CN115466868A - Manufacturing method of novel medical oral cavity corrosion-resistant antibacterial titanium alloy - Google Patents
Manufacturing method of novel medical oral cavity corrosion-resistant antibacterial titanium alloy Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
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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
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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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- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Abstract
The invention discloses a manufacturing method of a novel medical oral corrosion-resistant antibacterial titanium alloy, which comprises the following steps: step 1, designing components of a titanium alloy; 1.1, corrosion resistance principle; because the corrosive components in the oral cavity are complex and changeable, the problem of corrosion resistance of the patent titanium alloy must be considered preferentially; the corrosion resistance of the titanium matrix is mainly reflected in the corrosion resistance of oxidizing acid and alkali, and the reduction acid resistance is not ideal; zirconium has excellent reducing acid resistance, and the titanium alloy has more comprehensive and complete corrosion resistance by adding a large amount (more than 10%) of zirconium into titanium; the titanium alloy has the characteristics of high strength, no aluminum and vanadium elements, and the addition of a large proportion of zirconium and trace antibacterial element silver which improve the corrosion resistance of the titanium alloy, improves the mechanical property, the corrosion resistance and the antibacterial property of the titanium alloy, becomes a novel Ti-Zr-Ag series titanium alloy containing trace silver, greatly improves the mechanical property, the corrosion resistance and the antibacterial property of the titanium alloy, and improves the cold and hot processability of the titanium alloy material.
Description
Technical Field
The invention belongs to the technical field of biomedical metal material manufacturing, and particularly relates to a manufacturing method of a novel medical oral corrosion-resistant antibacterial titanium alloy.
Background
Titanium and its alloys are used more and more widely in clinical practice due to their similar elastic modulus to human skeleton, good biocompatibility and excellent corrosion resistance in biological environment. The titanium alloy applied to clinic at present is mainly represented by pure titanium and Ti-6 Al-4V. Pure titanium has good corrosion resistance in physiological environment, but has low strength and poor abrasion resistance, so that the application of the pure titanium to parts with large bearing capacity is limited, and the pure titanium is mainly used for oral repair and bone replacement of parts with small bearing capacity. The Ti-6Al-4V titanium alloy has higher strength and better processing performance, and has wider biomedical application range.
Pure titanium and Ti-6Al-4V titanium alloy are not antibacterial, and the clinical cases of implantation failure due to the inflammatory reaction of human tissues around the implant and the antibacterial failure of the medicament often occur. Particularly for the restoration and implantation of teeth in the oral cavity, the food remains and decays at the root of the teeth due to the very complicated environment in the oral cavity, and higher requirements are put on the corrosion resistance of crowns, denture brackets and implants. Therefore, the research on the aspect of antibacterial titanium alloy is noticed at home and abroad, and the technical route has various characteristics and has not been clinically applied. Therefore, the research and development of the antibacterial titanium alloy not only needs medical development, but also has actual market needs.
Although pure titanium is a main material used for the existing oral implant, the pure titanium is easy to deform and fall off under stress due to low strength, and the service life of teeth is seriously influenced, particularly the rear teeth with the largest stress of chewing are implanted. The Ti-6Al-4V titanium alloy has high strength, but the alloy contains aluminum and vanadium, so that the corrosion resistance of the alloy in oral environment is insufficient for a long time, and the aluminum and the vanadium have adverse effects on human tissues.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the existing defects and provide a manufacturing method of a novel medical oral corrosion-resistant antibacterial titanium alloy, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a manufacturing method of a novel medical oral corrosion-resistant antibacterial titanium alloy comprises the following steps:
step 1, designing components of a titanium alloy;
1.1, corrosion resistance principle;
because the corrosive components in the oral cavity are complex and changeable, the problem of corrosion resistance of the patent titanium alloy must be considered preferentially; the corrosion resistance of the titanium matrix is mainly reflected in the corrosion resistance of oxidizing acid and alkali, and the reduction acid resistance is not ideal; the zirconium has excellent reducing acid resistant effect, and the titanium alloy has more comprehensive and complete corrosion resistance by adding a large amount (more than 10 percent) of zirconium into the titanium;
1.2, strengthening the titanium alloy;
in order to improve the service performance of the medical oral titanium alloy, the strength of the titanium alloy must be strengthened by adding a solid solution strengthening element on the basis of pure titanium; zirconium is infinitely solid-dissolved in titanium, and a brittle phase cannot be generated; meanwhile, the addition of zirconium has little influence on the phase change point of the titanium alloy, heat treatment strengthening is not needed, and the manufacturing procedures are reduced; the cost factor is comprehensively considered, and the adding amount of zirconium in the titanium alloy is controlled to be 10-20%;
1.3, antibacterial principle;
at present, no antibacterial titanium alloy appears in medical oral materials used at home and abroad, but with the wide application of tooth implantation technology, the antibacterial property of commonly used pure titanium implants is insufficient, and the antibacterial effect is more and more important; silver is one of the elements with the best antibacterial property, silver can perform eutectoid reaction in the titanium alloy, and the silver can form silver-rich layers with different gradients from the surface to the inside on the surface of a medical titanium alloy metal device after heat treatment at a certain temperature, so that the antibacterial property of the titanium alloy is greatly improved, and the antibacterial property can be met by adding a trace amount of silver (less than 0.5%) in consideration of comprehensive cost and performance;
step 2, intermediate alloy smelting technology;
2.1, in the Ti-Zr-Ag titanium alloy, titanium and zirconium are infinitely solid-dissolved, so that the titanium and the zirconium are added in a pure metal state in the smelting process; silver is very easy to segregate in the process of smelting and alloying because the melting point of silver in the titanium alloy is greatly different from that of titanium, and the traditional adding method is to add pure silver, but the segregation of ingot components is difficult to control, so that the adding of silver in a zirconium-silver intermediate alloy mode is the best scheme;
2.2, because the zirconium sponge which is the raw material of zirconium has great chemical activity and is very easy to oxidize, the zirconium-silver intermediate alloy must be smelted by a smelting furnace with high vacuum degree, and the intermediate alloy is smelted by a vacuum electron beam furnace with high vacuum degree;
step 3, producing a titanium alloy ingot;
the titanium alloy ingot is a basic raw material for manufacturing any titanium alloy processing material and product, and the quality of the titanium alloy ingot determines the quality of the titanium alloy material product; therefore, the vacuum consumable furnace self-made by a company and provided with a plurality of patent technologies is adopted for smelting production, and the vacuum consumable furnace is subjected to vacuum consumable smelting for more than two times, and because the vacuum consumable furnace adopts a water-cooled copper crucible and a computer controls the smelting and cooling speed, the titanium alloy ingot casting without other impurity pollution and with high cleanliness is ensured to be produced; because the method of adding elements into the intermediate alloy is adopted, the titanium alloy ingot casting has high uniformity and consistency of the alloy components, and reaches the leading medical titanium alloy ingot casting standard at home and abroad;
step 4, producing the titanium alloy bar for the oral cavity;
in order to ensure the structure and mechanical property of the titanium alloy material for the oral cavity, the patent adopts the high-precision warm drawing process of repeated upsetting free forging cogging, radial forging rough forging, rolling of a hot rolling mill and self-patented technology, so that the titanium alloy bar product has no anisotropy, uniform and fine structure and high consistency;
4.1, the production process of the titanium alloy bar comprises the following steps:
heating a titanium alloy cast ingot by an electric furnace, freely forging and cogging a hydraulic quick forging machine, grinding a blank, sawing and blanking, upsetting and forging the hydraulic quick forging machine for more than three times, grinding a thick bar blank, finely forging a bar by a radial forging machine, grinding the surface of the bar, rolling the thin bar by a hot rolling machine, peeling and grinding the surface of the bar, drawing by self-patented technology at a high temperature, straightening the bar, polishing the bar, detecting mechanical properties, detecting tissues, detecting surface quality, detecting defects, detecting dimension specification and tolerance, and packaging and warehousing;
cogging temperature: 1100-1150 deg.C
The precision forging temperature: 930-980 deg.C
Hot rolling temperature: 950-980 deg.C
Temperature of warm drawing: 600-800 ℃;
4.2, controlling the mechanical property range of the oral rod;
mechanical Properties of the working Material (annealed State)
σb1050-1200MPa
σ0.2990--1030MPa
δ18-22％
Ψ21--28％
The comprehensive performance of the alloy exceeds that of all medical titanium alloys used at present;
4.3, tissue control;
the titanium alloy is alpha-structure titanium alloy, and the grain size is controlled to be above grade 3 of the international medical titanium alloy standard;
step 5, performing an antibacterial treatment process on the titanium alloy dental product;
titanium alloy dental products represented by implants are combined with gingival tissues, and the antibiosis is realized by higher silver ions on the surfaces of the implants; according to the characteristics of silver element in titanium alloy, providing a heat treatment method in which the silver content is gradually reduced from the surface of the implant to the inside;
the treatment process comprises the following steps: cleaning a mechanically processed finished product of the implant, placing the mechanically processed finished product into a vacuum heat treatment furnace, vacuumizing, heating to 450-650 ℃, preserving heat for more than 8 hours, cooling, discharging, detecting and packaging;
step 6, performing a corrosion resistance experiment on the titanium alloy;
sulfuric acid: the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
hydrochloric acid: the concentration is 1-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
acetic acid: the concentration is 7-9%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
brine: the concentration is 5-15%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
pure alkaline water; the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
step 7, performing an antibacterial experiment;
the inventor entrusts a certain hospital in Shenyang to carry out an antibacterial experiment, and the experimental result is as follows: the common anaerobic bacteria inactivation rate of 3 gingival periodontal tissues is more than 90%.
Preferably, the range of the main components of the titanium alloy in the step one; 12-17% Zr, ag0.2-0.5% and the balance Ti.
Preferably, in step two: the master alloy comprises the following components: ag8.00-10.00% and the rest is Zr.
Preferably, in step two: the production process of the zirconium-silver intermediate alloy comprises the following steps: mixing sponge zirconium (Zr is more than 99.9 percent) and silver powder (Ag is more than 99.90 percent), placing the mixture into a vacuum electron beam furnace charge box, vacuumizing the vacuum electron beam furnace, smelting a zirconium-silver alloy cast ingot in a high vacuum state, cooling an intermediate alloy cast ingot along with the furnace in the high vacuum state, breaking vacuum at room temperature, discharging the intermediate alloy cast ingot, analyzing the components of the intermediate alloy, mechanically processing the intermediate alloy cast ingot to particles (or cutting), detecting and packaging for later use.
Preferably, in step three: the production process flow of the titanium alloy ingot casting is as follows: titanium sponge (more than GB0 level), zirconium sponge (more than 1 level), zirconium-silver intermediate alloy, titanium alloy consumable electrode blocks are extruded by a hydraulic press, titanium alloy consumable electrodes are assembled and welded in a vacuum welding box, a vacuum consumable furnace is smelted for the first time, ingots are cooled along with the furnace and taken out of the furnace, the head and the tail of the once consumable ingots are machined, secondary consumable electrodes are assembled and welded, the vacuum consumable furnace is smelted for the second time, the titanium alloy ingots are cooled by argon assistance, the ingots are broken in vacuum at room temperature and taken out of the furnace, the head and the tail of the ingots are machined, the surfaces of the ingots are pulled, the alloy components and impurities are sampled at five points from top to bottom of the ingots, and the ingots are detected and put in storage for later use.
Preferably, in the third step: controlling the range of ingot casting components; main component Zr13.00-17.00%, ag0.30-0.45%, and the rest is Ti.
Preferably, in the third step: controlling the range of impurities; o is less than 0.12 percent, N is less than 0.002 percent, H is less than 0.001 percent, C is less than 0.008 percent, and Fe is less than 0.05 percent.
Compared with the prior art, the invention provides a manufacturing method of a novel medical oral cavity corrosion-resistant antibacterial titanium alloy, which has the following beneficial effects:
the titanium alloy has high strength, does not contain aluminum and vanadium elements, is added with zirconium and trace antibacterial element silver which are used for improving the corrosion resistance of the titanium alloy in a larger proportion, improves the mechanical property, the corrosion resistance and the antibacterial property of the titanium alloy, becomes a novel Ti-Zr-Ag series titanium alloy containing trace silver, greatly improves the mechanical property, the corrosion resistance and the antibacterial property of the titanium alloy, and improves the cold and hot processing performance of the titanium alloy material.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a manufacturing method of a novel medical oral cavity corrosion-resistant antibacterial titanium alloy comprises the following steps:
step 1, designing components of a titanium alloy;
1.1, corrosion resistance principle;
because the corrosive components in the oral cavity are complex and changeable, the problem of corrosion resistance of the patent titanium alloy must be considered preferentially; the corrosion resistance of the titanium matrix is mainly reflected in the corrosion resistance of oxidizing acid and alkali, and the reduction acid resistance is not ideal; zirconium has excellent reducing acid resistance, and the titanium alloy has more comprehensive and complete corrosion resistance by adding a large amount (more than 10%) of zirconium into titanium;
1.2, titanium alloy strengthening principle;
in order to improve the service performance of the medical oral titanium alloy, the strength of the titanium alloy must be strengthened by adding a solid solution strengthening element on the basis of pure titanium; zirconium is infinitely solid-dissolved in titanium, and a brittle phase cannot be generated; meanwhile, the addition of zirconium has little influence on the phase change point of the titanium alloy, heat treatment strengthening is not needed, and the manufacturing procedures are reduced; the cost factor is comprehensively considered, and the adding amount of zirconium in the titanium alloy is controlled to be 10-20%;
1.3, antibacterial principle;
at present, no antibacterial titanium alloy appears in medical oral cavity materials used at home and abroad, but with the wide application of tooth implantation technology, the antibacterial property of commonly used pure titanium implants is insufficient, and the antibacterial function is more and more important; silver is one of the elements with the best antibacterial property, silver can perform eutectoid reaction in the titanium alloy, and the silver can form silver-rich layers with different gradients from the surface to the inside on the surface of a medical titanium alloy metal device after heat treatment at a certain temperature, so that the antibacterial property of the titanium alloy is greatly improved, and the antibacterial property can be met by adding a trace amount of silver (less than 0.5%) in consideration of comprehensive cost and performance;
step 2, intermediate alloy smelting technology;
2.1 in the Ti-Zr-Ag titanium alloy, titanium and zirconium are infinitely solid-dissolved, so that the titanium and the zirconium are added in a pure metal state in the smelting process; silver is very easy to segregate in the process of smelting and alloying because the melting point of silver is greatly different from that of titanium in the titanium alloy, and the traditional adding method is to add pure silver, but the segregation of ingot components is difficult to control, so that the silver is added in a zirconium-silver intermediate alloy mode to be the best scheme;
2.2, because the zirconium sponge which is the raw material of zirconium has great chemical activity and is very easy to oxidize, the zirconium-silver intermediate alloy must be smelted by a smelting furnace with high vacuum degree, and the intermediate alloy is smelted by a vacuum electron beam furnace with high vacuum degree;
step 3, producing a titanium alloy ingot;
the titanium alloy ingot is a basic raw material for manufacturing any titanium alloy processing material and product, and the quality of the titanium alloy ingot determines the quality of the titanium alloy material product; therefore, the self-made vacuum consumable furnace with multiple patent technologies by a company is adopted for smelting production, and through more than two times of vacuum consumable smelting, because the vacuum consumable furnace adopts a water-cooled copper crucible and a computer controls the smelting and cooling speed, the titanium alloy ingot casting with no other impurity pollution and high cleanliness is ensured to be produced; because the method of adding elements into the intermediate alloy is adopted, the titanium alloy ingot casting has high uniformity and consistency of the alloy components, and reaches the leading medical titanium alloy ingot casting standard at home and abroad;
step 4, producing the titanium alloy bar for the oral cavity;
in order to ensure the structure and mechanical property of the titanium alloy material for the oral cavity, the patent adopts the high-precision warm drawing process of repeated upsetting free forging cogging, radial forging rough forging, rolling of a hot rolling mill and self-patented technology, so that the titanium alloy bar product has no anisotropy, uniform and fine structure and high consistency;
4.1, the production process of the titanium alloy bar comprises the following steps:
heating a titanium alloy cast ingot by an electric furnace, freely forging and cogging a hydraulic quick forging machine, grinding a blank, sawing and blanking, upsetting and forging the hydraulic quick forging machine for more than three times, grinding a thick bar blank, finely forging a bar by a radial forging machine, grinding the surface of the bar, rolling the thin bar by a hot rolling machine, peeling and grinding the surface of the bar, drawing by self-patented technology at a high temperature, straightening the bar, polishing the bar, detecting mechanical properties, detecting tissues, detecting surface quality, detecting defects, detecting dimension specification and tolerance, and packaging and warehousing;
cogging temperature: 1100-1150 deg.C
The precision forging temperature: 930-980 deg.C
Hot rolling temperature: 950-980 deg.C
Temperature of warm drawing: 600-800 ℃;
4.2, controlling the mechanical property range of the bar for oral cavity;
mechanical Properties of working Material (annealed State)
σb1050-1200MPa
σ0.2990--1030MPa
δ18-22％
Ψ21--28％
The comprehensive performance of the alloy exceeds that of all medical titanium alloys used at present;
4.3, tissue control;
the titanium alloy is alpha-structure titanium alloy, and the grain size is controlled to be above grade 3 of the international medical titanium alloy standard;
step 5, performing an antibacterial treatment process on the titanium alloy dental product;
titanium alloy dental products represented by implants are combined with gingival tissues, and the antibiosis is realized by higher silver ions on the surfaces of the implants; according to the characteristics of silver element in titanium alloy, a heat treatment method with the silver content gradually reduced from the surface of the implant to the inside is provided;
the treatment process comprises the following steps: cleaning a mechanically processed finished product of the implant, placing the mechanically processed finished product into a vacuum heat treatment furnace, vacuumizing, heating to 450-650 ℃, preserving heat for more than 8 hours, cooling, discharging, detecting and packaging;
step 6, performing a corrosion resistance experiment on the titanium alloy;
sulfuric acid: the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
hydrochloric acid: the concentration is 1-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
acetic acid: the concentration is 7-9%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
brine: the concentration is 5-15%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
pure alkaline water; the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
step 7, antibacterial experiment;
the Shenyang hospital is entrusted to carry out an antibacterial experiment, and the experimental result is as follows: the common anaerobic bacteria inactivation rate of 3 gingival periodontal tissues is more than 90%.
In the invention, preferably, the range of the main components of the titanium alloy in the step one; 12-17% Zr, ag0.2-0.5% and the balance Ti.
In the present invention, preferably, in step two: the master alloy comprises the following components: ag8.00-10.00% and the balance Zr.
In the present invention, preferably, in step two: the production process of the zirconium-silver intermediate alloy comprises the following steps: mixing zirconium sponge (Zr is more than 99.9 percent), silver powder (Ag is more than 99.90 percent), placing the mixture into a vacuum electron beam furnace charge box, vacuumizing the vacuum electron beam furnace, smelting a zirconium-silver alloy cast ingot in a high vacuum state, cooling an intermediate alloy cast ingot along with the furnace in the high vacuum state, breaking vacuum at room temperature, discharging the intermediate alloy cast ingot, analyzing the components of the intermediate alloy, mechanically processing the intermediate alloy cast ingot to particles (or cutting), detecting and packaging for later use.
In the present invention, preferably, in step three: the production process flow of the titanium alloy ingot comprises the following steps: titanium sponge (more than GB0 level), zirconium sponge (more than 1 level), zirconium-silver intermediate alloy, titanium alloy consumable electrode blocks are extruded by a hydraulic press, titanium alloy consumable electrodes are assembled and welded in a vacuum welding box, a vacuum consumable furnace is smelted for the first time, ingots are cooled along with the furnace and taken out of the furnace, the head and the tail of the once consumable ingots are machined, secondary consumable electrodes are assembled and welded, the vacuum consumable furnace is smelted for the second time, the titanium alloy ingots are cooled by argon assistance, the ingots are broken in vacuum at room temperature and taken out of the furnace, the head and the tail of the ingots are machined, the surfaces of the ingots are pulled, the alloy components and impurities are sampled at five points from top to bottom of the ingots, and the ingots are detected and put in storage for later use.
In the present invention, preferably, in step three: controlling the range of ingot casting components; 13.00 to 17.00 percent of main component ZrZr0.30 to 0.45 percent of Ag0 and the balance Ti.
In the present invention, preferably, in step three: controlling the range of impurities; less than 0.12 percent of O, less than 0.002 percent of N, less than 0.001 percent of H, less than 0.008 percent of C and less than 0.05 percent of Fe.
Example one
A manufacturing method of a novel medical oral cavity corrosion-resistant antibacterial titanium alloy comprises the following steps of designing components of the titanium alloy;
1. corrosion resistance principle;
because the corrosive components in the oral cavity are complex and changeable, the corrosion resistance problem of the patent titanium alloy must be considered preferentially; the corrosion resistance of the titanium matrix is mainly reflected in the corrosion resistance of oxidizing acid and alkali, and the reduction acid resistance is not ideal; zirconium has excellent reducing acid resistance, and the titanium alloy has more comprehensive and complete corrosion resistance by adding a large amount (more than 10%) of zirconium into titanium;
2. strengthening the titanium alloy;
in order to improve the service performance of the medical oral titanium alloy, the strength of the titanium alloy must be strengthened by adding a solid solution strengthening element on the basis of pure titanium; zirconium is infinitely solid-dissolved in titanium, and a brittle phase cannot be generated; meanwhile, the addition of zirconium has little influence on the phase change point of the titanium alloy, heat treatment strengthening is not needed, and the manufacturing procedures are reduced; the cost factor is comprehensively considered, and the adding amount of zirconium in the titanium alloy is controlled to be between 10 and 20 percent;
3. the antibacterial principle;
at present, no antibacterial titanium alloy appears in medical oral materials used at home and abroad, but with the wide application of tooth implantation technology, the antibacterial property of commonly used pure titanium implants is insufficient, and the antibacterial effect is more and more important; silver is one of the elements with the best antibacterial property, silver can perform eutectoid reaction in the titanium alloy, and the silver can form silver-rich layers with different gradients from the surface to the inside on the surface of a medical titanium alloy metal device after heat treatment at a certain temperature, so that the antibacterial property of the titanium alloy is greatly improved, and the antibacterial property can be met by adding a trace amount of silver (less than 0.5%) in consideration of comprehensive cost and performance;
4. the range of the main components of the titanium alloy is as follows;
12-17% Zr, ag0.2-0.5% and the balance Ti.
Example two
A manufacturing method of a novel medical oral corrosion-resistant antibacterial titanium alloy comprises an intermediate alloy smelting technology;
1. in the Ti-Zr-Ag titanium alloy, titanium and zirconium are infinitely solid-dissolved, so that the titanium and the zirconium are added in a pure metal state in the smelting process; silver is very easy to segregate in the process of smelting and alloying because the melting point of silver in the titanium alloy is greatly different from that of titanium, and the traditional adding method is to add pure silver, but the segregation of ingot components is difficult to control, so that the adding of silver in a zirconium-silver intermediate alloy mode is the best scheme;
2. because the raw material of zirconium, namely sponge zirconium, has great chemical activity and is easy to oxidize, the zirconium-silver intermediate alloy must be smelted by a smelting furnace with high vacuum degree, and the intermediate alloy is smelted by a vacuum electron beam furnace with high vacuum degree;
the master alloy comprises the following components: ag8.00-10.00% of Zr for the rest;
3. the production process of the zirconium-silver intermediate alloy comprises the following steps:
mixing sponge zirconium (Zr is more than 99.9 percent) and silver powder (Ag is more than 99.90 percent), placing the mixture into a vacuum electron beam furnace charge box, vacuumizing the vacuum electron beam furnace, smelting a zirconium-silver alloy cast ingot in a high vacuum state, cooling an intermediate alloy cast ingot along with the furnace in the high vacuum state, breaking vacuum at room temperature, discharging the intermediate alloy cast ingot, analyzing the components of the intermediate alloy, mechanically processing the intermediate alloy cast ingot to particles (or cutting), detecting and packaging for later use.
EXAMPLE III
A manufacturing method of a novel medical oral cavity corrosion-resistant antibacterial titanium alloy comprises the steps of producing a titanium alloy ingot;
the titanium alloy ingot is a basic raw material for manufacturing any titanium alloy processing material and product, and the quality of the titanium alloy ingot determines the quality of the titanium alloy material product; therefore, the method adopts a vacuum consumable furnace which is self-made by a company and has a plurality of patent technologies to carry out smelting production, and the vacuum consumable furnace carries out vacuum consumable smelting for more than two times; because the method of adding elements into the intermediate alloy is adopted, the titanium alloy ingot casting has high uniformity and consistency of the alloy components, and reaches the leading medical titanium alloy ingot casting standard at home and abroad;
1. the production process flow of the titanium alloy ingot comprises the following steps:
titanium sponge (GB above 0 level), zirconium sponge (GB above 1 level), zirconium-silver intermediate alloy, a titanium alloy consumable electrode block is extruded by a hydraulic machine, a titanium alloy consumable electrode is assembled and welded in a vacuum welding box, a vacuum consumable furnace is melted for the first time, an ingot is cooled with the furnace and taken out of the furnace, the head and the tail of the first consumable ingot are mechanically processed, a secondary consumable electrode is assembled and welded, the vacuum consumable furnace is melted for the second time, a titanium alloy ingot is cooled by the aid of argon, the ingot is taken out of the furnace by breaking vacuum at room temperature, the head and the tail of the ingot are mechanically processed, the surface of the ingot is pulled, the alloy components and impurities are sampled at five points from the top to the bottom of the ingot are analyzed, and the components and the impurities are detected and put into a warehouse for standby;
2. range of ingot composition control
Principal component
Zr13.00-17.00％
Ag0.30-0.45％
Balance of Ti
Range of impurity control
O＜0.12％
N＜0.002％
H＜0.001％
C＜0.008％
Fe＜0.05％。
Example four
A manufacturing method of a novel medical oral corrosion-resistant antibacterial titanium alloy comprises the steps of producing an oral titanium alloy bar;
in order to ensure the structure and mechanical property of the titanium alloy material for the oral cavity, the patent adopts the high-precision warm drawing process of repeated upsetting free forging cogging, radial forging rough forging, rolling of a hot rolling mill and self-patented technology, so that the titanium alloy bar product has no anisotropy, uniform and fine structure and high consistency;
1. the production process of the titanium alloy bar comprises the following steps:
heating a titanium alloy cast ingot in an electric furnace, freely forging and cogging by using a hydraulic quick forging machine, grinding a blank, sawing and blanking, upsetting and forging by using the hydraulic quick forging machine for more than three times, grinding a thick bar blank, finely forging a bar by using a radial forging machine, grinding the surface of the bar, rolling a thin bar by using a hot rolling machine, peeling and grinding the surface of the bar, automatically drawing by using a proprietary technology, straightening the bar, grinding the bar, detecting mechanical properties, detecting tissues, detecting surface quality, detecting flaw, detecting dimension and specification and tolerance, and packaging and warehousing;
cogging temperature: 1100-1150 deg.C
Precision forging temperature: 930-980 deg.C
Hot rolling temperature: 950-980 deg.C
Temperature of warm drawing: 600-800 ℃;
2. controlling the range of the mechanical property of the bar for oral cavity;
mechanical Properties of the working Material (annealed State)
σb1050-1200MPa
σ0.2990--1030MPa
δ18-22％
Ψ21--28％
The comprehensive performance of the alloy exceeds that of all medical titanium alloys used at present;
3. controlling the organization;
the titanium alloy is alpha-structure titanium alloy, and the grain size is controlled to be above grade 3 of the international medical titanium alloy standard;
EXAMPLE five
A manufacturing method of a novel medical oral cavity corrosion-resistant antibacterial titanium alloy comprises an antibacterial treatment process of a titanium alloy dental product;
titanium alloy dental products represented by implants are combined with gingival tissues, and the antibiosis is realized by higher silver ions on the surfaces of the implants; according to the characteristics of silver element in titanium alloy, providing a heat treatment method in which the silver content is gradually reduced from the surface of the implant to the inside;
the treatment process comprises the following steps: cleaning a mechanically processed finished product of the implant, placing the mechanically processed finished product into a vacuum heat treatment furnace, vacuumizing, heating to 450-650 ℃, preserving heat for more than 8 hours, cooling, discharging, detecting and packaging;
example six
A manufacturing method of a novel medical oral corrosion-resistant antibacterial titanium alloy comprises a titanium alloy corrosion-resistant experiment;
sulfuric acid: the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
hydrochloric acid: the concentration is 1-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
acetic acid: the concentration is 7-9%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
brine: the concentration is 5-15%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
pure alkaline water; the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
EXAMPLE seven
A manufacturing method of a novel medical oral cavity corrosion-resistant antibacterial titanium alloy comprises an antibacterial experiment;
the Shenyang hospital is entrusted to carry out an antibacterial experiment, and the experimental result is as follows: the common anaerobic bacteria inactivation rate of 3 gingival periodontal tissues is more than 90%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A manufacturing method of a novel medical oral cavity corrosion-resistant antibacterial titanium alloy is characterized by comprising the following steps:
step 1, designing components of a titanium alloy;
1.1, corrosion resistance principle;
because the corrosive components in the oral cavity are complex and changeable, the problem of corrosion resistance of the patent titanium alloy must be considered preferentially; the corrosion resistance of the titanium matrix is mainly reflected in the corrosion resistance of oxidizing acid and alkali, and the reduction acid resistance is not ideal; zirconium has excellent reducing acid resistance, and the titanium alloy has more comprehensive and complete corrosion resistance by adding a large amount (more than 10%) of zirconium into titanium;
1.2, strengthening the titanium alloy;
in order to improve the service performance of the medical oral titanium alloy, the strength of the titanium alloy must be strengthened by adding a solid solution strengthening element on the basis of pure titanium; zirconium is infinitely solid-dissolved in titanium, and a brittle phase cannot be generated; meanwhile, the addition of zirconium has little influence on the phase change point of the titanium alloy, heat treatment strengthening is not needed, and the manufacturing procedures are reduced; the cost factor is comprehensively considered, and the adding amount of zirconium in the titanium alloy is controlled to be between 10 and 20 percent;
1.3, antibacterial principle;
at present, no antibacterial titanium alloy appears in medical oral cavity materials used at home and abroad, but with the wide application of tooth implantation technology, the antibacterial property of commonly used pure titanium implants is insufficient, and the antibacterial function is more and more important; silver is one of the elements with the best antibacterial property, silver can perform eutectoid reaction in the titanium alloy, and the silver can form silver-rich layers with different gradients from the surface to the inside on the surface of a medical titanium alloy metal device after heat treatment at a certain temperature, so that the antibacterial property of the titanium alloy is greatly improved, and the antibacterial property can be met by adding a trace amount of silver (less than 0.5%) in consideration of comprehensive cost and performance;
step 2, intermediate alloy smelting technology;
2.1, in the Ti-Zr-Ag titanium alloy, titanium and zirconium are infinitely solid-dissolved, so that the titanium and the zirconium are added in a pure metal state in the smelting process; silver is very easy to segregate in the process of smelting and alloying because the melting point of silver in the titanium alloy is greatly different from that of titanium, and the traditional adding method is to add pure silver, but the segregation of ingot components is difficult to control, so that the adding of silver in a zirconium-silver intermediate alloy mode is the best scheme;
2.2, because the zirconium sponge which is the raw material of zirconium has great chemical activity and is easy to oxidize, the zirconium-silver intermediate alloy must be smelted by a smelting furnace with high vacuum degree, and the intermediate alloy is smelted by a vacuum electron beam furnace with high vacuum degree;
step 3, producing a titanium alloy ingot;
the titanium alloy ingot is a basic raw material for manufacturing any titanium alloy processing material and product, and the quality of the titanium alloy ingot determines the quality of the titanium alloy material product; therefore, the vacuum consumable furnace self-made by a company and provided with a plurality of patent technologies is adopted for smelting production, and the vacuum consumable furnace is subjected to vacuum consumable smelting for more than two times, and because the vacuum consumable furnace adopts a water-cooled copper crucible and a computer controls the smelting and cooling speed, the titanium alloy ingot casting without other impurity pollution and with high cleanliness is ensured to be produced; because the method of adding elements into the intermediate alloy is adopted, the titanium alloy ingot casting has high uniformity and consistency of the alloy components, and reaches the leading medical titanium alloy ingot casting standard at home and abroad;
step 4, producing the titanium alloy bar for the oral cavity;
in order to ensure the structure and mechanical property of the titanium alloy material for the oral cavity, the patent adopts the high-precision warm drawing process of repeated upsetting free forging cogging, radial forging rough forging, rolling of a hot rolling mill and self-patented technology, so that the titanium alloy bar product has no anisotropy, uniform and fine structure and high consistency;
4.1, the production process of the titanium alloy bar comprises the following steps:
heating a titanium alloy cast ingot in an electric furnace, freely forging and cogging by using a hydraulic quick forging machine, grinding a blank, sawing and blanking, upsetting and forging by using the hydraulic quick forging machine for more than three times, grinding a thick bar blank, finely forging a bar by using a radial forging machine, grinding the surface of the bar, rolling a thin bar by using a hot rolling machine, peeling and grinding the surface of the bar, automatically drawing by using a proprietary technology, straightening the bar, grinding the bar, detecting mechanical properties, detecting tissues, detecting surface quality, detecting flaw, detecting dimension and specification and tolerance, and packaging and warehousing;
cogging temperature: 1100-1150 deg.C
Precision forging temperature: 930-980 deg.C
Hot rolling temperature: 950-980 deg.C
Temperature of warm drawing: 600-800 ℃;
4.2, controlling the mechanical property range of the bar for oral cavity;
mechanical Properties of the working Material (annealed State)
σb 1050-1200MPa
σ0.2 990--1030MPa
δ 18-22％
Ψ 21--28％
The comprehensive performance of the alloy exceeds that of all medical titanium alloys used at present;
4.3, tissue control;
the titanium alloy is alpha-structure titanium alloy, and the grain size is controlled to be above grade 3 of international medical titanium alloy standard;
step 5, performing an antibacterial treatment process on the titanium alloy dental product;
titanium alloy dental products represented by implants are combined with gingival tissues, and the antibiosis is realized by higher silver ions on the surfaces of the implants; according to the characteristics of silver element in titanium alloy, a heat treatment method with the silver content gradually reduced from the surface of the implant to the inside is provided;
the treatment process comprises the following steps: cleaning mechanically processed implant finished products, placing the mechanically processed implant finished products into a vacuum heat treatment furnace, vacuumizing, heating to 450-650 ℃, preserving heat for more than 8 hours, cooling and discharging, detecting and packaging;
step 6, performing a corrosion resistance experiment on the titanium alloy;
sulfuric acid: the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
hydrochloric acid: the concentration is 1-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.01 mm/year;
acetic acid: the concentration is 7-9%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
saline water: the concentration is 5-15%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
pure alkaline water; the concentration is 3-5%; temperature: room temperature; time: 180 days; corrosion rate: less than 0.001 mm/year;
step 7, performing an antibacterial experiment;
the Shenyang hospital is entrusted to carry out an antibacterial experiment, and the experimental result is as follows: the common anaerobic bacteria inactivation rate of 3 gingival periodontal tissues is more than 90%.
2. The manufacturing method of the novel medical oral corrosion-resistant antibacterial titanium alloy according to claim 1, is characterized in that: the range of main components of the titanium alloy in the step one; zr12-17%, ag0.2-0.5% and the balance Ti.
3. The manufacturing method of the novel medical oral corrosion-resistant antibacterial titanium alloy according to claim 1, is characterized in that: in the second step: the master alloy comprises the following components: ag8.00-10.00% and the balance Zr.
4. The manufacturing method of the novel medical oral corrosion-resistant antibacterial titanium alloy according to claim 1, is characterized in that: in the second step: the production process of the zirconium-silver intermediate alloy comprises the following steps: mixing sponge zirconium (Zr is more than 99.9 percent) and silver powder (Ag is more than 99.90 percent), placing the mixture into a vacuum electron beam furnace charge box, vacuumizing the vacuum electron beam furnace, smelting a zirconium-silver alloy cast ingot in a high vacuum state, cooling an intermediate alloy cast ingot along with the furnace in the high vacuum state, breaking vacuum at room temperature, discharging the intermediate alloy cast ingot, analyzing the components of the intermediate alloy, mechanically processing the intermediate alloy cast ingot to particles (or cutting), detecting and packaging for later use.
5. The manufacturing method of the novel medical oral corrosion-resistant antibacterial titanium alloy according to claim 1, is characterized in that: the third step is as follows: the production process flow of the titanium alloy ingot comprises the following steps: titanium sponge (GB 0 grade or above), zirconium sponge (GB 1 grade or above), zirconium-silver intermediate alloy, titanium alloy consumable electrode blocks extruded by a hydraulic press, titanium alloy consumable electrodes assembled and welded in a vacuum welding box, primary smelting of a vacuum consumable furnace, ingot casting and furnace cooling discharging, primary consumable ingot casting head and tail machining and surface machining, secondary consumable electrodes assembled and welded, secondary smelting of the vacuum consumable furnace, auxiliary cooling of titanium alloy ingot casting by argon, ingot casting room-temperature vacuum breaking and discharging, mechanical machining of ingot casting head and tail, ingot casting surface peeling, analysis of alloy components and impurities sampled at five points above and below the ingot casting, detection and warehousing for later use.
6. The manufacturing method of the novel medical oral corrosion-resistant antibacterial titanium alloy according to claim 1, is characterized in that: in the third step: controlling the range of ingot casting components; 13.00 to 17.00 percent of Zr, 0.30 to 0.45 percent of Ag0 and the balance of Ti.
7. The manufacturing method of the novel medical oral corrosion-resistant antibacterial titanium alloy according to claim 1, is characterized in that: in the third step: controlling the range of impurities; less than 0.12 percent of O, less than 0.002 percent of N, less than 0.001 percent of H, less than 0.008 percent of C and less than 0.05 percent of Fe.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2134925A1 (en) * | 1970-07-13 | 1972-01-20 | Straumann Inst Ag | Cast and forged alloy for surgical and dental implants |
| CN105838910A (en) * | 2016-05-31 | 2016-08-10 | 沈阳中核舰航特材科技有限公司 | Manufacturing method of antibacterial titanium alloy for bio-medical treatment |
| CN112195366A (en) * | 2020-09-29 | 2021-01-08 | 中国科学院金属研究所 | High-thermal-stability equiaxial nanocrystalline Ti-Zr-Ag alloy and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2134925A1 (en) * | 1970-07-13 | 1972-01-20 | Straumann Inst Ag | Cast and forged alloy for surgical and dental implants |
| CN105838910A (en) * | 2016-05-31 | 2016-08-10 | 沈阳中核舰航特材科技有限公司 | Manufacturing method of antibacterial titanium alloy for bio-medical treatment |
| CN112195366A (en) * | 2020-09-29 | 2021-01-08 | 中国科学院金属研究所 | High-thermal-stability equiaxial nanocrystalline Ti-Zr-Ag alloy and preparation method thereof |
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