloy as a cathode, immersing the platinum electrode and the magnesium alloy in an electrolyte solution, placing the cathode and the anode in parallel, keeping the distance at 2cm, switching on a direct current stabilized voltage power supply, and adjusting the current density to 1mA/cm 2 The deposition temperature is 85 ℃, and the deposition time is 1h;
(4) And (3) post-treatment: and (3) placing the deposited sample in a 1mol/L NaOH solution for alkali heat treatment at 90 ℃ for 2 hours, washing the sample with deionized water, and drying to form a compact hydroxyapatite coating on the surface of the magnesium alloy substrate.
Example 5:
(1) Pretreatment of the magnesium alloy substrate: sequentially polishing medical magnesium alloy samples by using 400#, 600#, 800# and 1200# sandpaper; sequentially carrying out ultrasonic cleaning on the polished magnesium alloy in absolute ethyl alcohol, acetone and deionized water for 10min by using an ultrasonic cleaning instrument, and drying;
(2) Preparing an electrolyte solution for electrochemical deposition: weighing Ca (NO) 3 ) 2 ·4H 2 O and NH 4 H 2 PO 4 Respectively dissolved in deionized water to make Ca (NO) 3 ) 2 ·4H 2 The concentration of O is 0.0417mol/L, NH 4 H 2 PO 4 The concentration of (A) is 0.025mol/L; uniformly mixing the two solutions according to the calcium-phosphorus ratio of 1.67:1 to obtain an electrolyte for electrochemical deposition;
(3) Electrochemical deposition: using a platinum electrode as an anode and magnesium alloy as a cathode, immersing the platinum electrode and the magnesium alloy in an electrolyte solution, placing the cathode and the anode in parallel, keeping the distance at 2cm, switching on a direct current stabilized voltage power supply, and adjusting the current density to 1.5mA/cm 2 The deposition temperature is 85 ℃, and the deposition time is 1h;
(4) And (3) post-treatment: and (3) placing the deposited sample in 0.1mol/L NaOH solution for alkali heat treatment at 80 ℃ for 4h, washing the sample with deionized water, and drying to form a compact hydroxyapatite coating on the surface of the magnesium alloy substrate.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (1)
1. A preparation method of a fine needle-shaped hydroxyapatite micro-nano structure coating on the surface of a magnesium alloy is characterized by comprising the following steps:
(1) Pretreatment of the magnesium alloy substrate: sequentially polishing medical magnesium alloy samples by using 400#, 600#, 800# and 1200# sandpaper; sequentially carrying out ultrasonic cleaning on the polished magnesium alloy in absolute ethyl alcohol, acetone and deionized water for 15min by using an ultrasonic cleaning instrument, and drying;
(2) Preparing an electrolyte solution for electrochemical deposition: weighing CaCl 2 And KH 2 PO 4 Respectively dissolving in deionized water to obtain CaCl 2 The concentration of (b) is 0.05mol/L, KH 2 PO 4 The concentration of (A) is 0.03mol/L; uniformly mixing the two solutions according to the calcium-phosphorus molar ratio of 1.67:1 to obtain an electrolyte for electrochemical deposition;
(3) Electrochemical deposition: using platinum electrode as anode and magnesium alloy as cathode, immersing in electrolyte solution, placing the cathode and anode in parallel, keeping distance at 2cm, switching on DC voltage-stabilizing power supply, and regulating current density at 2.5mA/cm 2 The deposition temperature is 85 ℃, the deposition time is 0.5h, magnetic stirring is carried out during deposition, and the rotating speed is 500rpm;
(4) And (3) post-treatment: and (3) placing the deposited sample in a 1mol/L NaOH solution, carrying out alkali heat treatment at 80 ℃ for 2h, washing the sample with deionized water, and drying to form a compact hydroxyapatite coating on the surface of the magnesium alloy substrate.
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| CN113425914B (en) * | 2021-06-17 | 2022-09-16 | 河北工业大学 | Medical material for promoting cell growth and inhibiting bacterial adhesion and processing method thereof |
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| CN105624753A (en) * | 2015-12-24 | 2016-06-01 | 广州中国科学院先进技术研究所 | Technology for uniform deposition of HA (hydroxyapatite) coatings on medical porous titanium and titanium alloy |
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| US20110089041A1 (en) * | 2009-10-19 | 2011-04-21 | Biomet Manufacturing Corp. | Methods of depositing discrete hydroxyapatite regions on medical implants |
| CN102560590B (en) * | 2012-02-14 | 2015-01-28 | 陕西科技大学 | Anode in-situ electrochemical method for preparing hydroxyapatite coating |
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| Title |
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| 《Electrodeposition of hydroxyapatite coating on AZ91D magnesium alloy for biomaterial application》;Y.W.Song 等;《Materials Letters》;20080630;第62卷(第17-18期);第3276-3278页 * |
| 《添加双氧水阴极沉积羟基磷灰石的研究》;陈爱良 等;《材料导报》;20060228;第20卷(第2期);第140-142页 * |
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