CN115069957B - A processing method for medical titanium alloy coronary artery drug-coated stent - Google Patents
A processing method for medical titanium alloy coronary artery drug-coated stent Download PDFInfo
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- 239000003814 drug Substances 0.000 title claims abstract description 60
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- 238000003672 processing method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- 238000000576 coating method Methods 0.000 claims abstract description 43
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- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
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- 238000005097 cold rolling Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000005498 polishing Methods 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 20
- 238000010622 cold drawing Methods 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- 238000003723 Smelting Methods 0.000 claims description 30
- 229910010389 TiMn Inorganic materials 0.000 claims description 30
- 238000005242 forging Methods 0.000 claims description 26
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 21
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- 238000001816 cooling Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 210000005077 saccule Anatomy 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/04—Hollow or tubular parts of organs, e.g. bladders, tracheae, bronchi or bile ducts
- A61F2/06—Blood vessels
- A61F2/07—Stent-grafts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2002/823—Stents, different from stent-grafts, adapted to cover an aneurysm
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Biomedical Technology (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Transplantation (AREA)
- Cardiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Pulmonology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Gastroenterology & Hepatology (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
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Abstract
The invention belongs to the technical field of cardiovascular stent processing, and relates to a processing method of a medical titanium alloy coronary artery drug coating stent. The titanium alloy comprises the following chemical components in percentage by mass of 5.0% -14.0% of Mn, less than or equal to 0.30% of Fe, less than or equal to 0.16% of O, less than or equal to 0.01% of N, less than or equal to 0.001% of H and the balance of Ti. The invention adopts a vacuum consumable arc furnace to smelt alloy cast ingots, forges and hot-rolls to prepare titanium alloy bars, then prepares finished titanium alloy capillaries through mechanical perforation, peeling, centerless grinding, cold rolling, cold drawing and straightening, and prepares metal brackets through microsecond optical fiber laser engraving, vacuum heat treatment, electrochemical polishing and other procedures. And then spraying the drug solution on the outer surface of the metal stent by using a spraying machine, and airing in a clean environment, thereby preparing the titanium alloy coronary artery drug coating stent.
Description
Technical Field
The invention belongs to the technical field of cardiovascular stent processing, and particularly relates to a processing method of a medical titanium alloy coronary artery drug coated stent, which is particularly suitable for a TiMn alloy coronary artery drug coated stent.
Background
Currently, coronary stents are typically made from 316L stainless steel (nominal composition: 00Cr17Ni12Mo 2), niTi alloy (nominal composition: ni55.8Ti), L605 cobalt alloy (nominal composition: co20Cr15W10 Ni) and MP35N cobalt alloy (nominal composition: co35Ni20Cr10 Mo). However, these alloys all contain Cr and Ni elements, and although they exist as metal compounds and are protected by surface passivation protective films, there is still a risk of ion precipitation of harmful elements after the metals are implanted into the human body, and it is necessary to evaluate corrosion resistance and biocompatibility of these materials in the human body environment for a long period of time. Searching a coronary stent metal material, solving the problem of precipitation risk of harmful element ions existing in the existing metal material and becoming the research front of material disciplines and medicine.
Disclosure of Invention
The invention provides a processing method of a TiMn medical titanium alloy coronary artery drug coating stent, which solves the problem that harmful metal ions are separated out and damage the health of patients due to the influence of corrosive media after the stent is implanted into a human body.
In order to solve the technical problems, the invention specifically provides the following technical scheme.
A medical titanium alloy coronary artery drug coating stent comprises the following chemical components, by mass, 5.0% -14.0% of Mn, less than or equal to 0.30% of Fe, less than or equal to 0.16% of O, less than or equal to 0.01% of N, less than or equal to 0.001% of H, and the balance of Ti.
The invention adopts a vacuum consumable arc furnace to smelt alloy cast ingots, then processes such as forging, hot rolling and the like are carried out to prepare titanium alloy bars, then the final finished titanium alloy capillary is prepared through mechanical perforation, peeling, centerless grinding, cold rolling, cold drawing and straightening, and finally the finished metal bracket is prepared through processes such as microsecond optical fiber laser engraving, vacuum heat treatment, electrochemical polishing and the like. And then mixing polylactic acid-glycolic acid copolymer (PLGA) and rapamycin according to a proportion to form a solution, uniformly spraying the drug solution on the outer surface of the metal stent by using a spraying machine, airing in a clean environment, and finally conveying the balloon to a proper position of the stent by using special press-holding machine equipment to prepare the titanium alloy coronary artery drug coating stent.
A processing method of a medical titanium alloy coronary artery drug coating stent specifically comprises the following steps:
firstly, preparing a titanium alloy cast ingot by adopting vacuum consumable smelting;
step two, forging by adopting a quick forging machine and a precision forging machine;
Step three, hot rolling is carried out by adopting a horizontal rolling mill, and a rough bar blank with proper size is prepared;
Step four, obtaining a rough tube blank after machining by adopting mechanical drilling, and improving the surface roughness by peeling and centerless grinding;
step five, cold rolling is carried out by a cold rolling mill, and a thin tube blank is obtained after repeated annealing treatment in the middle;
step six, drawing deformation of the tube blank is carried out by adopting drawing equipment, and a capillary tube blank is obtained;
step seven, straightening the wire by adopting a slide block straightener;
step eight, carving a coronary artery stent blank by adopting microsecond fiber laser;
step nine, carrying out vacuum heat treatment on the bracket blank;
step ten, carrying out electrochemical polishing on the bracket blank to prepare a finished metal bracket;
Step eleven, preparing a drug solution of polylactic acid-glycolic acid copolymer (PLGA) and rapamycin;
and twelve, uniformly spraying the drug solution on the outer surface of the metal stent by using a spraying machine, airing in a clean environment, and conveying the balloon to a proper position of the stent by using special press-holding machine equipment to prepare the titanium alloy coronary artery drug coating stent.
In the first step, titanium sponge, metal Mn, metal Fe and a compound TiO 2 are required to be adopted, the ingredients are mixed according to the titanium alloy components, three times of vacuum self-consumption smelting are adopted, argon is filled in the smelting process, the argon filling pressure is 5000-10000 Pa in the primary smelting process, and the argon filling pressure is 20000-30000 Pa in the secondary and tertiary smelting processes, so that the TiMn titanium alloy cast ingot is obtained.
In the second step, cogging forging is required to be carried out at 1000-1100 ℃, finish forging is required to be carried out at 800-950 ℃, the heat preservation time is controlled to be 1-6 h, and the deformation amount per fire is not less than 60%.
In the third step, the rolling temperature is controlled to be 750-850 ℃, the heat preservation time is controlled to be 1-2 hours, and the deformation of each pass is controlled to be within 15%.
In the fourth step, firstly, the rolled bar blank is machined to be of a proper length, then, a precise drilling process is adopted to prepare the rolled blank into a TiMn alloy tube blank, the roughness Ra of the inner surface of the TiMn alloy tube blank is controlled within 1.6 mu m, and the roughness Ra of the outer surface of the TiMn alloy tube blank is controlled within 1.6 mu m through a peeling process and a centerless grinding process.
In the fifth step, the cold tube mill is adopted to perform multi-pass cold rolling deformation of the tube blank, the single-pass deformation is controlled to be 10-25%, then intermediate vacuum annealing treatment is performed, and then cold rolling is continued, so that the thin-specification TiMn alloy tube blank is finally prepared.
In the sixth step, the thin tube blank is subjected to multi-pass cold drawing deformation by adopting a drawing machine, the single-pass deformation is controlled to be 10-20%, then intermediate vacuum annealing treatment is performed, and cold drawing is continued, so that the TiMn alloy capillary tube blank is finally prepared.
Further, in the seventh step, straightening of the capillary tube is performed by using a straightener, and the bending degree is required to be ensured to be smaller than 0.3mm/m.
In the eighth step, firstly, a long capillary tube is processed into a length required by a coronary stent, then a microsecond optical fiber laser is used for carving a coronary stent blank, the pulse width is 10-30 mu s, the laser power is 100-300W, and the pulse frequency is 8000-15000 Hz.
Further, in the step nine, vacuum heat treatment is carried out on the coronary artery blank, the heat treatment temperature is 600-700 ℃, the heat preservation is carried out for 5-15 min, the furnace is discharged after the rapid cooling through liquid nitrogen, the aim of eliminating the internal stress formed on the bracket blank during laser engraving is achieved, and the mechanical property of the bracket is further adjusted.
In the step ten, electrochemical polishing is carried out on the bracket blank, the polishing solution is 6 vol percent of perchloric acid, 35: 35 vol percent of n-butyl alcohol and 59: 59 vol percent of methanol, the voltage is 10-20V, the temperature is-20 to-30 ℃, and the roughness Ra value of the inner surface and the outer surface is less than 0.1 mu m, so that the finished titanium alloy bracket is prepared.
In the eleventh step, PLGA is dissolved in ethyl acetate or tetrahydrofuran and fully stirred, then a proper amount of rapamycin is added, and even solution is formed after further fully stirring, so that the drug loading rate in the finished stent coating is ensured to be 2-3 mug/mm 2.
In the step twelve, a metal bracket is placed into a sleeve and fixed on automatic ultrasonic spraying equipment, ultrasonic atomization spraying is carried out, the spraying air pressure is 0.2-0.28 MPa, the atomization power is 1.2-2.0W, the liquid inlet rate is 0.1-0.2 mL/min, the coating thickness is 5-6 mu m, and after spraying, the metal bracket is dried in a clean environment and then dried in vacuum for 24-48 h. And conveying the saccule to a proper position of the stent by using special press-holding machine equipment, so as to prepare the titanium alloy coronary artery drug coating stent.
The design idea of the invention is as follows:
The alloy comprises, by mass, 5.8% -6.2% of Al element, 3.8% -4.2% of V element, 0.15% -0.2% of Fe element, 0.08% -0.13% of O element, less than or equal to 0.05% of C element, less than or equal to 0.005% of H element, less than or equal to 0.01% of N element and the balance of Ti, wherein the design concept of the components is that the strength of the titanium is improved by adding Mn element necessary for a human body to form a medical titanium alloy, the risk of human body damage caused by precipitation of harmful elements is thoroughly eliminated, and the requirement of a coronary artery drug coating bracket on the performance of raw materials is met.
The invention adopts special processing technology, adopts a vacuum consumable arc furnace to smelt alloy cast ingots, then adopts working procedures such as forging, hot rolling and the like, can effectively control the strength and the grain size of the alloy by controlling the heating temperature and the deformation during hot working, realizes reasonable matching of the strength and the plasticity, prepares titanium alloy bars, can effectively control the strength and the plasticity of the alloy by mechanical perforation, peeling, centerless grinding, cold rolling, cold drawing and straightening, and the deformation of cold rolling and drawing and the intermediate annealing temperature, thereby preparing a final finished titanium alloy capillary, finally, finely engraves a bracket structure by microsecond optical fiber laser to realize the accurate forming of the bracket, adds a hole and electrochemical polishing by a high-precision machine, effectively reduces the roughness of the inner surface and the outer surface of the bracket, thereby preparing a qualified coronary artery metal bracket, and finally prepares the titanium alloy coronary artery drug coating bracket by mixing PLGA and rapamycin solution, spraying the solution on the metal bracket by an ultrasonic atomizing sprayer and drying.
Compared with the prior art, the invention has the following advantages and beneficial effects.
1. The invention provides a preparation method of a medical titanium alloy coronary artery drug coating stent, by which titanium alloy bars, tubes and coronary artery stents with various specifications can be produced, and alloy raw materials are provided for medical instruments of cardiovascular department.
2. According to the invention, the strength of titanium is improved by adding Mn element necessary for human body, so that a medical titanium alloy is formed, the risk of human body injury caused by precipitation of harmful elements is thoroughly eliminated, and the requirement of the coronary stent on the performance of raw materials is met.
3. The invention finely engraves the stent structure by microsecond optical fiber laser to realize the accurate forming of the stent, and effectively reduces the roughness of the inner surface and the outer surface of the stent by high-precision machining holes and electrochemical polishing, thereby preparing the qualified coronary artery drug coating stent.
Drawings
FIG. 1 microstructure of TiMn alloy tubing of the 4.0mm gauge phi prepared in example 1.
FIG. 2 microstructure of 3.0mm gauge TiMn alloy tubing prepared in example 2.
FIG. 3 microstructure of 2.75mm gauge TiMn alloy tubing prepared in example 3.
FIG. 4 microstructure of a 2.25mm gauge TiMn alloy tubing prepared in example 4.
Detailed Description
Some embodiments of the invention are disclosed below and one skilled in the art can, based on the disclosure herein, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
A medical titanium alloy coronary artery drug coating stent comprises the following chemical components, by mass, 5.0% -14.0% of Mn, less than or equal to 0.30% of Fe, less than or equal to 0.16% of O, less than or equal to 0.01% of N, less than or equal to 0.001% of H, and the balance of Ti.
A processing method of a medical titanium alloy coronary artery drug coating stent specifically comprises the following steps:
firstly, preparing a titanium alloy cast ingot by adopting vacuum consumable smelting;
step two, forging by adopting a quick forging machine and a precision forging machine;
Step three, hot rolling is carried out by adopting a horizontal rolling mill, and a rough bar blank with proper size is prepared;
Step four, obtaining a rough tube blank after machining by adopting mechanical drilling, and improving the surface roughness by peeling and centerless grinding;
step five, cold rolling is carried out by a cold rolling mill, and a thin tube blank is obtained after repeated annealing treatment in the middle;
step six, drawing deformation of the tube blank is carried out by adopting drawing equipment, and a capillary tube blank is obtained;
step seven, straightening the wire by adopting a slide block straightener;
step eight, carving a coronary artery stent blank by adopting microsecond fiber laser;
step nine, carrying out vacuum heat treatment on the bracket blank;
step ten, carrying out electrochemical polishing on the bracket blank to prepare a finished metal bracket;
Step eleven, preparing a drug solution of polylactic acid-glycolic acid copolymer (PLGA) and rapamycin;
and twelve, uniformly spraying the drug solution on the outer surface of the metal stent by using a spraying machine, airing in a clean environment, and conveying the balloon to a proper position of the stent by using special press-holding machine equipment to prepare the titanium alloy coronary artery drug coating stent.
In the first step, titanium sponge, metal Mn, metal Fe and a compound TiO 2 are required to be adopted, the ingredients are mixed according to the titanium alloy components, three times of vacuum self-consumption smelting are adopted, argon is filled in the smelting process, the argon filling pressure is 5000-10000 Pa in the primary smelting process, and the argon filling pressure is 20000-30000 Pa in the secondary and tertiary smelting processes, so that the TiMn titanium alloy cast ingot is obtained.
In the second step, cogging forging is required to be carried out at 1000-1100 ℃, finish forging is required to be carried out at 800-950 ℃, the heat preservation time is controlled to be 1-6 h, and the deformation amount per fire is not less than 60%.
In the third step, the rolling temperature is controlled to be 750-850 ℃, the heat preservation time is controlled to be 1-2 hours, and the deformation of each pass is controlled to be within 15%.
In the fourth step, firstly, the rolled bar blank is machined to be of a proper length, then, a precise drilling process is adopted to prepare the rolled blank into a TiMn alloy tube blank, the roughness Ra of the inner surface of the TiMn alloy tube blank is controlled within 1.6 mu m, and the roughness Ra of the outer surface of the TiMn alloy tube blank is controlled within 1.6 mu m through a peeling process and a centerless grinding process.
In the fifth step, the cold tube mill is adopted to perform multi-pass cold rolling deformation of the tube blank, the single-pass deformation is controlled to be 10-25%, then intermediate vacuum annealing treatment is performed, and then cold rolling is continued, so that the thin-specification TiMn alloy tube blank is finally prepared.
In the sixth step, the thin tube blank is subjected to multi-pass cold drawing deformation by adopting a drawing machine, the single-pass deformation is controlled to be 10-20%, then intermediate vacuum annealing treatment is performed, and cold drawing is continued, so that the TiMn alloy capillary tube blank is finally prepared.
Further, in the seventh step, straightening of the capillary tube is performed by using a straightener, and the bending degree is required to be ensured to be smaller than 0.3mm/m.
In the eighth step, firstly, a long capillary tube is processed into a length required by a coronary stent, then a microsecond optical fiber laser is used for carving a coronary stent blank, the pulse width is 10-30 mu s, the laser power is 100-300W, and the pulse frequency is 8000-15000 Hz.
Further, in the step nine, vacuum heat treatment is carried out on the coronary artery blank, the heat treatment temperature is 600-700 ℃, the heat preservation is carried out for 5-15 min, the furnace is discharged after the rapid cooling through liquid nitrogen, the aim of eliminating the internal stress formed on the bracket blank during laser engraving is achieved, and the mechanical property of the bracket is further adjusted.
In the step ten, electrochemical polishing is carried out on the bracket blank, the polishing solution is 6 vol percent of perchloric acid, 35: 35 vol percent of n-butyl alcohol and 59: 59 vol percent of methanol, the voltage is 10-20V, the temperature is-20 to-30 ℃, and the roughness Ra value of the inner surface and the outer surface is less than 0.1 mu m, so that the finished titanium alloy bracket is prepared.
In the eleventh step, PLGA is dissolved in ethyl acetate or tetrahydrofuran and fully stirred, then a proper amount of rapamycin is added, and even solution is formed after further fully stirring, so that the drug loading rate in the finished stent coating is ensured to be 2-3 mug/mm 2.
In the step twelve, a metal bracket is placed into a sleeve and fixed on automatic ultrasonic spraying equipment, ultrasonic atomization spraying is carried out, the spraying air pressure is 0.2-0.28 MPa, the atomization power is 1.2-2.0W, the liquid inlet rate is 0.1-0.2 mL/min, the coating thickness is 5-6 mu m, and after spraying, the metal bracket is dried in a clean environment and then dried in vacuum for 24-48 h. And conveying the saccule to a proper position of the stent by using special press-holding machine equipment, so as to prepare the titanium alloy coronary artery drug coating stent.
Example 1.
The titanium alloy Kirschner wire comprises 6.04% of Mn element, 0.18% of Fe element, 0.10% of O element, 0.0007% of H element, 0.005% of N element and the balance of Ti by mass percent.
The processing method of the titanium alloy coronary artery drug coating stent comprises the following steps:
Firstly, adopting titanium sponge, metal Mn, metal Fe and a compound TiO 2, mixing according to the titanium alloy components, adopting vacuum consumable three-time smelting, wherein the argon filling pressure in the primary smelting is 7600MPa, the argon filling pressure in the secondary smelting is 25300Pa, and the argon filling pressure in the three-time smelting is 28700Pa, so that a titanium alloy cast ingot with the phi 365mm with stable and uniform components is obtained.
Step two, cogging and forging at 1070 ℃, and finish forging at 850 ℃, wherein the heat preservation time is controlled to be 5 hours, and the deformation amount at each firing is controlled to be 72 percent.
And thirdly, rolling the forged crude bar blank by adopting a transverse rolling mill, wherein the rolling temperature is 800 ℃, the heat preservation time is 1.5h, and the deformation of each pass is controlled to be 15%, so that the titanium bar blank with the diameter of 20mm is prepared.
And step four, processing the rolled bar blank into a proper length, then adopting a drilling process to prepare a TiMn alloy tube blank, controlling the roughness Ra of the inner surface to be 1.6 mu m, and controlling the roughness Ra of the outer surface of the tube blank to be within 1.6 mu m through a peeling and centerless grinding process.
And fifthly, cold rolling and deforming the rough pipe blank on a cold pilger mill, controlling the deformation amount of a single pass to be 21%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing the oil, vacuum annealing at 700 ℃ for 1h, then cold rolling and deforming, and recycling multiple passes to finally prepare the titanium alloy pipe blank with phi 8 mm.
And step six, cold-drawing and deforming the titanium alloy tube blank on drawing equipment, controlling the deformation amount of a single pass to be 10-18%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing oil, vacuum annealing at 650 ℃, keeping the temperature for 1h, and then cold-drawing and deforming, so that multiple passes are circulated, and finally preparing the titanium alloy capillary tube with the diameter of 4.0 mm.
And step seven, straightening the capillary tube by using a straightener, wherein the straightness after straightening is less than 0.3mm/m. The room temperature tensile properties of the capillaries are shown in Table 1.
Table 1 mechanical properties test results of TiMn alloy tubing of phi 4.0mm gauge prepared in example 1.
Step eight, firstly processing a long capillary tube into a length required by the coronary stent, and then carving a coronary stent blank by adopting microsecond fiber laser, wherein the pulse width is 18 mu s, the laser power is 193W, and the pulse frequency is 13200Hz.
And step nine, carrying out vacuum heat treatment on the coronary stent blank, wherein the heat treatment temperature is 680 ℃, preserving heat for 11min, and discharging after rapidly cooling by liquid nitrogen.
And step ten, carrying out electrochemical polishing on the bracket blank, wherein the polishing solution is 6 vol percent of perchloric acid, 35 vol percent of n-butyl alcohol and 59 vol percent of methanol, the voltage is 17V, the temperature is-22 ℃, and the roughness Ra value of the inner surface and the outer surface is less than 0.1 mu m, so that the finished titanium alloy bracket is prepared.
Step eleven, dissolving PLGA in ethyl acetate, fully stirring, then adding a proper amount of rapamycin, and fully stirring to form a uniform solution, thereby ensuring the drug loading rate in the finished stent coating to be 2.8 mug/mm 2.
And twelve, placing the metal bracket into a sleeve, fixing the sleeve on automatic ultrasonic spraying equipment, then carrying out ultrasonic atomization spraying, wherein the spraying air pressure is 0.21MPa, the atomization power is 2.0W, the liquid inlet rate is 0.17 mL/min, the coating thickness is 5.9 mu m, and after the spraying, airing in a clean environment, and then carrying out vacuum drying for 46h. And conveying the saccule to a proper position of the stent by using special press-holding machine equipment, so as to prepare the titanium alloy coronary artery drug coating stent.
Example 2.
The titanium alloy Kirschner wire comprises, by mass, 13.4% of Mn element, 0.15% of Fe element, 0.12% of O element, 0.0004% of H element, 0.003% of N element and the balance of Ti.
The processing method of the titanium alloy coronary artery drug coating stent comprises the following steps:
Firstly, adopting titanium sponge, metal Mn, metal Fe and a compound TiO 2, mixing according to the titanium alloy components, adopting vacuum consumable three-time smelting, wherein the argon filling pressure in the primary smelting is 9700MPa, the argon filling pressure in the secondary smelting is 27000Pa, and the argon filling pressure in the three-time smelting is 29400Pa, so that a titanium alloy cast ingot with the phi 365mm with stable and uniform components is obtained.
Step two, cogging and forging at 1050 ℃, and finish forging at 930 ℃, wherein the heat preservation time is controlled to be 4 hours, and the deformation amount at each firing is controlled to be 75%.
And thirdly, rolling the forged crude bar blank by adopting a horizontal rolling mill, wherein the rolling temperature is 830 ℃, the heat preservation time is 2h, and the deformation of each pass is controlled at 12%, so that the titanium bar blank with phi of 16mm is prepared.
And step four, processing the rolled bar blank into a proper length, then adopting a drilling process to prepare a TiMn alloy tube blank, controlling the roughness Ra of the inner surface to be 1.6 mu m, and controlling the roughness Ra of the outer surface of the tube blank to be within 1.6 mu m through a peeling and centerless grinding process.
And fifthly, cold rolling and deforming the rough pipe blank on a cold pilger mill, controlling the deformation amount of a single pass to be 23%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing the oil, vacuum annealing at 720 ℃ for 1.5h, then cold rolling and deforming, and recycling multiple passes to finally prepare the titanium alloy pipe blank with the diameter of 6 mm.
And step six, cold-drawing and deforming the titanium alloy tube blank on drawing equipment, controlling the deformation amount of a single pass to be 15-20%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing oil, vacuum annealing at 660 ℃, keeping the temperature for 0.5h, and then cold-drawing and deforming, so that multiple passes are circulated, and finally preparing the titanium alloy capillary tube with the diameter of 3.0 mm.
And step seven, straightening the capillary tube by using a straightener, wherein the straightness after straightening is less than 0.3mm/m. The room temperature tensile properties of the capillaries are shown in Table 2.
Table 2 mechanical properties test results of TiMn alloy tubing of 3.0mm gauge prepared in example 2.
Step eight, firstly processing a long capillary tube into a length required by the coronary stent, and then carving a coronary stent blank by adopting microsecond fiber laser, wherein the pulse width is 26 mu s, the laser power is 276W, and the pulse frequency is 11500Hz.
And step nine, carrying out vacuum heat treatment on the coronary stent blank, wherein the heat treatment temperature is 650 ℃, preserving the heat for 8min, and discharging the coronary stent blank after quick cooling by liquid nitrogen.
And step ten, carrying out electrochemical polishing on the bracket blank, wherein the polishing solution is 6 vol percent of perchloric acid, 35 vol percent of n-butyl alcohol and 59 vol percent of methanol, the voltage is 15V, the temperature is minus 28 ℃, and the roughness Ra value of the inner surface and the outer surface is smaller than 0.1 mu m, so that the finished titanium alloy bracket is prepared.
Step eleven, dissolving PLGA in tetrahydrofuran, fully stirring, then adding a proper amount of rapamycin, and fully stirring to form a uniform solution, thereby ensuring the drug loading rate in the finished stent coating to be 2.6 mug/mm 2.
And twelve, placing the metal bracket into a sleeve, fixing the sleeve on automatic ultrasonic spraying equipment, then carrying out ultrasonic atomization spraying, wherein the spraying air pressure is 0.25MPa, the atomization power is 1.8W, the liquid inlet rate is 0.16 mL/min, the coating thickness is 5.5 mu m, and after the spraying, airing in a clean environment, and then carrying out vacuum drying for 36h. And conveying the saccule to a proper position of the stent by using special press-holding machine equipment, so as to prepare the titanium alloy coronary artery drug coating stent.
Example 3.
The titanium alloy Kirschner wire comprises 8.7% of Mn element, 0.11% of Fe element, 0.15% of O element, 0.0005% of H element, 0.006% of N element and the balance of Ti by mass percent.
The processing method of the titanium alloy coronary artery drug coating stent comprises the following steps:
Firstly, adopting titanium sponge, metal Mn, metal Fe and a compound TiO 2, mixing according to the titanium alloy components, adopting vacuum consumable three-time smelting, wherein the argon filling pressure in the primary smelting is 5800MPa, the argon filling pressure in the secondary smelting is 22000Pa, and the argon filling pressure in the three-time smelting is 24900Pa, so that a titanium alloy cast ingot with the phi 365mm with stable and uniform components is obtained.
Step two, cogging and forging at 1050 ℃, and finish forging at 820 ℃, wherein the heat preservation time is controlled to be 3 hours, and the deformation amount per fire is controlled to be 78%.
And thirdly, rolling the forged crude bar blank by adopting a transverse rolling mill, wherein the rolling temperature is 780 ℃, the heat preservation time is 1h, and the deformation of each pass is controlled to be 15%, so that the titanium bar blank with phi 18mm is prepared.
And step four, processing the rolled bar blank into a proper length, then adopting a drilling process to prepare a TiMn alloy tube blank, controlling the roughness Ra of the inner surface to be 1.6 mu m, and controlling the roughness Ra of the outer surface of the tube blank to be within 1.6 mu m through a peeling and centerless grinding process.
And fifthly, cold rolling and deforming the rough pipe blank on a cold pilger mill, controlling the deformation amount of a single pass to be 18%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing oil, vacuum annealing at 680 ℃ for 0.6 h ℃ and then cold rolling and deforming, and recycling multiple passes to finally prepare the titanium alloy pipe blank with the diameter of 5.5 mm.
And step six, cold-drawing and deforming the titanium alloy tube blank on drawing equipment, controlling the deformation amount of a single pass to be 10-17%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing oil, vacuum annealing at 640 ℃ for 0.5h, and then cold-drawing and deforming, and recycling multiple passes to finally prepare the titanium alloy capillary tube with phi of 2.75 mm.
And step seven, straightening the capillary tube by using a straightener, wherein the straightness after straightening is less than 0.3mm/m. The room temperature tensile properties of the capillaries are shown in Table 3.
Table 3 mechanical properties test results of TiMn alloy tubing of 2.75mm gauge prepared in example 3.
Step eight, firstly processing a long capillary tube into a length required by the coronary stent, and then carving a coronary stent blank by adopting microsecond fiber laser, wherein the pulse width is 12 mu s, the laser power is 137W, and the pulse frequency is 9600Hz.
And step nine, carrying out vacuum heat treatment on the coronary stent blank, wherein the heat treatment temperature is 650 ℃, preserving the heat for 6min, and discharging the coronary stent blank after quick cooling by liquid nitrogen.
And step ten, carrying out electrochemical polishing on the bracket blank, wherein the polishing solution is 6 vol percent of perchloric acid, 35 vol percent of n-butyl alcohol and 59 vol percent of methanol, the voltage is 12V, the temperature is-27 ℃, and the roughness Ra value of the inner surface and the outer surface is less than 0.1 mu m, so that the finished titanium alloy bracket is prepared.
Step eleven, dissolving PLGA in ethyl acetate, fully stirring, then adding a proper amount of rapamycin, and fully stirring to form a uniform solution, thereby ensuring the drug loading rate in the finished stent coating to be 2.5 mug/mm 2.
And twelve, placing the metal bracket into a sleeve, fixing the sleeve on automatic ultrasonic spraying equipment, then carrying out ultrasonic atomization spraying, wherein the spraying air pressure is 0.29MPa, the atomization power is 1.4W, the liquid inlet rate is 0.14 mL/min, the coating thickness is 5.4 mu m, and after the spraying, airing in a clean environment, and then carrying out vacuum drying for 32h. And conveying the saccule to a proper position of the stent by using special press-holding machine equipment, so as to prepare the titanium alloy coronary artery drug coating stent.
Example 4.
The titanium alloy Kirschner wire comprises, by mass, 11.3% of Mn element, 0.16% of Fe element, 0.095% of O element, 0.0004% of H element, 0.008% of N element, and the balance of Ti.
The processing method of the titanium alloy coronary artery drug coating stent comprises the following steps:
Firstly, adopting titanium sponge, metal Mn, metal Fe and a compound TiO 2, mixing according to the titanium alloy components, adopting vacuum consumable three-time smelting, wherein the argon filling pressure in the primary smelting is 8300MPa, the argon filling pressure in the secondary smelting is 26800Pa, and the argon filling pressure in the three-time smelting is 29200Pa, so that a titanium alloy cast ingot with the phi 365mm with stable and uniform components is obtained.
Step two, cogging and forging at 1020 ℃, and finish forging at 820 ℃, wherein the heat preservation time is controlled to be 2 hours, and the deformation amount per fire is controlled to be 65%.
And thirdly, rolling the forged crude bar blank by adopting a horizontal rolling mill, wherein the rolling temperature is 760 ℃, the heat preservation time is 2h, and the deformation of each pass is controlled to be 15%, so that the titanium bar blank with the diameter of 14mm is prepared.
And step four, processing the rolled bar blank into a proper length, then adopting a drilling process to prepare a TiMn alloy tube blank, controlling the roughness Ra of the inner surface to be 1.6 mu m, and controlling the roughness Ra of the outer surface of the tube blank to be within 1.6 mu m through a peeling and centerless grinding process.
And fifthly, cold rolling and deforming the rough pipe blank on a cold pilger mill, controlling the deformation amount of a single pass to be 13%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing the oil, vacuum annealing at 640 ℃ for 0.8h, then cold rolling and deforming, and recycling multiple passes to finally prepare the titanium alloy pipe blank with the diameter of 6 mm.
And step six, cold-drawing and deforming the titanium alloy tube blank on drawing equipment, controlling the deformation amount of a single pass to be 12-20%, selecting a high-speed steel material for the core rod, selecting lubricating oil for lubrication, removing oil, vacuum annealing at 600 ℃ for 0.6h, and then cold-drawing and deforming, and recycling multiple passes to finally prepare the titanium alloy capillary tube with the diameter of 2.25 mm.
And step seven, straightening the capillary tube by using a straightener, wherein the straightness after straightening is less than 0.3mm/m. The room temperature tensile properties of the capillaries are shown in Table 4.
Table 4 mechanical properties test results of TiMn alloy tubing of 2.25mm gauge prepared in example 4.
Step eight, firstly processing a long capillary tube into a length required by the coronary stent, and then carving a coronary stent blank by adopting microsecond fiber laser, wherein the pulse width is 12 mu s, the laser power is 129W, and the pulse frequency is 11500Hz.
And step nine, carrying out vacuum heat treatment on the coronary stent blank, wherein the heat treatment temperature is 620 ℃, preserving the heat for 15min, and discharging the coronary stent blank after quick cooling by liquid nitrogen.
And step ten, carrying out electrochemical polishing on the bracket blank, wherein the polishing solution is 6 vol percent of perchloric acid, 35 vol percent of n-butyl alcohol and 59 vol percent of methanol, the voltage is 15V, the temperature is-25 ℃, and the roughness Ra value of the inner surface and the outer surface is less than 0.1 mu m, so that the finished titanium alloy bracket is prepared.
Step eleven, dissolving PLGA in tetrahydrofuran, fully stirring, then adding a proper amount of rapamycin, and fully stirring to form a uniform solution, thereby ensuring the drug loading rate in the finished stent coating to be 2.2 mug/mm 2.
And twelve, placing the metal bracket into a sleeve, fixing the sleeve on automatic ultrasonic spraying equipment, then carrying out ultrasonic atomization spraying, wherein the spraying air pressure is 0.23 MPa, the atomization power is 1.6W, the liquid inlet rate is 0.11 mL/min, the coating thickness is 5.2 mu m, and after the spraying, airing in a clean environment, and then carrying out vacuum drying for 25h. And conveying the saccule to a proper position of the stent by using special press-holding machine equipment, so as to prepare the titanium alloy coronary artery drug coating stent.
The embodiment results show that the medical titanium alloy coronary artery drug coating bracket processing method comprises the steps of adopting a vacuum consumable arc furnace to smelt alloy cast ingots, then adopting a forging process, a hot rolling process and the like, controlling the heating temperature and the deformation in the hot working process, effectively controlling the strength and the grain size of the alloy, realizing reasonable matching of the strength and the plasticity, preparing a titanium alloy bar, then adopting a mechanical perforation process, a peeling process, a centerless grinding process, a rolling process, a drawing process and a straightening process, effectively controlling the strength and the plasticity of the alloy through the deformation of the cold rolling process and the drawing process and the intermediate annealing temperature, thereby preparing a final finished titanium alloy capillary tube, having excellent mechanical properties, adopting a microsecond optical fiber laser to finely carve a bracket structure, realizing the accurate forming of the bracket, adopting a high-precision machine to add holes and an electrochemical polishing process, effectively reducing the roughness of the inner surface and the outer surface of the bracket, further preparing a qualified coronary artery metal bracket, adopting a PLGA and rapamycin solution, adopting an ultrasonic atomization spraying machine to spray the solution on the metal bracket, and drying the coronary artery, thus preparing the titanium alloy drug coating bracket.
Claims (10)
1. A processing method of a medical titanium alloy coronary artery drug coating bracket is characterized in that the titanium alloy Kirschner wire comprises the following chemical components, by mass, 5.0% -14.0% of Mn, less than or equal to 0.30% of Fe, less than or equal to 0.16% of O, less than or equal to 0.01% of N, less than or equal to 0.001% of H, and the balance of Ti;
The method comprises the following steps:
Firstly, adopting titanium sponge, metal Mn, metal Fe and a compound TiO 2, mixing according to titanium alloy components, adopting vacuum consumable three times of smelting, filling argon in the smelting process, filling the argon at the argon filling pressure of 5000-10000 Pa in the primary smelting, and filling the argon at the argon filling pressure of 20000-30000 Pa in the secondary and tertiary smelting to obtain TiMn titanium alloy cast ingots;
step two, forging by adopting a quick forging machine and a precision forging machine;
step three, hot rolling is carried out by adopting a horizontal rolling mill, the rolling temperature is controlled to be 750-850 ℃, the heat preservation time is controlled to be 1-2 hours, the deformation of each pass is controlled to be within 15%, and a rough bar blank with proper size is prepared;
Step four, obtaining a rough tube blank after machining by adopting mechanical drilling, and improving the surface roughness by peeling and centerless grinding;
step five, cold rolling is carried out by a cold rolling mill, and a thin tube blank is obtained after repeated annealing treatment in the middle;
step six, drawing deformation of the tube blank is carried out by adopting drawing equipment, and a capillary tube blank is obtained;
Step seven, straightening the wire by adopting a slide block straightener, wherein the curvature is smaller than 0.3mm/m;
step eight, carving a coronary artery stent blank by adopting microsecond fiber laser;
step nine, carrying out vacuum heat treatment on the bracket blank;
step ten, carrying out electrochemical polishing on the bracket blank to prepare a finished metal bracket;
Step eleven, preparing a drug solution of polylactic acid-glycolic acid copolymer (PLGA) and rapamycin;
and twelve, uniformly spraying the drug solution on the outer surface of the metal stent by using a spraying machine, airing in a clean environment, and conveying the balloon to a proper position of the stent by using special press-holding machine equipment to prepare the titanium alloy coronary artery drug coating stent.
2. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, wherein in the second step, cogging forging is required at 1000-1100 ℃, finish forging is required at 800-950 ℃, the heat preservation time is controlled to be 1-6 h, and the deformation amount per fire is not less than 60%.
3. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, wherein in the fourth step, firstly, a rolled bar blank is machined into a proper length, then a precise drilling process is adopted to prepare a TiMn alloy tube blank from the rolled blank, the inner surface roughness Ra is controlled within 1.6 mu m, and the outer surface roughness Ra of the tube blank is controlled within 1.6 mu m through a peeling process and a centerless grinding process.
4. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, which is characterized in that in the fifth step, the cold rolling tube mill is adopted to carry out multi-pass cold rolling deformation of the tube blank, the single-pass deformation is controlled to be 10-25%, then intermediate vacuum annealing treatment is carried out, and then cold rolling is continued, so that the thin-specification TiMn alloy tube blank is finally prepared.
5. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, which is characterized in that in the step six, a drawing machine is adopted to carry out multi-pass cold drawing deformation of a thin tube blank, the single-pass deformation amount is controlled to be 10-20%, then intermediate vacuum annealing treatment is carried out, and cold drawing is continued, so that the TiMn alloy capillary tube blank is finally prepared.
6. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, wherein in the eighth step, a long capillary tube is firstly processed into a length required by the coronary artery stent, and then a microsecond fiber laser is adopted to engrave a coronary artery stent blank, the pulse width is 10-30 mu s, the laser power is 100-300W, and the pulse frequency is 8000-15000 Hz.
7. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, which is characterized in that in the step nine, the coronary artery blank is subjected to vacuum heat treatment, the heat treatment temperature is 600-700 ℃, the heat is preserved for 5-15 min, and the coronary artery blank is discharged after being rapidly cooled by liquid nitrogen.
8. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, which is characterized in that in the step ten, electrochemical polishing is carried out on a stent blank, the polishing solution is 6 vol percent perchloric acid +35 vol percent n-butyl alcohol +59 vol percent methanol, the voltage is 10-20V, the temperature is-20 to-30 ℃, and the roughness Ra value of the inner surface and the outer surface is less than 0.1 mu m, so that the finished titanium alloy stent is prepared.
9. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, wherein in the step eleven, PLGA is dissolved in ethyl acetate or tetrahydrofuran and fully stirred, then a proper amount of rapamycin is added, and even solution is formed after further fully stirring, so that the drug loading rate in the finished stent coating is ensured to be 2-3 mug/mm 2.
10. The method for processing the medical titanium alloy coronary artery drug coated stent according to claim 1, which is characterized by comprising the steps of placing a metal stent into a sleeve, fixing the sleeve on automatic ultrasonic spraying equipment, then performing ultrasonic atomization spraying, wherein the spraying air pressure is 0.2-0.28 MPa, the atomization power is 1.2-2.0W, the liquid inlet rate is 0.1-0.2 mL/min, the coating thickness is 5-6 mu m, airing the titanium alloy coronary artery drug coated stent in a clean environment after spraying, then drying the titanium alloy coronary artery drug coated stent in vacuum for 24-48 h, and conveying a balloon to a proper position of the stent by using special press-holding machine equipment, thereby preparing the titanium alloy coronary artery drug coated stent.
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| CN106493187A (en) * | 2016-10-27 | 2017-03-15 | 南京宝泰特种材料股份有限公司 | A kind of heavy caliber thick wall titanium and its low-cost manufacture method of alloy seamless tubing |
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