CN114182151A - Degradable molybdenum-based alloy implantation material and preparation method and application thereof - Google Patents

Degradable molybdenum-based alloy implantation material and preparation method and application thereof Download PDF

Info

Publication number
CN114182151A
CN114182151A CN202111557162.1A CN202111557162A CN114182151A CN 114182151 A CN114182151 A CN 114182151A CN 202111557162 A CN202111557162 A CN 202111557162A CN 114182151 A CN114182151 A CN 114182151A
Authority
CN
China
Prior art keywords
molybdenum
alloy
molybdenum alloy
degradable
implant material
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.)
Pending
Application number
CN202111557162.1A
Other languages
Chinese (zh)
Inventor
张海军
周超
刘翠
冯相蓺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Rientech Medical Technology Co ltd
Original Assignee
Shandong Rientech Medical Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shandong Rientech Medical Technology Co ltd filed Critical Shandong Rientech Medical Technology Co ltd
Priority to CN202111557162.1A priority Critical patent/CN114182151A/en
Publication of CN114182151A publication Critical patent/CN114182151A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a degradable molybdenum-based alloy implant material and a preparation method and application thereof, which comprises 0wt% -5wt% of Re, 0wt% -5wt% of functional elements and the balance of molybdenum according to mass percentage; the method comprises the following steps: the molybdenum alloy is prepared through powder metallurgy, the size of alloy crystal grains is reduced through plastic deformation such as hot rolling, hot extrusion, hot drawing and the like, and a molybdenum alloy bracket is prepared by combining a corresponding annealing process, so that the mechanical property of the molybdenum alloy is comprehensively improved, the degradation uniformity and the degradation rate of the molybdenum alloy are controlled, and the application effect of the molybdenum alloy as an implant material is improved; the molybdenum alloy plate or foil and the molybdenum alloy stent prepared by the method have excellent mechanical property and moderate degradation rate, and can be applied to stents (blood vessels, urethral tubes, esophageal stents and the like) and orthopedic fixture devices (bone nails, thin bone plates and the like).

Description

Degradable molybdenum-based alloy implantation material and preparation method and application thereof
Technical Field
The invention relates to the field of medical implant materials, in particular to a degradable molybdenum-based alloy implant material and a preparation method and application thereof.
Background
The biodegradable metal serving as a novel biomedical implant material can provide enough mechanical support for an injured part in the early stage, and is degraded and absorbed by an organism at a proper rate along with the healing of tissues on the premise of not generating toxic and side effects; the degradable metal implant material should have: the mechanical property is excellent, the degradation rate is proper, and the biocompatibility is good; two promising applications for biodegradable metals are stent fabrication (thin walled tubes: blood vessels, urethral tubes, esophagus, etc.) and orthopedic fixation devices (bone screws, bone plates, etc.).
The most researched degradable metal iron-based alloy, magnesium-based alloy, zinc-based alloy and the like at present have defects in the aspects of corrosion rate and mechanical property, and the clinical application of biodegradable metal is restricted; the magnesium-based alloy has over-high degradation rate and uneven degradation mode in vivo, has low mechanical property and generates hydrogen in the degradation process; the iron-based alloy has good biocompatibility, but the degradation rate in vivo is too slow, and the iron has magnetism to influence some imaging detection (MRI and the like); the zinc-based alloy has moderate degradation rate but poor mechanical property, and the research on the degradable metal is still in the clinical stage basically.
Molybdenum has rarely been studied as a candidate degradable metal element; molybdenum is a trace element necessary for human bodies, the content of molybdenum in adult bodies is about 9mg, and the impurity levels of molybdenum in oral and parenteral medicines allowed by United states pharmacopoeia are 3mg/d and 1.5mg/d respectively; molybdenum can maintain myocardial energy metabolism, prevent keshan disease, maintain elasticity of artery, prevent cardiovascular disease, etc.; pure molybdenum shows uniform degradation behavior in a simulated physiological solution (C-SBF-Ca, pH = 7.4), the corrosion rate is about 10 μm/year, and the degradation rate meeting the requirements of the vascular stent is less than 20 μm/year; the pure molybdenum has good biocompatibility, and molybdenum ions generated by the degradation of the pure molybdenum stent can not trigger the apoptosis or necrosis of human endothelial cells or smooth muscle cells and can be implanted into the vascular wall; molybdenum is not magnetic, is suitable for Magnetic Resonance Imaging (MRI), and has great advantages in clinical implants; when the wall thickness of the alloy stent is less than 100 mu m, the degradation mode of the stent after endothelialization is uniform degradation, which requires that the alloy has good stent processability, currently, degradable metals can be rarely processed into thin-walled tubes, and the molybdenum alloy has the potential of thin-walled tube forming; the processed molybdenum alloy has great potential in orthopedics, the appearance can be designed according to the specific bone structure of a patient without generating cracks, and a small-sized high-strength implant can be designed and manufactured, so that the invasion to the surrounding bone tissue is reduced, meanwhile, the outward protrusion is avoided, and the natural shape of the bone is better fused.
The pure molybdenum has room temperature brittleness and is not beneficial to material processing, the low strength and ductility of the pure molybdenum are always the bottleneck for limiting the application of the pure molybdenum, the alloy structure can be improved through alloying and plastic deformation, the mechanical property of the molybdenum alloy is further improved, and the material processing and forming are facilitated; the molybdenum alloy is classified into low-content solid solution strengthening alloy (namely MO-Ti and Mo-ZrO)2) Continuous solid solution strengthening alloy (Mo-W, Mo-Re), carbide dispersion strengthening alloy (including TZM and TZC series alloy), rare earth oxide dispersion strengthening alloy (including Mo-La)2O3、Mo-Y2O3) Etc.; at present, the research on molybdenum alloy as an implant material is relatively few, and documents and patent reports that binary and ternary molybdenum alloys are applied to the field of degradable biomedical materials are lacked.
Therefore, the ideal molybdenum alloy material for adapting to different implantation requirements of human body is the focus of research in the field, including stents (blood vessels, urethral tubes, esophageal stents, etc.) and orthopedic fixation devices (bone nails, bone plates, etc.).
Disclosure of Invention
The invention aims to provide a degradable molybdenum-based alloy implant material on the one hand and a preparation method and application of the degradable molybdenum-based alloy implant material on the other hand, aiming at the feasibility of the existing degradable alloy.
In order to achieve the purpose, the technical scheme of the degradable molybdenum-based alloy implant material is as follows.
A degradable molybdenum-based alloy implant material comprises, by mass, 0wt% -5wt% of Re, 0wt% -5wt% of functional elements and the balance of molybdenum, and preferably comprises 0.5wt% -5wt% of Re and the balance of molybdenum.
A degradable molybdenum-base alloy implant material, the function of which isThe element includes but is not limited to one or more of Cu, W, Zr, Y and La, wherein Zr, Y and La are ZrO2、Y2O3And La2O3Exists in the form of (1); preferably, 0.5 to 5wt% Re, 0.1 to 1wt% Cu, 0.1 to 0.5wt% W, 0.1 to 0.5wt% Zr, 0.1 to 1wt% Y2O3、0.1wt%-1 wt% La2O3。
The purities of Mo, Re and the functional elements are more than 99.99 percent, and the content of C, O, N impurity elements is less than or equal to 0.01 percent.
Re is introduced as a component of the molybdenum-based alloy material, can greatly reduce the plastic-brittle transition temperature of molybdenum and improve the room-temperature plasticity and strength of the molybdenum, belongs to a solid solution strengthening type alloy, and Mo-Re is proved to be harmless to human health.
The molybdenum and the copper are non-magnetic, and the Cu is introduced as a component to reduce the higher hardness of the pure molybdenum, increase the plasticity of the molybdenum alloy and facilitate the machining into a complex shape; degradation product of copper, Cu2+Has certain antibacterial property, is beneficial to the proliferation of vascular endothelial cells, and is suitable for the vascular stent material.
W is easy to form a substitutional solid solution with molybdenum, and the strengthening mechanism is solid solution strengthening; tungstate ions have very low cytotoxicity on endothelial cells, smooth muscle cells and fibroblasts.
La is introduced as a component of the molybdenum-based alloy material, La existing in the molybdenum matrix2O3The particles can form second phase dispersed particles in the crystal or in the crystal boundary, refine the crystal structure, purify the crystal boundary and improve the strength and the toughness of the molybdenum alloy.
Y is introduced as a component of the molybdenum-based alloy material, Y2O3As the melting point of the second phase is close to that of pure molybdenum, dispersed particles of the second phase can be formed in the crystal or in the crystal boundary, the pinning effect on dislocation is formed in the plastic deformation process, the toughness is improved, and meanwhile, the second phase particles are combined with harmful elements such as O, N and the like in the crystal boundary to form the second phase particles, so that the effect of purifying the crystal boundary is achieved, and the comprehensive mechanical property of the alloy is improved.
The trace element Zr is introduced as the component of the molybdenum-based alloy material, and can perform obvious dispersion strengthening and solid solution strengthening on molybdenumEffect of ZrO2The high-temperature molybdenum alloy absorbs a large amount of O, H, N and other elements in the heating process, can effectively improve the room-temperature brittleness of the sintered molybdenum alloy, is beneficial to the processing and forming of the molybdenum alloy, and in addition, Zr element is proved to be harmless to human bodies and is a beneficial element when being added as an alloy element.
At present, pure molybdenum has room temperature brittleness and is not beneficial to material processing; meanwhile, the molybdenum alloy has less data as an implant material and is not applied to degradable binary and ternary molybdenum alloy materials. The processing performance of the molybdenum alloy can be improved by adding alloy elements and carrying out plastic deformation, so that the molybdenum alloy has the characteristics of good mechanical property and uniform corrosion.
The invention provides a degradable molybdenum-based alloy implant material, which is prepared by adding Re and one or more of functional elements Cu, W, Zr, Y and La in pure molybdenum to prepare binary and ternary molybdenum alloys, wherein Zr, Y and La are respectively ZrO2、Y2O3、La2O3Is added in the form of (1); the molybdenum alloy obtained through plastic deformation has good mechanical property, uniform degradation and moderate corrosion rate, and has good application prospect when being used as a degradable metal implant material.
The technical scheme of the preparation method of the degradable molybdenum-based alloy implant material provided by the invention is as follows:
a preparation method and application of a degradable molybdenum-based alloy implant material comprise the following steps:
1. preparing a molybdenum alloy ingot through powder metallurgy (sequentially carrying out powder mixing, pressing and sintering), and obtaining a smooth molybdenum alloy ingot through rough turning;
2. annealing the optical molybdenum alloy ingot to eliminate alloy residual stress to obtain a molybdenum alloy ingot;
3. roughly turning the molybdenum alloy ingot obtained in the step 2 into a plate, and carrying out multi-pass hot rolling and annealing treatment to obtain a molybdenum alloy rolled plate or foil which can be used for orthopedic implantation (bone nails, thin bone plates and the like);
4. and (3) carrying out hot extrusion and annealing treatment on the molybdenum alloy ingot obtained in the step (2) to obtain a molybdenum alloy pipe, and carrying out hot drawing with a mandrel to finally obtain the thin-wall molybdenum alloy pipe which can be used for blood vessels, urethral tubes, esophagus and other stents to solve the problems of narrow tube cavity and the like.
According to the preparation method of the degradable molybdenum-based alloy implant material, the alloy strengthening is carried out by alloying addition of alloy elements, the grain size is refined by combining plastic deformation such as hot rolling, hot extrusion, hot drawing and the like, and corresponding annealing treatment is carried out, so that the mechanical property of the molybdenum alloy is comprehensively improved, the degradation uniformity and the degradation rate are controlled, and the application effect of the molybdenum alloy as the implant material is improved.
In order to further prepare molybdenum alloy and optimize the alloying effect, molybdenum powder with higher purity and small particle size is selected as a raw material in the powder metallurgy in the step 1, and the molybdenum powder and other element powder are mixed for 4 hours by using a mixer to obtain uniformly mixed alloy powder; performing cold isostatic pressing treatment to obtain a pressed blank, wherein the pressure is 150-300 MPa, and the pressure maintaining time is 10-30 min; sintering treatment is carried out in a hydrogen atmosphere, the sintering temperature is 1200-2300 ℃, and the heat preservation time is 1-5 h; roughly turning to obtain a smooth molybdenum alloy ingot with the diameter of 25mm and the height of 20 mm.
In order to further enhance the plasticity of the molybdenum alloy, annealing treatment is carried out in the step 2, and heat preservation is carried out for 10-120min at the temperature of 800-1600 ℃.
In order to further refine the crystal grains to obtain a molybdenum alloy plate, in step 3, a molybdenum alloy cast ingot is roughly turned into a plate with the wall thickness of 10mm and the length of 20 mm; the rolling heating temperature is 700-1300 ℃, and the heating time is 10-120 min; and (3) carrying out 6-15-pass rolling, wherein the pass reduction rate of single-pass deformation is 10-20%, the total reduction amount is 80-96%, and annealing is carried out once every two passes (keeping the temperature at 800-1500 ℃ for 10-120 min) to obtain the molybdenum alloy rolled plate or foil with the thickness of 0.2-2 mm.
In order to further refine the crystal grains to obtain the molybdenum alloy pipe, in the step 4, the extrusion heating temperature is 700-1300 ℃, the extrusion ratio is 22: 1; then annealing (keeping the temperature at 800-1500 ℃ for 10-120 min) to obtain the molybdenum alloy pipe with the outer diameter of 8mm and the wall thickness of 1 mm.
In order to further refine the crystal grains to obtain the molybdenum alloy pipe, in the step 4, multi-pass hot drawing is adopted, the heating temperature is 700-1400 ℃, the drawing speed is 1-5 mm/s, the pass processing deformation is 5-20%, and when the deformation is more than 50%, annealing treatment is carried out in each pass (heat preservation is carried out for 10-120min at 800-1500 ℃), and finally the thin-wall molybdenum alloy pipe with the outer diameter of 2.5mm and the wall thickness of 0.2mm is obtained.
The corrosion rate of the molybdenum alloy plate or foil and the molybdenum alloy bracket prepared by the invention in simulated body fluid is 8-15 mu m/year.
Compared with the prior art, the degradable molybdenum-based alloy implant material and the preparation method and application thereof have the beneficial effects that:
(1) the invention provides a degradable molybdenum-based alloy for an implant material, which has the effects of solid solution strengthening and dispersion strengthening on molybdenum through alloy elements, so that the plastic-brittle transition temperature of pure molybdenum is substantially reduced, and the room-temperature plasticity and strength of the molybdenum alloy are improved;
(2) the invention combines large plastic deformation modes such as hot rolling, hot extrusion, hot drawing and the like to refine the grain size of the molybdenum alloy, and carries out corresponding annealing process, thereby comprehensively improving the mechanical property of the molybdenum alloy and controlling the degradation uniformity and the degradation rate of the molybdenum alloy, and further improving the application effect of the molybdenum alloy as an implant material;
(3) the molybdenum alloy rolled plate or foil prepared by the invention can be used for orthopedic implantation (bone nails, thin bone plates and the like) through processing; the thin-wall molybdenum alloy pipe can be used for stents such as blood vessels, urethral tubes, esophagus and the like by processing so as to solve the problems of narrow tube cavity and the like;
(4) the molybdenum alloy prepared by the method is uniform in degradation, moderate in corrosion rate and good in biocompatibility.
Drawings
FIG. 1 is a schematic process flow diagram of a method for preparing a molybdenum-based alloy implant material according to the present invention.
Detailed Description
The degradable molybdenum-based alloy implant material provided by the invention comprises, by mass, 0wt% -5wt% of Re, 0wt% -5wt% of functional elements and the balance of molybdenum, and preferably comprises 0.5wt% -5wt% of Re and the balance of molybdenum; the functional elements can be selected from one or more of Cu, W, Zr, Y and La to prepare binary and ternary molybdenum alloys, wherein Zr, Y and La are respectively ZrO2、Y2O3、La2O3Shape ofIs added, preferably, 0.1wt% to 1wt% of Cu, 0.1wt% to 0.5wt% of W, 0.1wt% to 0.5wt% of Zr, 0.1wt% to 1wt% of Y2O3、0.1wt%-1 wt% La2O3。
The invention provides a preparation method and application of a degradable molybdenum-based alloy implant material, wherein a molybdenum alloy rolling plate or foil and a thin-wall molybdenum alloy pipe are obtained by combining powder metallurgy with large plastic deformation modes such as hot rolling, hot extrusion, hot drawing and the like and corresponding annealing processes.
The following examples test corrosion rates the solutions used were SBF solutions with the following composition: na (Na)+(142mmol/L)、K+(5.0mmol/L)、Ca2+(2.5mmol/L)、Mg2+(1.5mmol/L)、Cl-(103.0mmol/L)、HCO3 -(27.0mmol/L)、HPO4 2-(1.0mmol/L)、SO4 2-(0.5 mmol/L); the soaking time is 7 days.
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the scope of the present invention.
Example 1: Mo-Re alloy
The degradable Mo-Re alloy of the embodiment is prepared by the following steps:
(1) mixing 3wt% Re and 97wt% Mo powder with the purity of 99.99% for 4h by a mixer according to mass percentage; performing cold isostatic pressing treatment at the pressure of 250MPa for 20min to obtain a Mo-3wt% Re alloy compact; sintering in hydrogen atmosphere at 2100-2200 ℃ for 2 h; roughly turning to obtain a smooth molybdenum alloy ingot with the diameter of 25mm and the height of 20 mm;
(2) in order to further enhance the plasticity of the molybdenum alloy, annealing the Mo-3wt% Re optical molybdenum alloy cast ingot, and keeping the temperature of 1450-1600 ℃ for 120 min;
(3) and (3) extruding the cast ingot for further refining the crystal grains, wherein the extrusion heating temperature is 1200 ℃, and the extrusion ratio is 22: 1, obtaining a pipe with the outer diameter of 8mm and the wall thickness of 1 mm; annealing (keeping the temperature at 1450-1600 ℃ for 120 min) to obtain a Mo-3wt% Re molybdenum alloy pipe;
(4) in order to obtain the thin-wall molybdenum alloy pipe, the molybdenum alloy pipe is subjected to multi-pass hot drawing at the heating temperature of 1200 ℃, the drawing speed is 5mm/s, the pass processing deformation is 5% -20%, and when the deformation is more than 50%, each pass is subjected to annealing treatment (the temperature is kept at 1450-1600 ℃ for 120 min), so that the thin-wall molybdenum alloy pipe with the outer diameter of 2.5mm and the wall thickness of 0.2mm is finally obtained.
Example 2: Mo-W-Cu alloy
The degradable Mo-W-Cu alloy of the embodiment is prepared by the following steps:
(1) mixing 1wt% Cu with the purity of 99.99%, 0.1wt% W and 98.9wt% Mo powder for 4h by a mixer according to mass percentage; performing cold isostatic pressing treatment at the pressure of 200MPa for 20min to obtain a molybdenum alloy green compact; sintering in hydrogen atmosphere at 1200-1400 deg.c for 1.5 hr; roughly turning to obtain a smooth molybdenum alloy ingot with the diameter of 25mm and the height of 20 mm;
(2) annealing the optical molybdenum alloy cast ingot, and keeping the temperature of 800-900 ℃ for 30 min;
(3) extruding the alloy cast ingot, wherein the heating temperature is 800 ℃, and the extrusion ratio is 22: 1, annealing (keeping the temperature at 800-900 ℃ for 30 min) to obtain a molybdenum alloy pipe with the outer diameter of 8mm and the wall thickness of 1 mm;
(4) and (3) carrying out multi-pass hot drawing on the molybdenum alloy pipe, wherein the heating temperature is 800 ℃, the drawing speed is 4mm/s, the pass processing deformation is 10-20%, and when the deformation is more than 50%, annealing treatment (heat preservation is carried out for 30min at 800-900 ℃) is carried out on each pass, so that the thin-wall molybdenum alloy pipe with the outer diameter of 2.5mm and the wall thickness of 0.2mm is finally obtained.
Example 3: Mo-La2O3Alloy (I)
Degradable Mo-La of the embodiment2O3The alloy is prepared by the following steps:
(1) according to the mass percentage, 0.5wt% of La with the purity of 99.99 percent is added2O3And 99.5wt% of Mo powder are mixed for 4 hours by a mixer; performing cold isostatic pressing treatment at 250MPa for 10min to obtain Mo-0.5wt% La2O3Alloy green compacts; sintering in hydrogen atmosphere at 2000 deg.c for 4 hr; roughly turning to obtain a smooth molybdenum alloy ingot with the diameter of 25mm and the height of 20 mm;
(2) to Mo-0.5wt%La2O3Annealing the optical molybdenum alloy cast ingot, and keeping the temperature at 1400-1550 ℃ for 30 min;
(3) roughly turning a molybdenum alloy ingot into a plate with the wall thickness of 10mm and the length of 20 mm; the rolling heating temperature is 1000 ℃, and the heating time is 30 min; rolling for 6-15 times, wherein the pass reduction rate of single-pass deformation is 15-20%, the total reduction is 80-96%, and annealing is carried out once every two times (heat preservation is carried out for 30min at 1400-1550 ℃) to obtain Mo-0.5wt% La with the thickness of 0.2-2mm2O3Rolling the molybdenum alloy into plate or foil.
Example 4: Mo-Y2O3Alloy (I)
Degradable Mo-Y of the example2O3The alloy is prepared by the following steps:
(1) according to the mass percentage, 0.4wt% of Y with the purity of 99.99 percent is added2O3And 99.6wt% of Mo powder are mixed for 4 hours by a mixer; performing cold isostatic pressing treatment at 250MPa for 15min to obtain Mo-0.4wt% Y2O3Alloy green compacts; sintering in hydrogen atmosphere (1950 ℃, and keeping the temperature for 5 hours); roughly turning to obtain a smooth molybdenum alloy ingot with the diameter of 25mm and the height of 20 mm;
(2) for Mo-0.4wt% Y2O3Annealing the optical molybdenum alloy cast ingot, and keeping the temperature of 1500-1600 ℃ for 60 min;
(3) roughly turning a molybdenum alloy ingot into a plate with the wall thickness of 10mm and the length of 20 mm; the rolling heating temperature is 950 ℃, and the heating time is 30 min; rolling for 6-15 times, wherein the pass reduction rate of single-pass deformation is 10-15%, the total reduction is 80-96%, and annealing is carried out once every two times (the temperature is kept at 1500-1600 ℃ for 60 min) to obtain Mo-0.4wt% Y with the thickness of 0.2-2mm2O3Rolling the molybdenum alloy into plate or foil.
Example 5: Mo-Re-Zr alloy
The degradable Mo-Re-Zr alloy of the embodiment is prepared by the following steps:
(1) according to the mass percentage, 0.5wt% Re and 0.5wt% ZrO with the purity of 99.99 percent are mixed2Mixing 99wt% of Mo powder for 4 hours by a mixer; performing cold isostatic pressing treatment at the pressure of 300MPa for 30min to obtain an alloy pressed blank; sintering in hydrogen atmosphere at a sintering temperature1900-; roughly turning to obtain a smooth molybdenum alloy ingot with the diameter of 25mm and the height of 20 mm;
(2) annealing the photo-molybdenum alloy ingot, and keeping the temperature of 1450-1500 ℃ for 30 min;
(3) extruding the alloy cast ingot, wherein the heating temperature is 1000 ℃, and the extrusion ratio is 22: 1, obtaining a pipe with the outer diameter of 8mm and the wall thickness of 1 mm; annealing (keeping the temperature at 1450-1500 ℃ for 30 min) to obtain a molybdenum alloy pipe;
(4) the molybdenum alloy pipe is subjected to multi-pass hot drawing, the heating temperature is 1000 ℃, the drawing speed is 3mm/s, the pass processing deformation is 10% -15%, and when the deformation is more than 50%, each pass is subjected to annealing treatment (the temperature is kept at 1450-1500 ℃ for 30 min), and finally the thin-wall molybdenum alloy pipe with the outer diameter of 2.5mm and the wall thickness of 0.2mm is obtained.
Example 6: the mechanical properties and corrosion performance in SBF solutions (7 days of immersion) are shown for examples 1-5;
Figure 856732DEST_PATH_IMAGE001
the degradable molybdenum alloy rolled plate or foil and thin-wall molybdenum alloy pipe has the corrosion rate of 8-15 mu m/year in simulated body fluid (SBF solution, soaking for 7 days), the yield strength of 800MPa for 550-.

Claims (8)

1. A degradable molybdenum-based alloy implant material and a preparation method and application thereof are characterized by being carried out according to the following technical scheme:
(1) a degradable molybdenum-based alloy implant material comprises 0wt% -5wt% of Re, 0wt% -5wt% of functional elements and the balance of molybdenum according to mass percentage, preferably 0.5wt% -5wt% of Re and the balance of molybdenum;
(2) the preparation process of the molybdenum alloy comprises the following steps:
the method comprises the following steps of: mixing, pressing and sintering the powder to prepare a molybdenum alloy ingot, and performing rough turning to obtain a smooth molybdenum alloy ingot;
annealing the optical molybdenum alloy ingot to eliminate alloy residual stress to obtain a molybdenum alloy ingot;
preparing a molybdenum alloy rolled plate or foil: roughly turning the molybdenum alloy ingot into a plate, and carrying out hot rolling and corresponding annealing treatment to obtain a molybdenum alloy rolled plate or foil with the thickness of 0.2-2 mm;
preparing a thin-wall molybdenum alloy pipe: and carrying out hot extrusion and hot drawing on the molybdenum alloy cast ingot and carrying out corresponding annealing treatment to obtain the thin-wall molybdenum alloy pipe with the outer diameter of 2.5mm and the wall thickness of 0.2 mm.
2. The degradable molybdenum-based alloy implant material as well as the preparation method and the application thereof according to claim 1, wherein the specific process parameters of the powder metallurgy are as follows: mixing the powder, namely mixing molybdenum powder and other element powder for 4 hours by using a mixer to obtain uniformly mixed alloy powder; the pressing adopts cold isostatic pressing, the pressure is 150-300 MPa, and the pressure maintaining time is 10-30 min; the sintering treatment is carried out in a hydrogen atmosphere, the sintering temperature is 1200-2300 ℃, and the heat preservation time is 1-5 h.
3. The degradable molybdenum-based alloy implant material as well as the preparation method and the application thereof according to claim 1, wherein the annealing process is carried out at 800-1600 ℃ for 10-120 min.
4. The degradable molybdenum-based alloy implant material as well as the preparation method and the application thereof according to claim 1 are characterized in that the parameters of the process for preparing the molybdenum alloy rolled plate or foil are as follows: firstly, roughly turning a molybdenum alloy ingot into a plate with the wall thickness of 10mm and the length of 20 mm; and (3) rolling and heating at 700-1300 ℃ for 10-120min, carrying out 6-15 times of hot rolling, wherein the pass reduction rate of single-pass deformation is 10-20%, the total reduction amount is 80-96%, and annealing is carried out every two times to obtain a molybdenum alloy rolled plate or foil with the thickness of 0.2-2 mm.
5. The degradable molybdenum-based alloy implant material as well as the preparation method and the application thereof according to claim 1 are characterized in that the parameters of the process for preparing the thin-wall molybdenum alloy pipe are as follows: firstly, obtaining a molybdenum alloy pipe with the outer diameter of 8mm and the wall thickness of 1mm by a hot extrusion and annealing process, wherein the heating temperature is 700-1300 ℃, and the extrusion ratio is 22: 1; and then obtaining a thin-wall molybdenum alloy pipe with the outer diameter of 2.5mm and the wall thickness of 0.2mm through a hot drawing and annealing process, and carrying out annealing treatment (keeping the temperature at 800-1500 ℃ for 10-120 min) in each pass when the multi-pass hot drawing is adopted, the heating temperature is 700-1400 ℃, the drawing speed is 1-5 mm/s, the pass processing deformation is 5-20%, and the deformation is more than 50%.
6. The degradable molybdenum-based alloy implant material as well as the preparation method and the application thereof according to claim 1, wherein the prepared molybdenum alloy plate or foil and molybdenum alloy stent are applied to stents (blood vessels, ureters, esophageal stents, etc.) and orthopedic fixture devices (bone nails, thin bone plates, etc.).
7. The degradable molybdenum-based alloy implant material as well as the preparation method and the application thereof as claimed in claim 1, characterized in that the corrosion rate of the prepared molybdenum alloy plate or foil and molybdenum alloy stent in simulated body fluid is 8-15 μm/year.
8. The degradable molybdenum-based alloy implant material as well as the preparation method and the application thereof as claimed in claim 1, wherein the yield strength of the prepared molybdenum alloy plate or foil and the molybdenum alloy bracket is 550-800MPa, the tensile strength is 650-900MPa, and the elongation is 12-35%.
CN202111557162.1A 2021-12-18 2021-12-18 Degradable molybdenum-based alloy implantation material and preparation method and application thereof Pending CN114182151A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111557162.1A CN114182151A (en) 2021-12-18 2021-12-18 Degradable molybdenum-based alloy implantation material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111557162.1A CN114182151A (en) 2021-12-18 2021-12-18 Degradable molybdenum-based alloy implantation material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114182151A true CN114182151A (en) 2022-03-15

Family

ID=80544466

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111557162.1A Pending CN114182151A (en) 2021-12-18 2021-12-18 Degradable molybdenum-based alloy implantation material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114182151A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116251240A (en) * 2023-02-06 2023-06-13 广东省人民医院 Thin-wall absorbable implantation instrument and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116251240A (en) * 2023-02-06 2023-06-13 广东省人民医院 Thin-wall absorbable implantation instrument and preparation method thereof

Similar Documents

Publication Publication Date Title
Ma et al. Research progress of titanium-based high entropy alloy: methods, properties, and applications
CN111020295B (en) High-performance biodegradable Zn-Cu-Li-X alloy and preparation and application methods thereof
CN101921929B (en) Medicinal oxygen-containing beta titanium alloy for orthopedic implantation and preparation method thereof
Narushima New-generation metallic biomaterials
Li et al. Fabrication of biomedical Ti-24Nb-4Zr-8Sn alloy with high strength and low elastic modulus by powder metallurgy
CN111187943A (en) Biomedical Zn-Cu-Mg alloy and preparation method thereof
CN109097629A (en) A kind of biodegradable Zn-Mo system kirsite and preparation method thereof
Yu et al. Designation and development of biomedical Ti alloys with finer biomechanical compatibility in long-term surgical implants
CN103028149B (en) Medical degradable Fe-Mg binary alloy material and preparation method thereof
CN110317973B (en) Biodegradable LiZn4-Zn complex phase material and preparation method thereof
CN108486408A (en) A kind of low elastic modulus dental filling beta titanium alloy and its manufacturing method
CN113234983B (en) NbTaTiZr double-equal atomic ratio high-entropy alloy and preparation method thereof
CN113481408B (en) Powder metallurgy Ti-Zr alloy for dentistry and preparation method thereof
CN108950336B (en) High-plasticity degradable biomedical Mg-Zn-Zr-Ca-Fe alloy material and preparation method thereof
CN111331128A (en) Method for preparing zinc alloy degradable material by sintering metal powder
CN114182151A (en) Degradable molybdenum-based alloy implantation material and preparation method and application thereof
Wang et al. Progress in partially degradable titanium-magnesium composites used as biomedical implants
Xie et al. Ti-10Mo/Hydroxyapatite composites for orthopedic applications: Microstructure, mechanical properties and biological activity
CN104831136A (en) Medical magnesium-based alloy material and preparation method thereof
CN111187965B (en) FeMn biodegradable alloy and preparation method thereof
CN117737548A (en) High-ductility cobalt-chromium-based alloy for biomedical capillary and preparation method thereof
CN108642359B (en) High-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material and preparation method thereof
Sa'aidi et al. Influence of processing parameters on dehydrogenation of TiH2 in the preparation of Ti–Nb: A review
CN114561579A (en) Biodegradable magnesium alloy without rare earth elements and preparation method and application thereof
CN110106413B (en) Mg-Si-Ca-Zn magnesium alloy and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
CB03 Change of inventor or designer information

Inventor after: Zhang Haijun

Inventor after: Zhou Chao

Inventor before: Zhang Haijun

Inventor before: Zhou Chao

Inventor before: Liu Cui

Inventor before: Feng Xiangsan

CB03 Change of inventor or designer information
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination