CN111485211A - Degradable magnesium alloy biological implantation material and preparation method thereof - Google Patents
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C23/00—Alloys based on magnesium
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- C—CHEMISTRY; METALLURGY
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- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention provides a degradable magnesium alloy biological implantation material and a preparation method thereof, wherein the degradable magnesium alloy biological implantation material comprises a magnesium alloy matrix and a magnesium metal layer which is formed on the magnesium alloy matrix in a magnetron sputtering mode, and the thickness of the magnesium metal layer is 0.1-5 mu m. The magnesium target material is bombarded by a large amount of ions generated by a magnetron sputtering process, magnesium metal atoms are generated from the magnesium target material and are deposited on the magnesium alloy matrix, and the magnesium alloy matrix is made of magnesium metal, so that a high-density surface layer is realized, and the deposition rate is high. The magnesium metal surface layer modified by magnetron sputtering not only changes the density of the sub-surface layer of the matrix, but also can improve the protection effect of corrosion resistance. The deposition thickness of the surface layer is controlled by a magnetron sputtering process, the in-vivo degradation time of the implant is met, the functionality of the degradable magnesium alloy biological implant is matched with the action time of pathological tissue repair, and the application range of the magnesium alloy biological implant material in the field of biomedicine is expanded.
Description
Technical Field
The invention belongs to the field of magnesium alloy, and particularly relates to a degradable magnesium alloy biological implantation material and a preparation method thereof.
Background
The magnesium alloy is formed by adding elements such as aluminum, zinc, manganese, rare earth and the like into magnesium serving as a matrix, has the advantages of high strength, high specific stiffness, good thermal conductivity, good plastic deformation capacity, recoverability and the like, is used as the lightest engineering material, and is mainly widely applied to the aspects of automobiles, aerospace, electronics, chemical engineering and the like. After the twenty-first century, researchers found that the young's modulus of magnesium alloys was closer to that of natural bone than other metallic implant materials. And the magnesium alloy implant does not damage the dynamic balance of the blood system of the human body after being implanted into the human body, and has anticoagulation property and osteoinductivity. The magnesium alloy has biodegradability in human body, degradation products are nontoxic oxides and hydroxides, the magnesium alloy degradation products can enhance osteoblast activity and keep osteoclast activity in the process of regenerating new bones, and after bone tissues heal, the magnesium alloy implant is finally replaced by natural tissues, so that the removal of secondary operations is avoided, namely, the cost is reduced and the pain of patients is also reduced. Thus, the magnesium alloy may be suitable for use as a short term or temporary bone implant.
The prior magnesium alloy is mostly cast, because the crystallization temperature interval of the magnesium alloy is wider and the magnesium alloy is easy to crystallize in a pasty solidification mode, a remarkable dendritic crystal structure exists, feeding is difficult to obtain, and because the ingate part is in an overheated state for a long time and the temperature is higher during casting and forming, the loose defect is easy to cause, so that the density of the prepared magnesium alloy is lower, and the degradation speed of the magnesium alloy is accelerated. Therefore, when the material is used as a biological implant material, such as a bone implant, the implant loses its integrity due to degradation before bone tissues are not sufficiently healed, so that the implantation operation fails, and the use of the material in the biological medicine field is greatly limited.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a degradable magnesium alloy bio-implant material and a preparation method thereof, wherein the degradable magnesium alloy bio-implant material has high density and slow degradation speed.
In order to achieve the purpose, the invention provides a degradable magnesium alloy biological implantation material on one hand, which comprises a magnesium alloy substrate and a magnesium metal layer formed on the magnesium alloy substrate through magnetron sputtering, wherein the thickness of the magnesium metal layer is 0.1-5 μm.
According to the magnesium alloy substrate, the magnesium metal layer is subjected to magnetron sputtering, a large amount of ions generated by a magnetron sputtering process bombard the magnesium target, magnesium metal atoms are generated from the magnesium target and are deposited on the magnesium alloy substrate, and the magnesium alloy substrate is made of metal magnesium, so that a high-density surface layer is realized, and the deposition rate is high. The magnesium metal surface layer modified by magnetron sputtering not only changes the density of the sub-surface layer of the matrix, but also can improve the protection effect of corrosion resistance. The deposition thickness of the surface layer is controlled by a magnetron sputtering process, the in-vivo degradation time of the implant is met, the functionality of the degradable magnesium alloy biological implant is matched with the action time of pathological tissue repair, and the application range of the magnesium alloy biological implant material in the field of biomedicine is expanded.
Preferably, the magnesium alloy matrix is made of one or more of magnesium aluminum alloy, magnesium manganese alloy, magnesium zinc alloy, magnesium lithium alloy and magnesium calcium alloy.
The invention also provides a preparation method of the degradable magnesium alloy biological implantation material, which comprises the following steps in sequence:
(1) performing film coating pretreatment on a magnesium alloy substrate;
(2) carrying out magnetron sputtering coating on the magnesium alloy matrix by adopting pure magnesium as a target material;
(3) and carrying out film coating post-treatment on the magnesium alloy substrate.
The degradable magnesium alloy biological implant material prepared by the method has high density, and can effectively control the degradation time, thereby meeting the use condition as a biomedical implant material.
Preferably, the coating pretreatment comprises polishing treatment, ultrasonic cleaning, washing and drying in sequence.
Preferably, the parameters of the magnetron sputtering coating are as follows: the argon pressure is 0.6-1.1 Pa, the current is 10-15A, and the coating time is 30-70 min.
Preferably, the post-coating treatment is an annealing treatment and then a cleaning treatment, and the annealing treatment is performed under the condition of vacuum annealing at 200-350 ℃ for 0.5-2 h.
Detailed Description
The degradable magnesium alloy biological implantation material comprises a magnesium alloy matrix and a magnesium metal layer formed on the magnesium alloy matrix through magnetron sputtering, wherein the thickness of the magnesium metal layer is 0.1-5 mu m. The specific thickness may be 0.1. mu.m, 0.5. mu.m, 1.0. mu.m, 1.5. mu.m, 2.0. mu.m, 3.0. mu.m, 4.0. mu.m, 5.0. mu.m. The magnesium alloy matrix comprises one or more of magnesium aluminum alloy, magnesium manganese alloy, magnesium zinc alloy, magnesium rare earth alloy, magnesium lithium alloy and magnesium calcium alloy.
The preparation method of the degradable magnesium alloy biological implantation material comprises the following steps in sequence:
(1) performing film coating pretreatment on a magnesium alloy substrate;
(2) carrying out magnetron sputtering coating on a magnesium alloy matrix by adopting pure magnesium as a target material;
(3) and (3) carrying out film coating post-treatment on the magnesium alloy substrate.
Wherein, the coating pretreatment comprises the steps of grinding, polishing, ultrasonic cleaning, washing and drying in sequence. The method comprises the specific steps of grinding and polishing a magnesium alloy matrix until the surface roughness is below 1um, washing with acetone after ultrasonic cleaning, and drying in vacuum. The parameters of the magnetron sputtering coating are as follows: the argon pressure is 0.6-1.1 Pa, the current is 10-15A, and the coating time is 30-70 min. The post-coating treatment is annealing treatment and then cleaning treatment, and the annealing treatment condition is vacuum annealing at 200-350 ℃ for 0.5-2 h. The crystal grains can be refined through annealing treatment, the structure is uniform, and the density of the magnesium alloy is further improved.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
Example 1
The degradable magnesium alloy biological implantation material comprises a magnesium-aluminum alloy matrix and a magnesium metal layer which is formed on the magnesium alloy matrix through magnetron sputtering, wherein the thickness of the magnesium metal layer is 3 mu m.
The preparation method comprises the following steps:
the preparation method of the degradable magnesium alloy biological implantation material comprises the following steps in sequence:
(1) sequentially carrying out grinding treatment, polishing treatment, ultrasonic cleaning, washing and drying on the magnesium-aluminum alloy substrate;
(2) carrying out magnetron sputtering coating on a magnesium-aluminum alloy substrate by adopting pure magnesium as a target material, wherein the parameters of the magnetron sputtering coating are as follows: argon pressure is 1.0Pa, current is 12A, and coating time is 60 min;
(3) and annealing the magnesium-aluminum alloy matrix, wherein the annealing condition is that the magnesium-aluminum alloy matrix is subjected to vacuum annealing at 300 ℃ for 1h, and finally, pure water cleaning is carried out to obtain the degradable magnesium alloy biological implantation material.
Example 2
The degradable magnesium alloy biological implantation material comprises a magnesium-aluminum alloy matrix and a magnesium metal layer which is formed on the magnesium-aluminum alloy matrix through magnetron sputtering, wherein the thickness of the magnesium metal layer is 5 mu m.
The preparation method comprises the following steps:
the preparation method of the degradable magnesium alloy biological implantation material comprises the following steps in sequence:
(1) sequentially carrying out grinding treatment, polishing treatment, ultrasonic cleaning, washing and drying on the magnesium-aluminum alloy substrate;
(2) carrying out magnetron sputtering coating on a magnesium-aluminum alloy substrate by adopting pure magnesium as a target material, wherein the parameters of the magnetron sputtering coating are as follows: argon pressure is 0.8Pa, current is 10A, and coating time is 60 min;
(3) and annealing the magnesium-aluminum alloy matrix, wherein the annealing condition is that the magnesium-aluminum alloy matrix is subjected to vacuum annealing at 250 ℃ for 2 hours, and finally, pure water cleaning is carried out to obtain the degradable magnesium alloy biological implantation material.
Example 3
The degradable magnesium alloy biological implantation material comprises a magnesium-calcium alloy matrix and a magnesium metal layer which is formed on the magnesium-calcium alloy matrix through magnetron sputtering, wherein the thickness of the magnesium metal layer is 2 mu m.
The preparation method comprises the following steps:
the preparation method of the degradable magnesium alloy biological implantation material comprises the following steps in sequence:
(1) sequentially carrying out grinding treatment, polishing treatment, ultrasonic cleaning, washing and drying on the magnesium-calcium alloy;
(2) carrying out magnetron sputtering coating on the magnesium-calcium alloy by adopting pure magnesium as a target material, wherein the parameters of the magnetron sputtering coating are as follows: argon pressure is 1.0Pa, current is 12A, and coating time is 60 min;
(3) and annealing the magnesium-calcium alloy, wherein the annealing condition is that the magnesium-calcium alloy is subjected to vacuum annealing at 300 ℃ for 1h, and finally, pure water cleaning is performed to obtain the degradable magnesium alloy biological implantation material.
Example 4
The degradable magnesium alloy biological implantation material comprises a magnesium-aluminum alloy matrix and a magnesium metal layer which is formed on the magnesium alloy matrix through magnetron sputtering, wherein the thickness of the magnesium metal layer is 3 mu m.
The preparation method comprises the following steps:
the preparation method of the degradable magnesium alloy biological implantation material comprises the following steps in sequence:
(1) sequentially carrying out grinding treatment, polishing treatment, ultrasonic cleaning, washing and drying on the magnesium-aluminum alloy substrate;
(2) carrying out magnetron sputtering coating on a magnesium-aluminum alloy substrate by adopting pure magnesium as a target material, wherein the parameters of the magnetron sputtering coating are as follows: argon pressure is 1.0Pa, current is 12A, and coating time is 60 min;
(3) and (3) washing the magnesium-aluminum alloy matrix with pure water to obtain the degradable magnesium alloy biological implant material.
Comparative example 1
A blank test without a metal layer and a magnesium aluminum alloy substrate with the same composition as in example 1.
Comparative example 2
The degradable magnesium alloy biological implant material comprises a magnesium-aluminum alloy matrix and a metal zinc layer deposited on the magnesium-aluminum alloy matrix, wherein the thickness of the metal zinc layer is 3 mu m.
The preparation method comprises the following steps:
the preparation method of the degradable magnesium alloy biological implantation material comprises the following steps in sequence:
(1) carrying out grinding treatment, polishing treatment, ultrasonic cleaning, washing and drying on the magnesium-aluminum alloy substrate;
(2) performing magnetron sputtering coating on the surface of the magnesium-aluminum alloy substrate by adopting metal zinc as a target material;
(3) and (3) washing the magnesium-aluminum alloy matrix with pure water to obtain the degradable magnesium alloy biological implant material.
The density and degradability tests of the degradable magnesium alloy bioimplantation materials of examples 1-4 and comparative examples 1-2 were carried out, and the results are shown in table 1.
The density of the sample is measured by a drainage method, and the operation process is as follows: cutting each sample into 3 parts, cleaning and drying the cut samples by using acetone in an ultrasonic cleaner, respectively obtaining the mass of the samples in air and distilled water at 20 ℃ by using an electronic balance, calculating the density of the samples according to the following formula, and taking an average value.
In the formula, m1The mass of the sample in air, g, m2The mass of the sample in distilled water at 20 ℃ is g,. rhoWater (W)Is the density of distilled water and is 1g/cm3。
The calculation formula of the density increase rate is as follows:
in the formula, ρ1Is the density of a magnesium alloy matrix with a metal layer, g/cm3，ρ2Is the density of a magnesium alloy matrix, g/cm3。
The degradability test is characterized by the amount of hydrogen evolved by the sample in the simulated body fluid, and is carried out by the hydrogen evolution method, and the test process is as follows:
1. in the degradable magnesium alloy biological implantation materials of examples 1-4 and comparative examples 1-2, 3 samples were taken from each group;
2. placing equal amounts of simulated body fluid hank's in each beaker, completely immersing all samples in a solution, wherein the solution is 250ml, filling a burette with scales with the hank's, sleeving the burette on a funnel, collecting hydrogen by using a liquid discharge method, and replacing the hank's solution after observing each time node;
3. testing environment requirements: the constant temperature shaking table is 30r/min, and the temperature is 37 +/-0.5 ℃;
4. reading H at 3 different time nodes2Three samples were averaged.
TABLE 1 compactness and degradability test results
From the results in table 1, it can be seen that, compared with the magnesium alloy base material, the volume of hydrogen gas evolved from the degradable magnesium alloy biological implantation material after magnetron sputtering of the magnesium metal layer is obviously reduced, and the density growth rate is obviously increased. Meanwhile, the density increase rate of the magnetron sputtering magnesium metal layer is higher than that of the zinc metal layer, and the volume of hydrogen is less than that of the zinc metal layer. The magnesium target material is bombarded by a large amount of ions generated by a magnetron sputtering process, so that magnesium metal atoms are generated from the magnesium target material and are deposited on the magnesium alloy matrix, and the magnesium alloy matrix is made of metal magnesium, so that a high-density surface layer is realized, and the deposition rate is high. Although the comparative example 2 also adopts magnetron sputtering to plate a zinc layer, the problem of porosity defect of the cast magnesium alloy cannot be changed well due to the different crystal phase structures of zinc and magnesium.
Meanwhile, as can be seen from comparison between example 1 and example 4, annealing treatment is performed after the magnetron sputtering magnesium metal layer is formed, so that the density of the magnesium alloy can be further improved, and the degradation rate can be reduced.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. The degradable magnesium alloy biological implantation material is characterized by comprising a magnesium alloy matrix and a magnesium metal layer formed on the magnesium alloy matrix through magnetron sputtering, wherein the thickness of the magnesium metal layer is 0.1-5 mu m.
2. The biodegradable magnesium alloy bioimplantation material as claimed in claim 1, wherein the magnesium alloy matrix comprises one or more of magnesium aluminum alloy, magnesium manganese alloy, magnesium zinc alloy, magnesium lithium alloy and magnesium calcium alloy.
3. The preparation method of the degradable magnesium alloy biological implantation material is characterized by comprising the following steps in sequence:
(1) performing film coating pretreatment on a magnesium alloy substrate;
(2) carrying out magnetron sputtering coating on the magnesium alloy matrix by adopting pure magnesium as a target material;
(3) and carrying out film coating post-treatment on the magnesium alloy substrate.
4. The method for preparing the degradable magnesium alloy bioimplantation material according to claim 3, wherein the pre-coating treatment comprises grinding treatment, polishing treatment, ultrasonic cleaning, washing and drying in sequence.
5. The method for preparing the biodegradable magnesium alloy biological implant material according to claim 3, wherein the parameters of the magnetron sputtering coating are as follows: the argon pressure is 0.6-1.1 Pa, the current is 10-15A, and the coating time is 30-70 min.
6. The method for preparing a degradable magnesium alloy bioimplantation material according to claim 3, wherein the post-coating treatment is an annealing treatment and then a cleaning treatment, and the annealing treatment is performed under a vacuum annealing condition at 200-350 ℃ for 0.5-2 h.
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