CN108728692A - A kind of medical use anti-infection material titanium alloy - Google Patents
A kind of medical use anti-infection material titanium alloy Download PDFInfo
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- CN108728692A CN108728692A CN201810301000.3A CN201810301000A CN108728692A CN 108728692 A CN108728692 A CN 108728692A CN 201810301000 A CN201810301000 A CN 201810301000A CN 108728692 A CN108728692 A CN 108728692A
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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
- 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
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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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- 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
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Abstract
The present invention relates to medical titanium alloy Material Field, specially a kind of infection-resistant medical titanium alloy.The chemical composition of the medical titanium alloy is following (weight %):Al:5.5-6.5%, V:3.5-4.5%, Ga:0.2-4.0%, surplus are Ti and other inevitable impurity elements.By adding suitable Ga elements in medical Ti 6Al4V alloy substrates, to assign Ti6Al4V medical titanium alloys excellent bacterial-infection resisting function.The alloy can be widely applied to all kinds of medical titanium alloy medical instruments used in the clinical fields such as orthopaedics, the department of stomatology, can significantly further reduce the bacterium infection risk caused in existing implantation material titanium alloy instrument use.
Description
Technical field
The present invention relates to medical titanium alloy Material Field, specially a kind of infection-resistant medical titanium alloy.
Background technology
Medical titanium alloy is due to nonmagnetic, non-toxic, excellent biocompatibility, good wear resistance and corrosion resistance and resultant force
Performance is learned, is a kind of medical metal material of current wide clinical application, has been widely used in joint prosthesis, solid in fracture
Determine numerous implantation instruments such as instrument, backbone correcting internal fixation system, gear division reparation.Ti6Al4V is that the first generation is widely used in manufacture
The medical titanium alloy of implantation instrument, its main alloy element are Al (5.5-6.5wt.%) and V (3.5-4.5wt.%).It compares
In pure titanium, Ti6Al4V is alpha and beta titanium alloy, has excellent mechanical property and good processing performance, as surgical repair material
Expect that such as bone plate, intramedullary nail have longer clinical application history.
However, in use, there is operative site bacterium infection in medical instrument, and by medical instrument institute
The localized bacterial infection of initiation is one of current most common complication, and the application of implanted medical device can further increase postoperative
The generation of infection.Postoperative infection does not only result in poor functional rehabilitation, and extends length of patient stay, and patient also needs experience again
Secondary operation takes out implanted medical device and removes lesion, and heavy financial burden and stress are brought to patient.World health
The statistical data of tissue shows that the daily whole world has more than the risk that 14,000,000 people experiencing nosocomial infection, wherein 60% it is thin
Bacterium infection is related to the medical instrument used.According to statistics, in the U.S. of medical level prosperity, orthopaedics implant infections relating
Annual morbidity has reached 4.3% or so.More serious bacterium infection problem not only brings huge body to patient at this stage
Pained bitter and heavy financial burden, can also cause hospital and society etc. different degrees of negative effect.
Therefore, the present invention has researched and developed a kind of Anti-infection medical titanium alloy, is innovatively proposed for the first time in common doctor
With Ga elements are added in the matrix of titanium alloy, by being heat-treated accordingly, assign material excellent anti-microbial property.
Invention content
The purpose of the present invention is to provide a kind of medical use anti-infection material titanium alloys, by medical Ti 6Al4V alloy-baseds
Suitable Ga elements are added in body, to assign Ti6Al4V medical titanium alloys excellent bacterial-infection resisting function.The alloy can be wide
The general all kinds of medical titanium alloy medical instruments for being applied to use in the clinical fields such as orthopaedics, the department of stomatology, can be significantly further
Reduce the bacterium infection risk caused in existing implantation material titanium alloy instrument use.
The technical scheme is that:
A kind of medical use anti-infection material titanium alloy, it is characterised in that:By weight percentage, the chemical composition of the material is:
Al:5.5-6.5 weight %, V:3.5-4.5 weight %, Ga:0.2-4.0 weight %;Remaining is Ti and inevitable impurity, is closed
Impurity content meets the corresponding requirements in medical titanium alloy national standard in gold.
As preferred technical solution:The ranging from Ga of Ga elements:1.0-2.0 weight %.
The present invention provides the preparation methods of above-mentioned medical use anti-infection material titanium alloy, it is characterised in that:The antibacterial
Titanium alloy is smelted using vacuum induction to be obtained, and wherein Ga elements are added in the form of Al-Ga intermediate alloys.
The present invention also provides the preparation methods of above-mentioned medical titanium alloy, it is characterised in that:The medical titanium for smelting gained is closed
Gold uses following hot-working and heat treatment process:
Hot-working:For alloy in 850-950 DEG C of Homogenization Treatments 1-3 hours, cogging forging divided multi-pass to be forged into blank,
Whole forging temperature is not less than 800 DEG C;
Solution heat treatment:750-900 DEG C of solution treatment 0.5-1 hours, air-cooled or water cooling to room temperature.
Ga elements are most important ingredients in the present invention, this is to ensure that material of the present invention has the root of bacterial-infection resisting function
This place, and main innovation point of the invention.Ga elements are widely used in semicon industry, have accounted for the 98% of commercial Ga
More than.It is normally metabolic that Ga elements can upset bacterium, and then kills bacterium.Metal Ga is that a kind of low melting point is high boiling
Metal, 2204 DEG C of boils up till.By Ti-Ga binary phase diagramls it is found that Ga elements have higher solid solution in β-Ti and α-Ti
Degree, this preparation also for the 6Al4V medical titanium alloys of medical Ti containing Ga provide necessary condition.It is dissolved out by titanium alloy surface
Ga ions can quickly kill bacterium, be the main innovation point of the present invention.
The beneficial effects of the invention are as follows:
The present invention innovatively proposes the concept that Ga elements are added in common medical titanium alloy for the first time, has devised one
Kind medical use anti-infection material titanium alloy.By regulating and controlling the content of Ga elements and corresponding heat treatment in steel, make medical titanium alloy table
Face dissolves out the Ga for having strong sterilizing ability3+Ion makes it have excellent anti-microbial property, has broad application prospects.
Description of the drawings
Fig. 1 is the anti-bacterial result of the embodiment (b) with comparative example (a) to Escherichia coli in the present invention.
Specific implementation mode
The present invention is further described with embodiment below.These embodiments are only to the best embodiment party of the present invention
The description of formula, does not have any restrictions to the scope of the present invention.
Embodiment:Embodiment 1-8 is the medical use anti-infection material titanium alloy containing Ga elements, and chemical composition is shown in Table 1.Root
Control smelting is carried out according to the chemical composition ranges of the present invention.
The forging technology used for:For alloy in 920 DEG C of Homogenization Treatments 2 hours, cogging forging divided multi-pass to forge diameter
For 10mm bars, final forging temperature is 820 DEG C;
The heat treatment process used is solid solubility temperature is 800 DEG C, and solution time is 40 minutes.
Comparative example:Comparative example 1 is common medical titanium alloy Ti6Al4V, and comparative example 2 is the medical titanium containing a small amount of Ga elements
Alloy, comparative example 3 are the medical titanium alloy containing volume Ga elements, and chemical composition is shown in Table 1, specific treatment process and embodiment
It is identical.
1 embodiment and comparative example material chemical composition (wt.%) of table
Material | Al | V | Ga | Ti |
Embodiment 1 | 5.7 | 3.9 | 0.2 | Surplus |
Embodiment 2 | 5.9 | 3.9 | 0.8 | Surplus |
Embodiment 3 | 6.1 | 4.1 | 1.0 | Surplus |
Embodiment 4 | 5.8 | 4.2 | 1.5 | Surplus |
Embodiment 5 | 5.6 | 3.8 | 2.0 | Surplus |
Embodiment 6 | 6.2 | 3.8 | 2.5 | Surplus |
Embodiment 7 | 6.1 | 4.3 | 3.0 | Surplus |
Embodiment 8 | 5.9 | 3.9 | 4.0 | Surplus |
Comparative example 1 | 6.1 | 4.1 | - | Surplus |
Comparative example 2 | 6.2 | 4.2 | 0.1 | Surplus |
Comparative example 3 | 5.8 | 3.7 | 5.0 | Surplus |
1, anti-microbial property detects
According to " JIS Z 2801-2000《Antibacterial fabricated product-antibiotic property test method and antibacterial effect》,GB/T
2591-2003《Antibiotic plastic anti-microbial property experimental method and antibacterial effect》" etc. correlation standards, quantitative test table 1 institute
Show the sterilization after multicomponent metallic acts on common infection bacterium (such as E. coli, staphylococcus aureus S.aureus)
Rate.The calculation formula of wherein sterilizing rate is:Sterilizing rate (%)=[(control sample viable count-Anti-infection medical titanium alloy viable bacteria
Number)/control sample viable count] × 100%, control sample viable count is progress bacterium training in general T i6Al4V titanium alloy samples
Viable count after supporting, Anti-infection medical titanium alloy viable count refer to that Anti-infection medical titanium alloy carries out the viable bacteria after Bacteria Culture
Number.Test result is shown in Table 2.
2, corrosion resistance
Anodic polarization curves test has been carried out to medical titanium alloy containing Ga of the embodiment of the present invention and comparative example medical titanium alloy.
Test result is shown in Table 2.
3, Cytotoxic evaluation
Bio-safety performance detection is carried out to embodiment and comparative example material.Cytotoxicity experiment is carried out using MTS reagent.
The reagent can be converted to water-soluble Xing Jia Za compounds by the dehydrogenase type in living cells, and dead cell is without this function.By culture bottle
In it is cells trypsinised after be configured to a concentration of 5 × 104The cell suspension of/ml is added in 96 orifice plates, is added per hole
Enter 100 μ l.In 5%CO2After cultivating 8h in incubator, former culture medium is abandoned in suction, and after gently cleaning 2 times with PBS, 100 μ l materials are added
Expect leaching liquor, while negative control group (complete medium is added) and positive controls (the complete training containing 10%DMSO are set
Support base).96 orifice plates are put back into CO2Continue in incubator culture for 24 hours, 48h and 72h.Given time point has been arrived, 96 orifice plates are taken out,
10 μ l MTS (Signalway Antibody, USA) are added to measure under microplate reader 490nm wavelength after being incubated 4h in incubator
Absorbance value, and calculate cell opposite proliferation rate (Relative growth rate, RGR), RGR=(experimental group OD values/culture
Base OD values) × 100%, then according to 5 grades of toxicity assessment standard gradings (0,1 grade meets bio-medical material requirement).Test knot
Fruit is shown in Table 2.
2 embodiment and comparative example material correlated performance detection result of table
It can be seen that from the result of table 2, (embodiment 1,2 and comparative example 2), alloy when the content of Ga elements in alloy is relatively low
Certain anti-microbial property is had been provided with, but sterilizing rate does not reach 90%.(>=1.0 weights when Ga constituent contents gradually increase
Measure %), alloy shows excellent anti-microbial property, and sterilizing rate has reached 99.9%, therefore preferably under Ga constituent content ingredients
It is limited to >=1.0 weight %.
For the corrosion resistance of alloy, when the content of Ga elements in alloy is relatively low (embodiment 1-5), the spot corrosion of alloy
Current potential and comparative example material are substantially suitable, when the content of Ga elements is more than 2.0 weight % (embodiment 6,7 and 8), the point of alloy
It loses current potential and downward trend is presented, and when the content of Ga elements reaches 5.0 weight % (comparative example 3), the spot corrosion electricity of alloy
Position is rapid to be declined, it is contemplated that the corrosion resistance of implantation material requires and material cost, and preferably Ga constituent contents ingredient is≤2.0 weights
Measure %.
In addition, for the biological safety of alloy, the cytotoxicity grade of alloy is respectively less than 2 grades, according to national standard
The regulation of GBT16886.5-2003, cytotoxicity is qualification less than 2 grades or less, therefore medical titanium alloy containing Ga meets implantation
The requirement of object biological safety.
By being analyzed above it is found that when the content of Ga elements is in preferred scope, medical titanium alloy containing Ga shows excellent
Different anti-microbial property, while being also equipped with good corrosion resisting property and biocompatibility.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of medical use anti-infection material titanium alloy, which is characterized in that its chemical composition is mass percent:Al:5.5-6.5
V:3.5-4.5, Ga:0.2-4.0;Surplus is Ti.
2. according to medical use anti-infection material titanium alloy described in claim 1, it is characterised in that:The ranging from Ga of Ga elements:1.0-
2.0wt.%.
3. the preparation method of medical use anti-infection material titanium alloy described in a kind of claims 1 or 2, it is characterised in that:The titanium closes
Gold is smelted using vacuum induction to be obtained, and wherein Ga elements are added in the form of Al-Ga intermediate alloys.
4. according to the preparation method of medical use anti-infection material titanium alloy described in claim 3, it is characterised in that:Smelt the doctor of gained
Following hot-working and heat treatment process are used with material titanium alloy:
Hot-working:For alloy in 850-950 DEG C of Homogenization Treatments 1-3 hours, cogging forging divided multi-pass to be forged into blank, finish-forging
It makes temperature and is not less than 800 DEG C;
Solution heat treatment:750-900 DEG C of solution treatment 0.5-1 hours, air-cooled or water cooling to room temperature.
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Cited By (1)
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CN110170069A (en) * | 2019-05-29 | 2019-08-27 | 中国科学院金属研究所 | A kind of enhancing anchorage micro-implant medical titanium alloy material and preparation method thereof |
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CN106148759A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院金属研究所 | Have and facilitate bone and the medical titanium alloy of revascularization biological function and preparation thereof |
CN107802378A (en) * | 2017-11-22 | 2018-03-16 | 华南理工大学 | Astragalus local route repair body and its design and production method with loose structure |
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CN106148759A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院金属研究所 | Have and facilitate bone and the medical titanium alloy of revascularization biological function and preparation thereof |
CN107802378A (en) * | 2017-11-22 | 2018-03-16 | 华南理工大学 | Astragalus local route repair body and its design and production method with loose structure |
Non-Patent Citations (1)
Title |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110170069A (en) * | 2019-05-29 | 2019-08-27 | 中国科学院金属研究所 | A kind of enhancing anchorage micro-implant medical titanium alloy material and preparation method thereof |
CN110170069B (en) * | 2019-05-29 | 2021-11-09 | 中国科学院金属研究所 | Medical titanium alloy material for reinforcing anchorage micro-implant and preparation method thereof |
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