CN117344177A - High-shear-strength bone needle capable of inhibiting drug-resistant bacterial biomembrane and preparation method thereof - Google Patents
High-shear-strength bone needle capable of inhibiting drug-resistant bacterial biomembrane and preparation method thereof Download PDFInfo
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- CN117344177A CN117344177A CN202311637336.4A CN202311637336A CN117344177A CN 117344177 A CN117344177 A CN 117344177A CN 202311637336 A CN202311637336 A CN 202311637336A CN 117344177 A CN117344177 A CN 117344177A
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 37
- 230000001580 bacterial effect Effects 0.000 title claims abstract description 21
- 229940079593 drug Drugs 0.000 title claims abstract description 13
- 239000003814 drug Substances 0.000 title claims abstract description 13
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 58
- 239000000956 alloy Substances 0.000 claims description 58
- 229910052782 aluminium Inorganic materials 0.000 claims description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 55
- 238000005242 forging Methods 0.000 claims description 25
- 238000003723 Smelting Methods 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 20
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- 238000005098 hot rolling Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 239000000498 cooling water Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910010165 TiCu Inorganic materials 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000003013 cytotoxicity Effects 0.000 claims description 2
- 231100000135 cytotoxicity Toxicity 0.000 claims description 2
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 abstract description 9
- 229910001069 Ti alloy Inorganic materials 0.000 abstract description 9
- 229960003085 meticillin Drugs 0.000 abstract description 9
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000007769 metal material Substances 0.000 abstract description 3
- 238000010008 shearing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
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- 229910052802 copper Inorganic materials 0.000 description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000006916 nutrient agar Substances 0.000 description 6
- 208000010392 Bone Fractures Diseases 0.000 description 5
- 206010017076 Fracture Diseases 0.000 description 5
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- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/72—Intramedullary pins, nails or other devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
-
- 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
-
- 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- 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
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/045—Manufacture of wire or bars with particular section or properties
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Health & Medical Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Surgery (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Mechanical Engineering (AREA)
- Public Health (AREA)
- Heart & Thoracic Surgery (AREA)
- Veterinary Medicine (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Molecular Biology (AREA)
- Biomedical Technology (AREA)
- Medical Informatics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Neurology (AREA)
- Thermal Sciences (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides a high shear strength spicule capable of inhibiting drug-resistant bacterial biomembrane and a preparation method thereof, and relates to the technical field of medical metal materials, wherein the spicule is prepared from medical titanium alloy, and the spicule comprises the following chemical components in percentage by weight: al: 5.2-6.5%, V: 3.6-4.6%, cu:4.3 to 6.1% of Ti and the balance. The titanium alloy is processed into the bone spicule by adopting a special process, so that the shearing strength of the bone spicule is further improved under the condition that the bone spicule has excellent tissue compatibility and strong plasticity, and the problem of fracture in the use process is prevented; meanwhile, the spicules can inhibit the methicillin-resistant staphylococcus aureus from forming a bacterial biofilm on the surfaces of the spicules.
Description
Technical Field
The invention relates to the technical field of medical metal materials, in particular to a high-shear-strength bone needle capable of inhibiting drug-resistant bacterial biomembrane and a preparation method thereof.
Background
In fracture treatment, internal fixation therapy is one of the more common treatments. The treatment adopts a combination of a closed reduction technology and a minimally invasive technology, and the bone needle is used independently or matched with other orthopedic medical instruments (such as a bone plate, an intramedullary nail, a spinal nail rod system, an artificial joint and the like), in the treatment, the head of the bone needle is generally held by a special tool, and in the rotating process, the bone needle is screwed into the bone to finish reduction fixation of a fracture part.
At present, the bone spicules are mostly prepared from titanium or titanium alloy, the titanium alloy is a metal with excellent biological safety, has higher specific strength, and is widely applied to the field of bone wound repair, such as bone spicules, intramedullary nails, bone plates, screws, artificial joints and the like. In the fracture recovery process, because the stability of the fracture end is poor, obvious shearing force can be generated on the bone needle, and the phenomenon of fracture of the bone needle can occur for patients with larger BMI index or patients with slow bone healing; if a bacterial biomembrane formed by methicillin-resistant staphylococcus aureus is formed on the surface of an implant in a patient, the sustained infection is very easy to cause, and due to the methicillin-resistant characteristic of the strain, the existing medicines such as antibiotics and the like are difficult to interfere or treat the infection, and the bone needle is loosened or even falls off due to the worsening of the infection.
Therefore, there is a need to develop a titanium alloy spicule with high shear strength that can inhibit the formation of bacterial biofilm by methicillin-resistant staphylococcus aureus.
Disclosure of Invention
The invention aims to provide a high-shear strength spicule capable of inhibiting drug-resistant bacterial biomembrane and a preparation method thereof, which can further inhibit adhesion and proliferation of methicillin-resistant staphylococcus aureus on the surface of the spicule under the condition of ensuring that the spicule has excellent tissue compatibility and strong plasticity so as to inhibit formation of bacterial biomembrane.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the present invention provides a high shear strength bone needle capable of inhibiting drug-resistant bacterial biofilm, prepared by a method comprising the steps of:
1) Smelting: the raw materials of sponge titanium, tiCu intermediate alloy, alV intermediate alloy, aluminum beans and aluminum mesh are proportioned according to the following components in percentage by weight: al: 5.2-6.5%, V: 3.6-4.6%, cu: 4.3-6.1% of Ti and the balance;
when in material mixing, an aluminum net is made into a container, the container is filled with titanium sponge, tiCu intermediate alloy, alV intermediate alloy and aluminum beans, an electrode die is used for pressing into a smelting electrode, and then alloy cast ingots are smelted;
2) Forging: heating the alloy ingot to 980-1170 ℃, preserving heat for 4-5 hours, and then performing hot forging, wherein the total forging ratio of the forging process is 5-6, forging into a plate blank along the axial direction of the ingot, and cutting the plate blank into square bars along the length direction; the square rod is heated to 840-1060 ℃ again, heat preservation is carried out for 0.5-1 h, and water cooling is carried out;
3) And (3) hot rolling: heating the alloy square bar to 700-850 ℃, carrying out hot rolling after heat preservation for 1.4-2.3 hours, carrying out rolling for 9-10 times, and rolling into a bar with the diameter of 10-13 mm, wherein the deformation of each pass in the 1 st-5 th passes is 10-15%, the interval time of two adjacent passes in the 1 st-5 th passes is 15-25 s, the deformation of each pass in the 6 th and subsequent passes is not higher than 22%, and the interval time of two adjacent passes in the 6 th and subsequent passes is 30-40 s;
4) Oxidation annealing treatment: oxidizing and annealing the bar at 570-750 ℃, preserving heat for 0.7-1.8 h, and air-cooling;
5) And (3) hot drawing: the bar after the oxidation annealing treatment is heated by a tube furnace to be subjected to hot drawing, and water cooling is carried out at an outlet, wherein the drawing temperature is 780-800 ℃, the drawing speed is 0.5-0.7 m/min, the drawing passes are 15-20 times, and the diameter size range of the bar obtained after drawing is 0.8-5 mm;
6) And carrying out vacuum hot straightening on the drawn bar, heating to 640-770 ℃, and longitudinally cutting the bar to obtain bone pins.
The following details the steps:
step 1):
the alloy cast ingot comprises the following chemical components in percentage by weight: al: 5.2-6.5% (e.g., 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%); v:3.6 to 4.6% (e.g., 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%), preferably 4.1 to 4.5%; cu:4.3 to 6.1% (e.g., 4.3%, 4.5%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.5%, 5.6%, 5.8%, 6.0%), preferably 4.8 to 5.8%, more preferably 5.2 to 5.6%; the balance of Ti;
the alloy cast ingot is formed by jointly pressing a raw material of sponge titanium, tiCu intermediate alloy, alV intermediate alloy, aluminum beans and a high-purity aluminum net serving as a container into an electrode and then smelting.
Preferably, the titanium sponge is grade 0 titanium sponge; the aluminum beans are high-purity aluminum beans with the purity of 99.99 percent.
Preferably, when the ingredients are mixed, the aluminum net is rolled into two cylindrical aluminum net barrels with unequal bottom diameters, the two aluminum net barrels are sleeved together, tiCu intermediate alloy is filled in the space between the two aluminum net barrels, and the mixture of aluminum beans, titanium sponge and AlV intermediate alloy is filled in the aluminum net barrels.
Then, embedding an aluminum net barrel into an electrode mould by using a mixture of aluminum beans and titanium sponge, pressing into a smelting electrode, and smelting into an alloy cast ingot with the components.
Preferably, the smelting is vacuum consumable furnace smelting.
Step 2):
heating the alloy ingot to 980-1170 ℃ (e.g. 990, 1000, 1050 and 1100 ℃), preserving heat for 4-5 hours, and performing hot forging, wherein the total forging ratio of the forging process is 5-6, and forging the alloy ingot into a slab with the thickness of 50-60 mm and the width of 500-550 mm along the axial direction of the ingot; cutting the slab into square bars along the length direction, heating to 840-1060 ℃ again (such as 850, 900, 950, 1000, 1050 ℃), preserving heat for 0.5-1 h, and water-cooling.
Step 3):
the alloy square bar is heated to 700-850 ℃ (such as 700, 750, 800 and 850 ℃), and is subjected to heat preservation for 1.4-2.3 hours (such as 1.5, 1.8, 2 and 2.2 hours), hot rolling is carried out for 9-10 times, and bar materials with the diameter of 10-13 mm are rolled, wherein the deformation amount of each time of the 1-5 times is 10-15% (such as 10%, 11%, 12%, 13%, 14 and 15%), the interval time of two adjacent times of the 1-5 times is 15-25 seconds (such as 15s, 16s, 17s, 18s, 20s, 22s, 24s and 25 s), and the deformation amount of each time of the 6 times and the subsequent times is not more than 22% (such as 10%, 12%, 14%, 15%, 16%, 18 and 20%), and the interval time of the adjacent times of the 6 times of the two times of the 6 times is 30-40 s (such as 30s, 32s, 34s, 35s, 36s, 38s and 40 s).
Step 4):
the oxidation annealing temperatures are 580, 600, 620, 650, 660, 680, 700, 720 ℃, and the incubation times are 0.8, 0.9, 1.0, 1.2, 1.5, 1.8 hours, for example.
Preferably, a centerless lathe is used to remove surface defects from the bar prior to the oxidative annealing process.
Step 5):
the drawing temperatures are 780, 790 and 800 ℃, the drawing speeds are 0.5, 0.6 and 0.7m/min, and the drawing passes are 15, 16, 17, 18, 19 and 20 times.
Preferably, the temperature of the water-cooled cooling water is 10-20 ℃ (such as 10, 12, 14, 15, 16, 18 and 20 ℃), the number of cooling water nozzles is 2-3, the water flow rate is 1.2-2.2 m/s (such as 1.2, 1.4, 1.5, 1.6, 1.8, 2.0 and 2.2 m/s), and preferably 1.6-1.8 m/s.
Step 6):
the hot straightening temperature is, for example, 650, 660, 680, 700, 720, 740, 750, 760 ℃;
preferably, the hot straightening is followed by centerless grinding, polishing and cleaning, and the bar is slit into bone pins.
The bone spicule has a size phi of 2.0-6.5mmx20-80 mm, a shear strength of 610-730MPa, an elongation of more than or equal to 12%, a cytotoxicity grade rating of less than or equal to 1 grade, and a pitting potential of more than or equal to 1720mV. Based on the co-culture results of TC4 titanium alloy contaminated with methicillin-resistant staphylococcus aureus as a comparison benchmark, the spicules can provide a relative antimicrobial rate of greater than 99% in a co-culture model of an implant contaminated with methicillin-resistant staphylococcus aureus.
According to a second aspect of the present invention, there is provided a method for preparing a high shear strength bone needle capable of inhibiting a drug-resistant bacterial biofilm, comprising the steps of:
1) Smelting: the raw materials of sponge titanium, tiCu intermediate alloy, alV intermediate alloy, aluminum beans and aluminum mesh are proportioned according to the following components in percentage by weight: al: 5.2-6.5%, V: 3.6-4.6%, cu: 4.3-6.1% of Ti and the balance;
making an aluminum net into a container, filling the container with titanium sponge, tiCu intermediate alloy, alV intermediate alloy and aluminum beans, pressing the container into a smelting electrode by using an electrode die, and smelting the smelting electrode into alloy cast ingots;
2) Forging: heating the alloy ingot to 980-1170 ℃, preserving heat for 4-5 hours, performing hot forging, wherein the total forging ratio is 5-6, forging into a plate blank along the axial direction of the ingot, and cutting the plate blank into square bars along the length direction; the square rod is heated to 840-1060 ℃ again, heat preservation is carried out for 0.5-1 h, and water cooling is carried out;
3) And (3) hot rolling: heating the alloy square bar to 700-850 ℃, carrying out hot rolling after heat preservation for 1.4-2.3 hours, carrying out rolling for 9-10 times, and rolling into a bar with the diameter of 10-13 mm, wherein the deformation of each pass in the 1 st-5 th passes is 10-15%, the interval time of two adjacent passes in the 1 st-5 th passes is 15-25 s, the deformation of each pass in the 6 th and subsequent passes is not higher than 22%, and the interval time of two adjacent passes in the 6 th and subsequent passes is 30-40 s;
4) Oxidation annealing treatment: oxidizing and annealing the bar at 570-750 ℃, preserving heat for 0.7-1.8 h, and air-cooling;
5) And (3) hot drawing: the bar after the oxidation annealing treatment is heated by a tube furnace to be subjected to hot drawing, and water cooling is carried out at an outlet, wherein the drawing temperature is 780-800 ℃, the drawing speed is 0.5-0.7 m/min, the drawing passes are 15-20 times, and the diameter size range of the bar obtained after drawing is 0.8-5 mm;
6) And carrying out vacuum hot straightening on the drawn bar, heating to 640-770 ℃, and longitudinally cutting the bar to obtain bone pins.
The content of the second aspect corresponds to the corresponding content of the first aspect, and is not described here again.
The beneficial effects are that: (1) Aiming at the application requirement of the spicules and the design of alloy components, the spicules with high shear strength and the drug-resistant bacterial biomembrane inhibition can be obtained by adopting a special processing technology, the required equipment and the processing technology are simple, and the mass production can be satisfied.
(2) The bone needle silk material produced by the invention can obtain higher shearing strength (610-730 MPa), and can ensure excellent strong plasticity. Spicules can provide a relative antimicrobial rate of greater than 99% in co-culture models of implants contaminated with methicillin-resistant staphylococcus aureus.
Drawings
FIG. 1 is a schematic cross-sectional view of a pressed double layer high purity aluminum mesh electrode.
Fig. 2 is a schematic structural diagram of a hot drawing water cooling device.
Reference numerals: 1-high-purity aluminum net barrel, 2-tube furnace, 3-cooling water nozzle and 4-drawing die.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
Raw materials: grade 0 titanium sponge (99.8%) available from jindati industries, inc.
Intermediate alloy: (1) TiCu intermediate alloy, which comprises the following components in percentage by mass: 50% Ti, 50% Cu; (2) AlV intermediate alloy, the components (mass percent): 40% Al, 60% V. Master alloys were purchased from beijing prosper source metal materials limited.
High purity aluminum beans (99.9%) were purchased from eastern high new metals materials limited.
High purity aluminum mesh (99.9%) from eastern high new metals materials limited.
A high shear strength bone pin capable of inhibiting drug-resistant bacterial biofilm, prepared by a method comprising the steps of:
1) Smelting: smelting by using a vacuum consumable furnace, wherein the raw materials are 0-level titanium sponge, tiCu intermediate alloy, alV intermediate alloy, high-purity aluminum beans and high-purity aluminum nets; mechanically and uniformly mixing the aluminum beans and the titanium sponge by using a mixer, rolling the aluminum net into a cylinder shape, sleeving two aluminum net barrels together, filling TiCu intermediate alloy between the two aluminum net barrels, and filling a mixture of the aluminum beans, the titanium sponge and the AlV intermediate alloy in the aluminum net barrels. Finally, embedding the aluminum net barrel into an electrode mold by using the mixture of aluminum beans and titanium sponge, pressing into a smelting electrode, and smelting the pressed electrode into an alloy cast ingot as shown in figure 1.
2) Forging: and heating the alloy ingot to 1000 ℃, preserving heat for 4 hours, performing hot forging, wherein the total forging ratio is 5-6, forging into a plate blank along the axial direction of the ingot, and cutting the plate blank into square bars along the length direction. And (5) heating the square rod to 900 ℃ again, preserving heat for 1h, and cooling with water.
3) And (3) hot rolling: the alloy square bar is heated to 820 ℃, and is kept for 2 hours for hot rolling, and rolling parameters are shown in table 2. Finally rolling the steel bar into a bar with the diameter of 10-13 mm.
4) Oxidation annealing treatment: the rolled bar is used for removing surface defects by a centerless lathe, the oxidation annealing temperature of the bar is 750 ℃, the heat preservation is carried out for 1.5h, and the air cooling is carried out.
5) And (3) hot drawing: the oxidized bar is subjected to hot drawing, and the hot drawing adopts a device with water cooling equipment, and the structure of the device is shown in figure 2, and the device comprises a tube furnace 2, a cooling water nozzle 3 and a drawing die 4. The bar enters into the tube furnace from one end and is heated, then passes through the other end, and is cooled by water at the cooling water nozzle of the outlet, and the drawing parameters are shown in Table 3.
6) And (3) carrying out vacuum hot straightening on the pulled bar, heating to 700 ℃, carrying out centerless grinding, polishing, and cleaning, and carrying out longitudinal cutting processing on the obtained bar to obtain the bone needle.
The alloy compositions and preparation processes of the respective examples and comparative examples are shown in table 1.
Table 1 titanium alloy compositions (wt.%) and preparation processes used in examples and comparative examples
。
Table 2 parameters of the rolling process
。
TABLE 3 thermal pullout process parameters
。
Test example 1 ingot uniformity detection
And detecting the distribution uniformity of copper elements of the smelted cast ingot. 7 point samples are uniformly taken along the diameter of the cross section on the riser, the middle part and the bottom of the cast ingot, the concentration of copper element of each sample is analyzed, wherein the difference between the highest value and the lowest value is recorded as the concentration difference of copper element on the cross section, and the result is shown in Table 4.
TABLE 4 copper element distribution concentration differences for examples and comparative examples
。
Test example 2 Performance test
The shear resistance of the example and comparative materials was tested using an XJ-A type shear strength tester. The loading speed is 10mm/min, three parallel samples are taken from each group, and the shear strength is obtained through experiments.
The room temperature tensile mechanical properties of the example and comparative example materials were tested using an Instron model 8872 tensile tester at a tensile rate of 0.5 mm/min. Before testing, the materials were machined into standard tensile samples with thread diameters of 10mm, gauge length diameters of 5mm and gauge length of 30 mm by using a lathe, three parallel samples were taken from each group of heat-treated samples, and the mechanical properties obtained by the experiment, including tensile strength and elongation, were shown in table 4.
According to national standard GBT16886.5-2017 medical instrument biological evaluation, thiazole blue (MTT) colorimetric method is adopted to measure cell survival rate, so that the biological safety of the titanium alloy of the examples and the comparative examples is evaluated. The results of each group were then rated according to a 5-level toxicity rating (0, 1 meeting the requirements of biomedical materials) and the results are shown in Table 5.
According to the change of pitting potential in electrochemical corrosion performance detection, the microbial corrosion resistance of the material can be reflected. The titanium alloys of examples and comparative examples were tested for corrosion resistance by obtaining anodic polarization curves using stainless steel pitting potential measurement method (national standard: GB/T17899-1999), and the test results are shown in Table 5.
Table 5 properties of the examples and comparative materials
。
Test example 3 in vitro Co-culture test
The methicillin-resistant staphylococcus aureus strain is inoculated on the inclined plane of a nutrient agar culture medium (NA), is cultured for 24 hours at the temperature of (37+/-1), and is preserved at the temperature of 0-5 ℃ for no more than 1 month to be used as the inclined plane preserving strain.
The slant-preserving bacteria are transferred onto a plate nutrient agar medium, and cultured for 24 hours at the temperature of (37+/-1) DEG C, and transferred 1 time a day for no more than 2 weeks. Fresh bacterial cultures (24 h in-transit) should be used for the test after 2 consecutive transfers.
Taking small amount (1-2 loops) of fresh bacteria from culture medium with inoculating loop, adding into culture solution, sequentially adding 10 times of dilution, counting with cell counting plate, and selecting bacterial solutionThe concentration is 5.0X10 5 cfu/ml～10.0×10 5 The cfu/ml dilution was used as the test bacterial liquid.
15 sterilization plates with phi 90mm are prepared, 5-6 sterile filter papers with phi 90mm are paved on the bottoms of the plates, and a proper amount of sterile purified water is poured into the plates to enable the filter papers to fully absorb water. The filter paper is preferably pressed with sterile forceps without precipitation of a large amount of water.
15 sterile filters of 0.24 μm. Times.50 mm were covered on sterile filters of each dish and spread flat. 0.2ml of the test bacterial liquid was dropped on a sterile filter membrane having a diameter of 0.24 μm X50 mm.
A negative control TC4 alloy sample (A), a blank control medical high-density polyethylene sample (B) and a sample supply (C) are clamped by using a sterilizing forceps, 5 samples are parallel to each other, and are covered on a sterile filter membrane with phi of 0.24 mu m multiplied by 50mm, so that bacterial liquid is uniformly contacted with the samples, and the samples are cultured for 24 hours under the condition of (37+/-1) DEG C.
Taking out the samples cultured for 24 hours, adding 20ml of eluent, repeatedly washing the sample A, the sample B, the sample C and the cover film (preferably, washing the film by clamping with forceps), and shaking thoroughly. 1ml of eluent stock solution is sucked by a sterilizing gun head and transferred into a sterile culture dish, nutrient agar culture medium cooled to 46 ℃ is timely injected into the culture dish for about 15ml, and the culture dish is rotated to be uniformly mixed. The plating operation was repeated 2 times to obtain 2 elution-crude culture dishes. And (3) slowly injecting 1ml of eluent stock solution into a test tube containing 9ml of sterilized normal saline along the tube wall (note that the tip of the gun head does not touch the diluent in the tube), shaking the test tube, and uniformly mixing to prepare the eluent with the ratio of 1:10. 1ml of the 1:10 elution diluent is transferred into a sterile culture dish, and the nutrient agar medium cooled to 46 ℃ is injected into about 15ml of the culture dish in time, and the culture dish is rotated to be uniformly mixed. The plating operation was repeated 2 times to obtain 2 plates of 1:10 elution diluent. Taking 1ml of 1:10 eluting diluent, slowly injecting into a test tube containing 9ml of sterilized normal saline along the tube wall (note that the tip of the gun head does not touch the diluent in the tube), shaking the test tube, and uniformly mixing to prepare 1:100 eluting diluent. 1ml of the 1:100 elution diluent is taken and transferred into a sterile culture dish, and the nutrient agar medium cooled to 46 ℃ is injected into about 15ml of the culture dish in time, and the culture dish is rotated to be uniformly mixed. The plating operation was repeated 2 times to obtain 2 plates of 1:100 elution diluent. Taking 1ml of 1:100 eluting diluent, slowly injecting into a test tube containing 9ml of sterilized normal saline along the tube wall (note that the tip of the gun head does not touch the diluent in the tube), shaking the test tube, and uniformly mixing to prepare the 1:1000 eluting diluent. 1ml of the 1:1000 eluting diluent is transferred into a sterile culture dish, and the nutrient agar medium cooled to 46 ℃ is injected into the culture dish for about 15ml in time, and the culture dish is rotated to be uniformly mixed. The plating operation was repeated 2 times to obtain 2 plates of 1:1000 elution diluent.
When plate colony counting is carried out, naked eyes can be used for observing, and magnifying glass is used for checking if necessary, so that omission is avoided. After counting the colonies of each plate, the average colony count of each plate at the same dilution was determined. Plates with colony numbers between 30 and 300 were selected as a colony count measurement standard. Two plates should be used for one dilution, an average number of two plates should be used, when one plate has larger plate-shaped colony growth, the plate without plate-shaped colony growth should not be used as the colony number of the dilution, if the plate-shaped colony is less than half of the plate, and the colony distribution in the other half is very uniform, the number of the whole dish colonies can be calculated by multiplying 2 after the half plate. If there is chain colony growth in the plate (there is no obvious limit between colonies), if there is only one chain, it can be regarded as one colony; if there are several strands of different origin, each strand should be considered as a colony meter. Dilutions should be selected with average colony counts between 30 and 300, multiplied by dilution fold to fill out the report. If there are two dilutions, the number of colonies grown is between 30 and 300, depending on the ratio of the two. If the ratio is less than or equal to 2, reporting the average; if greater than 2, the smaller number is reported. If the average colony count for all dilutions is greater than 300, the dilution should be reported as the average colony count for the highest dilution multiplied by the dilution. If the average colony count for all dilutions is less than 30, the average colony count at the lowest dilution should be reported as multiplied by the dilution. If all dilutions were sterile, they were reported as less than 1 times the lowest dilution (see example 6 in table 6). If the average colony count for all dilutions is not between 30 and 300, with a fraction greater than 300 or less than 30, the average colony count closest to 30 or 300 is multiplied by the dilution fold report (see example 7 in Table 6).
Colony numbers are reported as actual numbers within 100, and at values greater than 100, two significant digits are employed, followed by a number after the two significant digits, calculated by rounding. To shorten the number zero after the number, it can also be expressed by an index of 10 (see table 6).
TABLE 6 dilution selection and colony count reporting method
。
Multiplying the measured viable count result by 100 to obtain actual viable count values of the recovered viable count after culturing the sample A, the sample B and the sample C for 24 hours, wherein the actual viable count values are A, B, C respectively, so that the test result meets the following requirements, and otherwise, the test is invalid:
the 5 parallel viable bacteria values of the same blank control sample B are in line with (the highest logarithmic value-the lowest logarithmic value)/the average viable bacteria value logarithmic value is not more than 0.3;
the actual recovery viable bacteria value A of the sample A should be not less than 1.0X10 5 cfu/tablet, and the actual recovery viable bacteria value B of the sample B should be no less than 1.0X10% 4 cfu/tablet.
The antibacterial ratio is calculated according to formula (A.1).
（A.1）
Wherein:
r-antibacterial rate,%;
b, average recovery bacteria number of a blank control sample, cfu/tablet;
c, average recovery bacteria number of antibacterial samples, cfu/tablet.
The results are shown in Table 7.
Table 7 antibacterial rate data for examples and comparative examples
。
The result shows that the segregation of copper element can be improved by using intermediate alloy and optimizing the raw material arrangement mode (using aluminum net to intensively distribute copper element), and the spicule with high shear strength and drug-resistant bacterial biomembrane can be inhibited by controlling alloy components and special processing technology.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A high shear strength bone pin capable of inhibiting drug-resistant bacterial biofilm, characterized by being prepared by a method comprising the following steps:
1) Smelting: the raw materials of sponge titanium, tiCu intermediate alloy, alV intermediate alloy, aluminum beans and aluminum mesh are proportioned according to the following components in percentage by weight: al: 5.2-6.5%, V: 3.6-4.6%, cu: 4.3-6.1% of Ti and the balance;
making an aluminum net into a container, filling the container with titanium sponge, tiCu intermediate alloy, alV intermediate alloy and aluminum beans, pressing the container into a smelting electrode by using an electrode die, and smelting the smelting electrode into alloy cast ingots;
2) Forging: heating the alloy ingot to 980-1170 ℃, preserving heat for 4-5 hours, and then performing hot forging, wherein the total forging ratio is 5-6, forging into a plate blank along the axial direction of the ingot, and cutting the plate blank into square bars along the length direction; the square rod is heated to 840-1060 ℃ again, heat preservation is carried out for 0.5-1 h, and water cooling is carried out;
3) And (3) hot rolling: heating the alloy square bar to 700-850 ℃, carrying out hot rolling after heat preservation for 1.4-2.3 hours, carrying out rolling for 9-10 times, and rolling into a bar with the diameter of 10-13 mm, wherein the deformation of each pass in the 1 st-5 th passes is 10-15%, the interval time of two adjacent passes in the 1 st-5 th passes is 15-25 s, the deformation of each pass in the 6 th and subsequent passes is not higher than 22%, and the interval time of two adjacent passes in the 6 th and subsequent passes is 30-40 s;
4) Oxidation annealing treatment: oxidizing and annealing the bar at 570-750 ℃, preserving heat for 0.7-1.8 h, and air-cooling;
5) And (3) hot drawing: the bar after the oxidation annealing treatment is heated by a tube furnace to be subjected to hot drawing, and water cooling is carried out at an outlet, wherein the drawing temperature is 780-800 ℃, the drawing speed is 0.5-0.7 m/min, the drawing passes are 15-20 times, and the diameter size range of the bar obtained after drawing is 0.8-5 mm;
6) And carrying out vacuum hot straightening on the drawn bar, heating to 640-770 ℃, and longitudinally cutting the bar to obtain bone pins.
2. The bone needle according to claim 1, wherein in step 1), the aluminum net is rolled into two cylindrical aluminum net barrels with unequal bottom diameters, the two aluminum net barrels are sleeved together, a TiCu intermediate alloy is filled in a space between the two aluminum net barrels, and a mixture of aluminum beans, titanium sponge and AlV intermediate alloy is filled in the aluminum net barrels.
3. The bone pin according to claim 1, wherein in step 4), the surface defects of the rod are removed by using a centerless lathe before the oxidation annealing treatment.
4. The bone needle according to claim 1, wherein in the step 5), the temperature of the water-cooled cooling water is 10-20 ℃, the number of cooling water nozzles is 2-3, and the water flow rate is 1.2-2.2 m/s.
5. The bone needle according to any one of claims 1 to 4, wherein the bone needle has a shear strength of 610 to 730mpa, an elongation of 12% or more, a cytotoxicity grade rating of 1% or less, and a pitting potential of 1720mV or more.
6. The preparation method of the high-shear-strength bone needle capable of inhibiting the formation of the drug-resistant bacterial biomembrane is characterized by comprising the following steps of:
1) Smelting: the raw materials of sponge titanium, tiCu intermediate alloy, alV intermediate alloy, aluminum beans and aluminum mesh are proportioned according to the following components in percentage by weight: al: 5.2-6.5%, V: 3.6-4.6%, cu: 4.3-6.1% of Ti and the balance;
making an aluminum net into a container, filling the container with titanium sponge, tiCu intermediate alloy, alV intermediate alloy and aluminum beans, pressing the container into a smelting electrode by using an electrode die, and smelting the smelting electrode into alloy cast ingots;
2) Forging: heating the alloy ingot to 980-1170 ℃, preserving heat for 4-5 hours, and then performing hot forging, wherein the total forging ratio is 5-6, forging into a plate blank along the axial direction of the ingot, and cutting the plate blank into square bars along the length direction; the square rod is heated to 840-1060 ℃ again, heat preservation is carried out for 0.5-1 h, and water cooling is carried out;
3) And (3) hot rolling: heating the alloy square bar to 700-850 ℃, carrying out hot rolling after heat preservation for 1.4-2.3 hours, carrying out rolling for 9-10 times, and rolling into a bar with the diameter of 10-13 mm, wherein the deformation of each pass in the 1 st-5 th passes is 10-15%, the interval time of two adjacent passes in the 1 st-5 th passes is 15-25 s, the deformation of each pass in the 6 th and subsequent passes is not higher than 22%, and the interval time of two adjacent passes in the 6 th and subsequent passes is 30-40 s;
4) Oxidation annealing treatment: oxidizing and annealing the bar at 570-750 ℃, preserving heat for 0.7-1.8 h, and air-cooling;
5) And (3) hot drawing: the bar after the oxidation annealing treatment is heated by a tube furnace to be subjected to hot drawing, and water cooling is carried out at an outlet, wherein the drawing temperature is 780-800 ℃, the drawing speed is 0.5-0.7 m/min, the drawing passes are 15-20 times, and the diameter size range of the bar obtained after drawing is 0.8-5 mm;
6) And carrying out vacuum hot straightening on the drawn bar, heating to 640-770 ℃, and longitudinally cutting the bar to obtain bone pins.
7. The method according to claim 6, wherein in step 1), the aluminum net is rolled into two cylindrical aluminum net barrels with unequal bottom diameters, the two aluminum net barrels are sleeved together, the space between the two aluminum net barrels is filled with TiCu intermediate alloy, and the inside of the aluminum net barrel is filled with a mixture of aluminum beans, titanium sponge and AlV intermediate alloy.
8. The method according to claim 6, wherein in step 4), defects on the surface of the bar are removed by using a centerless lathe before the oxidation annealing treatment.
9. The preparation method according to claim 6, wherein in the step 5), the temperature of the water-cooled cooling water is 10-20 ℃, the number of cooling water nozzles is 2-3, and the water flow rate is 1.2-2.2 m/s.
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Effective date of registration: 20240222 Address after: Building 1, Building 7, Lianfa Industrial Park, No. 158 Hongye Road, Suzhou Industrial Park, Suzhou City, Jiangsu Province, 215124 Applicant after: Suzhou senfeng Medical Equipment Co.,Ltd. Country or region after: China Address before: 100070, 6M Floor, Building 5, Zone 4, Hanwei International Plaza, Fengtai District, Beijing Applicant before: Beijing Zhongke Wande Innovation Technology Co.,Ltd. Country or region before: China Applicant before: Suzhou senfeng Medical Equipment Co.,Ltd. |
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