Application of amorphous alloy in field of biological metal materials
By replacing copper with iron in Zr-Cu-Al-Ag alloys, the biocompatibility and corrosion resistance of non-crystalline alloys are enhanced, addressing issues of harmful elements and corrosion in biomedical applications.
Patent Information
- Application Number
- CN202510430916.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-08
- Publication Date
- 2025-07-15
AI Technical Summary
Existing Zr-Cu-Al-Ag non-crystalline alloys contain harmful elements that can cause cell death, tissue necrosis, and immune reactions when used as biomedical implants, limiting their application in the field of biological metals due to potential corrosion issues.
A non-crystalline alloy with reduced copper content and added iron (Zr50Cu(34-x)FexAl8Ag8) is developed, which replaces part of the copper with iron to enhance biocompatibility and corrosion resistance.
The alloy exhibits improved biocompatibility and corrosion resistance, reducing adverse reactions and extending the usability of non-crystalline alloys in biomedical applications.
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Figure CN120311068A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of biometal materials, and particularly to the application of amorphous alloys in the field of biometal materials. Background Art
[0002] Amorphous alloys, also known as metallic glasses, are a class of metallic materials with an amorphous atomic structure. Their atomic arrangement is disordered in the long range but ordered in the short range, in sharp contrast to the periodic arrangement of atoms in traditional crystalline alloys. Due to their unique structure, these materials exhibit excellent mechanical, physical, and chemical properties and have attracted much attention in the field of materials science and engineering. Zr-based amorphous alloys such as Zr-Cu-Al-Ag have a series of excellent properties due to their unique composition design and amorphous structure. Their compressive strength can reach 1.5 - 2.5 GPa, and their hardness is significantly higher than that of traditional crystalline alloys such as stainless steel and titanium alloys. In addition, the elastic modulus of Zr-based amorphous alloys is close to that of human bones, which can reduce the "stress shielding" effect and is suitable as an orthopedic implant material.
[0003] In the prior art, for example, Zr-Cu-Al-Ag contains relatively more harmful elements. When these harmful elements come into contact with human cells, they may cause cell death, tissue necrosis, and even organ dysfunction, etc. Especially when used as an implant material, there may be rejection reactions or failures, which limit its application in the field of biometal materials. Therefore, it is necessary to reduce the content of harmful elements in amorphous alloys to obtain alloy compositions with excellent corrosion resistance in biological corrosion media and promote the application of alloys in the field of biometal materials. Summary of the Invention
[0004] To solve the above problems, the present invention provides an application of an amorphous alloy in the field of biometal materials, which is used to apply Zr 50 Cu (34-x) Fe x Al8Ag8 to biometal materials to obtain better corrosion resistance in biological media compared to Zr-Cu-Al-Ag and reduce the content of harmful element Cu in the alloy.
[0005] To achieve the above object, the technical solution of the present invention is as follows: An application of an amorphous alloy in the field of biometal materials, including:
[0006] Applying the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 as a biometal material.
[0007] Further, applying the amorphous alloy Zr 50 Cu (34-x) Fe xAl8Ag8 is applied as a material for manufacturing surgical devices.
[0008] Furthermore, the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 is applied as a material for body implants.
[0009] Furthermore, the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 is applied as a material for manufacturing in-vivo sensors.
[0010] Furthermore, Zr 50 Cu (34-x) Fe x The preparation method of Al8Ag8 includes preparing raw materials of Zr, Cu, Al, Ag, and Fe, configuring the raw materials into an alloy ingot of Zr 50 Cu (34-x) Fe x Al8Ag8, and putting it into a vacuum non-consumable arc melting furnace for melting, and then performing suction casting to obtain amorphous alloy bars.
[0011] Furthermore, the purity of the raw materials of Zr, Cu, Al, Ag, and Fe is all greater than 99.99%.
[0012] The technical principle of the above solution is as follows:
[0013] 1. Cu is an essential trace element in the human body, but excessive copper ions are toxic to human cells and tissues. Excessive copper ions may cause neurotoxicity, affect the function of neurons, and trigger a series of nervous system diseases, making materials containing Cu may pose safety hazards when in long-term contact with organisms, especially when used as implants, there may be rejection reactions or failures.
[0014] Compared with Cu, the Fe element is more suitable for adding to biomaterials. Fe is widely present in hemoglobin and myoglobin and participates in physiological processes such as oxygen transport. The degradation products of Fe in the body can be absorbed by the human body, gradually replacing the original metal material, without causing long-term residues or requiring secondary surgery for removal. This degradation characteristic is of significant value in applications such as bone repair and wound repair. Fe and its alloys usually have good mechanical properties, high strength and good toughness, and are suitable for implants that bear large mechanical loads.
[0015] In this solution, compared with the conventional amorphous alloy Zr-Cu-Al-Ag, the Fe element is additionally configured, and part of the Cu element is replaced by the Fe element, reducing the proportion of the Cu element in the amorphous alloy, so that the obtained Zr 50 Cu(34-x) Fe x Al8Ag8 has better biocompatibility.
[0016] 2. In this solution, in addition to being able to reduce the proportion of Cu element, the amorphous alloy containing Fe has a passivation phenomenon during the corrosion process, which can reduce the corrosion current density, increase the corrosion potential, and improve the corrosion resistance, thereby further improving the biocompatibility and obtaining a better biocompatibility effect, and having a good performance as a biometal material.
[0017] Additional aspects and advantages of the present invention will be given in part in the following description, will become apparent in part from the following description, or will be understood through the practice of the present invention. Brief Description of the Drawings
[0018] Figure 1 Schematic diagram of the amorphous alloy bar for the application example of the amorphous alloy of the present invention in the field of biometal materials;
[0019] Figure 2 Schematic diagram of the XRD curve of the amorphous alloy bar for the application example of the amorphous alloy of the present invention in the field of biometal materials;
[0020] Figure 3 Schematic diagram of the comparison of the corrosion performance of the amorphous alloy for the application example of the amorphous alloy of the present invention in the field of biometal materials in a biological medium. Detailed Embodiments
[0021] The technical solutions of the present invention will be described clearly and completely below with reference to the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.
[0022] In the description of the present invention, it should be noted that the orientation or positional relationship indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. is based on the orientation or positional relationship shown in the accompanying drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention. In addition, the terms "first", "second", "third" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.
[0023] In the description of the present invention, it should be noted that unless otherwise clearly specified and defined, the terms "installation", "connection", and "coupling" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
[0024] The following is a further detailed description through specific embodiments:
[0025] Example 1:
[0026] As shown in the Figures 1 - 3 accompanying drawings: An application of an amorphous alloy in the field of biomaterials includes applying the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 as a biomaterial, where x is taken as 4.
[0027] Zr 50 Cu (34-x) Fe x The preparation method of Al8Ag8 includes preparing raw materials of Zr, Cu, Al, Ag, and Fe. The purity of the raw materials of Zr, Cu, Al, Ag, and Fe is greater than 99.99%. The raw materials are configured into an alloy ingot with the component ratio of Zr 50 Cu (34-x) Fe x Al8Ag8, and is put into a vacuum non-consumable arc melting furnace for melting, and then suction casting is carried out to prepare amorphous alloy bars.
[0028] The accumulation of excessive copper ions in the body can produce various toxic effects on cells, tissues, and organs. Cu 2+ generates reactive oxygen species (ROS) through the Fenton reaction, leading to lipid peroxidation, protein denaturation, and DNA damage, and triggering apoptosis or necrosis of cells.
[0029] Copper ions accumulate in mitochondria, interfering with the electron transport chain (ETC), resulting in reduced ATP synthesis and exacerbating ROS generation. Copper binds to enzymes containing sulfhydryl groups (-SH) (such as superoxide dismutase SOD), destroying its antioxidant function.
[0030] Cu is mainly metabolized by the liver. Excess can cause hepatocyte necrosis, cholestasis, and even liver cirrhosis. In addition, after Cu penetrates the blood-brain barrier and deposits in the basal ganglia, it causes movement disorders such as tremors, dystonia, and cognitive decline and other complications.
[0031] When Cu is added to the implant material, Cu will be released after corrosion in body fluids. 2+ , if the proportion of Cu in the implant is too high, causing Cu 2+ to exceed the safety threshold, it may lead to inflammation of the tissues around the implant area or failure of bone integration.
[0032] In this embodiment, 4% atomic percentage of Cu in the amorphous alloy is replaced by Fe element, reducing the content of harmful element Cu in the alloy, thereby reducing the side effects of Cu element in the amorphous alloy to improve the biocompatibility of the amorphous alloy.
[0033] Compared with Cu, Fe element is more suitable for adding to biomaterials. Fe is widely present in hemoglobin and myoglobin and participates in physiological processes such as oxygen transportation. The degradation products of Fe in the body can be absorbed by the human body, gradually replacing the original metal material without causing long-term residues or requiring secondary surgery for removal. This degradation characteristic is of significant value in applications such as bone repair and wound repair. Fe and its alloys usually have good mechanical properties, high strength and good toughness, and are suitable for implants that bear large mechanical loads.
[0034] In addition to reducing the proportion of Cu element, the addition of Fe results in passivation during the corrosion process of the Fe-containing amorphous alloy, which can reduce the corrosion current density, increase the corrosion potential, and improve the corrosion resistance, thereby further improving the biocompatibility and obtaining better biocompatibility effects, showing good performance as a biomedical metal material.
[0035] Example 2:
[0036] The difference from the above embodiment is that the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 is used as a material for manufacturing surgical devices.
[0037] Surgical instruments are used in scenarios where they directly contact human tissues or body fluids. Using Zr 50 Cu (34-x) Fe x Al8Ag8 can reduce the side effects on patients compared to other amorphous alloys.
[0038] Example 3:
[0039] The difference from the above embodiment is that the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 is used as a material for body implants.
[0040] The specific implementation process is as follows: Most body implants directly contact the human internal environment. Using Zr50 Cu (34-x) Fe x Al8Ag8 can reduce the side effects on patients compared with other amorphous alloys.
[0041] Example 4:
[0042] The difference from the above example is that the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 is applied as a material for fabricating in-vivo sensors
[0043] The specific implementation process is as follows: Most in-vivo sensors will directly contact the human internal environment. Using Zr 50 Cu (34-x) Fe x Al8Ag8 can reduce the side effects on patients compared with other amorphous alloys.
[0044] Experimental verification:
[0045] 1. Structure analysis: The phase analysis of the amorphous alloy rods was carried out using an X-ray diffractometer. The XRD curves of the obtained amorphous alloy rods are as Figure 2 shown. The broadened "bread-like peak" appearing in the range of 20 - 50° on the abscissa is a typical feature of the amorphous alloy, resulting from the diffuse scattering caused by short-range order.
[0046] 2. Preparation of corrosion specimens: Before testing, the surface of the amorphous alloy specimen to be tested was polished with sandpaper, and then the surface to be tested was polished to a mirror surface with a polishing solution. The specimen was cleaned ultrasonically with alcohol and deionized water in sequence.
[0047] Take the specimen for corrosion tests in biological corrosion media. Common biological corrosion media mainly include simulated body fluid and phosphate buffer solution. The ion concentrations (mM) of the simulated body fluid are 142Na + , 5K + , 1.5Mg 2+ , 2.5Ca 2+ , 147.8Cl - , 4.2HCO 3- , 1HPO4 2- and 0.5SO4 2- . The ion concentrations (mM) contained in the phosphate buffer solution are 153Na + , 4.7K + , 139.7Cl - , 8HPO4 2- and 2H2PO 4-The traditional three - electrode method is adopted to test the electrochemical impedance spectrum, including the working electrode, reference electrode and counter electrode. After obtaining the stable open - circuit potential, the electrochemical impedance spectrum performance of the amorphous alloy is tested using an electrochemical comprehensive test system. After testing the electrochemical impedance spectrum, the Tafel curve performance of the amorphous alloy sample is tested using the electrochemical comprehensive test system, and the environment is the same as that for the electrochemical impedance spectrum test. A scanning electron microscope is used to observe the surface morphology of the amorphous alloy sample before and after corrosion in the biological corrosion medium.
[0048] The corrosion performance results of the amorphous alloy in the biological medium are as Figure 3 shown. The red curve is the amorphous alloy without Fe, and the blue curve is the amorphous alloy with Fe. The corrosion current generated by the blue curve is lower than that of the red curve in most intervals. Therefore, the amorphous alloy containing Fe has a passivation phenomenon during the corrosion process, the corrosion current density decreases, the corrosion potential increases, and the corrosion resistance is improved.
[0049] Obviously, the above - mentioned embodiments are only examples for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.
Claims
1. Application of an amorphous alloy in the field of biometal materials, characterized in that Including applying amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 as a biomaterial, where the range of x is 0 - 8.
2. The application of the amorphous alloy according to claim 1 in the field of biometal materials, characterized in that Apply amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 as a material for manufacturing surgical devices.
3. The application of the amorphous alloy according to claim 2 in the field of biometal materials, characterized in that, Apply the amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 as a material for body implants.
4. The application of the amorphous alloy according to claim 3 in the field of biometal materials, characterized in that, Apply amorphous alloy Zr 50 Cu (34-x) Fe x Al8Ag8 as a material for fabricating in-vivo sensors.
5. The application of the amorphous alloy according to claim 4 in the field of biometal materials, characterized in that, Zr 50 Cu (34-x) Fe x The preparation method of Al8Ag8 includes preparing raw materials of Zr, Cu, Al, Ag and Fe, and configuring the raw materials into an alloy ingot of Zr 50 Cu (34-x) Fe x Al8Ag8 according to atomic percentages, and putting the alloy ingot into a vacuum non-consumable arc melting furnace for melting, and then performing suction casting to obtain an amorphous alloy rod.
6. The use of the amorphous alloy according to claim 5 in the field of biomaterials, characterized in that, The purity of the raw materials of Zr, Cu, Al, Ag and Fe is greater than 99.99%.