Magnesium alloy material with hierarchical pore structure on surface as well as preparation method and application of magnesium alloy material
The AZ31 magnesium alloy material with a multi-level porous structure on the surface is prepared by electrochemical method, which solves the problems of insufficient mechanical properties and processing difficulties of existing oral repair membrane materials, achieves low-cost, efficient preparation and improved biocompatibility, and is suitable for orthopedic dental repair products.
Patent Information
- Application Number
- CN202510687183.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-27
- Publication Date
- 2025-09-12
AI Technical Summary
Existing oral restoration guide membrane materials have problems such as insufficient mechanical properties, high cost, cumbersome processing and secondary surgical injuries. Traditional magnesium alloy additive manufacturing has processing difficulties and material cost control problems, and unreasonable pore structure design affects mechanical properties and degradation properties.
AZ31 magnesium alloy was pretreated and electrochemically corroded by an electrochemical method to prepare a multi-level pore structure on the surface. Multi-level pores were manufactured under low DC voltage using a two-electrode system, and the pore size and porosity were optimized by combining grinding, polishing and pickling steps.
The rapid and low-cost preparation of multi-level porous magnesium alloy materials has been achieved, which enhances the biocompatibility and cell adhesion properties of the materials, making them suitable for bone repair scenarios and meeting bone integration requirements.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of magnesium alloy materials, and specifically relates to a method for preparing a magnesium alloy material with a surface multi-level pore microstructure. The surface multi-level pore sample is prepared by an electrochemical method and is used in the preparation of bone and dental restoration products such as human oral craniofacial and oral guided repair membranes (GBR). Background Art
[0002] When dental implants are needed due to tooth loss caused by illness, tooth loss, or accidents, the patient may have insufficient alveolar bone thickness, making implant placement impossible or potentially causing loss. To achieve good long-term outcomes, osseointegrated implants require sufficient bone mass at the implant site, so it is often considered necessary to improve the implant site. Guided bone regeneration (GBR) technology utilizes a biocompatible membrane as a physical barrier, preventing non-osteogenic tissue from interfering with the bone defect and promoting bone cell growth. Currently, traditional guide membranes for oral restorations primarily consist of non-degradable metal membranes and collagen membranes. Titanium membranes are the most common non-degradable metal membrane. While they offer excellent mechanical properties, their non-degradability requires secondary surgical removal after use, which can cause secondary damage to the patient. Collagen membranes, as degradable membranes, avoid secondary trauma and have demonstrated some therapeutic benefits in guided alveolar bone restoration. However, these membranes have poor mechanical properties, present a risk of wear during chewing after implantation, and are expensive. Therefore, it is necessary to develop a degradable metal-based oral guide membrane with excellent mechanical properties, good quality and low price.
[0003] In recent years, some researchers have focused on biodegradable magnesium alloys. Mg and its alloys are among the most commonly used metallic structural and functional materials in nature. They have low melting points, low elastic moduli, and are easily deformed during processing. Mg, in particular, is biodegradable in the human body and has no toxic side effects on tissues and organs (it is a beneficial trace element essential for biological functions such as cellular immunity and metabolism). In recent years, it has developed into an advanced medical metal material suitable for use in implantable medical devices.
[0004] Research has shown that porous structures can enhance the biocompatibility of materials, promoting not only alveolar bone repair but also bone induction and regeneration. Therefore, the preparation of a magnesium alloy with a porous surface is of great significance to oral restoration membranes and dentistry. Surface porous structures have become a key research and development focus for future oral restoration membranes and other bone repair products.
[0005] The surface properties of bone defect repair materials have a decisive influence on their bioactivity and bone integration effects. Traditional research has focused on large-sized pore structures (such as 100-500 μm), believing that they can provide space for cell migration and vascularization. However, such pore structures may limit their application in high-stress bone repair scenarios due to insufficient mechanical strength or excessive porosity. In recent years, the design of micro- and nano-scale pores (such as around 3 μm) has gradually attracted attention. By simulating the microscopic topological structure of natural bone matrix, it exhibits unique biological advantages.
[0006] Studies have shown that small-sized pores (such as 1-10 μm) can significantly enhance the adhesion and early differentiation behavior of osteoblasts by regulating the local mechanical microenvironment of the extracellular matrix. For example, pores around 3 μm can promote integrin-mediated cell anchoring, activate osteogenesis-related signaling pathways (such as BMP / Smad, Wnt / β-catenin), and facilitate the local enrichment and sustained release of growth factors such as bone morphogenetic proteins (BMPs). In addition, this type of microporous structure has advantages in maintaining the overall mechanical properties of the material (such as compressive strength and wear resistance), and is particularly suitable for the modification design of load-bearing bones or surface coating materials.
[0007] Currently, there is not much research on metal-based degradable oral guide membranes. However, with the recent emergence and rise of various additive manufacturing methods, they can also be used to prepare degradable metal-based oral guide repair membrane materials. The porous structure of the surface can be pre-designed with a computer and then completed in one go during 3D printing.
[0008] Although the above method has certain advantages, it also has certain disadvantages: First, magnesium and magnesium alloys are very active, and inert gas protection is required during additive manufacturing to avoid explosion in a confined space; second, although additive manufacturing can accurately control the surface pore size and porosity, its processing method is slow, cumbersome and expensive, which is a more difficult problem for controlling the cost of implanted raw materials; third, when additive manufacturing samples are made, the samples are prone to residual processing stress during rapid cooling, causing fine cracks on the surface or inside, which has a greater impact on the mechanical properties and degradation properties of the samples; fourth, if the temperature, speed, power and other parameters are set improperly before processing, the quality of the molten pool will be poor, and uneven stirring will also cause burrs, cracks and other problems in the samples. Summary of the Invention
[0009] In response to the clinical demand for oral craniofacial oral repair guide membrane implants and the problems existing in the production and preparation of existing oral repair guide membranes, the primary purpose of the present invention is to provide a method for preparing a magnesium alloy material with a multi-level porous structure on the surface. The biodegradable metal AZ31 magnesium alloy is selected from the market for customization or self-made, and the sample is pre-treated by a grinder and polisher. After sealing, electrochemical treatment is performed to prepare a multi-level porous structure on the surface, so that the above-mentioned oral repair guide membrane can be designed, processed and evaluated for performance quickly, efficiently and at low cost, thereby meeting the needs of the biomedical engineering field for the development and application of such advanced porous bone repair membranes.
[0010] Another object of the present invention is to provide a magnesium alloy material with a multi-level porous structure on the surface obtained by the above preparation method.
[0011] Another object of the present invention is to provide an application of the above-mentioned magnesium alloy material with a multi-level porous surface structure in the preparation of orthopedic and dental restoration products.
[0012] The purpose of the present invention is achieved through the following technical solutions:
[0013] A method for preparing a magnesium alloy material with a multi-level porous surface structure comprises the following steps:
[0014] The pretreated bulk AZ31 magnesium alloy material is used as the anode, the platinum electrode is used as the cathode, and the alkaline solution is used as the electrolyte. The pretreated bulk AZ31 magnesium alloy material is electrochemically corroded for 20 to 50 minutes at a DC voltage of 1.6 to 3 V to manufacture a multi-level porous structure on the surface of the magnesium alloy material. After cleaning, a magnesium alloy material with a multi-level porous structure on the surface is obtained.
[0015] Preferably, the pretreated bulk AZ31 magnesium alloy material is obtained by the following method: polishing and cleaning the bulk AZ31 magnesium alloy material, winding a wire, exposing one working surface, and sealing the remaining surfaces with glue.
[0016] More preferably, the size of the block-shaped AZ31 magnesium alloy material is 10×10×5 to 20×20×10 mm.
[0017] More preferably, the polishing refers to polishing the block of AZ31 magnesium alloy material with 500-5000 grit sandpaper.
[0018] More preferably, the conductor is a copper wire; the glue is silicone; more preferably, it is Kraft glue.
[0019] Preferably, the concentration of the alkaline solution is 0.5 to 2 mol / L; and the alkali in the alkaline solution is at least one of NaOH and KOH.
[0020] Preferably, in the preparation method of the magnesium alloy material with a multi-level porous structure on the surface, the cleaning method is: first, the corroded magnesium alloy material is rinsed with water, then placed in anhydrous ethanol for ultrasonic treatment for 10 to 30 minutes, then immersed in a 10 to 30wt% chromic acid solution for pickling for 10 to 30 minutes, and finally rinsed with water and placed in anhydrous ethanol for ultrasonic treatment for 10 to 30 minutes.
[0021] The present invention provides a magnesium alloy material with a multi-level pore structure on the surface obtained by the above preparation method.
[0022] The present invention provides the use of the above-mentioned magnesium alloy material with a multi-level surface pore structure in the preparation of orthopedic and dental restoration products.
[0023] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0024] (1) The present invention has the characteristics of simple and fast preparation method, high efficiency and practicality, and low production cost.
[0025] (2) The present invention uses a two-electrode system and a low DC voltage to obtain a multi-level pore structure without the need for an excessively high DC voltage.
[0026] (3) The present invention can achieve a certain degree of contact antibacterial and enhanced bone cell adhesion behavior by preparing a multi-level porous structure.
[0027] (4) The present invention can meet the requirements of being a bone tissue implant by enhancing cell adhesion. This advantage can be further studied based on the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 This is the SEM image of the AZ31 sample surface before electrochemical corrosion cleaning in Comparative Example 1.
[0029] Figure 2 This is the SEM image of the AZ31 sample surface after electrochemical corrosion cleaning in Example 1.
[0030] Figure 3 This is the SEM image of the AZ31 sample surface after electrochemical corrosion cleaning in Example 2.
[0031] Figure 4 This is the SEM image of the AZ91 sample surface after electrochemical corrosion cleaning in Comparative Example 2.
[0032] Figure 5 This is the SEM image of the AZ91 sample surface after electrochemical corrosion cleaning in Comparative Example 3. DETAILED DESCRIPTION
[0033] The present invention will be described in further detail below with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
[0034] In the examples of the present invention, if the specific conditions are not specified, the experiments were carried out according to conventional conditions or the conditions recommended by the manufacturer. All raw materials and reagents used without specifying the manufacturer are conventional products that can be purchased from the market.
[0035] Comparative Example 1
[0036] AZ31 magnesium alloy plates of 400×200×5mm purchased from the market were selected and cut into 10×10×5mm specimens using a wire cutting machine. The samples were polished with 500, 1000, 2000, and 5000 grit sandpapers in sequence using a grinder and polisher, and then cleaned with alcohol and dried for later use.
[0037] The sample to be processed was wrapped with copper wire, and after wrapping, the remaining five sides of the sample were wrapped with Kraft glue, leaving only one working surface (10 mm) exposed.
[0038] The electrochemical corrosion experiment was conducted using a platinum electrode as the cathode and the sample as the anode in a 1 mol / L NaOH solution. The voltage was adjusted to 1.6 V and the duration was set to 30 minutes.
[0039] After the test, the sample was removed, rinsed with deionized water, and then ultrasonically cleaned in anhydrous ethanol for 20 minutes. The surface-porous sample was removed and dried. The sample had a porosity of approximately 59.856% and a pore size of 2.13 ± 1.22 μm.
[0040] Example 1
[0041] AZ31 magnesium alloy plates of 400×200×5mm purchased from the market were selected and cut into 10×10×5mm specimens using a wire cutting machine. The samples were polished with 500, 1000, 2000, and 5000 grit sandpapers in sequence using a grinder and polisher, and then cleaned with alcohol and dried for later use.
[0042] The sample to be processed was wrapped with copper wire, and after wrapping, the remaining five sides of the sample were wrapped with Kraft glue, leaving only one working surface (10 mm) exposed.
[0043] The electrochemical corrosion experiment was conducted using a platinum electrode as the cathode and the sample as the anode in a 1 mol / L NaOH solution. The voltage was adjusted to 1.6 V and the duration was set to 30 minutes.
[0044] After the test, the sample was removed, rinsed with deionized water, and then ultrasonically cleaned in anhydrous ethanol for 20 minutes. After drying, the sample was pickled in a 20wt% chromic acid solution for 20 minutes to remove surface impurities and oxides. The sample was rinsed with deionized water and ultrasonically cleaned in anhydrous ethanol for 20 minutes, then removed and dried to obtain a sample with multi-level surface pores. The sample had a porosity of approximately 73.686%, and a pore size of 2.42±2.02μm.
[0045] Example 2
[0046] AZ31 magnesium alloy plates of 400×200×5mm purchased from the market were selected and cut into 10×10×5mm specimens using a wire cutting machine. The samples were polished with 500, 1000, 2000, and 5000 grit sandpapers in sequence using a grinder and polisher, and then cleaned with alcohol and dried for later use.
[0047] The sample to be processed was wrapped with copper wire, and after wrapping, the remaining five sides of the sample were wrapped with Kraft glue, leaving only one working surface (10 mm) exposed.
[0048] The electrochemical corrosion experiment was conducted using a platinum electrode as the cathode and the sample as the anode in a 1 mol / L NaOH solution. The voltage was adjusted to 3 V and the duration was set to 30 minutes.
[0049] After completion, the sample was removed, rinsed with deionized water, and then ultrasonically cleaned in anhydrous ethanol for 20 minutes. After drying, the sample was pickled in a 20wt% chromic acid solution for 20 minutes to remove surface impurities and oxides. The sample was rinsed with deionized water and ultrasonically cleaned in anhydrous ethanol for 20 minutes, then removed and dried to obtain a sample with multi-level surface pores. The sample had a porosity of approximately 87.935%, and a pore size of approximately 3.03±2.77μm.
[0050] Comparative Example 2
[0051] AZ91 magnesium alloy plates of 400×200×5mm purchased from the market were selected and cut into 10×10×5mm specimens using a wire cutting machine. The samples were polished with 500, 1000, 2000, and 5000 grit sandpaper in sequence using a grinder and polisher, and then cleaned with alcohol and dried for later use.
[0052] The sample to be processed was wrapped with copper wire, and after wrapping, the remaining five sides of the sample were wrapped with Kraft glue, leaving only one working surface (10 mm) exposed.
[0053] The platinum electrode was used as the cathode, the sample was used as the anode, and the electrolysis environment was 1 mol / L NaOH solution. The electrochemical workstation voltage was adjusted to 1.6 V and the time was set to 30 minutes to begin the electrochemical corrosion experiment.
[0054] After completion, the sample was removed, rinsed with deionized water, and then ultrasonically cleaned in anhydrous ethanol for 20 minutes. After drying, it was pickled in a 20wt% chromic acid solution for 20 minutes to remove surface impurities and oxides. The sample was then rinsed with deionized water and ultrasonically cleaned in anhydrous ethanol for 20 minutes, then removed and dried. It can be observed that the AZ91 alloy does not exhibit significant porosity or pore size on its surface, nor does it exhibit a related multi-level pore structure.
[0055] Comparative Example 3
[0056] AZ91 magnesium alloy plates of 200×200×5mm purchased from the market were selected and cut into 10×10×5mm specimens using a wire cutting machine. The samples were polished with 500, 1000, 2000, and 5000 grit sandpapers in sequence using a grinder and polisher, and then cleaned with alcohol and dried for later use.
[0057] The sample to be processed was wrapped with copper wire, and after wrapping, the remaining five sides of the sample were wrapped with Kraft glue, leaving only one working surface (10 mm) exposed.
[0058] The electrochemical corrosion experiment was conducted using a platinum electrode as the cathode and the sample as the anode in a 1 mol / L NaOH solution. The voltage was adjusted to 3 V and the duration was set to 30 minutes.
[0059] After completion, the sample was removed, rinsed with deionized water, and then ultrasonically cleaned in anhydrous ethanol for 20 minutes. After drying, it was pickled in a 20wt% chromic acid solution for 20 minutes to remove surface impurities and oxides. The sample was then rinsed with deionized water and ultrasonically cleaned in anhydrous ethanol for 20 minutes, then removed and dried. It can be observed that the AZ91 alloy does not exhibit significant porosity or pore size on its surface, nor does it exhibit a related multi-level pore structure.
[0060] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.
Claims
1. A method for preparing a magnesium alloy material with a multi-level porous structure on the surface, characterized in that: The following steps are involved: The pretreated bulk AZ31 magnesium alloy material is used as the anode, the platinum electrode is used as the cathode, and the alkaline solution is used as the electrolyte. The pretreated bulk AZ31 magnesium alloy material is electrochemically corroded at a DC voltage of 1.6 to 3 V to produce a multi-level porous structure on the surface of the magnesium alloy material. After cleaning, a magnesium alloy material with a multi-level porous structure on the surface is obtained.
2. The method for preparing a magnesium alloy material with a multi-level porous surface structure according to claim 1, characterized in that: The electrochemical corrosion time is 20 to 50 minutes.
3. The method for preparing a magnesium alloy material with a multi-level porous surface structure according to claim 2, characterized in that: The electrochemical corrosion time is 30 minutes.
4. The method for preparing a magnesium alloy material with a multi-level porous surface structure according to claim 1 or 2, characterized in that: The pretreated bulk AZ31 magnesium alloy material is obtained by the following method: the bulk AZ31 magnesium alloy material is polished and cleaned, then wound with a wire to expose one working surface, and the remaining surfaces are sealed with glue.
5. The method for preparing a magnesium alloy material with a multi-level porous surface structure according to claim 1 or 2, characterized in that: The size of the block-shaped AZ31 magnesium alloy material is 10×10×5 to 20×20×10 mm.
6. The method for preparing a magnesium alloy material with a multi-level porous surface structure according to claim 1 or 2, characterized in that: In the preparation method of the magnesium alloy material with a multi-level porous structure on the surface, the cleaning method is: first, the corroded magnesium alloy material is rinsed with water, then placed in anhydrous ethanol for ultrasonic treatment for 10 to 30 minutes, then immersed in a 10 to 30wt% chromic acid solution for pickling for 10 to 30 minutes, and finally rinsed with water and placed in anhydrous ethanol for ultrasonic treatment for 10 to 30 minutes.
7. The method for preparing a magnesium alloy material with a multi-level porous surface structure according to claim 1 or 2, characterized in that: The concentration of the alkaline solution is 0.5 to 2 mol / L; And / or, the alkali in the alkaline solution is at least one of NaOH and KOH.
8. The method for preparing a magnesium alloy material with a multi-level porous surface structure according to claim 4, characterized in that: The polishing refers to polishing the block of AZ31 magnesium alloy material with 500-5000 grit sandpaper; And / or, the conductive wire is a copper wire; and the glue is silicone.
9. A magnesium alloy material with a multi-level porous structure on the surface obtained by the preparation method according to any one of claims 1 to 8.
10. Use of the magnesium alloy material with a multi-level surface porous structure according to claim 9 in the preparation of orthopedic and dental restoration products.