CN117965957A - Magnetic compatible beta biomedical zirconium alloy and preparation method and application thereof - Google Patents
Magnetic compatible beta biomedical zirconium alloy and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910001093 Zr alloy Inorganic materials 0.000 title description 7
- 239000010949 copper Substances 0.000 claims abstract description 42
- 239000002763 biomedical alloy Substances 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010955 niobium Substances 0.000 claims abstract description 20
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 48
- 239000000956 alloy Substances 0.000 claims description 48
- 238000003723 Smelting Methods 0.000 claims description 28
- 239000007943 implant Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003870 refractory metal Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002595 magnetic resonance imaging Methods 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 5
- 239000007769 metal material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004098 selected area electron diffraction Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003745 diagnosis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 210000004394 hip joint Anatomy 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 210000000629 knee joint Anatomy 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005404 magnetometry Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000065 noncytotoxic Toxicity 0.000 description 1
- 230000002020 noncytotoxic effect Effects 0.000 description 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 210000000323 shoulder joint Anatomy 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- 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
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- 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
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- Thermal Sciences (AREA)
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- Dermatology (AREA)
- Physics & Mathematics (AREA)
- Animal Behavior & Ethology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Epidemiology (AREA)
- Transplantation (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The invention discloses a magnetic compatible beta-Zr biomedical alloy, a preparation method and application thereof, wherein the biomedical alloy comprises the following chemical components in percentage by weight: 21.0 to 23.0 percent of niobium, 2.8 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities. The beta-Zr biomedical alloy has lower magnetic susceptibility and lower elastic modulus than the current common biomedical alloy, does not contain biotoxic elements, and can better serve the magnetic resonance imaging technology under higher magnetic field.
Description
Technical Field
The invention belongs to the field of metal materials, relates to a zirconium-based biomedical alloy, and in particular relates to a magnetic compatible beta-type biomedical zirconium alloy and a preparation method and application thereof.
Background
Nuclear magnetic resonance imaging MRI (Magneticresonanceimaging) is a novel medical imaging technique. Protons (1H) of hydrogen atoms in the substance generate resonance phenomenon with radio frequency with a certain frequency under the action of an external magnetic field, after the radio frequency is canceled, the protons generate weak radio signals in the process of returning to an initial state, 1H of different tissues generate different radio signals, and a technology for acquiring and applying the radio signals to perform three-dimensional imaging is called magnetic resonance imaging. The higher the magnetic field strength, the higher the resolution of MRI, and in recent years, the research of "the electrician theory and key technology of the advanced magnetic resonance imaging system" is one of the important projects of engineering and materials, and the research aims to solve the problems of the magnetic performance degradation of the MRI system under the ultra-high magnetic field and ensure the autonomous controllability of the advanced MRI technology.
The magnetic susceptibility of biomedical implants is particularly critical under the ultra-high magnetic field, and the strong magnetic field can cause three adverse effects of ① displacement and dislocation of the metal implants; ② Heating affects surrounding tissue; ③ Artifacts are created upon imaging. The artifact area is related to the difference in magnetization between the implant and the human tissue (-10 to-7 x 10 -6), the larger the difference in magnetization, the larger the artifact area. Zr (109×10 -6) has lower bulk susceptibility than the pure Ti (170×10 -6)、Ti-6Al-4V(179×10-6), stainless steel (3520 to 6700×10 -6) and co—cr (960×10 -6) alloys currently in use. In addition, for Zr, its phase composition is closely related to magnetic susceptibility (χ), generally χ ω<χα<χβ.
The beta-type titanium-based metal material has low elastic modulus and is widely applied to the biomedical metal-based implant field. However, with the popularization of high-intensity magnetic field MRI, the β -type titanium-based metal material will generate artifacts when imaging under a high magnetic field due to its high magnetic susceptibility. Therefore, developing a novel metal-based biomedical material with low magnetic susceptibility and lower elastic modulus is a research hotspot in the field.
Beta-Zr has lower mass susceptibility than beta-Ti, and at the same time has mechanical properties, corrosion resistance and biocompatibility that are not input to titanium alloys. beta-Zr with lower magnetic susceptibility has been reported to have higher magnetic susceptibility than alpha-Zr and omega-Zr, so that the magnetic susceptibility can generate larger artifacts under MRI. Zirconium alloy research in MRI has focused mainly on alpha-type alloys or alpha + omega-type alloys with lower magnetic susceptibility, while beta-Zr has less relevant reports due to higher magnetic susceptibility.
Disclosure of Invention
The invention aims to provide a magnetic compatible beta-Zr biomedical alloy, which aims to solve the problem that the existing biomedical alloy with higher magnetic susceptibility generates artifacts in strong magnetic field diagnosis. It has good biocompatibility, good mechanical property and corrosion resistance, and simultaneously has lower magnetic susceptibility and elastic modulus.
The invention adopts the following technical scheme for realizing the purpose:
A magnetic compatible beta-Zr biomedical alloy comprises the following chemical components in percentage by weight: 21.0 to 23.0 percent of niobium, 2.8 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities.
Preferably, the biomedical alloy comprises the following chemical components in percentage by weight: 21.5 to 22.5 percent of niobium, 3.0 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities.
Preferably, the biomedical alloy comprises the following chemical components in percentage by weight: 21.5 to 22.5 percent of niobium, 6.0 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities; preferably 22% niobium and 6.0-15.0% copper.
Preferably, the biomedical alloy comprises the following chemical components in percentage by weight: 21.5 to 22.5 percent of niobium, 10.0 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities; preferably 21.5 to 22.5 percent of niobium and 13.0 to 15.0 percent of copper; further preferably 22.0% niobium and 15.0% copper;
The biomedical alloy has the mass magnetic susceptibility of 0.95-1.70X10 -6cm3g-1, the volume magnetic susceptibility of 77-138X 10 -6 and the elastic modulus of 68.8-82.9 GPa.
The preparation method of the magnetic compatible beta-Zr biomedical alloy, which comprises the following steps:
(1) Weighing the raw materials: weighing raw materials Zr, nb and Cu according to weight percentage;
(2) Alloy smelting: the smelting temperature is 2700-3000 ℃, inert gas is filled into smelting equipment to smelt the cast ingot in protective atmosphere, and then quenching is carried out to obtain the alloy.
The raw materials are zirconium sponge, niobium block and copper block, and the purity of the raw materials is above 99.0 wt%.
Preferably, smelting is carried out by adopting refractory metal suspension smelting equipment, the vacuum degree of the smelting equipment is regulated to be 4 multiplied by 10 - 3 MPa, and in order to ensure the components to be uniform, the cast ingot is repeatedly turned over and remelted for at least three times; smelting by adopting refractory metal suspension smelting equipment, wherein the smelting temperature is 2700-3000 ℃, the vacuum degree of the smelting equipment is regulated to 4 multiplied by 10 -3 MPa, smelting is carried out under the protection of argon, the cast ingot is repeatedly turned over and remelted for at least three times to ensure the components to be uniform, and then the alloy is quenched at 950-990 ℃ and then cooled to room temperature by water.
The invention also provides application of the alloy in any one of the above to preparation of biomedical implants.
Preferably, the biomedical implant is a human implant, such as a bone fixation clamp, a cranium, a hip joint, a shoulder joint, a knee joint, a vascular dilator, a heart valve, or the like.
The invention adopts the method that beta-Zr segregation elements Cu with different contents are added into beta-Zr-Nb alloy to alloy the Zr alloy to form Zr 2 Cu second phase particles with low magnetic susceptibility so as to reduce the magnetic susceptibility of the Zr alloy. The magnetic susceptibility of the alloy is evaluated according to an empirical formula χ m=χβVβ+χZr2CuVZr2Cu, and the volume of Zr 2 Cu in the alloy is increased by increasing the content of Cu element in the alloy, so that the magnetic susceptibility of the alloy is reduced.
The technical scheme of the invention has the following beneficial effects:
① The magnetic compatible beta-Zr biomedical alloy has lower magnetic susceptibility (the mass magnetic susceptibility is 0.95-1.70 multiplied by 10 -6cm3g-1, the volume magnetic susceptibility is 77-138 multiplied by 10 -6) and simultaneously ensures lower elastic modulus (68.8-82.9 GPa) so as to match human tissues during MRI diagnosis; ② The magnetic compatible beta-Zr biomedical alloy has the advantages that all alloy elements selected by the magnetic compatible beta-Zr biomedical alloy are non-cytotoxic elements, so that the harm to human bodies is avoided. ③ Experiments show that when the addition amount of copper element is 15wt%, the alloy has the lowest magnetic susceptibility and has the potential of becoming a medical orthopedic implant compatible with magnetism. ④ The alloy prepared by the invention can be applied to MRI with higher magnetic field, and makes up the performance deficiency of the traditional biomedical alloy in the biomedical field.
Drawings
Fig. 1 is an SEM image of the alloy of example 1 of the present invention.
Fig. 2 is an SEM image of the alloy of example 2 of the present invention.
Fig. 3 is an SEM image of the alloy of example 3 of the present invention.
Fig. 4 is an SEM image of the alloy of comparative example 1 of the present invention.
FIG. 5 shows the mass susceptibility and elastic modulus results for the alloys of examples 1-3 and comparative examples 1-3 of the present invention.
FIG. 6 shows the bulk magnetic susceptibility and elastic modulus results for the alloys of examples 1-3 and comparative examples 1-3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments for a full understanding of the objects, features, and effects of the present invention. The technical method or the device related to the invention is a conventional method or device in the field unless specifically stated. The following terms have the meanings commonly understood by those skilled in the art unless otherwise indicated.
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention.
The magnetic compatible beta-Zr biomedical alloy comprises the following chemical components in percentage by weight: 21-23% of niobium (Nb), 2.8-15.2% of copper (Cu), and the balance of zirconium (Zr) and unavoidable impurities.
The magnetic compatible beta-Zr biomedical alloy of the invention is prepared by a conventional method in the field, for example, the following method can be adopted, and the following steps are adopted:
(1) Weighing the raw materials: according to the types of alloy element components, selecting sponge zirconium, niobium blocks and copper blocks with the industrial purity of more than 99.0 weight percent as raw materials, and weighing and proportioning according to the weight percentage.
(2) Alloy smelting: smelting by adopting refractory metal suspension smelting equipment, wherein the smelting temperature is 2700-3000 ℃, the vacuum degree of the smelting equipment is regulated to be 4 multiplied by 10 -3 MPa, smelting is carried out under the protection of argon, in order to ensure the components to be uniform, the cast ingot is repeatedly turned over and remelted for at least three times, then the alloy is quenched at 950-990 ℃, the temperature is kept for 30min, and then the alloy is cooled to room temperature by water.
Zr alloys of examples 1 to 3 and comparative example 1, whose chemical compositions in weight percent are shown in table 1, were prepared according to the above method.
And detecting the magnetic susceptibility and the elastic modulus of the alloy product:
1. The magnetic susceptibility measurement method refers to GB/Z26082-2010 "method for measuring DC magnetic susceptibility (magnetic moment) of nanomaterial" and document (Suyalatu,N.Nomura,K.Oya,et al.Acta Biomaterialia 6(2010)1033-1038.Doi:10.1016/j.actbio.2009.09.013), specifically as follows: and cutting a square sample of 4 x 2mm on the cast ingot by linear cutting, adopting metallographic sand paper to clean surface oxide skin, and then placing the polished surface oxide skin in a vibrating magnetometer (VSM), wherein the magnetic field strength is 3T, and the magnetic field direction is perpendicular to a plane of 4 x 4 mm. The obtained data are subjected to linear fitting by adopting origin software, the slope of a straight line is the mass magnetic susceptibility (χ m), and the mass magnetic susceptibility (χ v) is converted into the volume magnetic susceptibility (χ v), and the formula is χ v=χm ×ρx4pi (ρ is alloy density and pi is circumference ratio).
2. The elastic modulus is measured by referring to GB/T8653-2007 test method for elastic modulus, string modulus and tangent modulus of metallic materials, and the specific measuring method is as follows: cutting square blocks with specific dimensions on an ingot by linear cutting, performing a corresponding heat treatment process, further processing by linear cutting to obtain a tensile sample, performing a tensile test by a universal tensile testing machine with an optical extensometer to obtain a stress-strain curve, and performing linear fitting to obtain a corresponding elastic modulus.
The detection results are shown in table 1.
TABLE 1 alloy proportions, magnetic susceptibility and elastic modulus of Zr-22Nb-xCu
The SEM image of the alloy sample obtained in example 1 and the selected area electron diffraction pattern of the white circle are shown in fig. 1, the white gray matrix is beta-Zr, the black particles or stripe phases in the matrix and at the grain boundary are Zr 2 Cu phases, the Zr 2 Cu phases are distributed in different forms in the grain boundary and the grain boundary, and the mass magnetic susceptibility and the elastic modulus are shown in fig. 5. The Zr-22Nb-3Cu alloy has the mass magnetic susceptibility of 1.70 multiplied by 10 - 6cm3g-1 and the elastic modulus of 68.8GPa.
The SEM image of the alloy sample obtained in example 2 is shown in fig. 2, and the selected area electron diffraction structure is the same as that in example 1, and the mass magnetic susceptibility and elastic modulus are shown in fig. 5. As Cu element increases, the volume of Zr 2 Cu phase gradually increases, and the magnetic susceptibility gradually decreases. The Zr-22Nb-6Cu alloy has the mass magnetic susceptibility of 1.39 multiplied by 10 -6cm3g-1 and the elastic modulus of 71.7GPa.
SEM images of the alloy samples obtained in example 3 are shown in fig. 3, and the selected area electron diffraction structure is the same as that in example 1, and the mass magnetic susceptibility and the elastic modulus are shown in fig. 5. As Cu element increases, the volume of Zr 2 Cu phase gradually increases, and the magnetic susceptibility gradually decreases. The Zr-22Nb-15Cu alloy has the mass magnetic susceptibility of 0.95 multiplied by 10 -6cm3g-1 and the elastic modulus of 82.9GPa.
As shown in FIG. 4, the SEM image of the alloy sample obtained in comparative example 1 shows that no Zr 2 Cu phase exists in the grain boundary and the crystal due to the small addition amount of Cu element. The mass susceptibility and elastic modulus are shown in figure 5. The Zr-22Nb-1Cu alloy has the mass magnetic susceptibility of 1.80 multiplied by 10 -6cm3g-1 and the elastic modulus of 62.5GPa. The magnetic susceptibility and the elastic modulus of comparative example 2 and comparative example 3 are shown in fig. 5 and 6. The material Ti-6Al-4V of comparative example 3 is the most widely used biological alloy at present, and as can be seen from Table 1, the alloy products of examples 1-3 have significantly lower magnetic susceptibility and elastic modulus than Ti-6Al-4V.
As can be seen from Table 1, as the copper element increases, the magnetic susceptibility gradually decreases and the elastic modulus gradually increases, because the magnetic susceptibility of the Zr 2 Cu phase generated by the copper element and the zirconium matrix is lower, but the elastic modulus is higher. The more copper element content, the larger the volume ratio of Zr 2 Cu phase in the alloy, so that the lower the magnetic susceptibility of the alloy. When the copper content reaches 15wt%, the design alloy has the lowest magnetic susceptibility than that of the alloy in comparative example 1 and the other two design alloys, about half of the copper content of 1wt% is added, and the lower elastic modulus is maintained, so that the potential of the alloy in MRI is higher.
Claims (10)
1. A magnetic compatible beta-Zr type biomedical alloy is characterized in that: the biomedical alloy comprises the following chemical components in percentage by weight: 21.0 to 23.0 percent of niobium, 2.8 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities.
2. The magnetically compatible β -Zr-type biomedical alloy according to claim 1, wherein: the biomedical alloy comprises the following chemical components in percentage by weight: 21.5 to 22.5 percent of niobium, 3.0 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities.
3. The magnetically compatible β -Zr-type biomedical alloy according to claim 2, wherein: the biomedical alloy comprises the following chemical components in percentage by weight: 21.5 to 22.5 percent of niobium, 6.0 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities; preferably 22% niobium and 6.0-15.0% copper.
4. The magnetically compatible β -Zr-type biomedical alloy according to claim 3, wherein: the biomedical alloy comprises the following chemical components in percentage by weight: 21.5 to 22.5 percent of niobium, 10.0 to 15.2 percent of copper and the balance of zirconium and unavoidable impurities; preferably 21.5 to 22.5 percent of niobium and 13.0 to 15.0 percent of copper; further preferably, the composition is 22.0% of niobium and 15.0% of copper.
5. The magnetically compatible β -Zr-type biomedical alloy according to claim 1, wherein: the biomedical alloy has the mass magnetic susceptibility of 0.95-1.70X10 -6cm3g-1, the volume magnetic susceptibility of 77-138X 10 -6 and the elastic modulus of 68.8-82.9 GPa.
6. The method for preparing a magnetic compatible β -Zr-type biomedical alloy according to any one of claims 1 to 5, comprising the steps of:
(1) Weighing the raw materials: weighing raw materials Zr, nb and Cu according to weight percentage;
(2) Alloy smelting: the smelting temperature is 2700-3000 ℃, inert gas is filled into smelting equipment to smelt the cast ingot in protective atmosphere, and then quenching is carried out to obtain the alloy.
7. The method of manufacturing according to claim 6, wherein: the raw materials are zirconium sponge, niobium block and copper block, and the purity of the raw materials is above 99.0 wt%.
8. The method of manufacturing according to claim 6, wherein: smelting by adopting refractory metal suspension smelting equipment, adjusting the vacuum degree of the smelting equipment to 4 multiplied by 10 -3 MPa, and repeatedly overturning and remelting the cast ingot for at least three times to ensure uniform components; smelting by adopting refractory metal suspension smelting equipment, wherein the smelting temperature is 2700-3000 ℃, the vacuum degree of the smelting equipment is regulated to 4 multiplied by 10 -3 MPa, smelting is carried out under the protection of argon, the cast ingot is repeatedly turned over and remelted for at least three times to ensure the components to be uniform, and then the alloy is quenched at 950-990 ℃ and then cooled to room temperature by water.
9. Use of an alloy according to any one of claims 1 to 5 for the preparation of biomedical implants.
10. The use according to claim 9, characterized in that: the biomedical implant is a human implant.
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CN118422025A (en) * | 2024-07-01 | 2024-08-02 | 汕头大学 | Plasticized wear-resistant alloy material and preparation method thereof |
CN118422025B (en) * | 2024-07-01 | 2024-10-18 | 汕头大学 | Plasticized wear-resistant alloy material and preparation method thereof |
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