CN111172426B - High-plasticity degradable LiZn4-X intermetallic compound and preparation method thereof - Google Patents
High-plasticity degradable LiZn4-X intermetallic compound and preparation method thereof Download PDFInfo
- Publication number
- CN111172426B CN111172426B CN202010006350.4A CN202010006350A CN111172426B CN 111172426 B CN111172426 B CN 111172426B CN 202010006350 A CN202010006350 A CN 202010006350A CN 111172426 B CN111172426 B CN 111172426B
- Authority
- CN
- China
- Prior art keywords
- intermetallic compound
- lizn
- temperature
- degradable
- plasticity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
Abstract
High-plasticity degradable LiZn4-X intermetallic compound and its preparation methodA preparation method. The X element is one or more of Cu, Mg, Ca, Sr, Mn, Fe, Ag, Co, Cr, Ti, Sn, Si, Se or Ge, and the balance is beta-LiZn4And (4) phase(s). The intermetallic compound is modified by a series of processing technologies of vacuum melting preparation, heat treatment, plastic deformation technology and low-temperature aging. The alloy is subjected to high-temperature heat treatment and consists of polycrystal and intragranular Zn + beta-LiZn4The lamellar tissue is formed into a multi-stage structure. The intermetallic compound has uniform structure, and the obtained intermetallic compound has the room-temperature tensile yield strength of 200-500 MPa, the tensile strength of 450-800 MPa and the elongation of 18-40%; the room-temperature compressive yield strength is 500-800 MPa, the compressive strength is 1000-2000 MPa, and the elongation is 15-45%. The degradation in the simulated body fluid is uniform, and the degradation rate is 0.008-0.5 mm/y; the contained elements are biosafety elements, the cytotoxicity to L929 osteoblast and MG63 is lower than 2 grade, and the use requirements of various human body implant device materials are met. The LiZn4the-X intermetallic compound has excellent performance, uniform degradation and good biocompatibility.
Description
Technical Field
The invention relates to a design and preparation method of a biodegradable medical material, in particular to high-plasticity degradable LiZn4-X intermetallic compound and a method for preparing the same.
Technical Field
Nowadays, the incidence of cardiovascular diseases is increased year by year along with the improvement of living standard of people, and becomes the first killer of non-infectious diseases worldwide. World health organization statistics show that about 170 million patients die from cardiovascular disease in 2008, and the estimated 2030-year death will rise to 250 million. Secondly, with the trend toward further aging worldwide, there is an increasing number of orthopedic disorders including degenerative diseases of bone tissue and sports injuries. In early clinical application, the implantation materials such as the vascular stent and the bone screw plate which are commonly used for treating the diseases mainly comprise bio-inert materials such as stainless steel, nickel titanium, cobalt-chromium alloy and the like, but the materials can be retained in a human body for a long time after being implanted for a long time, the vascular stent has the problems of thrombus, new atherosclerosis or restenosis and the like after the operation is healed, and the orthopedic implant needs to be taken out for a second operation, so that the recovery period is further prolonged, and the economic and psychological burdens of patients are increased. In order to solve the above problems, degradable materials such as Fe-based materials, Mg-based materials, Zn-based materials, and polymer materials have become a new research hotspot. In summary, the degradable materials for clinical applications in existence fall into two categories: degradable metals and high molecular materials. The invention firstly provides a third material which can be clinically applied in the future: the intermetallic compound may be degraded.
Disclosure of Invention
The existing intermetallic compound is non-degradable and has extremely poor plasticity, so that the ZrO and Al are non-degradable2O3MgO, SiC, TiAl and TiO2The room temperature plasticity of the representative intermetallic compound is generally not more than 5%, and it is difficult to satisfy the plasticity (elongation) required for the human body implant>15-18%). The invention aims to design a brand-new degradable LiZn with extremely high plasticity4The room temperature plasticity and the processability of the intermetallic compound are obviously higher than those of the common intermetallic compound, and the intermetallic compound can be used for human body implantation and can meet the mechanical support required by human body tissue repair.
The gist of the present invention to solve the above object is as follows:
high-plasticity degradable LiZn4-X intermetallic compound, characterized in that the mass percentages of the components in the alloy are: the X element is one or a mixture of more of Cu, Mg, Ca, Sr, Mn, Fe, Ag, Co, Cr, Ti, Sn, Si, Se or Ge, wherein Cu is 0.01-11.7 wt%, Mg is 0.01-9.9 wt%, Ca is 0.01-5.8 wt%, Sr is 0.01-9.5 wt%, Mn is 0.01-8.5 wt%, Fe is 0.01-6.1 wt%, Ag is 0.01-10.5 wt%, Co is 0.01-6.4 wt%, Cr is 0.01-4.4 wt%, Ti is 0.01-4.8 wt%, Sn is 0.01-5 wt%, Si is 0.01-5 wt%, Se is 0.01-5 wt%, Ge is 0.01-5 wt%, and the balance is beta-LiZn4Phase, beta-LiZn4The content of the Li element is 0.91-1.6 wt%.
Cu in the elements is a trace element necessary for human beings, and has a certain antibacterial effect. The medicine containing Li can be used for treating diseases such as mania, Parkinson's disease, amyotrophy sclerosis and the like, and the daily intake of Li in adults is recommended to be 0.65-3.1 mg. Mg, Ca and Sr in the human body are mainly present in the bone, and the rest of Mg is distributed in various soft tissues and body fluids. Fe combines with stranguria and protein in human body to form red bloodProtein and myoglobin, have oxygen transport and storage effects. Serum of adults contains a small amount of Se, which is an essential trace element for animals and humans. Mn plays an important role in the growth and development of animal bones. The content of Sn in the adult is about 17mg, and the Sn is mainly stored in organ tissues such as fat, skin, bones, lung and the like. A large number of experiments prove that the Ag has the effects of sterilization and disinfection and can promote the recovery of organisms. Co is an essential component of vitamin B12, and can promote the development and maturation of erythrocytes. Cr is mainly Cr in vivo3+The existing form has important function in maintaining normal glucose tolerance and blood lipid metabolism of organism. Ti and Ti alloy are the main application materials for clinical implantation at present and have good biocompatibility. The above elements are suitable as alloying elements for biodegradable intermetallic compounds.
The high-plasticity degradable LiZn4-X intermetallic compound preparation method, characterized in that said intermetallic compound adopts vacuum melting, said pure beta-LiZn4The phase material and the X-containing material are in CO2And SF6Or under the protection of high-purity argon, smelting in a vacuum smelting furnace, pouring and cooling to obtain LiZn4-an X intermetallic ingot; wherein the smelting temperature is 550-700 ℃, the standing time is 2-5 min, and the casting temperature is 430-600 ℃.
As can be seen from the electrochemical tests performed by the researchers of this group, beta-LiZn4The self-corrosion potential of the phase is lower than that of Zn by 0.18V, and the self-corrosion current density is higher than that of Zn by 2 muA/cm2Therefore, beta-LiZn4The phase will corrode prior to Zn in a body fluid environment. Thus, with beta-LiZn4The Zn-Li intermetallic compound taking the phase as the matrix can be completely degraded in a body fluid environment.
Further, the intermetallic compound can be modified by the processing technologies of high-temperature homogenization treatment → plastic deformation → low-temperature aging and the like, and the steps are as follows:
(1) the high-temperature homogenization treatment process of the intermetallic compound before plastic processing comprises the steps of heating to 220-260 ℃ at the speed of 1-20 ℃/min, then heating to 280-360 ℃ at the speed of 0.5-5 ℃/min, and preserving heat for 1 DEG CAfter 7 hours, quenching in water or oil at 0-100 ℃. By reacting an intermetallic compound beta-LiZn4Performing high-temperature heat treatment to obtain high-hardness beta-LiZn4Multiple needle-like Zn with similar size and approximately parallel arrangement can be separated out by taking the phase as a matrix, the needle-like Zn is limited in the same crystal grain, and a polycrystalline structure is formed in the final intermetallic compound, wherein the polycrystalline structure is based on Zn + beta-LiZn4A multi-level structure of lamellar organization. The orientation of the polycrystalline structure is anisotropic, so that the mechanical properties of the material have no obvious difference in each orientation, and the subsequent plastic processing forming is facilitated. Zn + beta-LiZn4The lamellar structure has high strength and high plasticity, the distance between adjacent lamellar layers is about 0.2-0.7 mu m, and the microhardness is 150-200 HV. Wherein the Zn hardness is lower and is a soft phase, which can coordinate plastic deformation and improve the plasticity of the intermetallic compound. The alloying element component adding interval is a solid solution and eutectic reaction interval, and a nano/micron-sized second term can be precipitated in the intermetallic compound through eutectic reaction and aging treatment during solidification, so that the alloy strength is further enhanced.
(2) The plastic deformation process of the intermetallic compound is at least one of rolling, extrusion and forging, and the deformation temperature is 210-360 ℃.
Further, the rolling is multi-pass rolling, the intermetallic compound and a roller of a rolling mill are preheated to 210-360 ℃ simultaneously and then start to be rolled, the pass reduction is 5-30%, the rolling is carried out for 5-15 min every two passes, and the rolling speed is 0.3-0.7 m/s.
Furthermore, the extrusion temperature is 210-360 ℃, the extrusion ratio is 10-70, the extrusion speed is 0.1-50 mm/s, and the extrusion can be made into various shapes such as bars, plates, pipes and the like through the design of the shape of the outlet of the die.
Further, the forging comprises the steps of preheating the intermetallic compound at 210-360 ℃, and then forging at 210-360 ℃, wherein the heat preservation time is 2-10 hours, and the forging speed is not less than 330 mm/s.
(3) After the high-temperature homogenization treatment and plastic deformation of the intermetallic compound, the process of low-temperature aging comprises the following steps: heating to 100-200 ℃ at the speed of 2-6 ℃/min, preserving heat for 5-60 hours, and cooling along with the furnace.
Furthermore, through plastic processing, the intermetallic compound can obtain an equiaxial crystal structure with the grain size of 5-50 mu m, and Zn + beta-LiZn is distributed in the crystal4The space between adjacent lamellae of the lamellar structure is 0.2-0.7 mu m, the microhardness is 150-200 HV, and the comprehensive mechanical property of the intermetallic compound is remarkably optimized. In addition, the low-temperature aging can promote the precipitation and recrystallization of Zn, enhance the plasticity of the intermetallic compound and further realize the optimization of the mechanical property of the intermetallic compound.
Furthermore, the room-temperature tensile yield strength of the intermetallic compound is 200-500 MPa, the tensile strength is 300-650 MPa, and the elongation is 18-40%; the room-temperature compressive yield strength is 500-800 MPa, the compressive strength is 1000-1700 MPa, and the elongation is 15-45%.
Furthermore, the intermetallic compound is characterized in that the degradation speed of the intermetallic compound in simulated body fluid is 0.008-0.5 mm/y. Meets the internationally recognized degradation rate standard of the vascular stent and the bone plastic repair material, wherein the degradation rate of the vascular stent material is less than 0.02mm/y, and the degradation rate of the bone plastic repair material is less than 0.5 mm/y. The cytotoxicity is lower than grade 2.
Furthermore, the intermetallic compound has high strength and good plasticity, the degradation rate meets the time required by the material to complete the structure supporting effect, and the intermetallic compound is suitable for various medical implants, and the application range of the intermetallic compound comprises at least one of degradable hemostatic clamps, degradable vascular stents, degradable orthopedic implants and degradable oral materials.
Compared with the existing degradable material literature, the invention has the advantages that:
1. the degradable material matrix is an intermetallic compound, and Zn is subjected to heat treatment on the intermetallic compound matrix beta-LiZn4Medium precipitation to obtain high-strength high-plasticity nano/micron multi-level Zn + beta-LiZn4Lamellar structure, finally forming a polycrystalline structure in the intermetallic compound, wherein the grain interior is Zn + beta-LiZn4A multi-level structure of lamellar organization. Further, LiZn4The hardness of the-X intermetallic compound is 150-200 HV and is obviously higher than that of three of Mg, Fe and ZnThe hardness (50-80 HV) of the existing degradable metal is high, so that the method has obvious innovation.
2. The intermetallic compound provided by the invention has high room temperature elongation (18-40%) which is far higher than the room temperature elongation (5%) of the common intermetallic compound, can be directly hot rolled and extruded to form, and the finished product has smooth surface and no cracks, which cannot be achieved by the existing intermetallic compound.
3. The fully-lamellar biodegradable intermetallic compound provided by the invention ensures the absolute uniformity of alloy tissues on a macroscopic scale, so that the intermetallic compound is uniformly corroded in a body fluid environment and is an ideal degradable implant material.
4. The intermetallic compound does not contain rare and precious elements and has good biocompatibility; can be processed and obtained by a simple plastic processing method, and is suitable for large-scale industrial production.
Drawings
Figure 1 example 1 metallograph of microstructure of intermetallic compound 1 after heat treatment.
Fig. 2 example 1 intermetallic compound 1X-ray diffraction pattern after heat treatment.
FIG. 3 photograph of the rolled plate of the intermetallic compound 1 of example 1.
Fig. 4 photograph of a hot-extruded rod of the intermetallic compound 2 of example 1.
Fig. 5 scanning electron micrograph of microstructure after hot rolling of intermetallic compound 1 of example 1.
Fig. 6 scanning electron micrograph of microstructure after hot extrusion of intermetallic compound 2 of example 1.
Fig. 7 room temperature tensile stress strain curve of intermetallic compound 1 of example 1 after hot rolling.
Fig. 8 room temperature compressive stress strain curve of intermetallic compound 2 of example 1 after hot extrusion.
Detailed Description
In order to make the technical solution of the present invention more apparent, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1: LiZn4-preparation and performance testing of the X intermetallic compound.
The biodegradable LiZn4The mass percentages of the chemical elements in the intermetallic compound of-X are shown in Table 1-1, and the balance is β -LiZn4. The preparation process flow of the intermetallic compound is high-temperature homogenization treatment → rolling or extrusion → low-temperature aging.
Homogenizing: placing the intermetallic compound cast ingot in a box type heating sintering furnace KSL-1400X, heating to 250 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours; then the temperature is raised to 350 ℃ at the speed of 1 ℃/min, and the temperature is kept for 2 hours and then the water quenching is carried out at the room temperature. A metallographic photograph of a microstructure of the obtained intermetallic compound 1 of the inventive example was shown in FIG. 1, in which the intermetallic compound was composed of coarse grains and the intragranular phase was Zn + β -LiZn4The distance between adjacent lamellae is 0.4-0.7 μm. FIG. 2 is an X-ray diffraction pattern of the intermetallic compound 1 of the present invention example, from which it is understood that the intermetallic compound is composed of Zn and β -LiZn4The two-phase composition can be determined to be Zn + beta-LiZn by combining the figure 14. The microhardness of the metal compound is 164 HV.
Homogenizing: placing the intermetallic compound cast ingot in a box type heating sintering furnace KSL-1400X, heating to 250 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours; then the temperature is raised to 350 ℃ at the speed of 1 ℃/min, and the temperature is kept for 2 hours and then the water quenching is carried out at the room temperature.
Hot rolling: preheating the cast ingot at 250-360 ℃ for 1 hour, rolling at 250-360 ℃ and at the rolling speed of 0.3 m/s; a first pass, rolling a sample of the intermetallic compound having a thickness of 20mm to a thickness of 16 mm; in the second pass, the rolled steel is rolled to 12mm, and the steel is returned to the furnace and kept for 15 minutes; the third time, rolling the steel plate to 8 mm; in the fourth pass, the rolled steel is rolled to 4mm, and the steel is returned to the furnace and kept for 15 minutes; in the last pass, it is rolled to a thickness of 2mm and quenched in water at 20 ℃ with a total deformation of 90%. The surface of the rolled piece is smooth and has no obvious edge crack. The picture of the resulting plate rolled with the intermetallic compound 1 of the invention is shown in FIG. 3.
Extruding: preheating is carried out at 210-300 ℃, heat preservation is carried out for 0.5-1 h, extrusion is carried out at 210-300 ℃, and the extrusion ratio is 20-30. The picture of the resulting intermetallic compound 2 extruded rod of the inventive example is shown in FIG. 4.
Low-temperature aging: heating to 100-200 ℃ at the speed of 2-6 ℃/min, preserving heat for 10-30 hours, and cooling along with the furnace.
The microstructure of the rolled and aged intermetallic compound 1 of the inventive example is shown in FIG. 5, and the microstructure of the extruded and aged intermetallic compound 2 of the inventive example is shown in FIG. 6. TABLE 1-1-variable morphology LiZn4The microstructure of the aged-X intermetallic compound consists of crystal grains with the size of 5-50 mu m, and Zn + beta-LiZn is arranged in the crystal grains4Lamellar tissue, the distance between lamellae is 0.2-0.6 μm, and nano/micron precipitated phase formed by added elements. The microhardness of the deformed metal compound is 183-196 HV.
The preparation method of the soaking corrosion sample comprises the steps of cutting the intermetallic compound section bar subjected to plastic deformation into a wafer-shaped sample, polishing the two sides of the wafer-shaped sample, cleaning the wafer-shaped sample with alcohol and drying the wafer-shaped sample with cold air. 3 parallel samples are selected in the immersion corrosion experiment, and the ratio of the simulated body fluid volume to the sample surface area is 20ml/cm2The temperature is kept at 37 ℃, the simulated body fluid is replaced once every 48 hours and is soaked for 30-90 days, the value of the simulated body fluid is maintained after the simulated body fluid is finished, the surface corrosion products are removed according to the national standard GB/T16545-2015, and the degradation rate is calculated according to the ASTM-G102-89 standard.
The preparation method of the cytotoxicity test sample is consistent with the method of soaking the corrosion test sample, the toxicity test is carried out according to the national standard GB/T16886.5-2003, the commonly used L929 and MG63 cells are selected, and the test result is representative. The cells were placed in LiZn soaked for 24 hours4And (3) culturing the-X intermetallic compound leaching solution in a carbon dioxide incubator at 37 ℃ for 1 day, 3 days and 5 days respectively, and then measuring the absorbance of the cells by using a method to calculate the relative increment rate of the cell.
The room temperature tensile and compression mechanical property test of the intermetallic compound comprises the steps of preparing tensile and compression test samples according to national standards GB/T228.1-2010 and GB/T7314-2017 respectively, and then performing tensile and compression tests at room temperature by using a universal material mechanical testing machine, wherein the strain rate is 10-4～10-3/s。
The immersion corrosion rate of 7 invention examples of intermetallic compounds in the table 1-1 in simulated body fluid is measured to be 0.008-0.1 mm/y.
The cytotoxicity of 7 invention intermetallic compounds in the table 1-1 is measured to be lower than 2 grades, and the compounds show good cell compatibility.
And testing the mechanical property of the aged deformed intermetallic compound by tensile and compression tests. The stress-strain curve of the intermetallic compound 1 in the invention example under the room temperature tensile engineering is shown in fig. 7, and the yield strength of 7 intermetallic compounds in the invention example in table 1-1 is 210-350 MPa, the tensile strength is 450-600 MPa, the elongation is 20-40%, and the mechanical property requirements of the human body implant device on the material are met. The compressive stress-strain curve of the intermetallic compound 2 of the invention example is shown in FIG. 8, and the compressive yield strength of 7 intermetallic compounds of the invention example in Table 1-1 is 600-700 MPa, the compressive strength is 1600-1850 MPa, and the elongation is 18-40%.
TABLE 1-1
Example 2: LiZn4-X1-X2Preparation and performance test of intermetallic compound.
The biodegradable LiZn4-X1-X2The mass percentages of the chemical elements in the intermetallic compound are shown in Table 2-1, and the balance is beta-LiZn4. The process flow of the preparation of the intermetallic compound is high-temperature homogenization treatment → extrusion or rolling → low-temperature aging treatment, and the smelting, homogenization heat treatment, extrusion, rolling and aging treatment are carried out according to the method provided in example 1. Morphic LiZn4-X1-X2The microstructure of the intermetallic compound after low-temperature aging consists of crystal grains with the size of 5-30 mu m, and Zn + beta-LiZn is arranged in the crystal grains4The structure of the lamella is formed, the distance between the lamellae is 0.3-0.7 mu m, and in addition, a nano/micron precipitated phase formed by the added elements is precipitated in the crystal and the crystal boundary.
And cutting a sample from the obtained section bar to test in-vitro corrosion, cytotoxicity and room temperature compression mechanical properties. The preparation and testing of the above samples was carried out as provided in example 1.
The immersion corrosion rate of 7 invention examples of intermetallic compounds in the table 2-1 in simulated body fluid is measured to be 0.05-0.3 mm/y.
The cytotoxicity of 7 invention intermetallic compounds in the table 2-1 is measured to be 2 grades, and the compounds show good cell compatibility
The room temperature mechanical properties of 7 inventive examples of intermetallic compounds in Table 2-1 were measured as follows: the yield strength is 300-550 MPa, the tensile strength is 550-700 MPa, the elongation is 18-30%, the compressive yield strength is 700-850 MPa, the compressive strength is 1700-1900 MPa, and the elongation is 15-25%.
TABLE 2-1
Example 3: LiZn4-X1-X2-X3Preparation and performance test of intermetallic compound.
The biodegradable LiZn4-X1-X2-X3The mass percentages of the chemical elements in the intermetallic compound are shown in Table 3-1, and the balance is beta-LiZn4. The process flow of the preparation of the intermetallic compound is high-temperature homogenization treatment → extrusion or rolling → low-temperature aging treatment, and the smelting, homogenization heat treatment, extrusion, rolling and aging treatment are carried out according to the method provided in example 1. Morphic LiZn4-X1-X2-X3The microstructure of the intermetallic compound after the homogenization heat treatment consists of crystal grains with the size of 5-30 mu m, and Zn + beta-LiZn is arranged in the crystal grains4The structure of the lamella is formed, the distance between the lamellae is 0.2-0.4 mu m, and in addition, a nano/micron precipitated phase formed by the added elements is precipitated in the crystal and in the crystal boundary.
And cutting a sample from the obtained section bar to test in-vitro corrosion, cytotoxicity and room temperature compression mechanical properties. The preparation and testing of the above samples was carried out as provided in example 1.
The immersion corrosion rate of 7 invention examples of intermetallic compounds in the table 3-1 in simulated body fluid is measured to be 0.1-0.5 mm/y.
The cytotoxicity of 7 inventive intermetallic compounds in the table 3-1 is measured to be 2 grade, and the compounds show good cell compatibility
The room temperature mechanical properties of 7 inventive examples of intermetallic compounds in Table 3-1 were measured as follows: the yield strength is 500-700 MPa, the tensile strength is 550-800 MPa, the elongation is 18-20%, the compressive yield strength is 750-900 MPa, the compressive strength is 1700-2000 MPa, and the elongation is 15-20%.
TABLE 3-1
Example 4: LiZn4-0.1X intermetallic compound bone screw preparation.
The intermetallic compound comprises the following components in percentage by mass: x is 0.1 wt% of any one of Cu, Ag, Mn, Mg, Ca, Fe and Sr, and the balance is beta-LiZn4. The process flow of the preparation of the metal compound is high-temperature homogenization treatment → extrusion → low-temperature aging treatment, and the smelting, homogenization heat treatment, extrusion and low-temperature aging treatment are all carried out according to the method provided by the embodiment 1.
LiZn formed by extrusion molding by using mechanical processing method4the-0.1X intermetallic compound bar is processed into a nail shape, external threads are carved on the screw rod, hexagonal grooves are cut on the round screw cap, and the overall strength is high. The bone screw can be degraded in human body, absorbed by human body and metabolized out of human body, has no metal stimulation reaction, and has good biocompatibility.
Claims (8)
1. High-plasticity degradable LiZn4-X intermetallic compound characterized in that: the intermetallic compound comprises the following components in percentage by mass: the X element is Cu, Mg, Ca, Sr, Mn, Fe, Ag, Co, Cr, Ti, Sn, Si, Se or Ge, wherein Cu is 0.01-2.75 wt%, Mg is 0.01-9.9 wt%, Ca is 0.01-5.8 wt%, Sr is 0.01-9.5 wt%, Mn is 0.01-8.5 wt%, Fe is 0.01-6.1 wt%, Ag is 0.01-10.5 wt%, Co is 0.01-6.4 wt%, Cr is 0.01-4.4 wt%, Ti is 0.01-4.8 wt%, Sn is 0.01-5 wt%, Si is 0.01-5 wt%, Se is 0.01-5 wt%, Ge is 0.01-5 wt%, and the balance is beta-LiZn4Phase, beta-LiZn4The content of the Li element is 0.91-1.6 wt%;
after the intermetallic compound is subjected to the processes of high-temperature homogenization treatment → plastic processing → low-temperature aging treatment, the microstructure of the intermetallic compound is a multilevel structure consisting of crystal grains with the size of 5-50 mu m and in-crystal micron/nanometer Zn + beta-LiZn4Lamellar structure, wherein the distance between adjacent lamellar layers is 0.2-0.7 mu m, and the microhardness is 150-200 HV;
the room-temperature tensile yield strength of the intermetallic compound is 200-500 MPa, the tensile strength is 450-800 MPa, and the elongation is 18-40%; the room-temperature compressive yield strength is 500-800 MPa, and the compressive strength is 1000-2000 MPa;
the degradation speed of the intermetallic compound in simulated body fluid is 0.008-0.5 mm/y; the cytotoxicity of the intermetallic compound on cells is lower than grade 2.
2. The high-plasticity degradable LiZn as claimed in claim 14The preparation method of the-X intermetallic compound is characterized by comprising the following smelting step, wherein the raw material X and the pure beta-LiZn are weighed according to the mass percent of each component in the intermetallic compound4Mixing the raw materials to obtain a mixture in CO2And SF6Or under the protection of high-purity argon, smelting in a vacuum smelting furnace, pouring and cooling to obtain the intermetallic compound; wherein the smelting temperature is 550-700 ℃, the standing time is 2-5 min, and the casting temperature is 430-600 ℃;
the preparation and processing flow of the intermetallic compound is as follows: the process of high-temperature homogenization treatment → plastic processing → low-temperature aging treatment comprises the following specific steps:
(1) the high-temperature homogenization treatment process of the intermetallic compound comprises the steps of heating to 220-260 ℃ at the speed of 1-20 ℃/min, then heating to 280-360 ℃ at the speed of 0.5-5 ℃/min, preserving heat for 1-7 hours, and then quenching in water or oil at the temperature of 0-100 ℃;
(2) the plastic deformation process of the intermetallic compound is at least one of rolling, extrusion and forging, and the deformation temperature is 210-360 ℃;
(3) the low-temperature aging process of the intermetallic compound comprises the steps of heating to 100-200 ℃ at the speed of 2-6 ℃/min, preserving heat for 5-60 hours, and cooling along with a furnace.
3. The high-plasticity degradable LiZn as claimed in claim 24The preparation method of the-X intermetallic compound is characterized in that the rolling is multi-pass rolling, the intermetallic compound and a rolling mill roller are preheated to 280-360 ℃ simultaneously and then start to be rolled, the pass reduction is 5-30%, the rolling is carried out for 5-15 min every two passes, and the rolling speed is 0.3-0.7 m/s.
4. The high-plasticity degradable LiZn as claimed in claim 24The preparation method of the-X intermetallic compound is characterized in that the extrusion temperature is 210-360 ℃, the extrusion ratio is 10-70, the extrusion speed is 0.1-50 mm/s, and the compound can be extruded into various shapes of bars, plates and pipes through the shape design of a die outlet.
5. The high-plasticity degradable LiZn as claimed in claim 24The preparation method of the intermetallic compound-X is characterized in that the forging comprises the step of preheating the intermetallic compound at 210-360 ℃, the forging temperature is 210-360 ℃, the heat preservation time is 2-10 hours, and the forging speed is not less than 330 mm/s.
6. The high-plasticity degradable LiZn as claimed in claim 14-X intermetallic compound application method, characterized in that: the intermetallic compound is suitable for various medical implants.
7. The high-plasticity degradable plastic of claim 6LiZn4-X intermetallic compound application method, characterized in that: the intermetallic compound is suitable for degradable orthopedic implants.
8. The high-plasticity degradable LiZn as claimed in claim 64-X intermetallic compound application method, characterized in that: the intermetallic compound is suitable for degradable oral materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010006350.4A CN111172426B (en) | 2020-01-03 | 2020-01-03 | High-plasticity degradable LiZn4-X intermetallic compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010006350.4A CN111172426B (en) | 2020-01-03 | 2020-01-03 | High-plasticity degradable LiZn4-X intermetallic compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111172426A CN111172426A (en) | 2020-05-19 |
| CN111172426B true CN111172426B (en) | 2021-05-07 |
Family
ID=70646423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010006350.4A Active CN111172426B (en) | 2020-01-03 | 2020-01-03 | High-plasticity degradable LiZn4-X intermetallic compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111172426B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113559333B (en) * | 2021-06-07 | 2022-11-08 | 中国科学院金属研究所 | Medical nickel-titanium alloy with high anticoagulation function without surface treatment |
| CN115198277B (en) * | 2022-06-30 | 2024-02-23 | 中国船舶重工集团公司第七二五研究所 | Zn-Li alloy sacrificial anode for deep sea and preparation method thereof |
| CN115874084B (en) * | 2022-12-23 | 2024-02-06 | 北京大学 | Zn-Li creep-resistant zinc alloy and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140376352A1 (en) * | 2013-06-24 | 2014-12-25 | Seagate Technology Llc | Materials for near field transducers, near field tranducers containing same, and methods of forming |
| CN108754232A (en) * | 2018-05-25 | 2018-11-06 | 北京科技大学 | High-strength high-plastic biodegradable Zn-Mn-Li systems kirsite of one kind and application thereof |
| CN110317973A (en) * | 2019-07-03 | 2019-10-11 | 北京科技大学 | A kind of biodegradable LiZn4- Zn composite diphase material and preparation method thereof |
-
2020
- 2020-01-03 CN CN202010006350.4A patent/CN111172426B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140376352A1 (en) * | 2013-06-24 | 2014-12-25 | Seagate Technology Llc | Materials for near field transducers, near field tranducers containing same, and methods of forming |
| CN108754232A (en) * | 2018-05-25 | 2018-11-06 | 北京科技大学 | High-strength high-plastic biodegradable Zn-Mn-Li systems kirsite of one kind and application thereof |
| CN110317973A (en) * | 2019-07-03 | 2019-10-11 | 北京科技大学 | A kind of biodegradable LiZn4- Zn composite diphase material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111172426A (en) | 2020-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Radha et al. | Insight of magnesium alloys and composites for orthopedic implant applications–a review | |
| CN111172426B (en) | High-plasticity degradable LiZn4-X intermetallic compound and preparation method thereof | |
| CN109097629B (en) | Biodegradable Zn-Mo series zinc alloy and preparation method thereof | |
| CN111020295B (en) | High-performance biodegradable Zn-Cu-Li-X alloy and preparation and application methods thereof | |
| AU2020102567A4 (en) | A high plasticity degradable LiZn4-X intermetallic compound and its preparation method | |
| WO2011160533A1 (en) | Magnesium alloy used for degradable implant material of bone in vivo and preparation method thereof | |
| Hon et al. | Composition/phase structure and properties of titanium-niobium alloys | |
| Bryła et al. | Microstructure, mechanical properties, and degradation of Mg-Ag alloy after equal-channel angular pressing | |
| CN109680195B (en) | Mg-RE series magnesium alloy and preparation method and application thereof | |
| CN108754232B (en) | High-strength high-plasticity biodegradable Zn-Mn-Li series zinc alloy and application thereof | |
| CN110317973B (en) | Biodegradable LiZn4-Zn complex phase material and preparation method thereof | |
| CN105349858B (en) | The bone fixation magnesium alloy implant material of degradable and preparation method | |
| CN101215655B (en) | Metastable beta type ti-nb-ta-zr-o alloy and preparation method thereof | |
| CN112251639B (en) | High-strength antibacterial titanium alloy bar, high-strength antibacterial titanium alloy wire and preparation method of high-strength antibacterial titanium alloy bar | |
| CN107557633B (en) | A kind of microalloying medical degradable magnesium alloy and preparation method thereof | |
| CN108315583B (en) | Zn-Li-Mn zinc alloy and preparation method and application thereof | |
| CN105986146B (en) | A kind of degradable medical is metal material embedded and preparation method thereof | |
| CN108588484A (en) | High-strength high-plastic biodegradable Zn-Mn-Mg systems kirsite of one kind and preparation method thereof | |
| CN108203778B (en) | Zr-based biomedical alloy and preparation method thereof | |
| Cheng et al. | Mechanical properties and corrosion behaviors of Mg− 4Zn− 0.2 Mn− 0.2 Ca alloy after long term in vitro degradation | |
| CN110241330A (en) | A kind of degradable Zn-Ag system kirsite and the preparation method and application thereof | |
| CN108165782B (en) | Medical zinc-based alloy strip and preparation method thereof | |
| CN108823476A (en) | The controllable Mg-Zn-Sn system magnesium alloy and its preparation method and application of degradation rate | |
| CN107198796B (en) | Biomedical Zn-Mn-Cu zinc alloy and preparation method thereof | |
| KR101374233B1 (en) | Method of manufacturing ultrafine-grained titanium rod for biomedical applications, and titanium rod manufactured by the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230307 Address after: Room 110, Building 6, Yard 26, Yongwang West Road, Daxing Biomedical Industry Base, Zhongguancun Science Park, Daxing District, Beijing 102629 (cluster registration) Patentee after: Beijing shangning Kezhi Medical Instrument Co.,Ltd. Address before: 100083 No. 30, Haidian District, Beijing, Xueyuan Road Patentee before: University OF SCIENCE AND TECHNOLOGY BEIJING |